新型化合物以及含有该化合物的放射线敏感性组合物 The novel compounds and a radiation-sensitive composition comprising the compound

技术领域 Technical Field

[0001] 本发明涉及作为光聚合引发剂而有用的新型化合物以及含有该新型化合物的放射线敏感性组合物。 [0001] The present invention relates to a photopolymerization initiator, and a novel compound useful radiation-sensitive compositions containing the novel compounds.

背景技术 Background

[0002] 放射线敏感性组合物由于可以通过涂布工艺大量且容易地形成固化物，该固化物的微细加工也容易等优点，所以除了作为液晶装置、半导体装置制作用材料等以外，还广泛用于光固化性油墨、感光性印刷版等中。 [0002] The radiation-sensitive composition due to the large and can be easily formed by the cured coating process, microfabrication of the cured product is also easy, etc., so in addition to as a liquid crystal device, other than the production of semiconductor devices and other materials, but also widely used the light-curable ink, photosensitive printing plates and the like. 这种放射线敏感性组合物代表性包含具有乙烯基不饱和键的聚合性化合物以及光聚合引发剂。 Representative of such radiation-sensitive composition comprising a polymerizable compound having ethylenically unsaturated bond and a photopolymerization initiator. 在上述固化物形成工艺中，可以通过将该放射线敏感性组合物涂布到玻璃基板等上形成覆膜，接着通过具有水银灯的曝光装置对该覆膜曝光，可以形成作为固化物的固化膜。 In the above-described cured product forming process, through the radiation-sensitive composition to form a coating film on a glass substrate, followed by exposure of the coating apparatus having a mercury lamp exposure, the cured product as a cured film can be formed.

[0003] 水银灯是在紫外〜可见光波长区域具有水银特有的亮线光谱的灯，在254nm、 365nm、405nm等具有强度大的水银灯特有的亮线。 [0003] is a mercury lamp bright line spectrum unique to mercury lamp in the ultraviolet to visible wavelength region, having a large specific strength mercury lamp bright line at 254nm, 365nm, 405nm and the like. 其中，开发出了有效利用365nm、405nm的亮线的高放射线灵敏度的光聚合引发剂（例如，参照专利文献1)。 Among them, the development of effective utilization 365nm, 405nm high radiation sensitivity of the bright line photopolymerization initiator (e.g., refer to Patent Document 1).

[0004] 上述这种高放射线灵敏度的光聚合引发剂大多是在可见光区域具有极大吸收的化合物，大多情况下略微带有红色。 [0004] Such high radiation sensitivity of the above photopolymerization initiator is a compound having mostly a maximum absorption in the visible region, most of the case with a slightly red. 而且，如果使用略微带有红色的光聚合引发剂，固化膜也同样略微呈现红色，透明性降低，所以可能无法适用于适合液晶装置等使用的在可见光区域必须有高的透过性的固化膜。 Furthermore, if a slightly red with a photopolymerization initiator, a cured film also slightly red, transparency is lowered, it may not be suitable for a liquid crystal device or the like for use in the visible region of the cured film must have a high permeability .

[0005] 另一方面，目前使用的乙酰苯类引发剂（例如，参照专利文献2)由于在300nm附近具有极大吸收，所以光聚合引发剂自身也大致是白色的，使用乙酰苯类引发剂的固化膜在可见光区域显示高的透明性。 [0005] On the other hand, acetophenones initiators currently used (e.g., refer to Patent Document 2) Since having a maximum absorption near 300nm, so the photopolymerization initiator itself is generally white, the use of an initiator acetophenones The cured film exhibits high transparency in the visible region. 但是，这种乙酰苯类引发剂的放射线灵敏度低，为了得到具有足够表面硬度的膜，必须要高的曝光量。 However, such acetophenones initiators low radiation sensitivity, in order to obtain a film having a sufficient surface hardness, must be high exposure. 此外，由于乙酰苯类引发剂具有升华性，所以近年来发现由于升华导致烘焙炉或曝光时的光掩模的污染等问题（例如，参照专利文献3)。 Further, since the initiator has acetophenones sublimable, so in recent years since the discovery of the sublimation lead to contamination of the photomask exposure baking furnace or the like problems (e.g., refer to Patent Document 3).

[0006] 相对于此，开发出了一种特定的肟酯化合物，该化合物是低挥发性且高放射线灵敏度，可以作为即使含有大量着色颜料也可以形成固化膜的光引发剂，且具有至少两个肟酯基（例如，参照专利文献4)。 [0006] On the other hand, developed a specific oxime ester compound which is a low volatility and a high radiation sensitivity, even if containing a large amount as a coloring pigment may be formed of a cured film photoinitiator, and having at least two an oxime ester group (e.g., refer to Patent Document 4). 然而，该肟酯化合物由于是用于形成着色的抗蚀膜的光引发剂，所以没有考虑使用该光引发剂的固化膜的透明性。 However, since the oxime ester compound is light colored resist film for forming initiators, it does not consider the use of the photoinitiator agent transparent cured film. 另外，认为上述肟酯化合物对放射线敏感性组合物的溶解性还不足，具有改良的余地。 Further, that the above-described oxime ester compounds of the radiation-sensitive composition also insufficient solubility, has room for improvement.

[0007] 根据上述问题，希望开发出一种升华性低，作为光聚合引发剂使用时，显示出高的放射线灵敏度，作为放射线敏感性组合物的光聚合引发剂使用时，可以得到具有高的透明性和表面硬度的固化膜，而且对放射线敏感性组合物的溶解性高的化合物。 [0007] According to the above questions, we hope to develop a low sublimation as a photopolymerization initiator, exhibits high radiation sensitivity, as the radiation-sensitive composition of the photopolymerization initiator can be obtained with high transparency and surface hardness of the cured film, and the radiation-sensitive composition is highly soluble compound.

[0008]【现有技术文献】 [0008] [CITATION]

[0009]【专利文献】 [0009] [Patent Document]

[0010]【专利文献1】日本特开2001-233842号公报 [0010] [Patent Document 1] Japanese Unexamined Patent Publication No. 2001-233842

[0011]【专利文献2】日本特开昭58-157805号公报 [0011] Japanese Unexamined Patent Publication No. 58-157805 [Patent Document 2] Gazette

[0012]【专利文献3】日本特开2007-86565号公报[0013]【专利文献4】日本特表2009-519904号公报发明内容 [0012] [Patent Document 3] Japanese Unexamined Patent Publication No. 2007-86565 [0013] [Patent Document 4] Japanese Patent No. 2009-519904 DISCLOSURE OF THE INVENTION

[0014] 本发明是基于上述问题提出的发明，其主要目的在于提供一种升华性低，作为光聚合引发剂使用时，具有高的放射线灵敏度，同时对放射线敏感性组合物的溶解性高的化合物。 [0014] The present invention was made based on the above-mentioned problems, and its main purpose is to provide a sublimable low as photopolymerization initiator, with high radiation sensitivity, while the solubility of the radiation-sensitive composition is high compound. 此外，本发明的其它目的是提供可以得到具有高的透明性和表面硬度的固化膜的放射线敏感性组合物。 Further, other object of the present invention is to provide a radiation-sensitive composition can be obtained having a high transparency and surface hardness of the cured film.

[0015] 为了解决上述问题而提出的本发明是下述式（1)所示的化合物。 [0015] The present invention is to solve the above problems is a compound of formula (1) by the following formula.

[0016] [0016]

[0017] 式（1)中，R1是碳原子数为1〜12的烷基、碳原子数为4〜20的环烷基、碳原子数为1〜6的卤代烷基、2-呋喃基、2-糠基、2-噻吩基、2-噻吩甲基、苯基或萘基，该苯基或萘基的氢原子的一部分或全部可以被碳原子数为1〜6的烷基、碳原子数为1〜6的烷氧基或卤原子取代。 [0017] Formula (1), R1 is 1~12 carbon atoms, an alkyl group having a carbon number 4~20 cycloalkyl, 1~6 carbon atoms, a haloalkyl group, 2-furyl, 2- furfuryl, 2-thienyl, 2-thienylmethyl, phenyl or naphthyl group, a part of the hydrogen atoms of the phenyl or naphthyl group or all carbon atoms may be an alkyl group, the carbon atoms of 1~6 atoms substituted alkoxy group or a halogen atom 1~6.

[0018] R2和R3各自独立地是碳原子数为1〜12的烷基或者碳原子数为3〜10的环烷基。 [0018] R2 and R3 are each independently alkyl carbon atoms or carbon atoms is 3~10 1~12 cycloalkyl.

[0019] R4是氢原子、碳原子数为1〜12的烷基、碳原子数为1〜12的烷氧基、卤原子、 2-呋喃基、2-糠基、2-噻吩基或者2-噻吩甲基。 [0019] R4 is a hydrogen atom, 1~12 carbon atoms, an alkyl group of 1~12 carbon atoms, an alkoxy group, a halogen atom, 2-furyl, 2-furfuryl, 2-thienyl or 2 - thienylmethyl.

[0020] R5是磺基或者S&R6、P (R7)2> PO (R8) 2或者Si (R9) 3所示的基团。 [0020] R5 is a sulfo group or a S & R6, P (R7) 2> PO (R8) 2 or Si (R9) 3 group represented.

[0021] R6是氢原子、甲基、碳原子数为2〜12的烷基、苯基或者萘基，上述碳原子数为2〜 12的烷基的氢原子的一部分或者全部可以被由羧基、甲氧羰基、乙氧羰基、碳原子数为1〜 6的酰氧基、苯甲酰氧基和碳原子数为1〜20的酰基构成的群组中选出的至少1种基团取代，上述苯基或者萘基的氢原子的一部分或者全部可以被碳原子数为1〜6的烷基、碳原子数为1〜6的烷氧基或者卤原子取代。 [0021] R6 is a hydrogen atom, a methyl group, 2~12 carbon atoms, an alkyl group, a phenyl group or a naphthyl group, a part of the carbon atoms of 2 ~ 12 hydrogen atoms or alkyl all of which may be carboxy substituted methoxycarbonyl, ethoxycarbonyl group, an acyloxy group having a carbon number of 1 ~ 6, and benzoyloxy group 1~20 carbon atoms selected from the group consisting of at least one kind of group , a portion of the hydrogen atoms of said phenyl or naphthyl group or all carbon atoms may be an alkyl group 1~6, 1~6 carbon atoms or an alkoxy group substituted with a halogen atom.

[0022] R7、R8和R9各自独立地是碳原子数为1〜12的烷基、苯基或者萘基，该苯基或者萘基的氢原子的一部分或者全部可以被碳原子数为1〜6的烷基、碳原子数为1〜6的烷氧基或者卤原子取代。 [0022] R7, R8 and R9 are each independently a carbon number 1~12 alkyl group, a phenyl group or a naphthyl group, a part of the hydrogen atoms of the phenyl or naphthyl group, or all of the carbon atoms may be 1 ~ alkyl carbon atoms is substituted with 1~6 6 alkoxy group or a halogen atom.

[0023] 该化合物在作为光聚合引发剂使用时，显现出高的放射线敏感度，其结果是，通过小的曝光量，可以得到具有正确的图案和足够的表面硬度的固化膜。 [0023] This compound when used as a photopolymerization initiator, exhibit high sensitivity to radiation, the result is that by a small amount of exposure can be obtained a cured film pattern having a proper and sufficient surface hardness. 另外，该化合物由于具有上述（1)所示的结构，所以具有低的升华性，可以有效地抑制升华对设备或光掩模的污染，同时对放射线敏感性组合物显示出高的溶解性。 Further, since the compound has a structure as shown in (1) above, it has a low sublimation, the sublimation can effectively suppress the contamination of the device or a photomask, while the radiation-sensitive composition shows high solubility. 此外，使用该化合物作为光聚合引发剂时，可以得到具有高的透明性的固化膜。 In addition, the use of the compound as a photopolymerization initiator, a cured film can be obtained having high transparency.

[0024] 在该化合物中，优选上述R1、R2、R3和R4各自独立地是碳原子数为1〜8的烷基， 上述R5是S02R6、P0 (R8)2或者Si (R9)3所示的基团，上述R6是氢原子的一部分或全部被乙酰氧基取代的碳原子数为2〜6的烷基，上述R8是苯基，上述R9是碳原子数为1〜6的烷基。 [0024] In the compound, preferably, the R1, R2, R3 and R4 are each independently 1 ~ 8 carbon atoms in the alkyl group, the above-described R5 is S02R6, P0 (R8) 2 or Si (R9) 3 shown group, R6 is a part of said hydrogen atoms are all carbon atoms or an acetyl group substituted with an alkyl group of 2 ~ 6, said R8 is phenyl, R9 is above 1~6 carbon atoms of the alkyl group. 通过在该化合物中导入这种结构，可以容易地制备该化合物，而且可以进一步提高对放射线敏感性组合物的溶解性，而且可以提高放射线敏感性组合物的放射线灵敏度。 By introducing such a structure in the compound, the compound can be easily prepared, and can further enhance the solubility of the radiation sensitive composition, and can increase the radiation sensitivity of the radiation sensitive composition.

[0025] 通过使用上述化合物作为[A]成分的光聚合引发剂，进而包含作为[B]成分的具有乙烯基不饱和双键的聚合性化合物的方式，可以构成放射线敏感性组合物。 [0025] By using the above compounds as [A] component photopolymerization initiator, and further comprises as component [B] in the manner having ethylenically unsaturated double bond polymerizable compound, may constitute radiation-sensitive composition. 这种放射线敏感性组合物由于含有上述化合物，所以具有高的放射线灵敏度，而且显示出低的升华性。 Such radiation-sensitive composition containing the above compound since, it has a high radiation sensitivity, and exhibits low sublimation property. 另外，从这种放射线敏感性组合物可以得到具有高的表面硬度和透明性的固化膜。 Further, from such radiation-sensitive composition can be obtained a cured film having high surface hardness and transparency.

[0026] 该放射线敏感性组合物优选进一步含有作为[C]成分的碱可溶性树脂。 [0026] The radiation-sensitive composition preferably further comprises as component [C] of the alkali-soluble resin. 该放射线敏感性组合物由于含有碱可溶性树脂，该碱可溶性树脂对显影工序中使用的碱显示出可溶性，其结果是显现出高的显影性，可以形成具有正确的图案的固化膜。 Because of the radiation-sensitive composition comprising an alkali-soluble resin, the alkali-soluble resin used in the step of alkali developable shows solubility, with the result that show high developability, it can form a cured film having the correct pattern.

[0027] 本发明的新型化合物在作为光聚合引发剂使用时，显示出高的放射线灵敏度，同时可以提供一种放射线敏感性组合物，该放射线敏感性组合物能够通过小的曝光量，形成具有正确的图案和足够的表面硬度的固化膜。 [0027] The novel compounds of the present invention, when used as a photopolymerization initiator, exhibits high radiation sensitivity, and can provide a radiation-sensitive composition, the radiation-sensitive composition through a small amount of exposure, to form a correct pattern and a sufficient surface hardness of a cured film. 另外，该化合物由于具有低的升华性，所以可以有效地抑制升华对设备等的污染。 In addition, the compound because of low sublimation resistance, it is possible to effectively suppress the contamination of the equipment, such as sublimation. 此外，该化合物对放射线敏感性组合物的溶解性良好， 所以容易制备放射线敏感性组合物，而且由使用该化合物的放射线敏感性组合物可以得到具有高的透明性的固化膜。 Furthermore, the solubility of the compound in the good radiation-sensitive composition, it is easy to prepare a radiation sensitive composition, and by the use of the radiation-sensitive compound is a cured film composition can be obtained having high transparency.

具体实施方式 DETAILED DESCRIPTION

[0028] <新型化合物> [0028] <novel compounds>

[0029] 本发明的化合物是上述式⑴所示的化合物。 [0029] The compound of the present invention is a compound of formula ⑴ shown. 在上述式⑴中，作为R1的碳原子数为1〜12的烷基，可以列举出例如甲基、乙基、正丙基、正丁基、正戊基、正己基、正辛基、 正十二烷基等直链烷基，异丙基、异丁基、叔丁基、新戊基、2-乙基己基等支链烷基等。 ⑴ In the above formula, the number of carbon atoms as R1 is 1~12 alkyl group, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n- dodecyl and the like straight chain alkyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-ethylhexyl branched chain alkyl group. 它们之中，优选甲基、乙基、正丙基、异丙基、正丁基等碳原子数为1〜6的烷基。 Among them, preferably methyl, ethyl, n-propyl, isopropyl, n-butyl 1~6 carbon atoms such as an alkyl group.

[0030] 在上述式（1)中，作为R1的碳原子数为4〜20的环烷基，可以列举出例如环丁基、 环戊基、环己基、环庚基、环辛基、降冰片烷基、金刚烷基等。 [0030] In the above formula (1), as the number of carbon atoms in R1 is 4~20 cycloalkyl, may, for example cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, drop borneol, adamantyl and the like.

[0031] 在上述式（1)中，作为R1的碳原子数为1〜6的卤代烷基是碳原子数为1〜6的烷基的氢原子的一部分或全部被卤原子取代的基团，可以列举出例如氯代甲基、氯代乙基、 氯代丙基、氯代丁基、氯代己基等。 [0031] In the above formula (1), as the number of carbon atoms of R1 is haloalkyl 1~6 carbon atoms as a part or all substituted by a halogen atom group hydrogen atom of the alkyl group of 1~6, It may include, for example chloromethyl, chloroethyl, chloropropyl, chlorobutyl, chloro hexyl and the like.

[0032] 在上述式⑴中，作为R1的碳原子数为1〜6的烷氧基，可以列举出例如甲氧基、 [0032] In the above formula ⑴, as the number of carbon atoms in R1 is 1~6 alkoxy group, and examples thereof include a methoxy group,

乙氧基、丙氧基、异丙氧基、丁氧基、戊氧基等。 Ethoxy, propoxy, isopropoxy, butoxy, pentoxy and the like.

[0033] 在上述式（1)中，作为R2和R3的碳原子数为1〜12的烷基，可以列举出和R1同样的基团，作为R2和R3的碳原子数为3〜10的环烷基，可以列举出例如环丙基、环丁基、环戊基、环己基、降冰片烷基等。 [0033] In the above formula (1) as the carbon atoms, R2 and R3 is 1~12 alkyl group include the same groups and R1, R2 and carbon atoms of R3 is 3~10 cycloalkyl groups may include for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and the like.

[0034] 在上述式⑴中，作为R4的碳原子数为1〜12的烷基，可以列举出和R1同样的基团，作为R4的碳原子数为1〜12的烷氧基，可以列举出例如甲氧基、乙氧基、正丙氧基、异丙氧基、丁氧基、戊氧基、辛氧基、癸氧基等。 [0034] In the above formula ⑴, as the number of carbon atoms R4 is 1~12 alkyl group, and R1 include the same groups as the number of carbon atoms R4 is 1~12 alkyl group include an example, methoxy, ethoxy, n-propoxy, isopropoxy, butoxy, pentyloxy, octyloxy, decyloxy and the like.

[0035] 在上述式⑴中，作为R6的碳原子数为1〜12的烷基，可以列举出和R1同样的基团，作为碳原子数为1〜6的酰氧基，可以列举出例如乙酰氧基、丙酰氧基等。 [0035] In the above formula ⑴, as the number of carbon atoms R6 is 1~12 alkyl group, and R1 include the same groups as 1~6 carbon atoms, acyloxy group includes, for example acetoxy, propionyloxy and the like. 作为碳原子数为1〜20的酰基，可以列举出例如甲酰基、乙酰基、丙酰基、丁酰基、异丁酰基、戊酰基、己酰基等。 1~20 carbon atoms of the acyl group may include e.g. formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl and the like. 作为R6的碳原子数为1〜6的烷基和碳原子数为1〜6的烷氧基，可以列举出和R1同样的基团。 Carbon atoms and R6 is an alkyl group having a carbon number of 1~6 1~6 alkoxy, and R1 include the same groups.

[0036] 作为R7、R8和R9中的碳原子数为1〜12的烷基和碳原子数为1〜6的烷氧基，可以列举出和R1同样的基团。 [0036] As R7, R8 and R9 are alkyl carbon atoms and carbon atoms of 1~6 1~12 alkoxy, and R1 include the same groups.

[0037] 在该化合物中，优选上述R1、R2、R3和R4分别是碳原子数为1〜8的烷基，上述R5 是S&R6、PO(R8)2或者Si (R9)3所示的基团，上述R6是氢原子的一部分或全部被乙酰氧基取代的碳原子数为2〜6的烷基，上述R8是苯基，上述R9是碳原子数为1〜6的烷基。 [0037] In the compound, preferably, the R1, R2, R3 and R4 are 1 ~ 8 carbon atoms in the alkyl group, the above-described R5 is S & R6, PO (R8) 2 or Si (R9) 3 group shown group, R6 is a part of said hydrogen atoms are all carbon atoms or an acetyl group substituted for 2 ~ 6 alkyl group, said R8 is phenyl, R9 is above 1~6 carbon atoms of the alkyl group. 通过在该化合物中导入这种结构，可以容易地制备该化合物，同时可以进一步提高对放射线敏感性组合物的溶解性。 By introducing such a structure in the compound, the compound can be easily prepared, and can further enhance the solubility of the radiation-sensitive composition.

[0038] 作为上述通式（1)所示的化合物的具体例子，可以列举出下述式O)〜（7)所示的化合物。 [0038] As the above-mentioned general formula (1) Specific examples of the compound represented may include) a compound represented by the following formula O ~ (7).

[0039] [0039]

[0040] [0040]

[0041] 该化合物作为光聚合引发剂显示出高的放射线灵敏度，不需要大的曝光量，可以得到具有高的表面硬度的固化膜。 [0041] The compound as the photopolymerization initiator exhibits high radiation sensitivity, does not require a large amount of exposure can be obtained a cured film having a high surface hardness. 另外，该化合物由于具有低的升华性，所以可以有效地防止烘焙炉或光掩模等的污染。 Further, since the compound has a low sublimation property, it is possible to effectively prevent contamination of the photomask baking furnace or the like. 这种低的升华性可以认为是化合物的分子结构引起的。 This low sublimation property can be considered as caused by the molecular structure of the compounds. 此外， 该化合物由于其自身的透明性优异，所以可以得到具有高的透明性的固化膜。 In addition, since the compound itself is excellent in transparency, it is possible to obtain a cured film having high transparency. 此外，该化合物由于对放射线敏感性组合物的溶解性高，所以可以容易地制备放射线敏感性组合物。 Further, since the solubility of the compound to radiation sensitive composition is high, it can be easily prepared radiation-sensitive composition.

[0042] <新型化合物的合成方法> [0042] <Synthesis of novel compounds>

[0043] 作为本发明的新型化合物的合成方法没有特别的限定，可以结合公知的技术进行合成，例如可以根据下述合成路线合成。 [0043] As a method of synthesizing the novel compounds of the present invention is not particularly limited, and can be combined with known synthetic techniques, e.g., may be synthesized according to the following synthetic scheme.

[0044] [0044]

[0045] 上述式中，R1〜R5和上述式（1)的定义相同。 [0045] In the above formula, R1~R5 and defined by the formula (1) is the same. X是卤原子。 X is a halogen atom.

[0046] 对上述合成路线的说明如下所示。 [0046] The above synthetic route description below. 首先，在碱的存在下，使卤代苯基烷基酮（化合物（A))和咔唑反应，形成叔胺结构（化合物（B))，将其和卤代-烷基取代的苯甲酰氯反应， 形成二酮化物（化合物（C))。 First, in the presence of a base, so that halophenyl alkyl ketone (compound (A)) and the carbazole reaction to form a tertiary amine structure (compound (B)), and its halo - alkyl substituted benzyl chloride, forming dione (Compound (C)). 该二酮化物（化合物（C))和酰氯反应，形成三酮化物（化合物（D))，然后通过苯基上的卤原子的取代等，得到化合物（E)。 The dione (Compound (C)) and acid chloride react to form trione compound (Compound (D)), and substituted by a halogen atom on the phenyl group and the like, to give compound (E). 接着，只选择性地将烷基酮部分肟化，形成化合物（F)，根据需要使用碱，通过羧酸酐，将羟基酰基化，可以得到目标化合物(G)。 Subsequently, only the selective oximation of the ketone moiety alkyl to form a compound (F), if necessary using a base, a carboxylic acid anhydride, hydroxyl acylation may give the target compound (G).

[0047] 另外，R5具有酰基时，在从化合物（D)到化合物（E)的反应中，将苯基上的卤原子取代为作为R5的前体的基团等，在用于得到化合物（G)的最终酰化时，将上述前体酰化，可以导入R5。 [0047] Further, when the R5 group has, in the reaction from the compound (D) into the compound (E) of the halogen atom as a substituent on the phenyl group, etc. R5 precursor, for obtaining the compound ( When G) of the final acylated, said acylation precursors can be imported R5. 另外，在上述路线中，也可以使用在苯环上具有取代基R4和R5的苯甲酰氯代替用于得到化合物（C)的上述卤代-烷基取代的苯甲酰氯。 In the above scheme, it may be used on the benzene ring with a substituent R4 and R5 are used instead of benzoyl chloride to give the compound (C) of the above-described halo - alkyl substituted benzoyl chloride. 此时，省略从化合物（D)到化合物(E)的步骤。 In this case, omit step from the compound (D) into the compound (E) of.

[0048] 具体地，作为上述式（¾所示的化合物的合成方法，代表性地可以列举出以下的过程。在碱的存在下，使咔唑和卤代苯基烷基酮反应，形成叔胺结构，将其和卤代-烷基取代的苯甲酰氯反应，形成二酮化物。使二酮化物和乙酰氯反应，形成三酮化物，然后使巯基乙醇反应，取代苯基上的卤素。接着，通过次氯酸钠将硫原子氧化，通过羟胺只将烷基酮部分选择性地肟化，根据需要使用碱，通过乙酸酐，将羟基乙酰化，可以得到目标化合物。式(3)〜（7)的化合物也可以根据上述过程，或者改变上述过程的一部分来合成。 [0048] Specifically, as a method of synthesizing a compound of the above formula (¾ shown, typically include the following process. In the presence of a base, so carbazole and halophenyl alkyl ketone to form a tertiary amine structure, and their halo - alkyl substituted benzoyl chloride to form a diketone compound so diketone compound and acetyl chloride to form trione compound, then the reaction mercaptoethanol, halogen substituted phenyl. Subsequently, the sulfur atom oxidized by sodium hypochlorite, hydroxylamine by only partially selectively alkyl ketone oximation, if necessary using a base, by acetic anhydride, the acetylation of hydroxy, can be obtained the target compound of formula (3) to (7) The compounds can also be in accordance with the above procedure, or changing a part of the process to synthesize.

[0049] <放射线敏感性组合物> [0049] <radiation-sensitive composition>

[0050] 本发明的放射线敏感性组合物含有作为[A]光聚合引发剂的上述化合物以及[B] 具有乙烯基不饱和双键的聚合性化合物，同时还可以含有其它任选成分（[C]碱可溶性树脂、[D]上述[A]成分以外的放射线敏感性聚合引发剂（以下，也简称为“其它放射线敏感性聚合引发剂”）、[E]多官能环氧化合物、[F]密合助剂、[G]表面活性剂等)。 [0050] The radiation sensitive composition of the present invention contains the above compounds as [A] and a photopolymerization initiator [B] having an ethylenically unsaturated double bond polymerizable compound, and can also contain other optional ingredients ([C ] alkali-soluble resin, [D] Radiation above [A] other than the component sensitive polymerization initiator (hereinafter, also referred to as "other radiation-sensitive polymerization initiator"), [E] a polyfunctional epoxy compound, [F] adhesion aid, [G] surfactant, etc.). 作为[A]成分的光聚合引发剂使用的化合物由于如上所示，所以在这里省略说明。 As the photopolymerizable compound [A] component initiator because as shown above, so description thereof is omitted here.

[0051] < [B]具有乙烯基不饱和双键的聚合性化合物> [0051] <[B] having an ethylenically unsaturated double bond polymerizable compound>

[0052] 作为该放射线敏感性组合物中使用的具有乙烯基不饱和双键的聚合性化合物的优选的例子，可以列举出例如单官能（甲基）丙烯酸酯、2官能（甲基）丙烯酸酯、或者3官能以上的（甲基）丙烯酸酯等。 [0052] As an example having a preferred ethylenically unsaturated double bond of the polymerizable compound in the radiation-sensitive composition is used, for example, may include monofunctional (meth) acrylate, a bifunctional (meth) acrylate or trifunctional or higher (meth) acrylate. 在该放射线敏感性组合物中，通过使用这些化合物，可以形成透明性和表面硬度高度均衡的固化膜。 In the radiation-sensitive composition through the use of these compounds, transparency and surface hardness can be highly balanced cured film.

[0053] 作为单官能（甲基）丙烯酸酯，可以列举出例如（甲基）丙烯酸2-羟基乙基酯、 (甲基）丙烯酸卡毕醇酯、（甲基）丙烯酸异佛尔酮酯、（甲基）丙烯酸3-甲氧基丁基酯、 2-(甲基）丙烯酰氧基乙基-2-羟基丙基邻苯二甲酸酯等。 [0053] as a single functional (meth) acrylate, may, for example (meth) acrylate, 2-hydroxyethyl acrylate, (meth) acrylic acid Charpy alcohol ester, (meth) acrylic acid ester isophorone, (meth) acrylate, 3-methoxybutyl acrylate, 2- (meth) acryloyloxyethyl 2-hydroxypropyl phthalate. 作为这些单官能（甲基）丙烯酸酯的商品的例子，可以列举出,口二7夕7 M-10U , 口二7夕7 M-IlU , 口二7夕7 M-114(東亞合成（株式会社）制造），KAYARAD TC-110S,KAYARAD TC-120S(日本化薬（株式会社）制造），e 7 二一卜158、e 7 二一卜2311 (大阪有機化学工業（株式会社）制造）寸。 As these examples commodity monofunctional (meth) acrylate may, for example, 7-port two evening 7 M-10U, the eve of opening two 7 7 M-IlU, 7-port two evening 7 M-114 (Toagosei (strain formula Clubs) manufactured), KAYARAD TC-110S, KAYARAD TC-120S (Nihon Pharmaceutical (Ltd.) manufactured), e 7 twenty-one Bu 158, e 7 twenty-one BU 2311 (Osaka Organic Chemical Industry (Co.) Ltd.) inch .

[0054] 作为2官能（甲基）丙烯酸酯，可以列举出例如乙二醇二（甲基）丙烯酸酯、1， 6-己二醇二（甲基）丙烯酸酯、1，9-壬二醇二（甲基）丙烯酸酯、聚丙二醇二（甲基）丙烯酸酯、四乙二醇二（甲基）丙烯酸酯、二苯氧基乙醇芴二（甲基）丙烯酸酯、二苯氧基乙醇芴二（甲基）丙烯酸酯等。 [0054] As bifunctional (meth) acrylate, and examples thereof include ethylene glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, 1,9-hexanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, diphenoxy ethanol fluorene di (meth) acrylate, fluorene ethanol diphenoxy di (meth) acrylate. 作为这些2官能（甲基）丙烯酸酯的商品，可以列举出例如 As the bifunctional (meth) acrylate of goods may include e.g.

口二·7 夕ζ Μ-210、7 口二7 夕7 Μ-240、7 口二7 夕7 Μ-6200(東亞合成（株式会社) Port two 5.7 Xi ζ Μ-210,7-port two 7 evening 7 Μ-240,7-port two 7 evening 7 Μ-6200 (Toagosei (Inc.)

制造)，kayarad hdda, kayaradhx-22。 Manufacturing), kayarad hdda, kayaradhx-22. 、kayarad r-604 (日本化薬（株式会社)制造)，匕7 二一卜洸0、ϋ' ^ ^ 一卜312、ϋ' ^ ^ 一卜3!35ΗΡ (大阪有機化学工業（株式会社）制造）[0055] 作为3官能以上的（甲基）丙烯酸酯，可以列举出例如三羟甲基丙烷三（甲基） 丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、三（（甲基）丙烯酰氧基乙基）磷酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、琥珀酸单[3-(3-(甲基）丙烯酰氧基-2，2-二（甲基）丙烯酰氧基甲基-丙氧基）-2，2_ 二(甲基）丙烯酰氧基甲基-丙基]酯、琥珀酸改性的季戊四醇三（甲基）丙烯酸酯等。 , Kayarad r-604 (Nihon Pharmaceutical (Ltd.) Ltd.), dagger 7 twenty-one BU Guang 0, ϋ '^ ^ a BU 312, ϋ' ^ ^ a BU 3! 35ΗΡ (Osaka Organic Chemical Industry (Ltd.) Manufacturing) [0055] As trifunctional or more (meth) acrylate, and examples thereof include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acrylate acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid mono [3- (3- (methyl ) acryloyloxy-2,2-di (meth) acryloyloxy-methyl - propoxy) -2,2_ two (meth) acryloyloxy methyl - propyl] ester, succinic acid change of pentaerythritol tri (meth) acrylate. 作为这些3官能以上的（甲基）丙烯酸酯的商品，可以列举出例如ζ m ”卞Μ-309、ζ 口二”卞Μ-400、ζ 口二7 夕叉M-405、了η 二” > Μ-450、了ο 二” 卞Μ—7100、ζ 口二？ As these products more than 3-functional (meth) acrylate, may, for example ζ m "Bian Μ-309, ζ mouth two" Bian Μ-400, ζ port two 7 evening fork M-405, the η II " > Μ-450, the ο two "Bian Μ-7100, ζ port two? 夕^ Μ-8030、τη" Μ-8060、了η “ Τ0-756 (東亞合成（株式会社)制造)， KAYARAD TMPTA, KAYARAD DPHA, KAYARADDPCA-20、KAYARAD DPCA-30、KAYARAD DPCA-60、 KAYARADDPCA-120 (日本化薬（株式会社)制造），ϋ' 7 二一卜四5、ϋ' 7 二一卜300、^ ^ 一卜360、ϋ' 7 二一卜GPT、ϋ' 7 二一卜3ΡΑ、ϋ' 7 二一卜400(大阪有機化学工業（株式会社）制造）等。 Xi ^ Μ-8030, τη "Μ-8060, the η" Τ0-756 (Toagosei (Inc.) manufactured), KAYARAD TMPTA, KAYARAD DPHA, KAYARADDPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARADDPCA- 120 (Nihon Pharmaceutical (Ltd.) manufactured), ϋ '7 twenty-one BU four 5, ϋ' 7 twenty-one Bu 300, a BU ^ ^ 360, ϋ '7 twenty-one BU GPT, ϋ' 7 twenty-one BU 3ΡΑ , ϋ '7 twenty-one BU 400 (Osaka Organic Chemical Industry (Co.) Ltd.).

[0056] 这些具有乙烯基不饱和双键的聚合性化合物中，从放射线敏感性组合物的固化性的观点出发，优选使用3官能以上的（甲基）丙烯酸酯。 [0056] These ethylenically unsaturated double bond-having polymerizable compound, from the viewpoint of curability of a radiation sensitive composition, it is preferable to use a trifunctional or more (meth) acrylate. 其中，特别优选三羟甲基丙烷三(甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇六（甲基）丙烯酸酯、琥珀酸单[3-(3-(甲基）丙烯酰氧基-2，2-二（甲基）丙烯酰氧基甲基-丙氧基）_2，2-二（甲基）丙烯酰氧基甲基-丙基]酯、琥珀酸改性的季戊四醇三（甲基）丙烯酸酯。 Wherein, particularly preferably trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, succinic acid mono [3- (3- (meth) acrylic acyloxy-2,2-di (meth) acryloyloxy-methyl - propoxy) _2,2- two (meth) acryloyloxy methyl - propyl] ester, succinic acid-modified pentaerythritol tri (meth) acrylate. 这些具有乙烯基不饱和双键的聚合性化合物可以单独或混合两种以上使用。 These ethylenically unsaturated double bond-having polymerizable compound may be used singly or in combination of two or more.

[0057] 该放射线敏感性组合物中的[B]成分的具有乙烯基不饱和键的聚合性化合物的用量没有特别的限定，相对于1质量份[A]成分的光聚合引发剂，优选为10〜200质量份， 更优选为20〜150质量份。 [0057] having an amount of polymerizable ethylenically unsaturated bond in the compound in the radiation-sensitive composition [B] component is not particularly limited with respect to 1 part by mass Photopolymerization [A] component initiator, preferably 10~200 parts by mass, more preferably 20~150 parts by mass. 通过使这种聚合性化合物的用量为上述范围，可以得到放射线灵敏度以及得到的固化膜的透明性高度均衡的放射线敏感性组合物。 By making such a polymerizable compound used in an amount within the above range, the radiation sensitivity can be obtained, and the transparency of a cured film obtained by highly balanced radiation-sensitive composition.

[0058] < [C]碱可溶性树脂〉 [0058] <[C] alkali-soluble resin>

[0059] 作为可以在该放射线敏感性组合物中含有的[C]碱可溶性树脂，只要是对在含有该成分的放射线敏感性组合物的显影处理工序中使用的碱显影液显示出可溶性，就没有特别的限定。 [0059] as [C] an alkali-soluble resin may be contained in the radiation-sensitive composition, as long as the alkali component developer containing the radiation-sensitive composition used in the step of development processing shows soluble, it It is not particularly limited. 作为这种碱可溶性树脂，优选具有羧基的碱可溶性树脂，特别优选（al)选自由不饱和羧酸和不饱和羧酸酐构成的群组的至少1种（以下，称作“化合物（al) ”）和（a2) (a 1)以外的不饱和化合物（以下，称作“化合物（a2)”）的共聚物（以下，称作共聚物[α])。 As such alkali-soluble resin, preferably alkali-soluble resin having a carboxyl group, and particularly preferably (al) is selected from the unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride group consisting of at least one kind (hereinafter referred to as "compound (al)" ) and (a2) (a 1) other than the unsaturated compound (hereinafter, referred to as "compound (a2)") copolymer (hereinafter referred to as copolymer [α]).

[0060] 作为化合物（al)的具体例子，可以列举出：丙烯酸、甲基丙烯酸、巴豆酸、2-丙烯酰氧基乙基琥珀酸、2-甲基丙烯酰氧基乙基琥珀酸、2-丙烯酰氧基乙基六氢邻苯二甲酸、 2-甲基丙烯酰氧基乙基六氢邻苯二甲酸等一元羧酸；马来酸、富马酸、柠康酸等二元羧酸； 上述二元羧酸的酸酐等。 [0060] Specific examples of the compound (al), and may include: acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinate, 2-acryloyloxyethyl succinic acid, 2 - acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl hexahydrophthalic acid and other monocarboxylic acids; maleic acid, fumaric acid, citraconic acid and other dicarboxylic said dicarboxylic acid anhydride and the like; acid.

[0061] 这些化合物（a 1)中，从共聚反应性以及得到的共聚物对碱性显影液的溶解性的观点出发，优选丙烯酸、甲基丙烯酸、2-丙烯酰氧基乙基琥珀酸、2-甲基丙烯酰氧基乙基琥珀酸、马来酸酐等。 [0061] The compounds (1 a), the copolymerization reaction of the copolymer obtained and from the viewpoint of the solubility in alkaline developer, it is preferable acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, maleic anhydride and the like.

[0062] 在共聚物[α ]中，化合物（al)可以单独或者混合两种以上使用。 [0062] In the copolymer [α], the compound (al) may be used singly or in combination of two or more. 在共聚物[α ] 中，来自化合物（a 1)的重复单元的含有率优选为5〜60质量％，更优选为7〜50质量％， 特别优选为8〜40质量％。 In the copolymer [α], the content is preferably repeating units derived from the compound (a 1) is a 5 to 60% by mass, more preferably 7~50% by mass, and particularly preferably 8~40% by mass. 通过使来自化合物（al)的重复单元的含有率为5〜60质量％，可以得到放射线灵敏度和显影性等各种性能更高水平均衡的放射线敏感性组合物。 By repeating units derived from the compound (al) the content rate of 5 to 60% by mass, the radiation sensitivity can be obtained and developability and other properties of higher levels of radiation-sensitive composition equilibrium.

[0063] 作为化合物（a2)的具体例子，可以列举出： [0063] Specific examples of the compound (a2) can include:

[0064] 丙烯酸甲酯、丙烯酸正丙酯、丙烯酸异丙酯、丙烯酸正丁基酯、丙烯酸仲丁基酯、丙烯酸叔丁基酯等丙烯酸烷基酯； [0064] methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate esters;

[0065] 甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸正丙酯、甲基丙烯酸异丙酯、甲基丙烯酸正丁酯、甲基丙烯酸仲丁酯、甲基丙烯酸叔丁酯等的甲基丙烯酸烷基酯； [0065] methyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl The alkyl methacrylate;

[0066] 丙烯酸环己基酯、丙烯酸2-甲基环己基酯、丙烯酸三环[5.2. 1. O2'6]癸-8-基酯、 丙烯酸2-(三环[5.2. 1.02'6]癸-8-基氧基）乙基酯、丙烯酸异佛尔酮基酯等丙烯酸脂环式酯； [0066] acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2. 1. O2'6] dec-8-yl acrylate, 2- (tricyclo [5.2. 1.02'6] dec 8-yl) ethyl acrylate, isophorone and other acrylate ester alicyclic ester;

[0067] 甲基丙烯酸环己基酯、甲基丙烯酸2-甲基环己基酯、甲基丙烯酸三环[5. 2. 1. O2' 6]癸-8-基酯、甲基丙烯酸2-(三环[5. 2. 1. O2'6]癸-8-基氧基）乙基酯、甲基丙烯酸异佛尔酮基酯等甲基丙烯酸脂环式酯； [0067] methacrylate, cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, tricyclo [5. 2. 1. O2 '6] dec-8-yl methacrylate, 2- ( tricyclo [5. 2. 1. O2'6] dec-8-yl) ethyl methacrylate, isophorone, etc. methacrylic ester alicyclic ester;

[0068] 丙烯酸苯酯、丙烯酸苄基酯等丙烯酸芳基酯或芳烷基酯； [0068] phenyl acrylate, benzyl acrylate and other acrylate esters aryl or aralkyl ester;

[0069] 甲基丙烯酸2-羟基乙基酯、甲基丙烯酸3-羟基丙基酯等甲基丙烯酸的羟基烷基酯类； [0069] methyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl ester of hydroxyalkyl esters of acrylic acid;

[0070] 甲基丙烯酸苯基酯、甲基丙烯酸苄基酯等甲基丙烯酸的芳基酯或芳烷基酯； [0070] methacrylate, phenyl methacrylate, benzyl methacrylate ester or aryl ester aralkyl esters;

[0071] 马来酸二乙酯、富马酸二乙酯等不饱和羧酸二烷基酯； [0071] diethyl maleate, diethyl fumarate, dialkyl esters of unsaturated carboxylic acids;

[0072] 丙烯酸四氢呋喃-2-基酯、丙烯酸四氢吡喃-2-基酯、丙烯酸2-甲基四氢吡喃-2-基酯等具有含氧5元杂环或含氧6元杂环的丙烯酸酯； [0072] tetrahydrofuran-2-yl acrylate, methacrylate, tetrahydropyran-2-yl acrylate, 2-methyl-tetrahydropyran-2-yl ester having an oxygen-containing 5-membered heterocyclic or a 6 membered heteroaryl containing oxygen acrylic ring;

[0073] 甲基丙烯酸四氢呋喃-2-基酯、甲基丙烯酸四氢吡喃-2-基酯、甲基丙烯酸2-甲基四氢吡喃-2-基酯等具有含氧5元杂环或含氧6元杂环的甲基丙烯酸酯； [0073] tetrahydrofuran-2-yl methacrylate, methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyl-tetrahydropyran-2-yl ester having an oxygen-containing 5-membered heterocyclic 6-membered heterocyclic or oxygen-containing methacrylate;

[0074] 苯乙烯、α -甲基苯乙烯、对甲氧基苯乙烯等乙烯基芳香族化合物； [0074] styrene, α - methylstyrene, p-methoxystyrene and other vinyl aromatic compounds;

[0075] 1，3-丁二烯、异戊二烯等共轭二烯系化合物； [0075] 1,3-butadiene, isoprene and other conjugated diene compound;

[0076] 以及丙烯腈、甲基丙烯腈、丙烯酰胺、甲基丙烯酰胺等。 [0076] as well as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide and the like.

[0077] 这些化合物（a2)中，从共聚反应性的观点出发，优选甲基丙烯酸正丁酯、甲基丙烯酸苄基酯、甲基丙烯酸三环[5. 2. 1. O2'6]癸-8-基酯、苯乙烯、对甲氧基苯乙烯、甲基丙烯酸四氢呋喃-2-基酯、1，3- 丁二烯、甲基丙烯酸2-羟基乙基酯等。 [0077] The compound (a2), and from the viewpoint of the copolymerization reaction, preferably n-butyl methacrylate, benzyl methacrylate, methacrylate, tricyclo [5. 2. 1. O2'6] dec 8-yl methacrylate, styrene, p-methoxy styrene, methacrylic esters tetrahydrofuran-2-yl, 1,3-butadiene, methacrylic acid, 2-hydroxyethyl acrylate.

[0078] 在共聚物[α ]中，化合物（^)可以单独或者混合两种以上使用。 [0078] In the copolymer [α], the compound (^) may be used singly or in combination of two or more. 在共聚物[α ] 中，来自化合物（a》的重复单元的含有率优选为10〜70质量％，更优选为20〜50质量％，特别优选为30〜50质量％。通过使化合物（U)的重复单元的含有率为10〜70质量％，可以容易地控制共聚物的分子量，得到显影性、放射线灵敏度等更高等级地均衡的放射线敏感性组合物。 In the copolymer [α], the content is preferably repeating units derived from the compound (a "is 10~70 mass% of, more preferably 20~50% by mass, and particularly preferably 30 ~ 50 mass%. By reacting the compound (U ) content rate of 10~70% by mass of the repeating unit, the molecular weight of the copolymer can be easily controlled to obtain developability, hierarchically higher radiation sensitivity of the radiation sensitive composition balanced.

[0079] 共聚物[α]可以通过在适当的溶剂中，在自由基聚合引发剂的存在下，使构成成分的单体聚合制造。 [0079] Copolymer [α] can be obtained by a suitable solvent in the presence of a radical polymerization initiator, monomers constituting the component manufacture. 作为这种聚合中使用的溶剂，优选二甘醇烷基醚、丙二醇单烷基醚乙酸酯、烷氧基丙酸烷基酯、乙酸酯等。 As such a polymerization solvent is used, preferably diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkoxy alkyl propionate, acetate and the like. 这些溶剂可以单独或混合两种以上使用。 These solvents may be used singly or as a mixture of two or more.

[0080] 另外，作为上述自由基聚合引发剂，没有特别的限定，可以列举出例如2，2' -偶氮二异丁腈、2，2' -偶氮二_(2，4- 二甲基戊腈）、2，2' -偶氮二44-甲氧基_2，4- 二甲基戊腈）、4，4' -偶氮二（4-氰基戊酸）、二甲基_2，2' -偶氮二甲基丙酸酯）、2，2' -偶氮二甲氧基-2，4-二甲基戊腈）等偶氮化合物。 [0080] Further, as the radical polymerization initiator is not particularly limited, and examples thereof include 2,2 '- azobisisobutyronitrile, 2,2' - azobis _ (2,4-dimethoxy yl valeronitrile), 2,2 '- azobis 44- methoxy _2,4- dimethyl valeronitrile), 4,4' - azobis (4-cyanovaleric acid), dimethyl _2,2 '- azobis methyl propionate), 2,2' - azobis-2,4-dimethoxy-dimethylvaleronitrile) and other azo compounds. 这些自由基聚合引发剂可以单独或混合两种以上使用。 These radical polymerization initiators may be used singly or in combination of two or more.

[0081] 共聚物[α ]通过凝胶渗透色谱法（GPC)得到的聚苯乙烯换算的重均分子量（以下，称作“Mw”）优选为2，000〜100，000，更优选5，000〜50，000。 [0081] Copolymer [α] determined by gel permeation chromatography (GPC) to obtain the polystyrene-equivalent weight average molecular weight (hereinafter, referred to as "Mw") preferably 2,000~100,000, more preferably 5, 000~50,000. 通过使共聚物[α ]的Mw为2，000〜100，000，可以得到显影性、放射线灵敏度等更高水平均衡的放射线敏感性组合物，以及耐热性高的固化膜。 By reacting the copolymer [α] Mw of 2,000~100,000, developability can be obtained, a higher level of radiation sensitivity of the radiation sensitive composition equilibrium, and heat resistance of a cured film high.

[0082] 该放射线敏感性组合物中的[C]成分的碱可溶性树脂的用量相对于1质量份[Α] 成分的光聚合引发剂，优选为10〜200质量份，更优选为20〜150质量份。 The amount of the alkali-soluble resin [0082] The radiation-sensitive composition [C] component with respect to 1 part by mass [Α] photopolymerization initiator component, preferably 10~200 parts by mass, more preferably 20~150 parts by mass. 通过使碱可溶性树脂的用量为上述范围，可以得到显影性优异的放射线敏感性组合物。 Alkali-soluble resin by an amount of the above-mentioned range, excellent developability can be obtained a radiation sensitive composition.

[0083] <[D]其它放射线敏感性聚合引发剂> [0083] <[D] other radiation-sensitive polymerization initiator>

[0084] 在该放射线敏感性组合物中，除了[A]成分以外，还可以加入作为[D]成分的其它放射线敏感性聚合引发剂。 [0084] In the radiation-sensitive composition, in addition to component [A] may also be added as [D] component of other radiation-sensitive polymerization initiators. 作为放射线敏感性聚合引发剂只要是感应放射线，产生能够引发具有乙烯基不饱和双键的聚合性化合物的聚合的活性种的成分，就没有特别的限定。 As long as the radiation-sensitive polymerization initiator is induced radiation, it generates an active species capable of initiating component having a vinyl polymerizable unsaturated double bond polymerizable compound is not particularly limited. 作为这种其它放射线敏感性聚合引发剂的例子，可以列举出0-酰基肟化合物、乙酰苯化合物、联咪唑化合物等。 As such other radiation-sensitive polymerization initiators examples include 0- acyl oxime compounds, acetophenone compounds, biimidazole compounds and the like.

[0085] 作为上述0-酰基肟化合物的具体例子，可以列举出乙酮-l-[9-乙基-6-(2-甲基苯甲酰基）-9H-咔唑-3-基]-1-(0-乙酰基肟）、1-[9-乙基-6-苯甲酰基-9H-咔唑-3-基]-辛-1-酮肟-0-乙酸酯、1-[9_乙基-6-(2-甲基苯甲酰基）-9H-咔唑-3-基]-乙-1-酮肟-0-苯甲酸酯、1- [9-正丁基-6- (2-乙基苯甲酰基）-9H-咔唑-3-基]-乙-1-酮肟-0-苯甲酸酯、乙酮-1-[9-乙基-6- (2-甲基-4-四氢呋喃基苯甲酰基）-9H-咔唑-3-基]-1-(0-乙酰基肟）、乙酮-1-[9-乙基-6- (2-甲基-4-四氢吡喃基苯甲酰基）-9H-咔唑-3-基]-1-(0-乙酰基肟）、乙酮-1- [9-乙基-6- (2-甲基-5-四氢呋喃基苯甲酰基)-9H-咔唑-3-基]-1-(0-乙酰基月亏)、乙酮-1-[9-乙基-6- {2-甲基-4- (2， 2- 二甲基-1，3- 二噁烷基）甲氧基苯甲酰基}-9H-咔唑-3-基]-1-(0-乙酰基肟）、乙酮-1- [9-乙基-6- (2-甲基-4-四氢呋喃基甲氧基苯甲酰基）-9H-咔唑-3-基]-1-(0-乙酰基肟）等（其中，除了[A]成分以外）。 [0085] Specific examples of the 0- acyl oxime compound include ethanone -l- [9- ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] - 1- (O-acetyl oxime), 1- [9-ethyl-6-benzoyl--9H- carbazol-3-yl] - oct-l-one oxime -0- acetate, 1- [ 9_ ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl] - ethyl-1-one oxime -0- benzoate, 1- [9-n-butyl - 6- (2-ethyl-benzoyl) -9H- carbazol-3-yl] - ethyl-1-one oxime -0- benzoate, ethanone 1- [9-ethyl-6- ( methyl-4-benzoyl-tetrahydrofuryl) -9H- carbazol-3-yl] -1- (O-acetyl oxime), ethanone 1- [9-ethyl-6- (2- methyl-4-tetrahydropyranyl benzoyl) -9H- carbazol-3-yl] -1- (O-acetyl oxime), ethanone 1- [9-ethyl-6- (2 - methyl-5-tetrahydrofuranyl benzoyl) -9H- carbazol-3-yl] -1- (O-acetyl waning), ethanone 1- [9-ethyl-6- {2- methyl-4- (2,2-dimethyl-1,3-dioxane-alkyl) methoxybenzoyl} -9H- carbazol-3-yl] -1- (O-acetyl oxime) , ethanone 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuryl methoxybenzoyl) -9H- carbazol-3-yl] -1- (O-acetyl oxime ), etc. (wherein, in addition to [A] other than the component).

[0086] 它们之中，作为优选的0-酰基肟化合物，可以列举出乙酮-l-[9-乙基-6-(2-甲基苯甲酰基）-9H-咔唑-3-基]-1-(0-乙酰基肟）、乙酮-1- [9-乙基-6- (2-甲基-4-四氢呋喃基甲氧基苯甲酰基）-9H-咔唑-3-基]-1- (0-乙酰基肟）、乙酮-1- [9-乙基-6- {2-甲基-4-(2，2- 二甲基-1，3- 二噁烷基）甲氧基苯甲酰基}-9H-咔唑-3-基]-1-(0-乙酰基肟）。 [0086] Among them, preferred 0- acyl oxime compound may include ethanone -l- [9- ethyl-6- (2-methylbenzoyl) -9H- carbazol-3-yl ] -1- (O-acetyl oxime), ethanone 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuryl methoxybenzoyl) -9H- carbazol-3 yl] -1- (O-acetyl oxime), ethanone 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxane yl) methoxy benzoyl} -9H- carbazol-3-yl] -1- (O-acetyl oxime). 这些0-酰基肟化合物可以单独或混合两种以上使用。 These 0- acyl oxime compound may be used singly or in combination of two or more.

[0087] 作为上述乙酰苯化合物，可以列举出例如α-氨基酮化合物、α-羟基酮化合物。 [0087] Examples of the acetophenone compound include e.g. α- aminoketone compound, α- hydroxy ketone compound.

[0088] 作为α-氨基酮化合物的具体例子，可以列举出2-苄基-2-二甲基氨基-1- (4-吗啉代苯基）-丁-1-酮、2- 二甲基氨基-2- (4-甲基苄基)-1-(4-吗啉-4-基苯基）_ 丁-1-酮、2-甲基-1-(4-甲基硫代苯基）-2-吗啉代丙-1-酮等。 [0088] Specific examples of α- aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) - butan-1-one, 2-dimethylamino -2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one _, 2-methyl-1- (4-methyl thio phenyl yl) -2-morpholino-propan-1-one.

[0089] 作为α-羟基酮化合物的具体例子，可以列举出1-苯基-2-羟基-2-甲基丙-1-酮、1- (4-异丙基苯基）-2-羟基-2-甲基丙-1-酮、4- (2-羟基乙氧基）苯基-(2-羟基-2-丙基）酮、1-羟基环己基苯基酮等。 [0089] Specific examples of α- hydroxy ketone compound include 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- -2-methyl-propan-1-one, 4- (2-hydroxyethoxy) phenyl - (2-hydroxy-2-propyl) ketone, 1-hydroxy cyclohexyl phenyl ketone.

[0090] 这些乙酰苯化合物中，优选α -氨基酮化合物，特别优选2-二甲基氨基-2-(4-甲基苄基）-1-(4-吗啉-4-基苯基）-丁-1-酮、2-甲基-1- (4-甲基硫代苯基）-2-吗啉代丙-ι-酮。 [0090] These acetophenone compounds, preferably α - aminoketone compound, particularly preferably 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) - butan-1-one, 2-methyl-1- (4-methylthio-phenyl) -2-morpholino-propan -ι- ketone. 这些乙酰苯化合物可以单独或混合两种以上使用。 These acetophenone compounds may be used singly or in combination of two or more.

[0091] 作为上述联咪唑化合物的具体例子，可以列举出2，2' - 二O-氯代苯基）_4，4'， 5，5，-四(4-乙氧基羰基苯基）_1，2，-联咪唑、2，2，- 二(2-氯代苯基）-4，4'，5，5' -四苯基-1，2'-联咪唑、2，2'_ 二0，4-二氯代苯基）-4，4'，5，5'_四苯基-1，2'-联咪唑、2， 2，- 二(2，4，6_三氯代苯基）-4，4，，5，5，-四苯基_1，2，-联咪唑等。 [0091] Specific examples of the biimidazole compound include 2,2 '- O- chlorophenyl) _4,4', 5,5, - tetrakis (4-ethoxycarbonyl phenyl) _1 2, - biimidazole, 2,2 - bis (2-chlorophenyl) -4,4 ', 5,5' - tetraphenyl-1,2'-biimidazole, two 2,2'_ 0,4- dichlorophenyl) -4,4 ', 1,2'-tetraphenyl biimidazole 5,5'_, 2, 2 - bis (2,4,6_ trichlorobenzene yl) -4,4, 5,5 - tetraphenyl _1,2 - United imidazole.

[0092] 这些联咪唑化合物中，优选2，2'_二（2-氯代苯基）-4，4'，5，5'_四苯基-1，2'_联咪唑、2，2，-二(2，4_ 二氯代苯基）-4，4，，5，5，-四苯基_1，2' -联咪唑、2，2，-二(2,4, 6-三氯代苯基）_4，4，，5，5，-四苯基-1，2，-联咪唑，特别优选2，2，- 二（2，4-二氯代苯基）-4，4'，5，5' -四苯基_1，2' -联咪唑。 [0092] These linking imidazole compounds, 2,2'_ bis (2-chlorophenyl) -4,4 ', 5,5'_ -1,2'_ tetraphenyl biimidazole, 2,2 , - bis (2,4_-dichlorophenyl) -4,4,, 5,5, - tetraphenyl _1,2 '- biimidazole, 2,2 - bis (2,4,6-tris chlorophenyl) _4,4,, 5,5, - tetraphenyl-1,2, - biimidazole, particularly preferably 2,2 - bis (2,4-dichlorophenyl) -4,4 ', 5,5' - tetraphenyl _1,2 '- biimidazole. 这些联咪唑化合物可以单独或混合两种以上使用。 The biimidazole compounds may be used singly or in combination of two or more.

[0093] 在本发明的放射线敏感性组合物中，在使用联咪唑化合物作为[D]成分的放射线敏感性聚合引发剂时，为了增加其灵敏度，可以添加具有二烷基氨基的脂肪族或芳香族化合物（以下，称作“氨基类增敏剂”）。 When [0093] In the radiation-sensitive composition of the present invention, the joint use of an imidazole compound as the component [D] of the radiation-sensitive polymerization initiators, in order to increase its sensitivity, may be added dialkylamino having aliphatic or aromatic compound (hereinafter, referred to as "amino-based sensitizer").

[0094] 作为该氨基类增敏剂，可以列举出例如4，4' - 二（二甲基氨基）二苯甲酮、4， 4' - 二（二乙基氨基）二苯甲酮等。 [0094] Examples of the amino-based sensitizers, include, for example 4,4 '- bis (dimethylamino) benzophenone, 4, 4' - bis (diethylamino) benzophenone. 这些氨基类增敏剂中，特别优选4，4' - 二（二乙基氨基）二苯甲酮。 These amino-based sensitizers, particularly preferably 4,4 '- bis (diethylamino) benzophenone. 上述氨基类增敏剂可以单独或混合两种以上使用。 The amino group class sensitizers may be used alone or in combination of two or more.

[0095] 此外，在该放射线敏感性组合物中，同时使用联咪唑化合物和氨基类增敏剂时，可以添加硫醇化合物作为氢自由基供体。 [0095] In addition, the radiation sensitive composition, using linked imidazole compounds and amino classes sensitizers, thiol compounds may be added as a hydrogen radical donor. 联咪唑化合物由于氨基类增敏剂增敏开裂，产生咪唑自由基，但是在这种状态下可能无法显现出高的聚合引发能。 Since the amino-based compounds biimidazole sensitizer sensitizing cracking, produce imidazole radical, but in this state may not exhibit high polymerization initiator can. 但是，通过在联咪唑化合物和氨基类增敏剂共存的体系中，添加硫醇化合物，从硫醇化合物往咪唑自由基提供氢自由基。 However, by the United imidazole compounds and amino-based sensitizer coexistence system, adding the thiol compound, the thiol compound to provide an imidazole radical hydrogen radicals. 结果是，咪唑自由基转变为中性的咪唑，产生具有聚合引发能高的硫自由基的成分，由此，即使是低放射线照射量，也可以形成表面硬度高的固化膜。 As a result, an imidazole radical into neutral imidazole, to produce a polymerization initiator having a sulfur radical component can be high, whereby, even low radiation exposure, high surface hardness may be formed of a cured film.

[0096] 作为该硫醇化合物的具体例子，可以列举出： [0096] Specific examples of the thiol compound include:

[0097] 2-巯基苯并噻唑、2-巯基苯并噁唑、2-巯基苯并咪唑、2-巯基_5_甲氧基苯并噻唑等芳香族硫醇化合物； [0097] thiazol-2-mercaptobenzothiazole, 2- mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-benzothiazole _5_ methoxy aromatic thiol compounds;

[0098] 3-巯基丙酸、3-巯基丙酸甲酯等脂肪族一元硫醇化合物； [0098] 3-mercaptopropionic acid, 3-mercapto propionate and other aliphatic monohydric thiol compound;

[0099] 季戊四醇四（巯基乙酸酯）、季戊四醇四（3-巯基丙酸酯）等2官能以上的脂肪族硫醇化合物。 [0099] pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptopropionate) and the like more bifunctional aliphatic thiol compound. 这些硫醇化合物中，特别优选2-巯基苯并噻唑。 These thiol compounds, particularly preferably 2-mercaptobenzothiazole thiazole.

[0100] 在将联咪唑化合物和氨基类增敏剂一起使用时，作为氨基类增敏剂的用量，相对于100质量份联咪唑化合物，优选为0. 1〜50质量份，更优选为1〜20质量份。 [0100] When used together the United imidazole compounds and amino-based sensitizers, as amino type sensitizer in an amount relative to 100 parts by mass of an imidazole compound linked to, preferably 0.1 1~50 parts by mass, more preferably from 1 ~ 20 parts by mass. 通过使氨基类增敏剂的用量为0. 1〜50质量份，可以提高放射线敏感性组合物曝光时的固化反应性，提高得到的固化膜的表面硬度。 By reacting an amino type sensitizer in an amount of 0.5 1~50 parts by mass, the curing reaction can be improved radiation-sensitive composition of the exposure time, improve the surface hardness of the cured film obtained.

[0101] 另外，在将联咪唑化合物、氨基类增敏剂和硫醇化合物一起使用时，作为硫醇化合物的用量，相对于100质量份联咪唑化合物，优选为0. 1〜50质量份，更优选为1〜20质量份。 100 parts by mass of an imidazole compound linking [0101] Further, when the biimidazole compound, an amino group, and thiol type compounds sensitizer used together, as the amount of the thiol compound with respect to, preferably 0. 1~50 parts by mass, more preferably 1~20 parts by mass. 通过使硫醇化合物的用量为0. 1〜50质量份，可以改善得到的固化膜的表面硬度。 By reacting the thiol compound in an amount of 0.5 parts by mass 1~50, we can improve the surface hardness of the cured film obtained.

[0102] 该放射线敏感性组合物优选含有选自由0-肟基酯化合物和乙酰苯化合物构成的群组的至少一种作为[D]成分的放射线敏感性聚合引发剂。 As at least one of [D] component radiation [0102] The radiation-sensitive composition is preferably selected from the group comprising 0- oxime ester compound and acetophenone compound constituted sensitive polymerization initiator. 另外，该放射线敏感性组合物可以含有选自由0-肟基酯化合物和乙酰苯化合物构成的群组的至少一种以及联咪唑化合物作为[D]成分的放射线敏感性组合物。 Further, the radiation-sensitive composition may contain a group selected from 0- oxime ester compound and acetophenone compound consisting of at least one compound, as well as linking imidazo [D] component of the radiation sensitive composition. [0103] 该放射线敏感性组合物中的[D]成分的放射线敏感性聚合引发剂的用量，相对于1质量份[A]成分，优选为0. 05〜10质量份，更优选为0. 1〜5质量份。 [0103] The radiation-sensitive composition of the radiation [D] component sensitive polymerization initiator is used in an amount of 1 part by mass with respect to component [A], preferably 0.1 05~10 parts by mass, more preferably 0. 1 ~ 5 parts by mass. 通过使[D]成分的用量为上述范围，该放射线敏感性组合物即使在低曝光量的情况下，也可以显示出高的放射线灵敏度，形成具有足够的表面硬度的固化膜。 By reacting [D] component is used in an amount within the above range, the radiation-sensitive composition even at a low exposure amount, it can also exhibit high radiation sensitivity, to form a cured film having a sufficient surface hardness.

[0104] <[E]多官能环氧化合物〉 [0104] <[E] multifunctional epoxy compounds>

[0105] [E]多官能环氧化合物是为了提高聚合反应性，进一步提高由放射线敏感性组合物形成的固化膜的表面硬度而添加到放射线敏感性组合物中。 [0105] [E] The polyfunctional epoxy compound to improve polymerization reactivity, and further improve the surface hardness of a cured film formed from the radiation-sensitive composition is added to the radiation-sensitive composition. 作为多官能环氧化合物，使用在1分子中具有两个以上的环氧基的阳离子聚合性化合物。 As the polyfunctional epoxy compound, a cationically polymerizable compound having two or more epoxy groups in one molecule.

[0106] 作为这种在1分子中具有两个以上的环氧基的阳离子聚合性化合物的具体例子， 可以列举出双酚A 二缩水甘油基醚、双酚F 二缩水甘油基醚、双酚S 二缩水甘油基醚、氢化双酚A 二缩水甘油基醚、氢化双酚F 二缩水甘油基醚、氢化双酚AD 二缩水甘油基醚等双酚的多缩水甘油基醚类；1，4_ 丁二醇二缩水甘油基醚、1，6_己二醇二缩水甘油基醚、甘油三缩水甘油基醚、三羟甲基丙烷三缩水甘油基醚、聚乙二醇二缩水甘油基醚、聚丙二醇二缩水甘油基醚等多元醇的多缩水甘油基醚类；在乙二醇、丙二醇、甘油等脂肪族多元醇中加成1 种或两种以上的烯化氧得到的聚醚聚醇的脂肪族聚缩水甘油醚类；在1分子中具有两个以上的3，4-环氧环己基的化合物；双酚A酚醛清漆型环氧树脂等苯酚酚醛清漆型环氧树脂； 甲酚酚醛清漆型环氧树脂；聚苯酚型环氧树脂；环状脂肪族环氧树脂；脂肪族长链二元酸的二缩水甘油基酯类；高级脂肪酸的缩水甘油基酯类；环氧化大豆油、环氧化亚麻油等。 [0106] Specific examples of such a cationically polymerizable compound having two or more epoxy groups in a molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD ​​diglycidyl ether of bisphenol polyglycidyl ethers; 1,4_ butanediol diglycidyl ether, 1,6_ hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polyglycidyl polypropylene glycol diglycidyl ether polyols such as glyceryl ethers; alkylene oxide adducts one kind or two or more of the resulting polyether polyol ethylene glycol, propylene glycol, glycerol and other aliphatic polyol aliphatic polyglycidyl ether type; a compound having two or more 3,4-epoxycyclohexyl groups in a molecule; bisphenol A novolac type epoxy resin, phenol novolac type epoxy resin; cresol novolac novolak type epoxy resins; poly-phenol type epoxy resins; alicyclic epoxy resins; aliphatic long-chain dibasic acid diglycidyl esters; glycidyl esters of higher fatty acids; epoxidized soybean oil, epoxidized linseed oil and the like. 在这些1分子中具有两个以上的环氧基的阳离子聚合性化合物中，优选苯酚酚醛清漆型环氧树脂和聚苯酚型环氧树脂。 A cationically polymerizable compound having two or more epoxy groups in one molecule in which, preferably a phenol novolak type epoxy resin and a polyphenol type epoxy resins.

[0107] 作为在1分子中具有两个以上的3，4_环氧环己基的化合物的具体例子，可以列举出3，4-环氧环己基甲基-3 '，4 ' -环氧环己烷羧酸酯、2- (3，4-环氧环己基-5，5-螺-3，4-环氧）环己烷-间二氧杂环己烷、二（3，4_环氧环己基甲基）己二酸酯、二（3，4_环氧-6-甲基环己基甲基）己二酸酯、3，4-环氧-6-甲基环己基-3'，4' -环氧-6' -甲基环己烷羧酸酯、亚甲基二（3，4_环氧环己烷）、二环氧化二环戊二烯、乙二醇的二（3，4_环氧环己基甲基）醚、亚乙基二（3，4_环氧环己烷羧酸酯）、内酯改性的3，4_环氧环己基甲基-3'，4'_环氧环己烷羧酸酯等。 [0107] Specific examples of the compound having two or more 3,4_ epoxycyclohexyl groups in a molecule include 3,4-epoxycyclohexylmethyl-3 ', 4' - epoxy ring hexane-carboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane - Room dioxane, di (cycloalkyl 3,4_ Oxygen cyclohexylmethyl) adipate, di (3,4_ epoxy-6-methyl-cyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ' , 4 '- epoxy-6' - methylcyclohexane carboxylate, methylene bis (3,4_-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4_ epoxycyclohexyl methyl) ether, ethylenebis (3,4_-epoxycyclohexane carboxylate), lactone-modified 3,4_ epoxycyclohexylmethyl-3 ', 4'_ epoxycyclohexane carboxylate and the like.

[0108] 作为在1分子中具有两个以上的环氧基的化合物的商品，可以列举出例如，作为 [0108] As a commodity the compound having two or more epoxy groups in one molecule may include, for example, as

双酚A型环氧树脂是工C 二一卜1001、工二一卜1002、工二一卜1003、工二一卜1004、工匕° 二一卜1007、工匕° 二一卜1009、工匕° 二一卜1010、工匕° 2 —卜828 (夕弋"° >工水。 Bisphenol A type epoxy resin is a working C twenty-one BU 1001, BU 1002 twenty-one workers, workers twenty-one BU 1003, BU 1004 twenty-one workers, workers dagger ° twenty-one BU 1007, BU workers dagger ° twenty-one 1009, workers dagger ° twenty-one BU 1010, workers dagger ° 2 - BU 828 (Xi Yi "°> Workers water.

矢* ^ ” > (株式会社）制造）；作为双酚F型环氧树脂是二- 一卜807( yi “ > 二求*〉> ” > (株式会社）制造）；作为苯酚酚醛清漆型环氧树脂（双酚A酚醛清漆型环氧树脂等）是工匕° 二一卜152、工匕° 二一卜154、工匕-一卜157S65 ( ” \ “ >工水。今〉> ” > Vector ^ * "> (manufactured) manufactured); bisphenol F type epoxy resin is a two - a BU 807 (yi"> two requirements * >> "> (manufactured) manufactured); as a phenol novolak type ring epoxy resin (bisphenol A novolac type epoxy resin, etc.) is the work of a divine dagger ° two 152 workers dagger BU 154 ° twenty-one workers dagger - a BU 157S65 ("\"> Water workers now >> ">

(株式会社）制造）、EPPN201、EPPN 202(日本化薬（株式会社）制造）；作为甲酚酚醛清漆型环氧树脂是EOCN 102, E0CN103S, E0CN104S, 1020,1025,1027 (日本化薬（株式会社）制造）、工if - 一卜180S75( ” ^ “ >工# * ^ ” > (株式会社）制造）；作为聚苯酚型环氧树脂是工匕。二一卜1032H60、工匕。二一卜XY-4000 ( ” \ “ >工水。矢* >夕> (株式会社) 制造）；作为环状脂肪族环氧树脂是CY-175、CY-177、C Y-179、” W]卜C Y-182、了' ^ 夕· ^ 卜CY 192、184( ' ^ -y ^ ^ r ir < ^ χ·(株式会社)制造)、ERL_4234、4299、4221、4206卬丄.（：公司制造）、* s 一夕w > 509(昭和電工（株式会社）制造）、二匕。 (Corporation) manufactured), EPPN201, EPPN 202 (Nihon Pharmaceutical (Ltd.) Ltd.); as cresol novolac epoxy resin is EOCN 102, E0CN103S, E0CN104S, 1020,1025,1027 (Japan of Medicine (type strains Clubs) Ltd.), work if - a BU 180S75 ("^"> work # * ^ "> (Ltd.) Ltd.); as polyphenol type epoxy resin is a divine work dagger two 1032H60, workers dagger twenty-one. Bu XY-4000 ("\"> work water vector *> Tokyo> (Corporation) manufactured); cyclic aliphatic epoxy resin is a CY-175, CY-177, C Y-179, "W] Bu C Y-182, the '^ * ^ Xi Bu CY 192,184 (' ^ -y ^ ^ r ir <^ χ · (Ltd.) manufactured), ERL_4234,4299,4221,4206 Ang Shang (: manufactured ), * s overnight w> 509 (Showa Denko (Ltd.), Ltd.), the second dagger. 夕口> 200、工匕。 Xi mouth> 200 workers dagger. 夕口> 400(大日本〗(株式会社）制造）、工匕。 Xi port> 400 (Dainippon〗 (Ltd.) Ltd.), workers dagger. 二一卜871、工匕。 Twenty-one BU 871 workers dagger. -一卜872 ( ” \ ^ 水。矢* l· 夕> (株式会社)制造)、ED-5661、ED-5662 (七，二一文.-一亏^ > V公司制造）；作为脂肪族聚缩水甘油基醚是工^卜100MF(共栄社化学（株式会社）制造）、工C * 一& TMP(日本油脂（株式会社）制造）。 - A BU 872 (. "\ ^ Water vector * l · eve> (Ltd.) manufactured), ED-5661, ED-5662 (seven two one text .- a deficit ^> V Inc.); as aliphatic polyglycidyl ether is working ^ BU 100MF (Kyoeisha Chemical (Co., Ltd.), Ltd.), a working C * & TMP (Nippon Oil (manufactured) Ltd.).

[0109] 这些[E]成分的多官能环氧化合物可以单独或混合两种以上使用。 [0109] The polyfunctional epoxy compound [E] component may be used singly or in combination of two or more. 该放射线敏感性组合物中的[E]成分的多官能环氧化合物的用量，相对于1质量份[A]成分的光聚合引发剂，优选为0. 05〜10质量份，更优选为0. 1〜5质量份。 The amount of the polyfunctional epoxy compound in the radiation-sensitive composition of [E] component with respect to 1 part by mass [A] component photopolymerization initiator, preferably 0. 05~10 parts by mass, more preferably 0 . 1 ~ 5 parts by mass. 通过使[E]成分的使用量为0. 05〜10质量份，可以提高聚合反应性，同时高水平地确保形成的固化膜的表面硬度。 By reacting [E] component is used in an amount of 0.5 05~10 parts by mass, the polymerization reaction can be improved, while ensuring a high level of surface hardness of a cured film formed.

[0110] < [F]密合助剂〉 [0110] <[F] adhesion aids>

[0111] [F]成分的密合助剂是为了提高得到的固化膜和基板的密合性而使用的。 [0111] [F] adhesion aid component is obtained in order to improve the adhesion between the cured film and the substrate and used. 作为这种密合助剂，优选具有羧基、甲基丙烯酰基、乙烯基、异氰酸酯基、环氧乙烷基等反应性官能团的官能性硅烷偶联剂。 As such adhesion aid, preferably carboxyl functional silane coupling agents, methacryloyl group, vinyl group, isocyanate group, ethylene oxide groups and other reactive functional groups. 作为密合助剂的具体例子，可以列举出Y-甲基丙烯酰氧基丙基三甲氧基硅烷、Y-异氰酸酯基丙基三乙氧基硅烷、Y-缩水甘油氧基丙基三甲氧基硅烷、 β-(3，4-环氧环己基）乙基三甲氧基硅烷等。 As specific examples of the adhesion aid include the Y- methacryloyloxy trimethoxysilane, Y- isocyanate triethoxysilane, Y- glycidoxypropyl trimethoxysilane silane, β- (3,4- epoxycyclohexyl) ethyl trimethoxysilane. 这些密合助剂可以单独或混合两种以上使用。 These adhesion aids may be used alone or as a mixture of two or more.

[0112] 该放射线敏感性组合物中的[F]成分的密合助剂的用量，相对于1质量份[Α]成分，是0. 05〜10质量份，更优选为0. 05〜8质量份。 [0112] The radiation-sensitive composition [F] adhesion aid component amount with respect to 1 part by mass [Α] component is 0. 05~10 parts by mass, more preferably 0. 05~8 parts by mass. 通过使密合助剂的用量为上述范围， 可以边改善固化膜对基板的密合性，边高水平地确保形成图案的能力。 By adhesion aid is used in an amount within the above range can be cured film on the substrate side to improve adhesion, while ensuring a high level of ability to form a pattern.

[0113] <[G]表面活性剂〉 [0113] <[G] Surfactants>

[0114] [G]成分的表面活性剂是为了进一步提高放射线敏感性组合物的涂膜形成性而使用的。 Surfactant [0114] [G] component is to further improve the radiation-sensitive coating film-forming composition and use. 作为这种表面活性剂，可以列举出例如含氟表面活性剂、有机硅类表面活性剂以及其它表面活性剂。 Examples of such surfactants include fluorinated surfactants e.g., silicone-based surfactants and other surfactants.

[0115] 作为含氟表面活性剂优选在末端、主链和侧链的至少任意部位具有氟代烷基和/ 或氟代亚烷基的化合物。 [0115] The fluorine-containing surfactant is preferably at least the end of any part of the main chain and a side chain fluorinated alkyl compound and / or fluorinated alkylene having. 作为含氟表面活性剂的例子，可以列举出1，1，2，2_四氟代-正辛基（1，1，2，2-四氟代-正丙基）醚、1，1，2，2-四氟代-正辛基（正己基）醚、六乙二醇二(1，1，2，2，3，3-六氟代-正戊基）醚、八乙二醇二（1，1，2，2-四氟代-正丁基）醚、六丙二醇二（1，1，2，2，3，3-六氟代-正戊基）醚、八丙二醇二（1，1，2，2-四氟代-正丁基）醚、全氟代-正十二烷基磺酸钠、1，1，2，2，3，3-六氟代-正癸烷、1，1，2，2，3，3，9，9，10，10-十氟代-正十二烷、氟代烷基苯磺酸钠、氟代烷基磷酸钠、氟代烷基羧酸钠、二甘油四（氟代烷基聚氧乙烯醚）、碘化氟代烷基铵、氟代烷基甜菜碱、其它氟代烷基聚氧乙烯醚、全氟代烷基聚氧乙醇、全氟代烷基烷氧化物、羧酸氟代烷基酯等。 Examples of fluorine-containing surfactant may include 1,1,2,2_ tetrafluoroethane - n-octyl (1,1,2,2-tetrafluoro-generation - n-propyl) ether, 1,1, 2,2-tetrafluoroethane - n-octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoro - n-pentyl) ether, ethylene glycol dimethyl eight (1,1,2,2-tetrafluoro-generation - n-butyl) ether, propylene glycol six (1,1,2,2,3,3-hexafluoro - n-pentyl) ether, eight glycol di (1 , 1,2,2-tetrafluoroethane - n-butyl) ether, perfluoro - n-dodecyl sulfonate, 1,1,2,2,3,3-hexafluoro - n-decane, 1,1,2,2,3,3,9,9,10,10- ten fluoro - n-dodecane, fluorinated benzene sulfonate, sodium fluoroalkyl group, fluoroalkyl carboxylic sodium, diglycerol tetrakis (fluorinated alkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluorinated alkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol , perfluoroalkyl alkoxylates, fluorinated alkyl carboxylic acid esters.

[0116] 作为含氟表面活性剂的商品，可以列举出例如BM-1000、BM-1100(以上，BM CHEMIE 公司制造）、乂办7 7 7 夕F 142D、Λ y 7 y 9 γ 172、> 労勹了、y ，Y 173、义为刀了'7 夕F 183、* m 了” Y 178、}节1 了” F191、乂办7 τ» ？ [0116] As a commodity the fluorinated surfactant may include for example, BM-1000, BM-1100 (above, BM CHEMIE Co., Ltd.), qe Office 777 Xi F 142D, Λ y 7 y 9 γ 172,> Lao Bao a, y, Y 173, defined as a knife '7 evening F 183, * m the "Y 178,} Section 1 of the" F191, qe do 7 τ »? 夕F47U 乂办7 τ» ？ Xi F47U qe do 7 τ »? 夕F476 (以上，大日本〗> #化学工業（株式会社）制造）、7 π，一K FC-170C、7 口，一卜·' FC-171、7 α 7 - F FC-430、7 口，一卜、FC-431 (以上，住友；^ >J 一工Λ (株式会社)制 Xi F476 (above Dainippon〗> # Chemical Industries (Ltd.) manufactured), 7 π, a K FC-170C, 7 ports, a BU · 'FC-171,7 α 7 - F FC-430,7 mouth , a BU, FC-431 (above, Sumitomo; ^> J Robarts Λ (Ltd.) system

造）、寸一7 口父S-112、寸一7 口父S-113、寸一7 口父S-131、寸一7 口父S—141、寸一7 口> S-145、寸一7 口> S-382、寸一7 口> SC-101、寸一7 口> SC—102、寸一7 口> SC—103、寸一7 口> SC-104、寸一7 α > SC-105、寸一7 α > SC-106 (以上，旭硝子（株式会社）制造）、工7卜” EF301、工7卜7 EF303、工7卜？ EF352 (以上，新秋田化成（株式会社)制造）、7夕一夕工> 卜FT-100、7夕一夕工> 卜FT-110、7夕一夕工> 卜FT-140A、7 夕一夕二>卜FT-150、7夕一夕二>卜FT-250、7夕一夕二>卜FT—251、7夕一夕二>卜FT-300、7 夕一夕工> 卜FT-310、7 夕一夕工> 卜FT—400S、7 夕一夕工> 卜FTX—218、7 夕一夕工> 卜FTX-251 (以上，（株式会社)才、才7制造）等。 Made), a 7-inch parent S-112, a 7-inch parent S-113, a 7-inch parent S-131, a 7-inch parent S-141, a 7-inch> S-145, an inch 7> S-382, a 7-inch> SC-101, a 7-inch> SC-102, a 7-inch> SC-103, a 7-inch> SC-104, inch a 7 α> SC- 105 inches a 7 α> SC-106 (above, Asahi Glass Co. (Ltd.) Ltd.), working 7 BU "EF301, working 7 BU 7 EF303, working 7 BU? EF352 (above, new Akita Kasei (Ltd.) Ltd.) 7 evening overnight work> BU FT-100,7 evening overnight work> BU FT-110,7 evening overnight work> BU FT-140A, 7 evening overnight two> BU FT-150,7 evening overnight two > BU FT-250,7 evening overnight two> BU FT-251,7 evening overnight two> BU FT-300,7 evening overnight work> BU FT-310,7 evening overnight work> BU FT-400S, 7 evening overnight work> BU FTX-218,7 evening overnight work> BU FTX-251 (above, (Ltd.) was only 7) and the like.

[0117] 作为有机硅类表面活性剂的具体例子，以市售的商品名表示，可以列举出例如卜一> 夕U 2 — > DC3PA> 卜一> 夕U - — > DC7PA> 卜一> 夕U ^ — > SH 11PA> 卜一> ν 'J - 一> SH21PA,卜一> ν U 2 — > SH28PA,卜一> ν U 2 — > SH29PA,卜一> ν U 二一> SH30PA,卜一> ν U - — > SH-190,卜一> ν U 二一> SH-193,卜一> ν U 二一> SZ-6032> 卜一> ν U 2 — > SF-8428> 卜一> ν U 2 — > DC-57> 卜一k ν U 2 — > DC-190、SH 8400FLUID (以上，東> · ” 二一二> 夕'· ν 'J 二一> (株式会社)制造)、 TSF-4440、TSF-4300、TSF-4445、TSF-4446、TSF-4460、TSF-4452 (以上，GE 東芝ν 'J 二一> (株式会社）制造）、才&力“* 口*寸> 7 — ΚΡ341 (信越化学工業（株式会社）制造）等。 [0117] Specific examples of silicone-based surfactants, marketed under the trade name indicates, may, for example BU> Tokyo U 2 -> DC3PA> BU> Tokyo U - -> DC7PA> BU> evening U ^ -> SH 11PA> BU> ν 'J - a> SH21PA, BU> ν U 2 -> SH28PA, BU> ν U 2 -> SH29PA, BU> ν U twenty-one> SH30PA, BU > ν U - -> SH-190, BU> ν U twenty-one> SH-193, BU> ν U twenty-one> SZ-6032> BU> ν U 2 -> SF-8428> BU> ν U 2 -> DC-57> BU k ν U 2 -> DC-190, SH 8400FLUID (above East> · "two hundred twelve> Xi '· ν' J twenty-one> (Ltd.) manufactured), TSF -4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above, GE Toshiba ν 'J twenty-one> (Ltd.) Ltd.), only & force "mouth * * inch> 7 - ΚΡ341 (Shin-Etsu Chemical (Co., Ltd.)) and the like.

[0118] 这些[G]成分的表面活性剂可以单独或混合两种以上使用。 [01] These [G] surfactant component may be used alone or in combination of two or more. 该放射线敏感性组合物中的[G]成分的表面活性剂的用量，相对于1质量份[Α]成分，是0. 001〜1质量份，更优选为0. 005〜0. 5质量份。 The amount of surfactant in the radiation-sensitive composition [G] component with respect to 1 part by mass [Α] component is 0. 001~1 parts by mass, more preferably 0.5 005~0. 5 parts by mass . 通过使表面活性剂的用量为上述范围，可以降低在基板上形成覆膜时的涂布不勻。 By surfactant is used in an amount within the above range, the coating can be reduced when forming a coating film on the substrate unevenness.

[0119] <放射线敏感性组合物的制备> [0119] <Preparation of radiation-sensitive composition>

[0120] 本发明的放射线敏感性组合物可以通过将上述[Α]光聚合引发剂和[B]具有乙烯基不饱和双键的聚合性化合物以及上述这样任意添加的其它成分均衡地混合制备。 [0120] The radiation sensitive composition of the present invention can be obtained by the above-mentioned [Α] and a photopolymerization agent [B] having an ethylenically unsaturated double bond polymerizable compound, and other ingredients added thus prepared by mixing any of the above balanced initiator. 该放射线敏感性组合物优选在溶解到的适当的溶剂中，以溶液状态使用。 The radiation-sensitive composition is preferably dissolved in a suitable solvent in order to use a solution state. 例如，将[Α]光聚合引发剂和[B]具有乙烯基不饱和双键的聚合性化合物以及任意添加的其它成分在溶剂中以规定的比例混合，可以制备溶液状态的放射线敏感性组合物。 For example, the [Α] and a photopolymerization initiator [B] having an ethylenically unsaturated double bond polymerizable compound and other components optionally added in a solvent to a predetermined mixing ratio, can be prepared in a solution state radiation-sensitive composition .

[0121] 作为该放射线敏感性组合物的制备中使用的溶剂，可以使用在均勻地溶解[Α]光聚合引发剂和[B]具有乙烯基不饱和双键的聚合性化合物以及其它任选成分的各成分的同时，不和各成分反应的溶剂。 [0121] As the solvent for preparing the radiation-sensitive composition used, may be used uniformly dissolved [Α] and a photopolymerization initiator [B] having an ethylenically unsaturated double bond polymerizable compound and other optional ingredients At the same time of each component, and the ingredients are not the reaction. 作为这种溶剂，可以列举出作为制造[C]碱可溶性树脂可以使用的溶剂而在上述例示的溶剂。 Examples of such solvents include solvents as producing [C] The solvent of the alkali-soluble resin may be used in the above-described embodiment illustrated.

[0122] 这种溶剂中，从各成分的溶解性，与和各成分的非反应性、覆膜形成的容易性等观点出发，特别优选使用二乙二醇单乙基醚乙酸酯、二乙二醇二乙基醚、二乙二醇乙基甲基醚、二乙二醇二甲基醚、丙二醇单甲基醚、乙二醇单丁基醚乙酸酯、丙二醇单甲基醚乙酸酯、 二丙二醇单甲基醚乙酸酯、3-甲氧基丁基乙酸酯、环己醇乙酸酯、苯甲醇、3-甲氧基丁醇。 [0122] Such a solvent, solubility of the components, and ease of view and the like of each component of non-reactive, film formation is particularly preferable to use diethylene glycol monoethyl ether acetate, diethylene ethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3- methoxybutanol. 这些溶剂可以单独只使用一种，也可以将二种以上混合使用。 These solvents may be used alone only one, two or more kinds may be used in combination.

[0123] 将该放射线敏感性组合物制备为溶液状态时，固体成分浓度（组合物溶液中占据的溶剂以外的成分，也就是上述[Α]成分和[B]成分以及其它任选成分的总量的比例）根据所使用目的以及所希望的膜厚的值等，可以设定为任意的浓度（例如5〜50质量％ )。 [0123] The radiation-sensitive composition is prepared as a solution state, the solid content concentration (composition solution occupies components other than the solvent, i.e. above [Α] and total component [B] component and other optional ingredients volume ratio) according to the desired purpose and thickness of the values ​​used, etc., can be set to an arbitrary concentration (for example, 5~50% by mass). 这样制备的放射线敏感性组合物的溶液也使用孔径0. 2〜0. 5 μ m这样的微孔过滤器等过滤后再使用。 The thus prepared solution of the radiation sensitive composition also pore size 0.5 2~0. 5 and other such microporous filter μ m filter before use. [0124]〈固化膜〉 [0124] <cured film>

[0125] 由本发明的放射线敏感性组合物形成的固化膜如后述的实施例所表明，具有高的表面硬度和优异的透明性。 [0125] cured film made of the radiation sensitive composition of the present invention is formed as described later in Example indicated, it has a high surface hardness and excellent transparency. 这种固化膜可以适用于要求高的表面硬度和透明性的技术用途，例如适合作为液晶装置以及半导体装置的保护膜、绝缘膜以及图案形成用材料使用。 This cured film may be applied to the technical requirements of high surface hardness and transparency purposes, e.g., as a protective film for a liquid crystal device and a semiconductor device, an insulating film and patterning material used.

[0126]〈固化膜的形成方法〉 [0126] <cured film forming method>

[0127] 接着，对使用本发明的放射线敏感性组合物形成固化膜的方法进行说明。 [0127] Next, the present invention is a radiation-sensitive composition of the cured film forming method will be described. 使用该放射线敏感性组合物的固化膜的形成方法的特征是至少包含下述记载的顺序的下述工序⑴〜G)。 The use of a cured film of the radiation sensitive composition forming method characterized by comprising at least the following order according to the following steps ⑴~G). 工序（3)可以在必须形成图案的情况下进行。 Step (3) can be carried out in the case of a pattern to be formed.

[0128] 也就是，固化膜的形成方法包括： [0128] That is, a cured film forming method comprising:

[0129] (1)在基板上形成本发明的放射线敏感性组合物的覆膜的工序， [0129] (1) a film on a radiation-sensitive composition of the present invention is formed on a substrate,

[0130] (2)对该覆膜的至少一部分照射放射线的工序， [0130] (2) coating at least a portion of the radiation irradiating step,

[0131] (3)将照射放射线后的覆膜显影的工序，以及 [0131] (3) after the irradiation of radiation film developing step, and

[0132] (4)将显影后的覆膜加热的工序。 [0132] (4) heating the film after the development step.

[0133] 以下，对这些各个工序依次进行说明。 [0133] In the following, each of these steps will be described in turn.

[0134] (1)在基板上形成本发明的放射线敏感性组合物的覆膜的工序 [0134] (1) The radiation-sensitive composition of the present invention form a film on a substrate

[0135] 作为这里使用的基板没有特别的限定，可以列举出透明基板以及金属基板等。 [0135] As the substrate used here is not particularly limited, and may include a transparent substrate and a metal substrate or the like. 作为该透明基板，可以列举出例如玻璃基板、树脂基板等，作为其具体例子，可以列举出钠钙玻璃、无碱玻璃等玻璃基板；由聚对苯二甲酸乙二酯、聚对苯二甲酸丁二酯、聚醚砜、聚碳酸酯、聚酰亚胺等塑料形成的树脂基板。 Examples of the transparent substrate, and examples thereof include a glass substrate, a resin substrate or the like, Specific examples include soda lime glass, alkali-free glass of the glass substrate; from polyethylene terephthalate, polyethylene terephthalate polybutylene terephthalate, polyether sulfone, polycarbonate, polyimide resin substrate is formed of plastic. 可以在这种透明基板的一面上形成透明导电膜，在该透明导电膜上形成放射线敏感性组合物的涂膜。 May be on one side of the transparent conductive film formed on the transparent substrate, the transparent conductive film coating the radiation sensitive composition is formed.

[0136] 作为设置在透明基板的一面上的透明导电膜，可以列举出由氧化锡（SnO2)形成的NESA膜（美国PPG公司的注册商标）、氧化铟-氧化锡（In2O3-SnO2)形成的ITO膜等。 [0136] As provided in the transparent substrate on one side of the transparent conductive film, it includes the NESA film (a registered trademark of PPG's) tin oxide (SnO2) formed indium - tin oxide (In2O3-SnO2) formed ITO film.

[0137] 在通过涂布法形成涂膜时，在透明导电膜上涂布放射线敏感性组合物的溶液后， 优选通过加热（预烘焙）涂布面，形成覆膜。 After [0137] In forming a coating film by a coating method, the transparent conductive film coating the radiation sensitive composition solution, preferably by heating (prebaking) the coated surface to form a coating film. 涂布法中使用的组合物溶液的固体成分浓度优选为5〜50质量％，更优选为10〜40质量％，进一步优选为15〜35质量％。 The solid content concentration of the coating composition used in the method of solution is preferably 5~50% by mass, and more preferably 10~40 wt%, more preferably 15~35% by mass. 作为组合物溶液的涂布方法，没有特别的限定，可以采用例如喷雾法、辊涂法、旋转涂布法（旋涂法）、缝模涂布法、棒式涂布法、喷墨涂布法等适当的方法。 As the composition of the solution coating method is not particularly limited, and may be employed such as spraying method, roll coating method, spin coating method (spin coating method), a slit die coating method, bar coating method, inkjet coating appropriate method method. 这些方法中，特别优选旋涂法或缝模涂布法。 Of these methods, particularly preferred spin coating method or a slit die coating method.

[0138] 上述预烘焙的条件根据各种成分的种类以及混合比例等而异，优选在70〜120°C 下进行1〜15分钟左右。 [0138] the pre-baking conditions depending on the kind and the mixing ratio of the various components and the like, is preferably carried out at 70~120 ° C 1~15 minutes. 作为预烘焙后的覆膜的厚度优选为0. 5〜10 μ m，更优选为1. 0〜 7. 0 μ m0 As a film thickness after pre-baking is preferably 0. 5~10 μ m, and more preferably 1. 0~ 7. 0 μ m0

[0139] (2)对该覆膜的至少一部分照射放射线的工序 [0139] (2) coating at least a portion of the radiation irradiating step

[0140] 接着，对形成的涂膜的至少一部分照射放射线。 [0140] Next, the coating film formed on at least a portion of the radiation is irradiated. 此时，在只照射覆膜的一部分时， 可以通过插入具有规定图案的掩模照射的方法进行。 At this time, when only a part of the irradiated coating can be inserted through a mask having a predetermined pattern irradiation method.

[0141] 作为照射使用的放射线，可以列举出可见光线、紫外线、远紫外线等。 [0141] As used in radiation exposure may include visible light, ultraviolet, far ultraviolet. 其中，优选波长在250〜550nm的范围内的放射线。 Wherein, preferably the wavelength of the radiation in the range of 250~550nm.

[0142] 放射线照射量（曝光量）是通过照度计（0ΑΙ model 356, OpticalAssociates Inc.制造），测定照射的放射线的波长365nm下的强度的值，优选为100〜5，000J/m2，更优选为200 〜3，000J/m2。 [0142] the amount of radiation exposure (exposure) is a value obtained by light meter (0ΑΙ model 356, OpticalAssociates Inc., Ltd.), the wavelength of radiation measured at 365nm irradiation intensity is preferably 100~5,000J / m2, more preferably of 200 ~3,000J / m2. [0143] (3)将照射放射线后的覆膜显影的工序 [0143] (3) a radiation irradiation step after film development

[0144] 接着，通过将照射放射线后的覆膜显影，除去不需要的部分，形成规定的图案。 [0144] Next, by developing the film after irradiating radiation to remove an unnecessary portion is formed in a predetermined pattern.

[0145] 作为显影使用的显影液，例如可以使用氢氧化钠、氢氧化钾、碳酸钠等无机碱；氢氧化四甲基铵、氢氧化四乙基铵等季铵盐等碱（碱性化合物）的水溶液。 [0145] As a developer to be used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate and other inorganic bases; tetramethyl ammonium hydroxide, tetraethyl ammonium base such as a quaternary ammonium salt (basic compound hydroxide ) in water. 在这些碱水溶液中还可以适量添加甲醇、乙醇等水溶性有机溶剂和/或表面活性剂使用。 Among these alkaline aqueous solutions can also add an appropriate amount of a water-soluble organic solvent such as methanol, ethanol and the like, and / or surface active agent. 碱水溶液中的碱的浓度从得到适当的显影性的观点出发，优选为0. 1质量％以上、5质量％以下。 The alkali concentration of the alkali aqueous solution obtained from the appropriate viewpoint of developability, preferably not less than 0.1 mass%, 5 mass% or less. 作为显影方法可以是液体堆积法、浸渍法、淋浴法等任意方法，显影时间优选在常温下进行10〜180 秒左右。 As the developing method may be any method of a liquid accumulation method, a dipping method, shower method or the like, the developing time is preferably at ambient temperature for about 10~180 seconds.

[0146] (4)将显影后的涂膜加热的工序 [0146] (4) heating the coating film after development step

[0147] 上述显影处理后，对形成图案的覆膜优选进行30〜90秒钟的流水洗涤后，通过压缩空气或压缩氮气风干。 After the [0147] The developing process for forming a pattern film is preferably carried out after the water washing 30~90 seconds by compressed air or compressed nitrogen dry. 接着，将得到的图案状覆膜通过热板、烘箱等适当的加热装置，在规定温度例如100〜250°C下，加热（后烘焙)规定时间，例如在热板上加热5〜30分钟， 在烘箱中加热30〜180分钟，可以得到具有高的表面硬度的固化膜。 Subsequently, a patterned coating film obtained by suitable heating means a hot plate, oven or the like, at a predetermined temperature, for example 100~250 ° C under heating (post-baking) a predetermined time, e.g., a hot plate heated at 5~30 minutes, heating 30~180 minutes in an oven, it is possible to obtain a cured film having a high surface hardness.

[0148]【实施例】 [0148] [Example]

[0149] 以下，通过合成例和实施例对本发明进行更详细地说明，但是本发明并不限于这些实施例。 [0149] Hereinafter, synthesis examples and examples of the present invention will be described in more detail, but the present invention is not limited to these examples.

[0150] <[A]成分的化合物（光聚合引发剂）的合成例> [0150] <[A] compound ingredients (photopolymerization initiator) Synthesis Example>

[0151][合成例A-1](化合物（AI)的合成） [0151] [A-1 Synthesis Example] (Synthesis of Compound (AI) in)

[0152] 根据下述合成路线，合成作为最终产物（viii)的化合物（AI)(上述式（¾所示的化合物）。 [0152] According to the following synthetic route, the final product of the synthesis of the compound (viii) of (AI) of the compound (the above formula (¾ shown).

[0153] [0153]

[0154] 式中、Me是甲基，Ac是乙酰基。 [0154] wherein, Me is methyl, Ac is acetyl.

[0155] 步骤（I)：通过1-(4-氟代苯基）_辛-1-酮⑴和咔唑的缩合合成中间体（ii) [0155] Step (I): via 1- (4-fluorophenyl) oct-1-one _ ⑴ and condensation of a synthetic intermediate carbazole (ii)

[0156] 在IL的三口烧瓶中安装冷却管，在氮气氛下，在500mL 二甲基亚砜中溶解50g(299mmol)咔唑。 [0156] condenser installed in IL three-necked flask, under a nitrogen atmosphere, dissolved in 500mL dimethyl sulfoxide 50g (299mmol) carbazole. 在其中加入63gQ84mmol)的1-½-氟代苯基）_辛-1-酮和103g(748mmol)碳酸钾，在135°C的反应温度下，加热搅拌12小时。 Added thereto 63gQ84mmol) of 1-½- fluorophenyl) _ oct-1-one and 103g (748mmol) of potassium carbonate, at a reaction temperature of 135 ° C, heated and stirred for 12 hours. 将反应液注入冰中，吸滤析出的固体，将固体再用蒸馏水洗涤。 The reaction mixture was poured into ice, the precipitated solid was filtered off with suction, the solid was washed with distilled water. 对这里得到的粗结晶通过叔丁基甲基醚重结晶，得到105g中间体(ii)。 The crude crystals obtained here by tert-butyl methyl ether to give 105g of intermediate (ii).

[0157] 步骤(II)：中间体(iii)的合成[0158] 在300mL的茄型烧瓶中加入25g (162mmol) 4_氟代_2_甲基苯甲酸和193g(1620mmol)亚硫酰氯，在室温25°C下搅拌，接着，加入ImL 二甲基甲酰胺，然后搅拌20 小时。 [0157] Step (II): Synthesis of Intermediate (iii), [0158] In an eggplant-shaped flask was added 300mL of 25g (162mmol) 4_ fluoro _2_ methylbenzoic acid and 193g (1620mmol) of thionyl chloride, at room temperature at 25 ° C with stirring, followed by addition of ImL dimethylformamide, and then stirred for 20 hours. 减压馏出反应液，得到观.Og的4-氟代-2-甲基苯甲酰氯。 The reaction solution was distilled off under reduced pressure to give the concept .Og 4-fluoro-2-methylbenzoyl chloride.

[0159] 在2L的茄子型烧瓶中加入59.8g(162mm0l)上述实验得到的中间体（ii)，在其中加入IOOOmL 二氯甲烷，使中间体（ii)溶解，然后添加75.6g(567mmol)氯化铝后，冰冷却，使反应液温度降到10°C。 [0159] was added in a 2L eggplant type flask 59.8g (162mm0l) above experiment obtained intermediate (ii), in methylene chloride was added thereto IOOOmL, the intermediate (ii) were dissolved, then added 75.6g (567mmol) chloro After aluminum, ice cooling, the reaction solution temperature dropped to 10 ° C. 对该反应体系，滴加在150mL 二氯甲烷中溶解了上述合成的28. 0g(162mmol)4-氟代-2-甲基苯甲酰氯的溶液。 The reaction system, the synthesized above was dissolved was added dropwise 28. 0g (162mmol) 4- fluoromethyl -2- chloride solution in 150mL dichloromethane. 滴加过程中，将反应温度保持在10〜 20°C。 During the dropwise addition, the reaction temperature was maintained at 10~ 20 ° C. 滴加结束后，将反应液在20°C下搅拌20小时。 After the addition, the reaction mixture was stirred at 20 ° C for 20 hours. 将反应液在400g冰水中骤冷搅拌，然后加入200mL水，通过500mL氯仿萃取3次，收集有机层，用饱和碳酸氢钠洗涤，接着，用蒸馏水洗涤，减压馏出溶剂，得到粗产物。 The reaction mixture was quenched with ice water and stirred at 400g, then 200mL of water was added, and extracted three times by 500mL of chloroform, and the organic layer was collected, washed with saturated sodium bicarbonate, then washed with distilled water, the solvent was distilled off under reduced pressure to give the crude product. 将该粗产物通过硅胶柱色谱精制，得到59g中间体 The crude product was purified by silica gel column chromatography to obtain 59g of Intermediate

(iii) ο (Iii) ο

[0160] 步骤（III)：中间体（iv)的合成 [0160] Step (III): Synthesis of Intermediate (iv) of

[0161] 在2L的茄型烧瓶中加入59.0g(117mmOl)上述实验得到的中间体（iii)，在其中加入IOOOmL 二氯甲烷，使中间体（iii)溶解，再添加M.6g(410mmol)氯化铝后，通过冰冷却，使反应液温度降低到0°C。 [0161] was added in a 2L round-bottom flask 59.0g (117mmOl) above experiment obtained intermediate (iii), IOOOmL methylene chloride was added thereto, the intermediate (iii) is dissolved, then add M.6g (410mmol) After the aluminum chloride, by ice-cooling, the reaction solution temperature was lowered to 0 ° C. 针对该反应体系，滴加27.5g(351mmol)乙酰氯。 For the reaction system was added dropwise 27.5g (351mmol) of acetyl chloride. 在滴加过程中，将反应液温度保持在10〜20°C。 During the addition, the reaction mixture temperature was maintained at 10~20 ° C. 滴加结束后，将反应液在20°C下搅拌20小时。 After the addition, the reaction mixture was stirred at 20 ° C for 20 hours. 将反应液在400g冰水中骤冷搅拌，然后加入200mL水，接着，通过500mL氯仿萃取3次。 The reaction mixture was quenched with ice water and stirred at 400g, then 200mL of water was added, followed by 500mL of chloroform and extracted 3 times. 收集有机层，通过饱和碳酸氢钠洗涤，接着用300mL蒸馏水洗涤，减压馏出溶剂后，得到粗产物。 The organic layer was collected, washed with saturated sodium bicarbonate through, followed by washing with 300mL of distilled water, after distilling off the solvent under reduced pressure to obtain a crude product. 该粗产物通过硅胶柱色谱精制，得到53. 2g中间体（iv)。 The crude product was purified by silica gel column chromatography to give 53. 2g of intermediate (iv).

[0162] 测定该中间体（iv)的1H-NMR时，如下所示。 [0162] When the measurement of the intermediate (iv) The 1H-NMR, as follows. 另外，在本实施例中，1H-NMR的测定通过7·· A力一株式会公司制造AVANCE500型进行。 Further, in this embodiment, the measurement of 1H-NMR force by 7 ·· A strain formula will be manufactured AVANCE500 type.

[0163] 1H-匪R(溶剂：CDC13)化学位移σ :8. 76ppm(咔唑环上的氢、1Η)、8· 59ppm(咔唑环上的氢、1H)、8. 26ppm(N-苯基上的氢、2H)、8. 12ppm(咔唑环上的氢、1H)、8. 01ppm(咔唑环上的氢、1H)、7. 69ppm (N-苯基上的氢、2H)、7. 46ppm (咔唑环上的氢、2H)、7. 40ppm (氟代苯环上的氢、1H)、7. 05ppm(氟代苯环上的氢、1H)、7. OOppm (氟代苯环上的氢、1H)、 3. 06ppm(N-苯基-C0-CH2-.2H)、2. 73ppm(苯环上甲基、3H)、2· 39ppm(乙酰基、3H)、 [0163] 1H- bandit R (solvent: CDC13) chemical shift σ:.. 8 76ppm (hydrogen carbazole ring, 1Η), 8 · 59ppm (hydrogen carbazole ring, 1H), 8 26ppm (N- hydrogen on the phenyl, 2H), 8. 12ppm hydrogen carbazole ring (, 1H), 8. 01ppm hydrogen carbazole ring (, 1H), 7. 69ppm (N- hydrogen on the phenyl, 2H ), 7. 46ppm hydrogen carbazole ring (, 2H), 7. 40ppm (fluorinated hydrogen on the benzene ring, 1H), 7. 05ppm (fluorinated hydrogen on the benzene ring, 1H), 7. OOppm ( fluorinated hydrogen on the benzene ring, 1H), 3. 06ppm (N- phenyl -C0-CH2-.2H), 2. 73ppm (meth benzene ring, 3H), 2 · 39ppm (acetyl, 3H) ,

I. 8Ippm(N-苯基-C0-CH2-CH2-、2H)、1.47 〜1. 25ppm(脂肪族长链亚甲基、8H)、 0. 9Ippm(甲基、3H)。 I. 8Ippm (N- phenyl -C0-CH2-CH2-, 2H), 1.47 ~1. 25ppm (aliphatic long chain methylene, 8H), 0. 9Ippm (methyl, 3H).

[0164] 步骤（IV)：和巯基乙醇的缩合——中间体（ν)的合成 [0164] Step (IV): and mercaptoethanol condensation - intermediate (ν) Synthesis

[0165] 在IL的茄型烧瓶中加入53. 2g(97. Immo 1)上述合成的中间体（iv)、 [0165] added IL eggplant type flask 53. 2g (97. Immo 1) synthesized above intermediate (iv),

II.4g(146mmol)巯基乙醇，将它们溶解到300mL 二甲基乙酰胺中。 II.4g (146mmol) mercaptoethanol, dissolving them into 300mL dimethyl acetamide. 在氮气氛下，添加26. 7g(194mmol)碳酸钾，在50°C下反应12小时。 Under a nitrogen atmosphere, add 26. 7g (194mmol) of potassium carbonate, the reaction at 50 ° C for 12 hours. 将反应液冷却到室温后，注入300mL蒸馏水，将其移往分液漏斗，用300mL乙酸乙酯萃取3次。 The reaction mixture was cooled to room temperature, 300mL distilled water injection, which was moved to a separatory funnel and extracted 3 times with 300mL ethyl acetate. 接着，收集有机层，用300mL蒸馏水洗涤2次，用无水硫酸镁干燥后，减压馏出溶剂，得到粗产物。 Subsequently, organic layer was collected, washed twice with 300mL distilled water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to give the crude product. 该粗产物通过硅胶柱色谱精制， 得到32. 9g中间体(ν)。 The crude product was purified by silica gel column chromatography to give 32. 9g of intermediate (ν).

[0166] 步骤（V)：硫原子的氧化——中间体（Vi)的合成 [0166] Step (V): The oxidation of the sulfur atom - intermediate (Vi) Synthesis of

[0167] 在IOOmL茄型烧瓶中，量取32.9g(M. 3mmol)上述合成的中间体（V)。 [0167] In IOOmL eggplant type flask, weighed 32.9g (M. 3mmol) synthesized above intermediate (V). 在其中添加12. 4g(109mmol)的30质量％过氧化氢水溶液和相当于0. 027mmol的量的根据文献(Tetrahedron 60(2004) 4087-4096)制备的PWAA(聚{PW1204广[(N-异丙基丙烯酰胺）与(丙烯酰胺和铵盐）的共聚物]3})，在25°C下搅拌10小时。 Added thereto 12. 4g (109mmol) of 30% by mass aqueous hydrogen peroxide and an amount equivalent to 0. 027mmol according to the literature (Tetrahedron 60 (2004) 4087-4096) prepared PWAA (poly {PW1204 wide [(N- isopropyl acrylamide) and (acrylamide and ammonium salt) copolymer] 3}) and stirred at 25 ° C for 10 hours. 接着，加入200mL甲苯，过滤， 将滤液移往分液漏斗，除去水层。 Subsequently, 200mL of toluene was added, filtered, and the filtrate was moved to a separatory funnel, the aqueous layer was removed. 之后，在该有机层中加入50mL饱和硫代硫酸钠水溶液，洗涤，通过50mL蒸馏水进行洗涤。 After that, 50mL of saturated aqueous sodium thiosulfate solution was added, the organic layer was washed, washed by 50mL of distilled water. 之后。 After that. 在有机层中加入硫酸镁干燥，减压馏出有机层，得到粗产物。 Was added to the organic layer dried over magnesium sulfate, the organic layer was distilled off under reduced pressure to give the crude product. 该粗产物通过硅胶柱色谱精制，得到30. 8g中间体（vi)。 The crude product was purified by silica gel column chromatography to give 30. 8g of intermediate (vi).

[0168] 另外，本步骤（V)的硫原子的氧化也可以通过以下的方法进行。 [0168] Further, the present oxidation step (V) of the sulfur atom can also be carried out by the following method. 将氧化钨溶解到蒸馏水中，制备1质量％的氧化钨水溶液。 The tungsten oxide was dissolved in distilled water to prepare a 1 mass% aqueous solution of tungsten oxide. 将中间体（ν)溶解到6L甲苯中，在其中加入30 质量％过氧化氢，然后加入溴化四丁基铵和1质量％氧化钨水溶液。 Intermediate (ν) was dissolved in 6L of toluene, to which 30 mass% hydrogen peroxide, followed by addition of tetrabutylammonium bromide and an aqueous solution of 1 mass% tungsten oxide. 将反应温度每分钟升温1°C，在70°C下搅拌2小时。 The reaction temperature was raised per minute 1 ° C, stirred at 70 ° C for 2 hours. 将反应溶液冷却到60°C后，移往分液漏斗，通过升温到60°C 的蒸馏水洗涤有机层。 The reaction solution was cooled to 60 ° C after moved to the separatory funnel, washed by heating to 60 ° C the organic layer was distilled. 接着，将加热到60°C的反应溶液用C盐过滤后，减压馏出。 Subsequently, the reaction was heated to 60 ° C after the solution was filtered with a salt C, distilled off under reduced pressure. 在得到的粗产物中加入700g氯仿、乙醇结晶。 700g chloroform was added the crude product obtained, crystallized from ethanol. 吸滤结晶、真空干燥，可以得到中间体（vi)。 Crystallization suction filtration, vacuum drying, yielding intermediate (vi).

[0169] 步骤(VI)：中间体(vii)的合成 [0169] Step (VI): Synthesis of Intermediate (vii) a

[0170] 在500mL的茄型烧瓶中，量取30.8g(48. 3mmol)上述合成的中间体（vi)，在其中加入250mL 二甲基乙酰胺，溶解中间体（vi)，然后加入4. 8g(120mmol)氢氧化钠，在65°C下搅拌1小时。 [0170] In a 500mL round-bottom flask, weighed 30.8g (48. 3mmol) synthesized above intermediate (vi), which was added in 250mL of dimethylacetamide, was dissolved Intermediate (vi), followed by addition of 4. 8g (120mmol) of sodium hydroxide, followed by stirring at 65 ° C for 1 hour. 在其中加入11.8g(170mmOl)氯化羟基铵，升温到90°C，搅拌1小时。 This was added 11.8g (170mmOl) hydroxyl ammonium chloride, warmed to 90 ° C, stirred for 1 hour. 接着，将反应液冷却到室温，加入200mL蒸馏水，通过200mL乙酸乙酯萃取3次。 Subsequently, the reaction solution was cooled to room temperature, 200mL of distilled water was added, was extracted by 200mL of ethyl acetate three times. 收集有机层，通过200mL蒸馏水洗涤，减压馏出有机层，得到26. Ig中间体（vii)。 The organic layer was collected, washed with 200mL of distilled water through the organic layer was distilled off under reduced pressure to afford 26. Ig of intermediate (vii).

[0171] 在测定该中间体（vii)的1H-NMR时，如下所示。 [0171] In the measurement of the intermediate (vii) The 1H-NMR, as follows.

[0172] 1H-NMR(溶剂:d6_丙酮)化学位移σ :8. 72ppm(咔唑环上的氢、1H)、8. 54ppm(咔唑环上的氢、1H)、8. Olppm(N-苯基上的氢、2H)、7. 98ppm(咔唑环上的氢、1H)、7. 95〜 7. 89ppm(咔唑环上的氢以及CO-Ph苯环上的氢、3H)、7. 70ppm(N-苯基上的氢、2H)、 7. 65ppm (CO-Ph苯环上的氢、1H)、7. 54ppm (咔唑环上的氢、1H)、7. 44ppm (咔唑环上的氢、 1H)、3. 97ppm(H0-CH2-.2H)、3. 52ppm(S02-CH2-.2H)、2. 94ppm(N-苯基-(CN)-CH2-.2H)、 2. 41ppm(苯环上甲基、3H)、2. 33ppm(CH3-C = Ν_、3Η)、1· 67ppm(N_ 苯基-(CN)-CH2-C型-、 2H)、1. 47ppm(N-苯基-(CN) -CH2-CH2-C型-、2H)、1. ；35 〜1. 25ppm(脂肪族长链亚甲基、6H)、 0. 89ppm(甲基、3H)。 [0172] 1H-NMR (solvent: d6_ acetone) chemical shift σ:... 8 72ppm (hydrogen carbazole ring, 1H), 8 54ppm (hydrogen carbazole ring, 1H), 8 Olppm (N - Hydrogen on the phenyl, 2H), 7 98ppm (hydrogen carbazole ring, 1H), hydrogen (carbazole ring 7 95~ 7. 89ppm and hydrogen on the benzene ring CO-Ph, 3H) , 7. 70ppm (N- hydrogen on the phenyl, 2H), 7. 65ppm (hydrogen on the benzene ring CO-Ph, 1H), 7. 54ppm (hydrogen carbazole ring, 1H), 7. 44ppm ( hydrogen carbazole ring, 1H), 3 97ppm. (H0-CH2-.2H), 3 52ppm (S02-CH2-.2H), 2 94ppm (N- phenyl -.. (CN) -CH2-. 2H), 2. 41ppm (meth benzene ring, 3H), 2 33ppm (CH3-C = Ν_, 3Η), 1 · 67ppm (N_ phenyl -. (CN) -CH2-C type -, 2H), 1. 47ppm (N- phenyl - (CN) -CH2-CH2-C type -, 2H), 1;.. 35 ~1 25ppm (aliphatic long chain methylene, 6H), 0. 89ppm (methyl, 3H).

[0173] 步骤（VII)：最终产物（viii)的合成 Synthesis of the final product (viii) of: [0173] Step (VII)

[0174] 接着，将中间体（vii)的游离体的3个羟基同时乙酰化，合成最终产物（viii)。 [0174] Next, the 3-hydroxy intermediate (vii) in the free form, while acetylation, the final synthesis product (viii).

[0175] 在500mL的茄型烧瓶中，量取沈.lg(39. lmmol)上述合成的中间体（vii)，加入IOOmL乙酸正丁酯，溶解中间体（vii)，然后加入15. 6g(152mmol)乙酸酐，在90°C下搅拌1 小时。 [0175] In a 500mL round-bottom flask, weighed Shen .lg (39. Lmmol) synthesized above intermediate (vii), n-butyl acetate was added IOOmL, dissolving intermediate (vii), followed by addition of 15. 6g ( 152mmol) of acetic anhydride, followed by stirring at 90 ° C for 1 hour. 将反应液冷却到室温，加入200mL水，萃取有机层，然后用IOOmL乙酸正丁酯萃取2 次。 The reaction mixture was cooled to room temperature, 200mL of water to extract the organic layer, and then IOOmL n-butyl acetate and extracted twice. 收集有机层，用200mL蒸馏水洗涤，减压馏出有机层，得到粗产物。 The organic layer was collected, 200mL washed with distilled water, the organic layer was distilled off under reduced pressure to give the crude product. 将该粗产物通过硅胶柱色谱精制，得到23. 9g最终产物（viii)。 The crude product was purified by silica gel column chromatography to give 23. 9g final product (viii). 将该得到的产物作为化合物（AI)。 The product was obtained as the compound (AI).

[0176]化合物(AI)的 1H-NMR, IR、UV、TG-DTA, LC-MS 如下测定。 [0176] Compound (AI) of 1H-NMR, IR, UV, TG-DTA, LC-MS was determined as follows. 进行1H-WR 测定( 1H-WR were measured (

^力一株式会社制造AVANCE500型）、顶测定（株式会社堀埸制作所制造的FT-720)、 UV测定（日本分光株式会社制造的V-570)、TG-DTA的分析（理学电气株式会社制造TG8120)、LC-MS分析（日本々才一夕一<株式会社制造ACQUITYUPLC&reg ；系统以及SYNAPT HDMS (High Definition Mass Spectrometry)系统），对化合物（A-1)进行分析。 ^ Force a K.K. AVANCE500 type), the top measurement (drinking places Seisakusho Co., Ltd. Horie's FT-720), UV measurement (manufactured by Japan Spectroscopy Corporation V-570), TG-DTA analysis (Rigaku Corporation Manufacturing TG8120), LC-MS analysis (Japan 々 overnight before a <K.K. ACQUITYUPLC & reg; systems and SYNAPT HDMS (High Definition Mass Spectrometry) system), compound (A-1) were analyzed. 分析结果如下所示。 The results are shown below.

[0177] 1H-NMR(溶剂：CDC13)化学位移δ :8. 50ppm(咔唑环上的氢、1Η)、8. 48ppm(咔唑环上的氢、1H)、8. Olppm(咔唑环上的氢和N-苯基上的氢以及CO-Ph苯环上的氢、4H)、 7. 95〜7. 89ppm(咔唑环上的氢以及CO-Ph苯环上的氢、3H)、7. 63ppm(N-苯基上的氢、 2H)、7. 55ppm (CO-Ph苯环上的氢、1H)、7. 45ppm (咔唑环上的氢、1H)、7. 4Ippm (咔唑环上的氢、1H)、450ppm(A c0-CH2-,2H)、3· 55ppm(S02-CH2-,2H)、2· 94ppm(N_ 苯基-(CN)-(：监-、 2H)、2· 52ppm(C迎-C = Ν-、3Η)、2· 43ppm (苯环上甲基、3H)、2· 30ppm(N_0C0C胆、 3H)、2. 28ppm(N-0C0C皿、3H)、1· 95ppm (S02-CH2-CH2-0C0CH3, 3Η)、1· 66ppm(N_ 苯基-(CN)-CH2-CH^-、2H)、1. 44ppm(N_ 苯基-(CN)-CH2-CH2-C巡-、2Η)、1. 35 〜1. 25ppm(脂肪族长链亚甲基、8H)、0. 90ppm(甲基、3H)。 [0177] 1H-NMR (solvent: CDC13) Chemical shift δ:. 8 50ppm (hydrogen carbazole ring, 1Η), 8 48ppm (hydrogen carbazole ring, 1H), 8 Olppm (carbazole ring. - hydrogen and N- phenyl and hydrogen on the benzene ring of CO-Ph, 4H), hydrogen (carbazole ring 7. 95~7. 89ppm and hydrogen on the benzene ring CO-Ph, 3H) , 7. 63ppm (N- hydrogen on the phenyl, 2H), 7. 55ppm (hydrogen on the benzene ring CO-Ph, 1H), 7. 45ppm (hydrogen carbazole ring, 1H), 7. 4Ippm ( tetrahydrocarbazole ring, 1H), 450ppm (A c0-CH2-, 2H), 3 · 55ppm (S02-CH2-, 2H), 2 · 94ppm (N_ phenyl - (CN) - (: Supervisor -, 2H), 2 · 52ppm (C Ying -C = Ν-, 3Η), 2 · 43ppm (methyl benzene ring, 3H), 2 · 30ppm (N_0C0C guts, 3H), 2. 28ppm (N-0C0C dish, 3H), 1 · 95ppm (S02-CH2-CH2-0C0CH3, 3Η), 1 · 66ppm (N_ phenyl - (CN) -CH2-CH ^ -, 2H), 1 44ppm (N_ phenyl - (CN). -CH2-CH2-C patrol -., 2Η), 1 35 ~1 25ppm (aliphatic long chain methylene, 8H), 0 90ppm (methyl, 3H)...

[0178] IR(KBr 片):30640^^29520^^2929011^28560^^17680^^17470^^16540^1, 1594cm_\l517cm_\l473cm_\l367cm_\l321cm_\l280cm_\l255cm_\l230cm_\l203cm_\ 1143cm"\935cm_1 [0178] IR (KBr tablets): 30640 ^^ 29520 ^^ 2929011 ^ 28560 ^^ 17680 ^^ 17470 ^^ 16540 ^ 1, 1594cm_ \ l517cm_ \ l473cm_ \ l367cm_ \ l321cm_ \ l280cm_ \ l255cm_ \ l230cm_ \ l203cm_ \ 1143cm " \ 935cm_1

[0179] UV (0. 02mM 乙醇溶液)：λ max :251nm、303nm、339nm [0179] UV (0. 02mM ethanol): λ max: 251nm, 303nm, 339nm

[0180] TG-DTA ：222°C (分解点) [0180] TG-DTA: 222 ° C (decomposition point)

[0181] LC-MS :m/z = 816. 2988 (M++Na :816. 2931 (计算值）) [0181] LC-MS: m / z = 816. 2988 (M ++ Na:. 816 2931 (calc))

[0182][合成例A-2](化合物（A-2)的合成) [0182] (Synthesis of Compound (A-2) a) [Synthesis Example A-2]

[0183] 改变上述（AI)的合成路线，合成上述式（4)所示的化合物。 [0183] Changes synthetic routes above (AI), the synthesis of compounds represented by formula (4). 在上述（AI)的合成路线的步骤（II)中，在200mL的茄型烧瓶中加入33.7g(162mm0l)的4-三甲基甲硅烷基-2-甲基苯甲酸和193g(1620mmol)亚硫酰氯，在室温25°C下搅拌，接着，加入ImL二甲基甲酰胺，然后搅拌20小时。 (II) was added 33.7g in the step (AI) synthetic routes in 200mL round-bottom flask (162mm0l) 4-trimethylsilyl-2-methyl-benzoic acid and 193g (1620mmol) Asia thionyl chloride, at room temperature of 25 ° C with stirring, followed by the addition ImL dimethylformamide, then stirred for 20 hours. 减压馏出反应液，得到36. 7g的4-三甲基甲硅烷基-2-甲基苯甲酰氯。 The reaction solution was distilled off under reduced pressure, to give 4-trimethylsilyl-2-methylbenzoyl chloride of 36. 7g.

[0184] 在2L的茄型烧瓶中，加入59.8g(162mm0l)上述得到的中间体（ii)，然后加入IOOOmL 二氯甲烷，溶解中间体（ii)，添加75. 6g (567mmol)氯化铝后，通过冰冷却，将反应液温度降温到10°c。 [0184] In a 2L round-bottom flask was added 59.8g (162mm0l) Intermediate (ii) obtained above, methylene chloride was then added IOOOmL dissolved intermediate (ii), added 75. 6g (567mmol) of aluminum chloride After cooling, the reaction solution was cooled to a temperature of 10 ° c by ice-cooling. 对该反应体系，滴加在150mL 二氯甲烷中溶解了36. 7g(162mmol)上述合成的4-三甲基甲硅烷基-2-甲基苯甲酰氯的溶液。 The reaction system was added dropwise dissolved 36. 7g (162mmol) synthesized above 4- trimethyl silyl-2-methylbenzoyl chloride solution in 150mL dichloromethane. 滴加过程中，将反应液温度保持在10〜 20°C。 During the dropwise addition, the reaction mixture was maintained at a temperature of 10~ 20 ° C. 滴加结束后，将反应液在20°C下搅拌20小时。 After the addition, the reaction mixture was stirred at 20 ° C for 20 hours. 反应液在400g冰水中骤冷搅拌，然后加入200mL水，用500mL氯仿萃取3次。 The reaction was quenched in ice cold stirring 400g, then 200mL of water was added, and extracted three times with 500mL of chloroform. 收集有机层，用饱和碳酸氢钠洗涤，接着用蒸馏水洗涤，减压馏出溶剂，得到粗产物。 The organic layer was collected, washed with saturated sodium bicarbonate, then washed with distilled water, the solvent was distilled off under reduced pressure to give the crude product. 该粗产物通过硅胶柱色谱精制，得到化合物（iii-1)。 The crude product was purified by silica gel column chromatography to give compound (iii-1).

[0185] 在下文中，除了使用中间体（iii-Ι)代替中间体（iii)，省略步骤（IV)和步骤（V) 以外，和合成例AI的情形同样地合成，得到化合物（A-2)。 [0185] In the following, except that Intermediate (iii-Ι) instead of intermediate (iii), except omitting the step (IV) and the step (V), and the AI ​​in the same manner as in Synthesis Example Synthesis case, to give Compound (A-2 ).

[0186] 测定该化合物（A-2)的1H-匪R和LC-MS时，如下所示。 [0186] When the measurement of the compound (A-2) of the 1H- bandit R and LC-MS, as shown below.

[0187] 1H-Iimr (溶剂：CDC13)化学位移δ :8. 77ppm(咔唑环上的氢、1Η)、8. 54ppm(咔唑环上的氢、1H)、8. 05ppm(咔唑环上的氢和N-苯基上的氢以及CO-Ph苯环上的氢、4H)、7. 88ppm(咔唑环上的氢以及CO-Ph苯环上的氢、3H)、7. 65ppm(N-苯基上的氢、2H)、7. 48ppm(咔唑环上的氢、1H)、7. 43ppm(咔唑环上的氢、1H)、2. 98ppm(N-苯基-(CN)-CH^-、2H)、2. 51ppm(苯环上甲基、3H)2. 30ppm (3 个乙酰氧基、9H)、1. 64ppm(N_ 苯基-(CN)-CH2-C型-、2H)、1. 4Ippm(N-苯基-(CN)-CH2-CH2-C型-、2H)、1. 35 〜1. 25ppm(脂肪族长链亚甲基、8H)、0. 87ppm(甲基、3H)、0. 19ppm(Si的甲基、9H)。 [0187] 1H-Iimr (Solvent: CDC13) Chemical shift δ:. 8 77ppm (hydrogen carbazole ring, 1Η), 8 54ppm (hydrogen carbazole ring, 1H), 8 05ppm (carbazole ring. hydrogen and hydrogen on the benzene ring hydrogen on the phenyl and N- CO-Ph, 4H), 7. 88ppm (hydrogen carbazole ring and hydrogen on the benzene ring CO-Ph, 3H), 7. 65ppm . (hydrogen on the phenyl N-, 2H), 7 48ppm (hydrogen carbazole ring, 1H), 7 43ppm (hydrogen carbazole ring, 1H), 2 98ppm (N- phenyl -. ( CN) -CH ^ -.., 2H), 2 51ppm (meth benzene ring, 3H) 2 30ppm (3 acetyl groups, 9H), 1 64ppm (N_ phenyl -. (CN) -CH2-C type -, 2H), 1 4Ippm. (N- phenyl - (CN) -CH2-CH2-C type -., 2H), 1 35 ~1 25ppm (aliphatic long chain methylene, 8H), 0.. 87ppm (methyl, 3H), 0. 19ppm (Si methyl, 9H).

[0188] LC-MS :m/z = 738. 3383 (M++Na :738. 3339(计算值)) [0188] LC-MS: m / z = 738. 3383 (M ++ Na:. 738 3339 (calc))

[0189][合成例A-3](化合物（A-3)的合成）[0190] 改变上述（AI)的合成路线，合成上述式（6)所示的化合物。 [0189] [Synthesis Example A-3] (Compound (A-3) Synthesis) [0190] Changes synthetic routes above (AI) and the compound (6) synthesized by the above formula. 在上述（AI)的合成路线的步骤（II)中，在200mL的茄型烧瓶中加入54.4g(162mm0l)的4-二苯基磷酰基-2-甲基苯甲酸和193g(1620mmol)亚硫酰氯，在室温25°C下搅拌，接着，加入ImL 二甲基甲酰胺，然后搅拌20小时。 In the step (AI) synthetic route (II) was added in 200mL round-bottom flask 54.4g (162mm0l) of 4-phenyl-2-methyl-benzoic acid and phosphorus 193g (1620mmol) thionyl chloride, at room temperature of 25 ° C with stirring, followed by addition of ImL of dimethylformamide, and then stirred for 20 hours. 减压馏出反应液，得到60. 9g的4- 二苯基磷酰基-2-甲基苯甲酰氯。 The reaction solution was distilled off under reduced pressure to give 60. 9g of 4-methyl-2-diphenylphosphoryl chloride.

[0191] 在2L的茄型烧瓶中，加入59. 8g(162mmol)上述得到的中间体(ii)，加入IOOOmL 二氯甲烷，溶解中间体（ii)，添加75. 6g(567mmol)氯化铝后，通过冰冷却，将反应液温度降温到10°C。 [0191] In a 2L eggplant type flask, 59. 8g (162mmol) of Intermediate (ii) obtained above, methylene chloride was added IOOOmL, dissolving intermediate (ii), added 75. 6g (567mmol) of aluminum chloride After cooling, the reaction solution was cooled to a temperature of 10 ° C by ice-cooling. 对该反应体系，滴加在150mL 二氯甲烷中溶解了60. 9g(162mm0l)上述合成的4-二苯基磷酰基-2-甲基苯甲酰氯的溶液。 The reaction system was added dropwise dissolved 60. 9g (162mm0l) synthesized above solution of 4-phenyl-phosphoryl-2-methylbenzoyl chloride in 150mL of dichloromethane. 滴加过程中，将反应液温度保持在10〜20°C。 Dropping, the reaction solution temperature was maintained at 10~20 ° C. 滴加结束后，将反应液在20°C下搅拌20小时。 After the addition, the reaction mixture was stirred at 20 ° C for 20 hours. 反应液在400g冰水中骤冷搅拌，然后加入200mL水，用500mL氯仿萃取3次。 The reaction was quenched in ice cold stirring 400g, then 200mL of water was added, and extracted three times with 500mL of chloroform. 收集有机层，用饱和碳酸氢钠洗涤，接着用蒸馏水洗涤， 减压馏出溶剂，得到粗产物。 The organic layer was collected, washed with saturated sodium bicarbonate, then washed with distilled water, the solvent was distilled off under reduced pressure to give the crude product. 该粗产物通过硅胶柱色谱精制，得到化合物（iii-2)。 The crude product was purified by silica gel column chromatography to give compound (iii-2).

[0192] 在下文中，除了使用中间体（iii-2)代替中间体（iii)，省略步骤（IV)和步骤（V) 以外，和合成例AI的情形同样地合成，得到化合物（A-3)。 [0192] In the following, except that Intermediate (iii-2) instead of intermediate (iii), except omitting the step (IV) and the step (V), and the case of the same manner as in Synthesis Example Synthesis of AI, to give Compound (A-3 ).

[0193] 测定该化合物（A-3)的1H-匪R和LC-MS时，如下所示。 [0193] Determination of the compound (A-3) of 1H- bandit when R and LC-MS, as shown below.

[0194] 1H-Iimr (溶剂：CDC13)化学位移δ :8. 77ppm(咔唑环上的氢、1Η)、8. 54ppm(咔唑环上的氢、1H)、8. 05ppm(咔唑环上的氢和N-苯基上的氢以及CO-Ph苯环上的氢、 4H)、7. 88ppm (咔唑环上的氢以及CO-Ph苯环上的氢、3H)、7. 65ppm (N-苯基上的氢、2H)、 7. 48ppm(咔唑环上的氢、1H)、7. 43ppm(咔唑环上的氢、1H)、7. 49〜7. 87ppm (-PO-Ph的氢、 10H)、2. 98ppm(N-苯基-(CN)-CH2-.2H)、2. 5Ippm(苯环上甲基、3H)、2. 30ppm(3 个乙酰氧基、9H)、1. 64ppm(N-苯基-(CN)-CH2-C型-、2H)、1. 4Ippm(N-苯基-(CN)-CH2-CH2-C胆-、 2H)、1· 35 〜1. 25ppm(脂肪族长链亚甲基、8H)、0. 87ppm(甲基、3H)。 [0194] 1H-Iimr (Solvent: CDC13) Chemical shift δ:. 8 77ppm (hydrogen carbazole ring, 1Η), 8 54ppm (hydrogen carbazole ring, 1H), 8 05ppm (carbazole ring. hydrogen and hydrogen on the benzene ring hydrogen on the phenyl and N- CO-Ph, 4H), 7. 88ppm (hydrogen carbazole ring and hydrogen on the benzene ring CO-Ph, 3H), 7. 65ppm (hydrogen on the phenyl N-, 2H), 7. 48ppm (hydrogen carbazole ring, 1H), 7. 43ppm (hydrogen carbazole ring, 1H), 7. 49~7. 87ppm (-PO -Ph hydrogen, 10H), 2 98ppm. (N- phenyl - (CN) -CH2-.2H), 2 5Ippm (meth benzene ring, 3H), 2 30ppm (3 acetyl group. 9H), 1 64ppm (N- phenyl - (CN). -CH2-C type -, 2H), 1 4Ippm. (N- phenyl - (CN) -CH2-CH2-C gall -, 2H), 1 · 35 ~1. 25ppm (aliphatic long chain methylene, 8H), 0. 87ppm (methyl, 3H).

[0195] LC-MS :m/z = 866. 3388 (M++Na :866. 3335 (计算值)) [0195] LC-MS: m / z = 866. 3388 (M ++ Na:. 866 3335 (calc))

[0196] <[C]成分的碱可溶性树脂（共聚物）的合成例> [0196] <alkali-soluble resin [C] component (copolymer) Synthesis Example>

[0197][合成例Cl](共聚物（CI)的合成） [0197] (Synthesis of copolymer (CI) a) [Synthesis Example Cl]

[0198] 在具有冷却管和搅拌器的烧瓶中，加入5质量份2，2' -偶氮二异丁腈和250质量份丙二醇单甲基醚乙酸酯，接着，加入18质量份甲基丙烯酸、25质量份甲基丙烯酸三环[5. 2. 1. O2'6]癸-8-基酯、5质量份苯乙烯、30质量份甲基丙烯酸2-羟基乙基酯和22质量份甲基丙烯酸苄基酯，氮气置换。 [0198] In a flask having a cooling tube and a stirrer was charged with 5 parts by weight of 2,2 '- azobisisobutyronitrile and 250 parts by mass of propylene glycol monomethyl ether acetate, followed by addition of 18 parts by mass Methyl acrylic acid, methacrylic acid, 25 parts by mass of tricyclo [5. 2. 1. O2'6] dec-8-yl methacrylate, 5 parts by mass of styrene, 30 parts by mass of methacrylic acid 2-hydroxyethyl acrylate and 22 parts by mass methacrylate, benzyl acrylate, purged with nitrogen. 接着，边缓慢搅拌，边将溶液的温度升高到70°C，保持该温度5小时进行聚合，得到固体成分浓度观.8质量％的共聚物（CI)溶液。 Then, while slowly stirring, the temperature of the solution was raised to 70 ° C, maintained at that temperature for 5 hours for polymerization to obtain a solid content concentration concept .8% by mass of the copolymer (CI) was added dropwise. 对得到的共聚物(CI)使用以下的装置和条件测定Mw时，是13，000。 The resulting copolymer (CI) using the following apparatus and conditions measured Mw, is 13,000.

[0199] 装置=GPC-IOl (昭和电工(株式会社)制造) [0199] device = GPC-IOl (Showa Denko (Ltd.) Ltd.)

[0200]柱：组合 GPC-KF-801、GPC-KF-802、GPC-KF-803 和GPC-KF-804 [0200] Column: a combination of GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

[0201] 移动相：四氢呋喃 [0201] Mobile phase: tetrahydrofuran

[0202] <放射线敏感性组合物的制备> [0202] <Preparation of radiation-sensitive composition>

[0203][实施例1] [0203] [Example 1]

[0204] 将相当于1质量份（固体成分）的量的作为[A]成分的合成例AI的含有化合物（AI)的溶液、100质量份作为[B]成分的二季戊四醇五丙烯酸酯和二季戊四醇六丙烯酸酯的混合物（日本化薬（株式会社）制造的“KAYARAD DPHA”）、5质量份作为[F]成分的Y-缩水甘油氧基丙基三甲氧基硅烷以及0.3质量份作为[G]成分的含氟表面活性剂((株）才、^ 7制造的“FTX-218”）混合，溶解到二乙二醇乙基甲基醚中以使固体成分浓度为30质量％后，通过口径0. 2 μ m的薄膜过滤器过滤，制备放射线敏感性组合物的溶液。 [0204] The equivalent of 1 part by mass (solid content) as a solution containing an amount of the compound (AI) [A] of Synthesis Example AI components, 100 parts by mass as the [B] component dipentaerythritol pentaacrylate and bis mixture of pentaerythritol hexaacrylate (Nihon Pharmaceutical (Ltd.), manufactured by "KAYARAD DPHA"), 5 parts by mass of [F] Y- component glycidoxy trimethoxysilane and 0.3 parts by mass [G ] fluorinated surfactant ingredient ((strain) before, ^ 7 manufactured "FTX-218") were mixed and dissolved to diethylene glycol ethyl methyl ether to give a solid content concentration of 30 mass%, the by caliber 0. 2 μ m membrane filter to prepare a radiation-sensitive composition solution.

[0205] [实施例2〜10和比较例1〜5] [0205] [Examples 2~10 and Comparative Examples 1 ~ 5]

[0206] 除了作为[A]〜[G]成分使用如表1记载的种类和量以外，和实施例1同样地制备放射线敏感性组合物的溶液。 [0206] In addition, as [A] ~ [G], such as the kind and amount of ingredients used in Table 1 other than described, and prepared in the same manner as the radiation sensitive composition solution of Example 1 embodiment.

[0207] 表1中，对[B]、[D]、[E]、[F]和[G]成分的简称分别是指下述化合物。 [0207] In Table 1, to [B], [D], [E], referred to [F] and [G] component refers to a compound, respectively.

[0208] BI ：二季戊四醇五丙烯酸酯和二季戊四醇六丙烯酸酯的混合物（日本化薬（株式会社）制造的“ KAYARAD DPHA") [0208] BI: dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture of esters (Nihon Pharmaceutical (Ltd.), manufactured by "KAYARAD DPHA")

[0209] B-2 ：琥珀酸改性的季戊四醇三丙烯酸酯（東亞合成（株式会社）制造的“ 7 口二”卞T0-756") [0209] B-2: acid-modified pentaerythritol triacrylate (manufactured by Toagosei (Inc.) manufactured by "seven two" Bian T0-756 ")

[0210] DI ：乙酮-l-[9-乙基-6-(2-甲基苯甲酰基）_9H_咔唑_3_基](0_乙酰基月亏）（子K · ^ ν ^ r ^ —.夂笑力卟文公司制造的“ 4卟办今二ζ 0XE02”) [0210] DI: ethyl ketone -l- [9- ethyl-6- (2-methylbenzoyl) _9H_ carbazole _3_ yl] (0_ acetyl waning) (sub K · ^ ν ^ r ^ -. Fan power porphyrin laugh manufactured article "4 porphyrin do this two ζ 0XE02")

[0211] D-2 :2-二甲基氨基-2-(4-甲基苄基）-1-(4_吗啉_4_基苯基）-丁酮（千A ·又《夕汶^ r 4 一·夕笑力）l·文公司制造的“ 4卟办今二7 379”) [0211] D-2: 2- dimethyl-2- (4-methyl-benzyl) -1- (4_ morpholinyl _4_-phenyl) - butanone (thousands of A · and "Xi Wen · Xi ^ r 4 a laugh force) l · text manufactured "4 of porphyrins do this two 7379")

[0212] D-3 ：2-甲基-1-(4-甲基硫代苯基）_2_吗啉代丙酮（商品名“ ^ >力1 二r 907”、子八· ^ ν ^ r ^ —.夂笑力卟文公司制造） [0212] D-3: 2- methyl-1- (4-methylthio-phenyl) _2_ morpholino-propanone (trade name "^> 1 two power r 907", the sub-eight · ^ ν ^ r ^ - laughing force porphyrin Wen Wen, Inc.)

[0213] EI ：苯酚酚醛清漆型环氧树脂（” ^ ^ # * ^夕> (株式会社)制造的 [0213] EI: phenol novolak type epoxy resin ("^ ^ # * ^ Xi> (Corporation) manufactured

“工If 2—卜152”） "Work If 2- BU 152")

[0214] E-2 ：双酚A酚醛清漆型环氧树脂（” ^ ^求# * ^夕> (株式会社）制造的“工if 2—卜157S65”） [0214] E-2: Bisphenol A novolac type epoxy resin ("seek # * ^ ^ ^ Xi> (Ltd.), manufactured by" work if 2- BU 157S65 ")

[0215] FI = Y-缩水甘油氧基丙基三甲氧基硅烷 [0215] FI = Y- glycidoxypropyl trimethoxysilane

[0216] GI ：含氟系表面活性剂((株)才、才^制造的“FTX-218，，） [0216] GI: fluorine-containing surfactant ((strain) was only ^ manufactured "FTX-218 ,,)

[0217] <放射线敏感性组合物和固化膜的性质评价> [0217] <radiation-sensitive composition and properties of the cured film evaluation>

[0218] 如上制备的放射线敏感性组合物以及由其形成的固化膜的评价如下进行。 [0218] Evaluation of radiation-sensitive composition prepared as described above and the cured film formed therefrom as follows. 评价结果在表1中表示。 The evaluation results are shown in Table 1 below.

[0219] (1)放射线敏感性组合物的放射线灵敏度的评价 [0219] (1) The radiation-sensitive composition of the radiation sensitivity of the evaluation

[0220] 在无碱玻璃基板上分别通过旋涂器涂布放射线敏感性组合物的溶液后，在80°C的热板上预烘焙3分钟，形成放射线敏感性组合物的覆膜（膜厚4. 0 μ m)。 After [0220] In the alkali-free glass substrate solution were radiation-sensitive composition was applied by spin coating, at 80 ° C for 3 minutes on a hot plate pre-baked to form a radiation-sensitive composition of the coating (film thickness 4. 0 μ m). 在得到的覆膜上使用具有残余多个直径15 μ m的圆形图案的光掩模曝光。 The residue using a photomask having a plurality of 15 μ m diameter circular pattern exposure on the film obtained. 此时，覆膜表面和光掩模间设置规定的间隙（曝光间隙）。 In this case, between the coating surface and a gap defined photomask (exposure gap). 接着，使用高压水银灯，通过上述光掩模，边改变曝光量边对覆膜曝光。 Next, using a high pressure mercury lamp, the light through the mask, while changing the amount of exposure to the film side exposed. 接着，使用浓度为0. 05质量％的氢氧化钾水溶液，在25°C，以20秒的显影时间，通过淋浴法显影后，纯水洗涤1分钟，然后在烘箱中，在230°C下后烘焙20分钟，形成圆形图案。 Next, using a concentration of 0.05% by mass potassium hydroxide aqueous solution, at 25 ° C, the development time to 20 seconds, after the shower by the developing method, pure water for 1 minute, and then in an oven at 230 ° C under After baking for 20 minutes to form a circular pattern. 后烘焙后的该圆形图案的高度使用激光显微镜（* 一工制造的VK-8500)测定。 Height after baking the circular pattern using a laser microscope (* a work produced VK-8500) was measured. 将该值用于下式，求得残膜率（％)。 This value is used by the following formula, calculated residual film ratio (%).

[0221] 残膜率（％)=(后烘焙后的图案高度/初期膜厚4.0 μ m) X 100 [0221] residual film rate (%) = (height of the pattern after post-baking / initial thickness of 4.0 μ m) X 100

[0222] 将该残膜率为90%以上的曝光量作为放射线敏感性组合物的放射线灵敏度，在表1中表示。 [0222] The residual film ratio of 90% or more as a radiation exposure of a radiation sensitive composition sensitivity, are shown in Table 1 below. 曝光量为600J/m2以下时，认为放射线灵敏度良好。 Exposure amount of 600J / m2 or less, that the radiation sensitivity is good.

[0223] (2)固化膜的透明性的评价[0224] 除了不使用光掩模，曝光量为600J/m2以外，和上述“（1)放射线敏感性组合物的放射线灵敏度的评价”同样地在玻璃基板（“NA35(NH ”"巧卞(株）公司制造）”） 上形成固化膜。 [0223] (2) the transparency of a cured film evaluation [0224] In addition to not using a photomask, an exposure amount of 600J / m2, and the above-mentioned "(1) a radiation-sensitive composition of the radiation sensitivity of the evaluation" in the same manner In the glass substrate ("NA35 (NH" "Qiao Bian (strain) Co., Ltd.)") is formed on the cured film. 使用分光光度计（“150-20型夕· Oe — A ((株）日立制作所制造”)，以没有保护膜的玻璃基板作为参照侧，在400〜SOOnm的范围的波长下，测定该具有固化膜的玻璃基板的光线透过率。将此时的最低光线透过率的值作为固化膜的透明性的评价，在表1中表示。该值为95%以上时，认为固化膜的透明性良好。 Using a spectrophotometer ("150-20 type evening · Oe - A ((strain) manufactured by Hitachi"), no protective film to the glass substrate side as a reference, in the wavelength range of 400~SOOnm determination that has light transmittance of the cured film of the glass substrate. In this case the minimum value of light transmittance as the evaluation of the transparency of the cured film, are shown in Table 1. When the value is more than 95%, that of the transparent cured film good.

[0225] (3)固化膜的铅笔硬度（表面硬度）的测定 [0225] (3) a cured film pencil hardness (surface hardness) was measured

[0226] 对具有和上述“⑵固化膜的透明性的评价”同样地形成的固化膜的基板，通过JIS K-5400-1990的8. 4. 1铅笔刮擦实验，测定固化膜的铅笔硬度（表面硬度），结果在表1中表示。 [0226] having and "transparency of a cured film rating ⑵" cured film substrate formed in the same manner described above, by JIS 8. 4. 1 pencil scratch test K-5400-1990, the determination of the cured film pencil hardness (surface hardness), the results are shown in Table 1 below. 该值为3H或者更大时，认为固化膜的表面硬度良好。 When the value is 3H or more, that a good surface hardness of cured film.

[0227] (4)升华物挥发量的评价 [0227] (4) The evaluation of the amount of volatile sublimate

[0228] 在硅基板上分别通过旋涂器涂布放射线敏感性组合物的溶液，形成涂布膜厚6.0μπι的覆膜。 [0228] In the silicon substrate by a spin coater, respectively, the radiation sensitive composition solution to form a coating thickness of the coating film 6.0μπι. 对该覆膜通过顶空气相色谱法/质量分析（顶空取样器：日本分析工業(株式会社）制造，型号名称“JHS-100A”;气相色谱/质量分析装置：日本電子（株式会社） 制造，“ JEOL JMS-AX505W型质量分析计”）进行分析。 The film by headspace gas chromatography / mass spectrometry (Headspace Sampler: Japan Analytical Industry (Ltd.) manufacture, model name "JHS-100A"; gas chromatograph / mass spectrometer: Japan Electronics (Ltd.) Manufacturing , "JEOL JMS-AX505W type mass spectrometer") for analysis. 以100°C/10分钟的净化条件，求得与由光聚合引发剂产生的挥发成分相关的峰面积A。 To 100 ° C / 10 min purification conditions, determined by the light polymerization initiator agent volatile components generated correlation peak area A. 使用正辛烷（比重：0. 701 ；注入量： 0. 02 μ L)作为标准物质，以该峰面积为基准，从下式求得正辛烷换算的来自光聚合引发剂的升华物挥发量，结果在表1中表示。 Using n-octane (specific gravity: 0 701; injection volume:. 0. 02 μ L) as a reference standard to the peak area of ​​the base, from the following equation n-octane conversion from light polymerization initiator volatile sublimate amount, results are shown in Table 1 below.

[0229] 升华物挥发量（μ g) = AX (正辛烷的量（μ g))/(正辛烷的峰面积） [0229] sublimate volatile content (μ g) = AX (the amount of n-octane (μ g)) / (n-octane peak area)

[0230] 该升华物的挥发量为1. 5μ g以下时，固化膜形成工艺中的升华物少，认为光聚合引发剂的升华性足够低。 When [0230] The amount of volatile matter was sublimed 1. 5μ g or less, a cured film formed was less sublimation process, a photopolymerization initiator that is sufficiently low sublimating agent.

[0231]【表1】 [0231] [Table 1]

[0232] [0232]

[0233] 从表1所示的结果可以知道：使用含有本发明的新型化合物的光聚合引发剂的放射线敏感性组合物的实施例1〜10与比较例1〜5相比，显示出更高的放射线灵敏度，得到的固化膜的透明性和表面硬度更优异，而且与比较例1〜5相比，升华物的挥发量大致降低；实施例的放射线敏感性组合物和固化膜可以更均衡地发挥出各种性质。 [0233] From the results shown in Table 1 can know: the use of novel compounds containing photopolymerizable embodiment of the present invention the initiator of the radiation-sensitive composition of 1~10 compared with Comparative Example 1 ~ 5, showing higher radiation sensitivity, transparency, and surface hardness of the obtained cured film more excellent, compared with Comparative Examples 1 ~ 5 and, sublimate substantially reduce the amount of volatiles; radiation-sensitive composition and a cured film of the embodiment may be more evenly play a variety of properties. 另外，在制备实施例1〜10的放射线敏感性组合物时，[A]成分的光聚合引发剂的溶解不要经过特别的步骤，可以顺利地溶解。 In addition, in the preparation of Example 1~10 of the radiation sensitive composition, [A] photopolymerization initiator component dissolving agent is not through a special procedure can dissolve smoothly.

[0234] 工业实用性 [0234] Industrial Applicability

[0235] 本发明的新型化合物在作为光聚合引发剂使用时，显示出高的放射线灵敏度，同时具有低的升华性，而且可以形成具有高的透明性和足够的表面硬度的固化膜，所以作为放射线敏感性组合物的成分极为有用。 [0235] The novel compounds of the present invention as a photo-polymerization initiator, exhibits high radiation sensitivity, while having a low sublimation resistance, and can form a high transparency and sufficient surface hardness of a cured film, so as component of the radiation sensitive composition is extremely useful.