新型芳香羟基酮和膦酰氧化物的光引发剂混合物及其与光吸收剂的复合体系 Novel aromatic hydroxyketones and phosphonomethyl oxide photoinitiator with light absorber mixture and its complex system

【技术领域】 TECHNICAL FIELD

[0001] 本发明涉及光辐射固化技术领域，特别涉及一些芳香羟基酮和酰基膦氧化合物复配组成的新型光敏引发剂体系，以及该类光敏引发剂体系和合适的具有红移光吸收特征的羟基苯并三唑类光吸收剂复配形成的可经由光（紫外光或可见光或等价光源）辐照固化的含烯不饱和体系。 [0001] The present invention relates to optical radiation curing technology, and particularly relates to a number of aromatic hydroxyketones and acylphosphine oxide compound complex consisting of novel photoinitiator systems, as well as the class and a suitable photoinitiator system has a red shift of the light absorption characteristics of hydroxybenzotriazole type light absorbers complex formed can be ethylenically unsaturated system via a light (ultraviolet or visible light or equivalent light source) radiation-curable.

【背景技术】 BACKGROUND OF THE INVENTION

[0002] 膦酰类化合物是重要的光引发剂，在专利文献中已由相当丰富的披露，例如EP1106627A1, EP0615980A2, W02006056541A1, W02011003772A1, CN1823077A, CN1659175A等。 [0002] phosphonooxymethyl compounds are important photoinitiator has been quite rich disclosure in the patent literature, for example EP1106627A1, EP0615980A2, W02006056541A1, W02011003772A1, CN1823077A, CN1659175A so on. 膦酰类化合物在实际应用场合所体现的一个特征性缺点是引发聚合时其空气氧阻效应显著，使得含有其的固化涂层表干（Surface Curing)效果欠佳。 Phosphonoacetyl compounds in practical applications embodied in a characteristic shortcoming is its air-initiated polymerization oxygen inhibition effect is remarkable, making it the cured coating containing dry (Surface Curing) ineffective. 有鉴于此，膦酰类化合物常常和羟基酮类光引发机复配使用，以取得平衡的表干和深层固化（Through Curing)固化效果。 In view of this, Phosphonoacetyl hydroxy compounds and ketones often photoinitiator machine mixed use, in order to obtain a balanced and deep dry cured (Through Curing) curing effect.

[0003] 我们近期在专利CN102060684中披露了一类新型的“间位取代型”羟基酮光引发齐U，该类轻基酮可以直接以传统市售产品例如Darocure 1173或Irgacure 184为原料衍生制备，具备优异的光引发活性和经济竞争力。 [0003] We have recently disclosed the preparation of a class of materials derived from the new "meta-substituted type" hydroxy ketone photoinitiator Qi U, such light ketone can be marketed directly to the traditional products such as Darocure 1173 or Irgacure 184 as in the patent CN102060684 , with excellent light triggered activity and economic competitiveness.

[0004] 现已发现，这类羟基酮化合物和文献已知的膦酰类化合物复配后是性能优异的新型混合光引发剂体系；同时进一步发现，这样形成的新型光引发剂体系和紫外光吸收剂(例如US5977219，US6187845) —特别是具有红移光吸收特征的羟基苯并三唑类紫外光吸收剂一进一步复配后可以有效克服光吸收剂的强烈光吸收干扰从而令人意外地取得了对含烯不饱和体系具有满意固化效果的混合物。 [0004] It has been found, and after this type of hydroxy ketone compounds known in the literature phosphonomethylglycine based compound complex is excellent in the performance of a new hybrid photoinitiator system; and further found that the thus formed new optical and UV initiator system absorbents (e.g. US5977219, US6187845) - particularly a red-shifted light absorption characteristics of hydroxybenzotriazole type ultraviolet light absorber after a further compound can overcome the strong light absorption interference light absorber thus surprisingly achieved a mixture containing ethylenically unsaturated system has a satisfactory curing effect.

【发明内容】 SUMMARY OF THE INVENTION

[0005] 定义下述酰基膦氧化合物，芳香羟基酮化合物，以及苯并三唑类化合物三种化合物体系: [0005] The following definitions acylphosphine oxide compounds, aromatic hydroxy ketone compound, and a benzotriazole compound system of three compounds:

[0006] 所述的酰基膦氧化合物可以含有单或多个酰基膦氧[即-P (O)-C (O)-单元]光引发活性官能团，其通式结构（I)为: [0006] The acyl phosphine oxide compound may contain a single or a plurality of acyl phosphine oxide [i.e. -P (O) -C (O) - unit] photoinitiator reactive functional groups, the structure of the general formula (I) is:

[0007] [0007]

[0008] 该通式（I)中，X是氧或硫，η和m各自独立地可以取值为I或2。 [0008] The formula (I), X is oxygen or sulfur, η and m may be independently a value of I or 2.

[0009] 当n = I时，R1是未取代的直链或支链的含有1-18个碳原子（标记为C1-C18)的烷基或含有2-18个碳原子（标记SC2-C18，下同）的烯基；或是含有一或多个取代基的直链或支链的含有1-18个碳原子的烷基或含有2-18个碳原子的烯基，这些一或多个取代基可以是卤素原子，-NCO基，-CN基，环氧乙烷基，N-烷基（C1-C8烷基）取代的酰亚胺基，_0R1(I 基,-CO-Rltl 基,-CONRltlR11 基,-NRltlR11 基,-SiRltlR11R12 基,-OSiRltlR11R12 基,-NR-CO-R10基，_NR_C0_0R1(l 基，-NR-CORltlR11 基，_SR1(I 基，-SO2Riq 基，_S02_0R1(l 基，-SO2-NR10R11基，-PO-OR10R11 基，-PO-R10R11 基，-COOR10 基，-OC (O) R10 基，-CH = CH-CO-OR10 基，或-C (C1-C4烧基）=C (C1-C4烧基）-CO-ORltl ;这里R1(l，R11, R12彼此独立地是氧，C1-C18烧基，为一或多个非连续性氧或硫或氮原子所间断的C2-C18基，含一或多个乙烯醇单元的取代基，C3-C12环状烷基，2-呋喃基，四氢呋喃基，苯基-C1-C4-亚烷基，苯基-C1-C4-烯基，含有卤素或环己基或环戊基或四氢呋喃基或呋喃基的C1-C6烷基，C2-C18烯基，苯基，未取代的萘基或联苯基，含有一至五个C1-C8烷基或C1-C8烷氧基或C1-C8烷硫基或卤素取代基的苯基或萘基或联苯基；R1(I，R11,或R12的一个或多个氢原子还可以被氟原子取代； [0009] When n = I when, R1 is an unsubstituted straight-chain or branched alkyl having 1 to 18 carbon atoms (labeled C1-C18) alkyl, or containing 2 to 18 carbon atoms (labeled SC2-C18 , the same below) alkenyl; or containing 1 to 18 carbon atoms, a straight-chain or branched-chain alkyl group containing one or more substituents containing 2-18 carbon atoms or an alkenyl group, one or more of these substituents can be halogen atoms, -NCO group, -CN group, oxirane group, N- alkyl (C1-C8 alkyl) substituted imide group, _0R1 (I-yl, -CO-Rltl yl , -CONRltlR11 group, -NRltlR11 group, -SiRltlR11R12 group, -OSiRltlR11R12 group, -NR-CO-R10 group, _NR_C0_0R1 (l-yl, -NR-CORltlR11 group, _SR1 (I group, -SO2Riq group, _S02_0R1 (l-yl, -SO2-NR10R11 group, -PO-OR10R11 group, -PO-R10R11 group, -COOR10 group, -OC (O) R10 group, -CH = CH-CO-OR10 groups, or -C (C1-C4 burn-yl) = C (C1-C4 burn-yl) -CO-ORltl; where R1 (l, R11, R12 independently of one another are oxygen, C1-C18 burn group, for one or more non-continuous oxygen or sulfur or nitrogen atoms interrupted The C2-C18 group containing one or more vinyl alcohol units substituent group, C3-C12 cyclic alkyl, 2-furyl, tetrahydrofuryl, phenyl -C1-C4- alkylene, phenylene -C1- C4- alkenyl, C1-C6 alkyl group containing a halogen or a cyclohexyl or cyclopentyl or tetrahydrofuran or furyl group, C2-C18 alkenyl, phenyl, unsubstituted naphthyl or biphenyl, containing one to five C1-C8 alkyl or C1-C8-alkoxy or C1-C8 alkylthio group or a halogen-substituted phenyl or naphthyl or biphenyl; a R1 (I, R11, or R12 has one or more hydrogen atoms may be substituted with a fluorine atom;

[0010]或R1 是-ORltl 基； [0010] or R1 is -ORltl group;

[0011 ]或R1 是被-CO-，-COO-, -0C0-, -0C00-, -CO-NR10-, -NR10-CO-, -NR10-CO-NR10-, -NR10-COO-, -COO-C1-C18-亚烧基，-COS-C1-C18-亚烧基，_S02_，_S02_0_, _S02_NR10_, - (CH3) 2Si~ [OSi(CH3) 2] m-(这里m = 1_6),苯基-C「C4_亚烧基-,-C6H4-,萘环,联苯环，C5-C12环,或含氧或硫或氮原子的五或六元杂环间断的C1-C18烷基或C2-C18烯基； [0011] or R1 is -CO -, - COO-, -0C0-, -0C00-, -CO-NR10-, -NR10-CO-, -NR10-CO-NR10-, -NR10-COO-, - COO-C1-C18- alkylene burn group, -COS-C1-C18- alkylene burn group, _S02 _, _ S02_0_, _S02_NR10_, - (CH3) 2Si ~ [OSi (CH3) 2] m- (where m = 1_6), benzene group -C "C4_ alkylene burn-yl -, - C6H4-, five or six membered heterocyclic ring a naphthalene ring, a biphenyl ring, C5-C12 ring, or an oxygen-containing or sulfur or nitrogen atoms interrupted C1-C18 alkyl or C2-C18 alkenyl;

[0012]或 R1 是三甲基硅基，Cl-(CH3) 2S1-[OSi (CH3) 2] s_，或_ (CH3) 3Si_ [OSi (CH3) 2] s_ (这Ms = 1-6)； [0012] or R1 is trimethylsilyl, Cl- (CH3) 2S1- [OSi (CH3) 2] s_, or _ (CH3) 3Si_ [OSi (CH3) 2] s_ (which Ms = 1-6) ;

[0013]或 R1 是-CO2H, -CO2R10, -CONRltlR11, -CO-乙烯-，-CO-苯基_(这里的苯基可以含有一或多个C1-C8烷基或C1-C8烷氧基或C1-C8烷硫基或氯原子)，或-CO-CRltlR11R12 ； [0013] or R1 is -CO2H, -CO2R10, -CONRltlR11, -CO- ethylene -, - CO- phenyl _ (where the phenyl group may contain one or more C1-C8 alkyl or C1-C8 alkoxy or C1-C8 alkylthio group or a chlorine atom), or -CO-CRltlR11R12;

[0014] 或R1是苯基-C1-C4-烷基，苯基，萘基，联苯基，C5-C12环烷基，或含氧或硫或氮原子的五或六元杂环；这里这些取代基均可以含有一或多个C1-C8烷基或C1-C8烷氧基或C1-C8烷硫基或氯原子或-NRltlR11取代基；` [0014] R1 is phenyl or -C1-C4- alkyl, a five- or six-membered heterocyclic ring, phenyl, naphthyl, biphenyl, C5-C12 cycloalkyl group, or an oxygen or sulfur or nitrogen atom; here These substituents each may contain one or more of C1-C8 alkyl or C1-C8-alkoxy or C1-C8 alkylthio group or a chlorine atom or a substituent -NRltlR11; `

[0015] 当η = 2时，R1是一个与上述R1(当η = I时）定义相符的二价基团，或R1是-CH2CH=CHCH2-, -CH2-C-炔键-C-CH2-, -CH2CH2-C6H4-CH2CH2-, -CH2CH2O-C6H4-OCH2CH2-, -CH2-CO2-Y-OCO-CH2-,或-C6H3R4-T-C6H3R5-;这里T 是一个单键，CH2, C(CH3)2, CH2CH2, 0，或S ；R4 和R5 彼此独立地是氢，C1-C8烷基，或C1-C8烷氧基；Y是C1-C18亚烷基或由一个或多个乙烯醇重复单元组成的二价联接体； [0015] When η = 2, R1 is one of the above R1 (when when η = I) is defined in line divalent group, or R1 is -CH2CH = CHCH2-, -CH2-C- alkynyl bond -C-CH2 -, -CH2CH2-C6H4-CH2CH2-, -CH2CH2O-C6H4-OCH2CH2-, -CH2-CO2-Y-OCO-CH2-, or -C6H3R4-T-C6H3R5-; where T is a single bond, CH2, C ( CH3) 2, CH2CH2, 0, or S; R4 and R5 independently of one another are hydrogen, C1-C8 alkyl, or C1-C8 alkoxy; Y is C1-C18 alkylene group or by one or more of vinyl alcohol repeating units of the bivalent coupling body;

[0016] R2是直链或支链的C1-C18烷基或C2-C18烯基，或含有一或多个卤素取代基的C1-C18烷基或C2-C18 烯基，或是-OR10, -COR10, -CO2R10, -CH = CH-CO2R10, -C (C1-C4 烷基)=C (C1-C4 烷基)-CO-OR10, -NR10-CO-R11，-CO-NR10R11, -CH = CH-Ph-, -C (C1-C4 烷基)=C (C1-C4 烷基)-Ph-,C3-C12环烧基，苯基-C1-C4烧基，苯基，奈基，恩基，联苯基，含氧或硫或氣原子的五或TK兀杂环，或含有一或多个C1-C8烷基或C1-C8烷氧基或C1-C8烷硫基或氯原子取代基的苯基，萘基，蒽基，联苯基，含氧或硫或氮原子的五或六元杂环； [0016] R2 is a straight-chain or branched C1-C18 alkyl or C2-C18 alkenyl group, or contains one or more halogen substituents C1-C18 alkyl or C2-C18 alkenyl group, or -OR10, -COR10, -CO2R10, -CH = CH-CO2R10, -C (C1-C4 alkyl) = C (C1-C4-alkyl) -CO-OR10, -NR10-CO-R11, -CO-NR10R11, -CH = CH-Ph-, -C (C1-C4 alkyl) = C (C1-C4 alkyl) -Ph-, C3-C12 ring burn, phenyl -C1-C4 burn, phenyl, Nike, Wu heterocyclic five- or TK Enki, biphenyl, or gas containing oxygen or sulfur atom, or containing one or more of C1-C8 alkyl or C1-C8-alkoxy or C1-C8 alkylthio group or a chlorine atom substituted five- or six-membered heterocyclic group phenyl, naphthyl, anthryl, biphenyl, containing oxygen or sulfur or nitrogen atom;

[0017] R3的定义与R1相同； [0017] R3 is the same as defined for R1;

[0018] 优选的符合通式结构（I)的酰基膦氧化合物例子包括但不局限于下述结构: [0018] Preferred structures conforming to the formula (I) of the acylphosphine oxide compounds include, but are not limited to the following structure:

[0019] [0019]

[0020] 所述的芳香羟基酮化合物可以含有一个或多个光引发活性的羟基酮官能团，其特征是在芳环上羟基酮结构和其它取代基呈现不同寻常的间位（meta)关系，其通式结构 [0020] The hydroxy aromatic ketone compounds may contain one or more photoinitiating functional groups reactive hydroxy ketone, characterized in that the hydroxy ketone in an aromatic ring structure and the other substituents exhibit unusual meta (meta) relationship, which general structure

(II)为: (II) is:

[0021] [0021]

[0022] 该通式（II)中，P取值为I至2000间的整数，优选的，P取值为I至20间的整数；更优选的，P取值为I至6间的整数；当P值远大于20时，其代表一个P重聚合型的结构 More preferably an integer of, P value is I to 6; and [0022] the formula (II), P is a value of an integer I to 2000, preferably, P value is an integer from I to 20 of ; when P is much greater than 20, which represents a heavy-polymer structure P

(II) ；R6和R7彼此独立地是苯基，直链或支链的C1-C12烷基，该烷基可以含有被一至五个Rw或ORltl或卤素取代的苯基或萘基或联苯基，或该烷基可以为一或多个非连续性氧或硫或氮原子所间断成和R7也可以形成一个5至10元的环状结构。 (II); R6 and R7 are each independently a phenyl group, a straight-chain or branched C1-C12 alkyl group, the alkyl group may contain substituted by one to five halogen Rw or ORltl or phenyl or naphthyl or biphenyl group, or the alkyl group may be one or more non-continuous oxygen or sulfur or nitrogen atom and R7 may also be interrupted to form a cyclic structure of a 5 to 10 yuan. 优选的例子是R6 = R7 = CH3,或R6和R7形成一个6元环（即环己烷基）； Preferred examples are R6 = R7 = CH3, or R6 and R7 form a 6-membered ring (i.e. cyclohexyl);

[0023] R8是氢或符合Rltl定义的基团，优选地R8是氢，C1-C6烷基，或含碳原子总数为C3-C12的硅烷基，该硅烷基碳链可以为一至四个非连续性氧或硫或氮原子所间断； [0023] R8 is hydrogen or a group as defined in line Rltl, preferably R8 is hydrogen, C1-C6 alkyl group, or the total number of atoms of C3-C12 carbon-containing silane group, the silyl group may be a carbon chain of one to four non- Continuity oxygen or sulfur or nitrogen atom interrupted;

[0024] R9是一个与上述R1定义相符的P价联结单元；优选的，当P取值为I时，R9是0H，Cl，SH，NH2, ORltl, SRltl, NHRltl, NRltlR11,或季胺盐阳离子形式(R10R11R12N+);当P 取值大于或等于2时，R9是N, NR10, SO2, P(O)O3, PO3,或R9 (H)p相应地是一个p元醇，p元硫醇，p元酹，p元羧酸，P元酰氯，P元胺，P元酰胺，或P元异氰酸酯。 [0024] R9 is a P valence coupling means consistent with the definition of R1 above; preferably, when the P value is when I, R9 is 0H, Cl, SH, NH2, ORltl, SRltl, NHRltl, NRltlR11, or quaternary amine salt cation form (R10R11R12N +); when the P value is greater than or equal to 2, R9 is N, NR10, SO2, P (O) O3, PO3, or R9 (H) p is a corresponding p monoalcohol, p monovalent mercaptan , p yuan sprinkle, p carboxylic acids, P yuan chloride, P monoamines, P yuan amide, or P element isocyanates. 当P取值为2时，R9也可以是个单键； When the P value of 2, R9 can also be a single bond;

[0025] 优选的P元醇或P元硫醇或P元酹例子是: [0025] Preferred monohydric or P P P Yuan Yuan thiol or sprinkle examples are:

[0026] [0026]

OH OH

[0027] 优选的p元羧酸例子是: [0027] Preferably p monocarboxylic examples are:

[0028] [0028]

[0029] 优选的ρ元酰氯的例子是上述P元羧酸例子相对应的酰氯结构； Examples [0029] Preferred ρ element chloride is an example of the P-monocarboxylic acid chloride corresponding to the structure;

[0030] 优选的ρ元胺或ρ元酰胺的例子是: [0030] Preferred examples of ρ or ρ monoamine yuan amides are:

[0031] [0031]

[0032] 优选的ρ元异氰酸酯的例子是: [0032] Examples of preferred ρ membered isocyanates are:

[0033] [0033]

[0034] 优选的，R9(H)p可以是p元I, 2-二醇，P元I, 2-硫醇，ρ元1,2-胺基醇,或ρ元1，2-Ν-取代胺基醇；当R9 (H)p取这些结构时，具有通式结构（II)的ρ元间位取代型芳香羟基酮化合物优选地是经由相应的单体化合物[即P取值为1，R9是0Η，SH, NH2，或NHRltl时的化合物（II)]和合适的P元环氧化合物经由经典的环氧开环反应得到的结构。 [0034] Preferably, R9 (H) p may be a p-ary I, 2- diol, P element I, 2- thiol, ρ membered 1,2-amino alcohols, or ρ membered 1,2-Ν- substituted amino alcohols; when R9 (H) p taking these structures, having the general structure (II), ρ meta meta-substituted aromatic hydroxy ketone type compound is preferably a monomer compound via the corresponding [i.e., P value is 1 , R9 is 0Η, SH compound NH2, or NHRltl when (II)] and a suitable P monovalent epoxy compound, ring-opening reaction of the resulting structure via a classic epoxy. 优选的P Preferred P

元环氧化合物的例子是: Examples yuan epoxy compounds are:

[0035] [0035]

[0036] Z 是氢或CH2R9 ； [0036] Z is hydrogen or CH2R9;

[0037] 优选的符合通式结构（II)的间位取代型芳香羟基酮化合物的例子包括但不局限于下述结构: [0037] Preferred structures conforming to the formula (II) is m-substituted type aromatic hydroxy ketone compounds include, but are not limited to the following structure:

[0038] [0038]

[0039] 所述的具有红移（Red-shifted)光吸收特征的羟基苯并三唑类紫外光吸收剂(Hydroxyphenylbenzotriazole UV absorber)的通式结构（III)为: [0039] having a red shift of the (Red-shifted) light absorption characteristic of hydroxybenzotriazole type ultraviolet light absorber (Hydroxyphenylbenzotriazole UV absorber) of the general structure (III) is:

[0040] [0040]

[0041] 在该通式（III)的（abc)三个结构中，R13和R' 13彼此独立地是氢或卤素；，R14和R，14 彼此独立的是卤素，-CF3, -NO2, -CN, -COR20, -CO2R20, -CONHR20, -CONR20R21,-POR20R21,-NR20-COR21, -OSR20, -O2SR2tl，或C1-C12 多氟取代烷基； [0041] In the three structural formula (III), (abc) in, R13 and R '13 are each independently hydrogen or halogen;, R14 and R, 14 independently of one another are halogen, -CF3, -NO2, -CN, -COR20, -CO2R20, -CONHR20, -CONR20R21, -POR20R21, -NR20-COR21, -OSR20, -O2SR2tl, or more fluoro-substituted C1-C12 alkyl;

[0042] R20和R21彼此独立地是氢，直链或支链的C1-C24烷基，直链或支链的C2-C24烯基，含C5-C24的环烷基，含C7-C15的苯基烷基，或苯基，该苯基烷基或苯基的苯环上可以含有1-4个C1-C4的烷基或烷氧取代基；R2(i和R21的链可以为不超过6个的非连续性氧或硫或氮原子所间断，也可含有不超过4个的0H，NH2，取代NH2, SH, NC0，或酯基； [0042] R20 and R21 are each independently hydrogen, a straight-chain or branched C1-C24 alkyl, linear or branched C2-C24 alkenyl group, containing C5-C24 cycloalkyl, C7-C15 containing the phenylalkyl, or phenyl, the phenyl ring of the phenyl group may contain an alkyl group or a phenyl group having 1 to 4 C1-C4 alkyl or alkoxy substituents; R2 (i and R21 may be a chain of no more than 6 discontinuity oxygen or sulfur or nitrogen atoms interrupted, may contain not more than 4 0H, NH2, substituted NH2, SH, NC0, or an ester group;

[0043] R15的定义和R2tl或R21相同；当R15是含C7-C15的苯基烷基，或苯基，该苯基烷基或苯基的苯环上可以含有1-4个C1-C4的烷基或烷氧取代基，此时R14可以是氢； The same definition and R2tl or [0043] R15 is R21; when R15 is a phenyl group containing C7-C15 alkyl, or phenyl, the phenyl ring of the phenyl alkyl or phenyl may contain 1 to 4 C1-C4 The alkyl or alkoxy substituent, then R14 can be hydrogen;

`[0044] R16和R' 16的定义彼此独立的和R2tl或R21相同； The definition of `[0044] R16 and R '16 independently of each other and the same R2tl or R21;

[0045] r取值I或2;q取值为0，1或2; [0045] r value of I or 2; q is 0, 1 or 2 values;

[0046] R17 是R20, -OR20, -NR20R21, -PO (OR20) 2, -OSi (R20) 3，或-OCO-R20 ； [0046] R17 is R20, -OR20, -NR20R21, -PO (OR20) 2, -OSi (R20) 3, or -OCO-R20;

[0047] Q是一个二价联结单元，其为含有C1-C24的烷基或C6-C24的取代的芳基；其链可以为不超过6个的非连续性氧或硫或氮原子所间断； [0047] Q is a divalent linking unit, which is containing a C1-C24 alkyl or substituted C6-C24 aryl; which chain may be interrupted by not more than 6 for a non-continuous oxygen or sulfur or nitrogen atom ;

[0048] 优选的符合通式结构（III)的羟基苯并三唑类类化合物的例子包括但不局限于 [0048] Preferred structures conforming to the formula (III), hydroxybenzotriazole type compounds include, but are not limited to,

下述结构: The following structure:

[0049] [0049]

[0050] 本申请的核心发明内容及权利要求如下: [0050] The core invention of the present application and the contents of the following claims:

[0051] I。 [0051] I. 本发明披露一种新型光引发剂复配混合物体系，该体系的特征是包含至少一种通式结构（I)所示的酰基膦氧化合物和至少一种通式结构（II)所示的芳香羟基酮化合物。 The present invention discloses a novel photoinitiator system complex mixture, characterized in that the system comprising at least one of the general structure (I) shown in the acylphosphine oxide compound and at least one general structure (II) shown in the aromatic hydroxy ketone compounds.

[0052] 2。 [0052] 2. 在权利要求⑴定义的复配光引发剂混合物体系中，以每单元份重量为100%计，其中通式结构（I)所示的酰基膦氧化合物的重量百分比可以在0.5%至99.5%之间变化，相应的，通式结构（II)所示的芳香羟基酮化合物的重量百分比可以在99.5%至0.5%之间变化。 ⑴ compound defined in claim photoinitiator mixture system, parts by weight per unit as 100%, wherein the percentages by weight of acylphosphine oxide compounds of general structure (I), may be in the 0.5 to 99.5% of the between changes, the weight percentage of the aromatic hydroxy ketone compound represented by the corresponding formula structure (II) may vary between 99.5 to 0.5 percent. [0053] 3。 [0053] 3. 本发明同时披露一种可经由光（紫外或可见光或等价光源）辐射固化的混合物，这种混合物的特征是含有至少一种可聚合的含烯不饱和化合物以及权利要求（I)定义的新型酰基膦氧/芳香羟基酮复配光引发剂体系。 The present invention is also disclosed a mixture of a radiation curable via light (ultraviolet or visible light or equivalent light sources), such a mixture is characterized by containing at least one polymerizable ethylenically unsaturated compound and in the claims (I) defines a novel acyl phosphine oxide / aromatic hydroxy ketone photoinitiator system complex. 以每100份重量的这样的含烯不饱和化合物总重计，权利要求（I)定义的酰基膦氧/芳香羟基酮复配光引发剂的使用量可以在 Such containing per 100 parts by weight of an ethylenically unsaturated compound on the total weight, (I) defined in claim acylphosphine oxide / aromatic hydroxy ketone compound a light amount of initiator used can be found in

0.01至20份之间变动，优选0.5至10份。 Vary between 0.01 to 20 parts, preferably from 0.5 to 10 parts.

[0054] 4。 [0054] 4. 本发明同时披露一种新型的可经由光（紫外或可见光或等价光源）辐射固化的混合物体系，该体系的特征是包含至少一种权利要求（I)定义的光引发剂混合物，至少一种通式结构（III)描述的羟基苯并三唑类光吸收剂化合物，以及至少一种可聚合的含烯不饱和化合物。 The present invention is also disclosed a novel via light (ultraviolet or visible light or equivalent light source) of a mixture of radiation curable systems, characterized in that the system is a photoinitiator mixture comprising at least one defined in claim (I), at least one hydroxybenzotriazole general structure (III) described light absorber and triazole compound, and at least one polymerizable ethylenically unsaturated compound.

[0055] 5。 [0055] 5. 在权利要求⑷定义的可光（紫外或可见光或等价光源）辐射固化混合物体系中，以其每100份重量计，通式结构（III)描述的羟基苯并三唑类化合物光吸收剂的含量可以在0.1至10份间变动，优选的，可以在0.5至5份间变动；而权利要求（I)定义的光引发剂含量可以在0.1至20份间变动，优选的，可以在I至10份间变动。 As defined in claim ⑷ photo (ultraviolet or visible light or equivalent light source) radiation curable mixture system, its per 100 parts by weight of hydroxyphenyl general structure (III) and the triazole-based compound described light absorber content may be between 0.1 to 10 parts change, preferably, may be varied between 0.5 and 5 parts; the photoinitiator content of claim (I) as defined can vary between 0.1 to 20 parts, preferably, to be in the I 10 parts between changes.

【具体实施方式】 [DETAILED DESCRIPTION]

[0056] 下面举例说明上述混合光引发剂体系及其与光吸收剂复配体系在含烯不饱和体系光固化过程中的实际应用。 [0056] The following examples illustrate the mixed photoinitiator system and its complex system with a light absorber ethylenically unsaturated system in light of the practical application of the curing process.

[0057] 按下述重量百分比（总计100份）配制光固化混合物体系，将此混合物搅拌分散或溶解后喷涂在铝板上（约20微米），以高压汞灯（400W/cm)为光源辐射引发聚合。 [0057] according to the following weight percent (total 100 parts) formulated photocurable mixture system, and the mixture was stirred for dispersing or dissolving the aluminum plate after spraying (about 20 microns), to a high pressure mercury lamp (400W / cm) as light source radiation initiation polymerization. 实施例使用的酰基膦氧化合物光引发剂和间位取代型羟基酮引发剂在每一例后均标明了结构。 An acyl phosphine oxide compound used in Example photoinitiator type and meta-substituted hydroxyketone initiators are marked in each case after the structure. 固化效率以指压法（即大拇指指甲压膜反复擦拭涂层不破损）判定光固化完成。 Curing efficiency with acupressure (ie, repeatedly wipe thumb nail laminated coating is not damaged) determination light curing is complete.

[0058] 实施例一:UV白色木器涂料 [0058] Embodiment 1: UV white coatings

[0059] 77.2份PEA，5.9份HDDA，2.9份TMPTA，2.5份酰基膦氧光引发剂，1.5份羟基酮光引发剂，10份TiO2。 [0059] 77.2 parts by PEA, 5.9 parts of HDDA, 2.9 parts of TMPTA, 2.5 parts acylphosphine oxide photoinitiator, 1.5 parts of hydroxyketone photoinitiator, 10 parts of TiO2.

[0060] [0060]

[0061] 实施例二:UV地板亚光面漆 II [0061] EXAMPLE: UV floor matt finish

[0062] 14.78 份高光泽UP (VP LS2100)，14.78 份Tromox R KB6, 7.39 份Banc-Fixe N, [0062] 14.78 parts of high-gloss UP (VP LS2100), 14.78 parts Tromox R KB6, 7.39 parts of Banc-Fixe N,

1.18份Lancowax HM 1666，2.95份TPGDA，混合研磨至10微米以下后再加入14.78份高光泽UP (VP LS2100)，5.91 份Gasil EBN，35.47 份TPGDA，0.06 份BYK 300，I 份酰基膦氧光引 1.18 parts Lancowax HM 1666,2.95 copies TPGDA, mixed ground to 10 microns or less and then adding 14.78 parts of high-gloss UP (VP LS2100), 5.91 parts Gasil EBN, 35.47 parts TPGDA, 0.06 parts BYK 300, I part acyl phosphine oxide photoinitiators

发剂，1.7份羟基酮光引发剂。 Initiator, 1.7 parts of hydroxy ketone photoinitiator.

[0063] [0063]

[0064] 实施例三:UV汽车底漆 [0064] in Example three: UV automotive primer

[0065] 55.17 份脂肪族PUA (VP LS 2258)，1.65 份EB168，10.98 份Ρ0ΕΑ，10.98 份滑石粉， [0065] 55.17 parts of aliphatic PUA (VP LS 2258), 1.65 parts EB168,10.98 copies Ρ0ΕΑ, 10.98 parts of talc,

10.98 份粘土，5.49 份Heucophos ZPA,1.38 份TiO2,0.08 份助剂Bayferrox 303T, 2.46 份 10.98 parts of clay, 5.49 parts Heucophos ZPA, 1.38 parts TiO2,0.08 parts adjuvant Bayferrox 303T, 2.46 parts of

羟基酮光引发剂，0.83份酰基膦氧光弓I发剂。 Hydroxy ketone photoinitiator, 0.83 parts of an acylphosphine oxide initiator I bow light.

[0066] [0066]

[0067] 实施例四:UV粉末涂料 [0067] Fourth Embodiment: UV powder coating

[0068] 62.7份UPE，12.8份乙烯基醚树脂，20.0份TiO2,1.5份流平剂，2.0份酰基膦氧光 [0068] 62.7 parts of UPE, 12.8 parts of vinyl ether resin, 20.0 parts TiO2,1.5 parts of leveling agent, 2.0 parts acylphosphines oxygen light

引发剂，1.0份羟基酮光引发剂。 Initiator, 1.0 parts of hydroxy ketone photoinitiator.

[0069] [0069]

[0070] 实施例五:UV水性木材涂料 V. [0070] EXAMPLE: UV waterborne wood coatings

[0071] 75.2份水性PUA分散体，16.2份75% TiO2颜料，3.3份助剂，1.3份去离子水，2.0份酰基膦氧光引发剂BAP0(50%水分散体），2.0份羟基酮光引发剂。 [0071] 75.2 parts by PUA aqueous dispersion, 16.2 parts of 75% TiO2 pigment, 3.3 parts of additives, 1.3 parts of deionized water, 2.0 parts acylphosphine oxide photoinitiator BAP0 (50% aqueous dispersion), 2.0 parts of hydroxyketone light initiator.

[0072] [0072]

[0073] 实施例六:UV光盘油墨 [0073] EXAMPLE six: UV inks CD

[0074] 20 份PEA (EB525)，20 份EB1710,15 份EO-TMPTA, 10 份TPGDA, 25 份TiO2, 2.5 份酰基膦氧光引发剂，2.5份羟基酮光引发剂，3.0份SiO2, 2.0份消泡剂Airex 900。 [0074] 20 parts by PEA (EB525), 20 parts EB1710,15 parts of EO-TMPTA, 10 parts of TPGDA, 25 parts of TiO2, 2.5 parts acylphosphine oxide photoinitiator, 2.5 parts of hydroxyketone photoinitiator, 3.0 parts SiO2, 2.0 copies of defoamers Airex 900.

[0075] [0075]

[0076] 实施例七:含光吸收剂UV油墨 [0076] EXAMPLE VII: Hanguangmen absorbent UV ink

[0077] 19.4份聚氨酯丙烯酸酯（沙多玛CN999)，19.4份乙氧基双酚A 二丙烯酸酯（沙多玛SR601)，31份沙多玛SR492，24份沙多玛SR355，0.32份酰基膦氧光引发剂，2.60份羟基酮光引发剂，3.28份羟基苯并三唑光吸收剂（注意:本样品的辐照在氮气保护气氛下进行）。 [0077] 19.4 parts of urethane acrylate (Sartomer CN999), 19.4 parts of ethoxylated bisphenol A diacrylate (Sartomer SR601), 31 parts Sartomer SR492,24 parts Sartomer SR355,0.32 parts acyl phosphine oxide photoinitiator, 2.60 parts of hydroxyketone photoinitiator, 3.28 parts of hydroxybenzotriazole light absorber (Note: The sample was irradiated under nitrogen atmosphere).

[0078] [0078]

[0079] 上述实施例光引发剂混合物均完成了体系充分固化，展现了优良的光聚合引发活性。 [0079] The mixture of Example photoinitiator system are completed sufficiently cured, exhibit excellent activity of the photopolymerization initiator.