可电离辐射成象的感光聚合物组合物 Photosensitive polymer composition can be imaged ionizing radiation

发明领域本发明公开了基本由下列化合物组成的组合物：(1)反应性单体，(2)多官能团交联剂，及至少(3)射线增感剂，(4)聚合物粘合剂，或(5)填料(含有粘合剂)，其在曝光于电离辐射，如X射线、电子束、离子束和γ射线时可被成象聚合/交联。 Field of the Invention The present invention discloses a composition consisting essentially consisting of the following compounds: (1) a reactive monomer, (2) a polyfunctional cross-linking agent, and at least (3) radiation sensitizers, (4) a polymeric binder , or (5) a filler (comprising a binder), which upon exposure to ionizing radiation, such as X-ray, electron beam, ion beam and γ-ray imaging can be polymerized / crosslinked. 本发明还公开了使用这些组合物进行陶瓷显微制造、立体平版印刷(stereolithography)及作为X射线、电子束和离子束平版印刷术中光刻胶的方法。 The present invention also discloses the use of these compositions were manufactured ceramic microstructure, stereolithography (stereolithography) and as X-ray, electron beam and ion beam lithography photoresist method.

这些问题可通过研制有用的X射线敏感感光聚合物而解决。 These problems can be useful to develop an X-ray sensitive photopolymer and resolved. X射线具有较深的穿透深度并且在平版印刷的情况下能够获得比基于光学技术更好的空间分辨力。 X-rays having a deeper depth of penetration and, in the case of lithographic printing can be obtained based on optical technology is better than the spatial resolution. 不幸的是，就本发明人所知，尚未研制出在相当短的持续时间内通过较低强度X射线束可聚合成象的材料。 Unfortunately, the best knowledge of the present inventors, has not been developed in a relatively short duration of the polymerizable imaging X-ray beam through the lower strength material. 有机物具有非常低的X射线吸收系数而且聚合反应即使可被X射线引发也倾向于是低效率的并且要求使用非常长的暴露时间或高功率X射线源，如同步辐射。 Organic compounds having a very low X-ray absorption coefficient and the polymerization initiator, even if the X-ray can be also tends to be inefficient and requires very long exposure times or high power X-ray source, such as synchrotron radiation. 此外，对于要求空间分辨力的应用，聚合反应在空间上必须限制在辐照区域。 In addition, the requirements for spatial resolution applications, the polymerization reaction must be limited in space irradiation.

如果这些材料存在则X射线敏感感光聚合物存在许多潜在的应用。 If these materials are present the X-ray sensitive photopolymer exist many potential applications. 陶瓷和金属的显微制造(例如等离子体平板显示器的阻挡凸缘加工；SWDepp和WEHoward,Sci.Amer.260,40,1993年3月)、立体平版印刷(3D-立体目标建模)(DCNeckers,Chemtech,10月号，615页，1990)及用于X射线或电子束或离子束平版印刷术的光刻胶(C.Grant Wilson的《微刻绪论》,LFThompson,CGWilson和MJBowden编，1994,American ChemicalSociety，第3章，139页)只是一些实例。 Microscopic ceramic and metal fabrication (eg blocking flange processing plasma flat panel displays; SWDepp and WEHoward, Sci.Amer.260,40,1993 March), stereolithography (3D- spatial object modeling) (DCNeckers , Chemtech, October, 615, 1990) and for X-rays or an electron beam or ion beam lithography photoresist (C.Grant Wilson's "microinscribing Introduction", LFThompson, CGWilson and MJBowden, eds., 1994 , American ChemicalSociety, Chapter 3, 139) are just some examples. 其它的应用包括X射线接触显微镜(Applied Physics Letters,72,258(1998),ACCefalas,P.Argitis,Z.Kollia,E.Sarantopoulou,TWFord,ADStead,A.Marranca,CNDanson,J.Knott和D.Neely)和制造具有光子带隙性能的光子晶体(Science,281,802(1998),JEGJWijnhoven和WLVos)。 Other applications include X-ray contact microscopy (Applied Physics Letters, 72,258 (1998), ACCefalas, P.Argitis, Z.Kollia, E.Sarantopoulou, TWFord, ADStead, A.Marranca, CNDanson, J.Knott and D.Neely) and manufacturing a photonic bandgap properties of the photonic crystal (Science, 281,802 (1998), JEGJWijnhoven and WLVos).

用电离辐射引发化学反应的基本原则可见AJSwallow的“辐射化学”,Wiley,1973；及MSMatheson和LMDorfman的“脉冲辐解”,MIT Press,1969。 The basic principles of ionizing radiation-induced chemical reactions visible AJSwallow of "Radiation Chemistry", Wiley, 1973; and MSMatheson and LMDorfman the "pulse radiolysis", MIT Press, 1969. 此处限定电离辐射包括X射线、γ射线、中子、带电粒子(粒子束)和电子束。 Ionizing radiation as defined herein include X-rays, γ-rays, neutrons, charged particles (particle beam), and electron beam. 用电离辐射辐照物体可产生激发态、自由基、阳离子和阴离子。 Objects can be irradiated with ionizing radiation to produce an excited state, a radical, cationic and anionic. 在适当条件下，这些反应性物种可引发化学反应如聚合、交联和键断裂。 Under appropriate conditions, these reactive species can cause chemical reactions such as polymerization, crosslinking and bond rupture.

一些专利公开了γ射线辐射在工业方面的应用。 Some patent discloses a γ-ray emission in the industrial area. US3,950,238(1976年4月13日，RJEldred)公开了一种可以通过电子束固化的丙烯腈-丁二烯弹性体组合物。 US3,950,238 (1976 年 4 月 13 日, RJEldred) discloses an electron beam curing by acrylonitrile - butadiene elastomer composition. US4,004,997(1977年1月25日,Tsukamoto,Matsumura,Sano)公开了一种使用放射线固化被粉状铁磁性物质填充树脂的方法。 US4,004,997 (1977 年 1 月 25 日, Tsukamoto, Matsumura, Sano) discloses a powdery ferromagnetic substance being cured resin filling method radiation. US4,303,696(1981年12月1日，Brack)描述了一种固化液态预聚物组合物在固体表面形成蜡状防粘涂料的方法。 US4,303,696 (1981 年 12 月 1 日, Brack) describes a curable liquid prepolymer composition to form a waxy solid surface release coating method. US4,319,942(1 982年3月16日，W.Brenner)公开了电子束固化用于构造絮状复合结构的含有弹性体的粘合剂组合物的方法。 US4,319,942 (1 982 年 3 月 16 日, W.Brenner) discloses a method for constructing a flocculent electron beam curing composite structure containing adhesive composition elastomer. US4,353,961(1982年10月12日，Gotcher,Germeraad)公开了辐射交联碳氟聚合物以改进机械强度的方法。 US4,353,961 (1982 年 10 月 12 日, Gotcher, Germeraad) discloses radiation crosslinked fluorocarbon polymers to improve the mechanical strength of the approach. US4,547,204(1985年10月1 5日，Caul)公开了可通过电子束固化用于涂布研磨应用的树脂组合物，如丙烯酸酯化环氧和酚醛树脂。 US4,547,204 (1985 年 10 月 5 日 1, Caul) disclosed by electron beam curing resin composition for coated abrasive material applications, such as acrylated epoxy and phenolic resins. US5,098,982(1992年3月24日，Long)公开热塑性聚氨酯的硬度可由电子束辐射改进。 US5,098,982 (1992 年 3 月 24 日, Long) thermoplastic polyurethane disclosed by electron beam radiation hardness improvement. US5,037,667(1991年8月6日，Dubrow,Dittmer))公开某些有机聚硅烷可通过电子束辐照接枝到聚合物载体上。 US5,037,667 (1991 年 8 月 6 日, Dubrow, Dittmer)) disclose certain organo silane grafted by electron beam irradiation to the polymer carrier. US5,332,769(1994年7月26日，Kakimoto,Eguchi,Kobayashi,Nishimoto,Iseki,Maruyama)公开了电子束固化用于粘结聚酯薄膜和金属平板的粘合剂的方法。 US5,332,769 (1994 年 7 月 26 日, Kakimoto, Eguchi, Kobayashi, Nishimoto, Iseki, Maruyama) discloses a method for bonding electron beam curing polyester film and adhesive metal plate. B.Baysal,G.Adler,D.Ballantine和P.Colombo在J.Polym.Sci.,XLIV,117-127(1960)中公开了由γ射线辐照引发丙烯酰胺固态聚合生产聚丙烯酰胺的方法。 B.Baysal, G.Adler, D.Ballantine and P.Colombo in J.Polym.Sci., XLIV, 117-127 (1960) discloses a method by γ-ray irradiation of solid state polymerization of acrylamide initiated production of polyacrylamide . 起始原料和产物之间溶解度的差别不足以在空间上限定成象。 Solubility differences between the starting material and product is not sufficient to define the image forming spatially. US4,115,339(1978年9月19日，AJRestaino)公开了γ射线引发含氮乙烯基单体聚合形成水溶性聚合物水凝胶的方法。 US4,115,339 (1978 年 9 月 19 日, AJRestaino) discloses a nitrogen-containing vinyl monomers to form a water-soluble polymer hydrogels γ-ray excitation. 起始原料和产物均为水溶性的，所以不能得到空间上限定的成象。 The starting materials and products are water-soluble, it can not be defined on the space forming.

所有上述专利和论文公开的方法或组合物均是在γ射线辐射下最常用于涂料和粘合剂应用的。 All of the above patents and papers methods or compositions are disclosed in the γ-ray radiation is most commonly used for coatings and adhesive applications. 效率一般很低并且图象应用所要求的空间分辨力未得到证明。 Efficiency is generally low and the image spatial resolution required for the application has not been proved.

最近，已经使用同步辐射来交联聚甲基丙烯酸甲酯以精确制造立体元件(Johnson,Milne,Siddons,Guckel,Klein,SynchrotronRadiation News,9,10(1996))。 Recently, it has been the use of synchrotron radiation crosslinked polymethyl methacrylate with precision manufacturing perspective element (Johnson, Milne, Siddons, Guckel, Klein, SynchrotronRadiation News, 9,10 (1996)). 同步辐射的强度比普通实验室的X射线仪器如本工作所用者高出约1百万倍。 Intensity synchrotron radiation X-rays than ordinary laboratory instrument about a million times higher as those used in this work. 同步辐射极高的强度意谓着聚合/交联反应可从几乎任何组合物引发(即没有区别)。 Synchrotron radiation of high strength means that the polymerization / crosslinking reaction may be induced from virtually any composition (i.e. no difference). 高强度还出现了图象应用必用面罩的损坏和加热问题。 High strength also appeared damaged and heating problems image application will use the mask. 由于同步机器的费用和有限的供应量，使用同步辐射是不实际的。 Because the cost of synchronous machines and limited supply, the use of synchrotron radiation is not practical. 本发明所公开的组合物允许使用通常提供的低强度X射线机器(或电子束和γ射线)以获得空间上限定的聚合/交联反应。 Compositions of the invention disclosed allows the use of low-intensity X-ray machines are generally provided (or the electron beam and γ-rays) in order to obtain the polymerization / crosslinking reaction defined spatially.

US5,556,716(Herron和Wang)公开了用于数字放射线照相术应用的X射线光敏光电导组合物。 US5,556,716 (Herron and Wang) discloses the X-ray sensitive photoconductive compositions for digital radiography applications. 该组合物包括混合的有机聚合物和无机微粒。 The composition comprising mixing the organic polymer and inorganic fine particles. 与本发明公开的材料不同，X射线在这些光电导体上产生的电子和空穴不引发任何化学反应；它们在高场下被从薄膜中分离并运出。 The materials disclosed in the present invention is different, electrons and holes on these X-rays generated by the photoconductor does not cause any chemical reaction; they are separated from the film at high field and shipped out.

本发明的一个公开内容为一种可通过电离辐射被成象聚合/交联的组合物，基本由下列物质组成：(A)10-90wt％带有至少一个酰胺官能团的反应性单体，所述单体选自： A disclosure of the present invention is a can be polymerized by ionizing radiation is imaged / crosslinked composition, substantially consisting essentially of: (A) 10-90wt% at least one amide functional group with a reactive monomer, the the monomer selected from: 其中R1、R2、R3、R4和R5选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；带有酰胺或丙烯酰胺取代基的脂族基团、和带有R'O-取代基的脂族基团，其中R'代表脂族基团，CnH2n+1和CnH2n-1(n=1-20)； Wherein R1, R2, R3, R4 and R5 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); with or acrylamide substituent aliphatic groups, and substituted with R'O- aliphatic group, wherein R 'represents an aliphatic group, CnH2n + 1 and CnH2n-1 (n = 1- 20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及乙酰胺； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and acetamide; 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；及不饱和脂族基团CnH2n-1(n=1-20)； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and unsaturated aliphatic radicals CnH2n-1 (n = 1-20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及氨基取代的脂族基团CnH2n+1和CnH2n-1(n=1-20)；(B)10-90wt％多官能团交联剂，所述交联剂由带有至少2个官能团的骨架构成，所述骨架选自：(1)线型或支化脂族链-(CRH)n-,n=1-1000，其中R代表脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)乙二醇链-(CH2CH2O)n-，其中n=1-1000；(3)丙二醇链-(CH(CH3)CH2O)n-，其中n=1-1000；(4)环己基；和(5)异氰脲酸酯C3N3O3；并且其中官能团选自：(a)丙烯酸酯 Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and an aliphatic substituted amino group CnH2n + 1 and CnH2n-1 (n = 1-20); (B) 10-90wt% polyfunctional crosslinking agent having at least two frame by functional groups constituting the skeleton selected from from: (1) a linear or branched aliphatic chain - (CRH) n-, n = 1-1000, wherein R represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2 ) glycol chain - (CH2CH2O) n-, where n = 1-1000; (3) Propylene glycol chain - (CH (CH3) CH2O) n-, where n = 1-1000; (4) cyclohexyl; and ( 5) isocyanurate C3N3O3; and wherein the functional group is selected from: (a) acrylates 其中R1、R2和R3选自氢及脂族基团CnH2n+1和CnH2n-1(n=1-20)；(b)羧酸-COOH；(c)环氧化物 Wherein R1, R2 and R3 are selected from hydrogen and aliphatic groups CnH2n + 1 and CnH2n-1 (n = 1-20); (b) a carboxylic acid -COOH; (c) epoxide 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(d)乙烯基 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (d) vinyl 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(C)0.1-80wt％粒度为1-1000纳米的无机射线增感剂，所述射线增感剂选自ⅤB-ⅥB半导体、ⅤB-ⅦB半导体、ⅡB-ⅥB半导体、ⅡB-ⅤB半导体、ⅢB-ⅤB半导体、ⅢB-ⅥB半导体、ⅠB-ⅥB半导体和ⅣB-ⅦB半导体。 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (C) 0.1-80wt% particle size of the inorganic radiation sensitizers 1-1000 nm, the radiation sensitizing agent is selected from ⅤB-ⅥB semiconductors, ⅤB-ⅦB semiconductors, ⅡB-ⅥB semiconductors, ⅡB-ⅤB semiconductors, ⅢB-ⅤB semiconductors, ⅢB-ⅥB semiconductors, ⅠB-ⅥB ⅣB-ⅦB semiconductors and semiconductor.

本发明还公开了一种可通过电离辐射被成象聚合/交联的组合物，基本由下列物质组成：(A)10-90wt％带有至少一个酰胺官能团的反应性单体，所述单体选自： The present invention also discloses a polymerized by ionizing radiation is imaged / crosslinked composition, substantially consisting essentially of: (A) 10-90wt% at least one amide functional group with a reactive monomer, said single is selected from: 其中R1、R2、R3、R4和R5选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；带有酰胺或丙烯酰胺取代基的脂族基团、和带有R'O-取代基的脂族基团，其中R'代表脂族基团，CnH2n+1和CnH2n-1(n=1-20)； Wherein R1, R2, R3, R4 and R5 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); with or acrylamide substituent aliphatic groups, and substituted with R'O- aliphatic group, wherein R 'represents an aliphatic group, CnH2n + 1 and CnH2n-1 (n = 1- 20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及乙酰胺； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and acetamide; 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；及不饱和脂族基团CnH2n-1(n=1-20)； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and unsaturated aliphatic radicals CnH2n-1 (n = 1-20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及氨基取代的脂族基团CnH2n+1和CnH2n-1(n=1-20)；(B)10-90wt％多官能团交联剂，所述交联剂由带有至少2个官能团的骨架构成，所述骨架选自：(1)线型或支化脂族链-(CRH)n-,n=1-1000，其中R代表脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)乙二醇链-(CH2CH2O)n-，其中n=1-1000；(3)丙二醇链-(CH(CH3)CH2O)n-，其中n=1-1000；(4)环己基；和(5)异氰脲酸酯C3N3O3；并且其中官能团选自：(a)丙烯酸酯 Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and an aliphatic substituted amino group CnH2n + 1 and CnH2n-1 (n = 1-20); (B) 10-90wt% polyfunctional crosslinking agent having at least two frame by functional groups constituting the skeleton selected from from: (1) a linear or branched aliphatic chain - (CRH) n-, n = 1-1000, wherein R represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2 ) glycol chain - (CH2CH2O) n-, where n = 1-1000; (3) Propylene glycol chain - (CH (CH3) CH2O) n-, where n = 1-1000; (4) cyclohexyl; and ( 5) isocyanurate C3N3O3; and wherein the functional group is selected from: (a) acrylates 其中R1、R2和R3选自氢及脂族基团CnH2n+1和CnH2n-1(n=1-20)；(b)羧酸-COOH；(c)环氧化物 Wherein R1, R2 and R3 are selected from hydrogen and aliphatic groups CnH2n + 1 and CnH2n-1 (n = 1-20); (b) a carboxylic acid -COOH; (c) epoxide

其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(d)乙烯基 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (d) vinyl 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；(C)0.1-80wt％粒度为1-1000纳米的无机射线增感剂，所述射线增感剂选自ⅤB-ⅥB半导体、ⅤB-ⅦB半导体、ⅡB-ⅥB半导体、ⅡB-ⅤB半导体、ⅢB-ⅤB半导体、ⅢB-ⅥB半导体、ⅠB-ⅥB半导体和ⅣB-ⅦB半导体；和(D)5-90wt％聚合物。 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (C) 0.1-80wt% particle size of the inorganic radiation sensitizers 1-1000 nm, the Ray described sensitizing agent is selected from ⅤB-ⅥB semiconductors, ⅤB-ⅦB semiconductors, ⅡB-ⅥB semiconductors, ⅡB-ⅤB semiconductors, ⅢB-ⅤB semiconductors, ⅢB-ⅥB semiconductors, ⅠB-ⅥB ⅣB-ⅦB semiconductors and semiconductor; and (D ) 5-90wt% polymer.

此外，本发明公开了一种可通过电离辐射被成象聚合/交联的组合物，基本由下列物质组成：(A)10-90wt％带有至少一个酰胺官能团的反应性单体，所述单体选自： Further, the present invention discloses a polymerizable by ionizing radiation is imaged / crosslinked composition, substantially consisting essentially of: (A) 10-90wt% at least one amide functional group with a reactive monomer, wherein monomer selected from: 其中R1、R2、R3、R4和R5选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；带有酰胺或丙烯酰胺取代基的脂族基团、和带有R'O-取代基的脂族基团，其中R'代表脂族基团，CnH2n+1和CnH2n-1(n=1-20)； Wherein R1, R2, R3, R4 and R5 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); with or acrylamide substituent aliphatic groups, and substituted with R'O- aliphatic group, wherein R 'represents an aliphatic group, CnH2n + 1 and CnH2n-1 (n = 1- 20);

其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及乙酰胺； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and acetamide; 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；及不饱和脂族基团CnH2n-1(n=1-20)； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and unsaturated aliphatic radicals CnH2n-1 (n = 1-20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及氨基取代的脂族基团CnH2n+1和CnH2n-1(n=1-20)；(B)10-90wt％多官能团交联剂，所述交联剂由带有至少2个官能团的骨架构成，所述骨架选自：(1)线型或支化脂族链-(CRH)n-,n=1-1000，其中R代表脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)乙二醇链-(CH2CH2O)n-，其中n=1-1000；(3)丙二醇链-(CH(CH3)CH2O)n-，其中n=1-1000；(4)环己基；和(5)异氰脲酸酯C3N3O3；并且其中官能团选自：(a)丙烯酸酯 Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and an aliphatic substituted amino group CnH2n + 1 and CnH2n-1 (n = 1-20); (B) 10-90wt% polyfunctional crosslinking agent having at least two frame by functional groups constituting the skeleton selected from from: (1) a linear or branched aliphatic chain - (CRH) n-, n = 1-1000, wherein R represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2 ) glycol chain - (CH2CH2O) n-, where n = 1-1000; (3) Propylene glycol chain - (CH (CH3) CH2O) n-, where n = 1-1000; (4) cyclohexyl; and ( 5) isocyanurate C3N3O3; and wherein the functional group is selected from: (a) acrylates 其中R1、R2和R3选自氢及脂族基团CnH2n+1和CnH2n-1(n=1-20)；(b)羧酸-COOH；(c)环氧化物 Wherein R1, R2 and R3 are selected from hydrogen and aliphatic groups CnH2n + 1 and CnH2n-1 (n = 1-20); (b) a carboxylic acid -COOH; (c) epoxide 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(d)乙烯基 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (d) vinyl 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；(C)0.1-80wt％粒度为1-1000纳米的无机射线增感剂，所述射线增感剂选自ⅤB-ⅥB半导体、ⅤB-ⅦB半导体、ⅡB-ⅥB半导体、ⅡB-ⅤB半导体、ⅢB-ⅤB半导体、ⅢB-ⅥB半导体、ⅠB-ⅥB半导体和ⅣB-ⅦB半导体；(D)5-90wt％聚合物粘合剂；和(E)5-90wt％金属粒子或陶瓷氧化物填料，所述金属填料选自Al、Ti、V、Cu、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、In和Sb；所述氧化物填料选自Al、Ti、V、Cu、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、In、Sb、Ta、W和Si。 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (C) 0.1-80wt% particle size of the inorganic radiation sensitizers 1-1000 nm, the Ray described sensitizing agent is selected from ⅤB-ⅥB semiconductors, ⅤB-ⅦB semiconductors, ⅡB-ⅥB semiconductors, ⅡB-ⅤB semiconductors, ⅢB-ⅤB semiconductors, ⅢB-ⅥB semiconductors, ⅠB-ⅥB ⅣB-ⅦB semiconductors and semiconductor; (D) 5-90wt% polymeric binder; and (E) 5-90wt% metal particles or ceramic oxide filler, the filler metal is selected from Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb; said oxide filler is selected from Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In , Sb, Ta, W and Si.

本发明的另一个公开内容为一种可通过电离辐射被成象聚合/交联的组合物，基本由下列物质组成：(A)10-90wt％带有至少一个酰胺官能团的反应性单体，所述单体选自： Another disclosure of the present invention is a can be polymerized by ionizing radiation is imaged / crosslinked composition, substantially consisting essentially of: (A) 10-90wt% at least one amide functional group with a reactive monomer, The monomers are selected from: 其中R1、R2、R3、R4和R5选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；带有酰胺或丙烯酰胺取代基的脂族基团、和带有R'O-取代基的脂族基团，其中R'代表脂族基团，CnH2n+1和CnH2n-1(n=1-20)； Wherein R1, R2, R3, R4 and R5 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); with or acrylamide substituent aliphatic groups, and substituted with R'O- aliphatic group, wherein R 'represents an aliphatic group, CnH2n + 1 and CnH2n-1 (n = 1- 20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及乙酰胺； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and acetamide; 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；及不饱和脂族基团CnH2n-1(n=1-20)； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and unsaturated aliphatic radicals CnH2n-1 (n = 1-20);

其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及氨基取代的脂族基团CnH2n+1和CnH2n-1(n=1-20)；(B)10-90wt％多官能团交联剂，所述交联剂由带有至少2个官能团的骨架构成，所述骨架选自：(1)线型或支化脂族链-(CRH)n-,n=1-1000，其中R代表脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)乙二醇链-(CH2CH2O)n-，其中n=1-1000；(3)丙二醇链-(CH(CH3)CH2O)n-，其中n=1-1000；(4)环己基；和(5)异氰脲酸酯C3N3O3；并且其中官能团选自：(a)丙烯酸酯 Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and an aliphatic substituted amino group CnH2n + 1 and CnH2n-1 (n = 1-20); (B) 10-90wt% polyfunctional crosslinking agent having at least two frame by functional groups constituting the skeleton selected from from: (1) a linear or branched aliphatic chain - (CRH) n-, n = 1-1000, wherein R represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2 ) glycol chain - (CH2CH2O) n-, where n = 1-1000; (3) Propylene glycol chain - (CH (CH3) CH2O) n-, where n = 1-1000; (4) cyclohexyl; and ( 5) isocyanurate C3N3O3; and wherein the functional group is selected from: (a) acrylates 其中R1、R2和R3选自氢及脂族基团CnH2n+1和CnH2n-1(n=1-20)；(b)羧酸-COOH；(c)环氧化物 Wherein R1, R2 and R3 are selected from hydrogen and aliphatic groups CnH2n + 1 and CnH2n-1 (n = 1-20); (b) a carboxylic acid -COOH; (c) epoxide 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(d)乙烯基 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (d) vinyl 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(C)5-90wt％聚合物粘合剂。 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (C) 5-90wt% polymeric binder.

本发明的另一个公开内容为一种组合物，该组合物可通过电离辐射被成象聚合/交联，基本由下列物质组成：(A)10-90wt％带有至少一个酰胺官能团的反应性单体，所述单体选自： Another disclosure of the present invention is a composition, the composition can be polymerized by ionizing radiation to be imaged / crosslinked, substantially consisting essentially of: (A) 10-90wt% at least one amide functional group having reactivity a monomer selected from: 其中R1、R2、R3、R4和R5选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；带有酰胺或丙烯酰胺取代基的脂族基团、和带有R'O-取代基的脂族基团，其中R'代表脂族基团，CnH2n+1和CnH2n-1(n=1-20)； Wherein R1, R2, R3, R4 and R5 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); with or acrylamide substituent aliphatic groups, and substituted with R'O- aliphatic group, wherein R 'represents an aliphatic group, CnH2n + 1 and CnH2n-1 (n = 1- 20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及乙酰胺； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and acetamide; 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；及不饱和脂族基团CnH2n-1(n=1-20)； Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and unsaturated aliphatic radicals CnH2n-1 (n = 1-20); 其中R1和R2选自氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；及氨基取代的脂族基团CnH2n+1和CnH2n-1(n=1-20)；(B)10-90wt％多官能团交联剂，所述交联剂由带有至少2个官能团的骨架构成，所述骨架选自：(1)线型或支化脂族链-(CRH)n-,n=1-1000，其中R代表脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)乙二醇链-(CH2CH2O)n-，其中n=1-1000；(3)丙二醇链-(CH(CH3)CH2O)n-，其中n=1-1000；(4)环己基；和(5)异氰脲酸酯C3N3O3；并且其中官能团选自：(a)丙烯酸酯 Wherein R1 and R2 are selected from hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); and an aliphatic substituted amino group CnH2n + 1 and CnH2n-1 (n = 1-20); (B) 10-90wt% polyfunctional crosslinking agent having at least two frame by functional groups constituting the skeleton selected from from: (1) a linear or branched aliphatic chain - (CRH) n-, n = 1-1000, wherein R represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2 ) glycol chain - (CH2CH2O) n-, where n = 1-1000; (3) Propylene glycol chain - (CH (CH3) CH2O) n-, where n = 1-1000; (4) cyclohexyl; and ( 5) isocyanurate C3N3O3; and wherein the functional group is selected from: (a) acrylates 其中R1、R2和R3选自氢及脂族基团CnH2n+1和CnH2n-1(n=1-20)；(b)羧酸-COOH； Wherein R1, R2 and R3 are selected from hydrogen and aliphatic groups CnH2n + 1 and CnH2n-1 (n = 1-20); (b) a carboxylic acid -COOH;

(c)环氧化物 (C) an epoxide 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(d)乙烯基 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (d) vinyl 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(C)5-90wt％聚合物粘合剂；和(D)5-90wt％金属或氧化物填料，所述金属填料选自Al、Ti、V、Cu、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、In和Sb；所述氧化物填料选自Al、Ti、V、Cu、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、In、Sb、Ta、W和Si。 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (C) 5-90wt% polymeric binder; and (D) 5-90wt % metal or oxide filler, the metal filler is selected from Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, and Sb; said oxide filler is selected from Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W and Si.

本发明还公开了使用这些组合物进行陶瓷显微制造、立体平版印刷及作为X射线、电子束和离子束平版印刷术中的光刻胶的方法。 The present invention also discloses a ceramic microstructure fabrication, and as a three-dimensional X-ray lithography, electron beam and ion beam lithography in photoresist using these compositions. 本发明中公开的是一种使用电离辐射在固体基材上显微制造陶瓷或金属图案的方法，包括下列步骤：(ⅰ)将基本由反应性单体、多官能团交联剂和填料组成的组合物混合在一起；所述混合过程任选通过加热组合物直至熔融或通过将组分溶解在共同溶剂(common solvent)中进行；任选在粘合剂存在下；并任选在射线增感剂存在下进行；(ⅱ)将组合物流铸在固体基材上形成所需厚度的薄膜；(ⅲ)使用电离辐射通过一个面罩辐照薄膜以形成聚合/交联图象；(ⅳ)通过在溶剂中漂洗被辐照的薄膜除去未被辐照组合物而使聚合/交联图象显影；并且(ⅴ)烧结聚合/交联图象成显微制造的陶瓷或金属图案。 The present invention is disclosed a use of ionizing radiation on a solid substrate microfabricated ceramic or metal pattern, comprising the steps of: (ⅰ) substantially by the reactive monomer, a polyfunctional cross-linking agent and a filler composed of composition are mixed together; the mixing process, optionally by heating the composition until molten or by dissolving the components in a common solvent (common solvent) is carried out; optionally in the presence of a binder; and optionally in the radiation sensitization agent under the presence of; (ⅱ) the composition flow cast film of desired thickness is formed on a solid substrate; (ⅲ) using ionizing radiation through a mask to form a polymerized thin film irradiated / crosslinking image; (ⅳ) by solvent rinsing the irradiated film was not irradiated is removed leaving the polymerized composition / cross-linking the image developing; and (ⅴ) sintering the polymerization / crosslinking microscopic image into a pattern made of ceramic or metal.

本发明还公开了一种使用电离辐射在半导体表面上进行平版印刷的方法，包括下列步骤：(ⅰ)将基本由反应性单体和多官能团交联剂组成的组合物混合在一起，任选通过(a)加热组合物直至熔融；或(b)通过溶解在共同溶剂中；任选在聚合物粘合剂存在下；并任选在射线增感剂存在下进行；(ⅱ)将组合物流铸在固体基材上以形成所需厚度的薄膜；(ⅲ)使用电离辐射通过面罩辐照薄膜以形成聚合/交联图象；并且(ⅳ)通过在溶剂中漂洗被辐照薄膜除去未被辐照组合物而使聚合/交联图象显影。 The present invention also discloses a use of ionizing radiation on the semiconductor surface of the lithographic printing method, comprising the steps of: (ⅰ) substantially by the reactive monomers and polyfunctional crosslinking agent composition are mixed together, optionally by (a) heating the composition until molten; or (b) by dissolution in a common solvent; optionally in the presence of a polymeric binder; and optionally in the presence of radiation sensitizer; (ⅱ) the combined stream cast on a solid substrate to form a film of a desired thickness; (ⅲ) irradiating ionizing radiation through the mask film to form a polymerized / crosslinked image; and (ⅳ) by rinsing in a solvent, the irradiated film was not removed Irradiation composition leaving the polymerization / crosslinking image developing.

本发明公开的另一种方法为使用电离辐射形成聚合物、陶瓷或金属的三维立体物品的方法，包括下列步骤：(ⅰ)将基本由反应性单体、多官能团交联剂和聚合物粘合剂组成的组合物混合在一起，所述混合过程任选通过溶解在共同溶剂中或通过将组合物倒入目标基材浸渍在其中的容器中而进行；任选在射线增感剂存在下；和任选在金属或氧化物填料存在下进行；(ⅱ)使用电离辐射通过面罩或电离辐射聚焦源辐照组合物以在目标基材上沉积材料层；(ⅲ)使基材跳返并辐照基材；(ⅳ)重复使基材跳返并辐照基材步骤直至形成所需的三维立体物品；并且任选后辐射处理该立体物品。 Another method disclosed in the present invention is the use of ionizing radiation for the polymer, the method of three-dimensional articles formed of ceramic or metal, comprising the steps of: (ⅰ) substantially by the reactive monomer, polyfunctional crosslinking agent and the polymer adhesive The composition agent composition are mixed together, the mixing process optionally by dissolving or by impregnating the composition into the target substrate in which the vessel, and carried out in a common solvent; optionally in the presence of radiation sensitizers ; and optionally in the presence of a metal or oxide filler; (ⅱ) using ionizing radiation or ionizing radiation through the mask to focus radiation source to deposit a layer of material composition on the target substrate; (ⅲ) jump back to the substrate and irradiating the substrate; (ⅳ) jump back and repeat the substrate irradiated substrates steps until the formation of the desired three-dimensional objects; and the three-dimensional radiation treatment after optional items.

图2为使用X射线可成象感光聚合物组合物制造三维陶瓷或金属物品的立体平版印刷方法的示意图。 Figure 2 is an X-ray imaging of the photosensitive polymer composition can be a three-dimensional schematic view of a ceramic or a stereolithography method of manufacturing a metal article.

图3为使用X射线可成象感光聚合物组合物进行X射线平版印刷方法的示意图。 Figure 3 is an X-ray imageable photopolymer composition schematic X-ray lithographic methods were.

图4为根据本申请实施例61显影的图象的光学显微照片。 Figure 4 is a picture of Example 61 of the present application developed an optical micrograph. 暗区代表聚合/交联区域，其宽度为约140微米。 Representative dark polymerization / crosslinking region having a width of about 140 microns. 附图详述图1为使用本发明公开的电离辐射可成象感光聚合物组合物显微制造陶瓷的方法的示意图。 DETAILED DESCRIPTION Figure 1 is the use of the present invention is disclosed a schematic diagram of ionizing radiation photosensitive imageable polymer composition a method of producing a ceramic microstructure. 此处提供的参考数字对应于图1的参考数字。 Reference numeral provided herein correspond to reference numerals in FIG. 1. 图1A显示了电离辐射可成象感光聚合物组合物1；和基材2。 Figure 1A shows the ionizing radiation photosensitive imageable polymer composition; and a substrate 2. 箭头3代表组合物按图象曝光于电离辐射。 Arrow 3 represents the composition is image-wise exposure to ionizing radiation. 图1B显示了面罩5；可成象感光聚合物组合物的未曝光区域(或未辐照组合物)1；和可成象感光聚合物组合物经电离辐射曝光产生的交联聚合物/陶瓷7。 Figure 1B shows the mask 5; available unexposed imaging area of ​​the photosensitive polymer composition (composition or irradiation) 1; and a crosslinked polymer forming the photosensitive polymer composition produced by ionizing radiation exposure / Ceramic 7. 图1C显示了除去溶剂以完成基材未曝光于电离辐射的区域的冲洗6和交联聚合物/陶瓷7。 Figure 1C shows the solvent was removed to complete the substrate is not exposed to ionizing radiation region 6 and the flushing crosslinked polymer / ceramic 7. 箭头8代表烧掉聚合物粘合剂的烧结步骤。 Arrow 8 represents a sintering step to burn the polymeric binder. 图1D显示了显微制造的陶瓷9和基材2。 Figure 1D shows a ceramic substrate microfabricated 9 and 2.

图2为使用X射线可成象感光聚合物组合物制造三维陶瓷或金属物品的立体平版印刷方法的示意图。 Figure 2 is an X-ray imaging of the photosensitive polymer composition can be a three-dimensional schematic view of a ceramic or a stereolithography method of manufacturing a metal article. 此处的参考数字对应于图2的参考数字。 Reference numerals here correspond to the reference numeral 2 of FIG. 图2A显示了基材的代表部分10，本发明公开的X射线可成象聚合物/陶瓷或聚合物/金属组合物11和容器12。 Figure 2A shows a representative portion of a substrate 10, X-ray image forming polymers of the present invention may be disclosed / ceramic or polymer / metal composition 11 and the container 12. 箭头13代表组合物第一次按图象曝光于电离辐射。 Arrow 13 represents the composition of the first press of the image exposure to ionizing radiation. 图2B显示了交联聚合物/陶瓷或聚合物/金属在第一次曝光于电离辐射扫描束15如X射线或电子束后的代表部分14。 Figure 2B shows a cross-linked polymer / ceramic or polymer / metal in the first exposure to ionizing radiation scanning beam 15, as the representative section X rays or electron beams after 14. 箭头16代表基材跳返以使组合物第二次按图象曝光于电离辐射。 Arrow 16 represents a substrate jump back so that the composition according to the second image exposure to ionizing radiation. 图2C代表在第二次曝光于电离辐射扫描束15如X射线或电子束后交联聚合物/陶瓷或聚合物/金属17。 Figure 2C represents the second exposure to ionizing radiation after scanning beam 15 as an X-ray or electron beam cross-linked polymer / ceramic or polymer / metal 17. 箭头18代表基材10跳返以使组合物第三次按图象曝光于电离辐射。 Arrow 18 denotes the substrate 10 to jump back to the composition according to the third image exposure to ionizing radiation. 图2D为交联聚合物/陶瓷或聚合物/金属在组合物第三次按图象曝光于电离辐射后的代表部分19。 2D is a cross-linked polymer / ceramic or polymer / metal in the composition according to the third part of the image exposure to ionizing radiation after representatives of 19. 箭头20代表跳返和曝光步骤重复进行直至达到所需的形状/厚度。 Arrow 20 represents a jump from and exposure step is repeated until the desired shape / thickness. 图21E为通过本发明方法形成的包括交联聚合物/陶瓷或聚合物/金属的物品的代表部分。 Figure 21E is formed by the method of the present invention comprises a representative part of the crosslinked polymer / ceramic or polymer / metal articles. 箭头22代表烧掉聚合物粘合剂的任选烧结步骤。 Representative arrows 22 burned optionally sintering step of the polymer binder. 图23F为由根据本发明方法陶瓷或金属制成的物品的代表。 Figure 23F representative articles by the method according to the invention made of ceramic or metal.

图3为使用X射线可成象感光聚合物组合物进行X射线平版印刷方法的示意图。 Figure 3 is an X-ray imageable photopolymer composition schematic X-ray lithographic methods were. 可以使用电子束代替X射线。 Electron beam can be used instead of X-rays. 此处提供的数字对应并指图3所示的参考数字。 Corresponding figures provided here and refers to reference numbers shown in Figure 3. 图3A显示了本发明公开的X射线可成象感光聚合物组合物100和基材101，如硅晶片。 3A shows the present invention discloses an X-ray imageable photopolymer composition 100 and substrate 101, such as a silicon wafer. 箭头102代表基材按图象曝光于X射线。 Arrow 102 represents the substrate exposed by the X-ray image. 图3B显示了X射线束103和X射线面罩104、X射线可成象感光聚合物组合物100的未曝光区及交联聚合物106。 Figure 3B shows the X-ray beam 103 and the X-ray mask 104, X-ray imageable photosensitive polymer composition of the unexposed areas 100 and 106 cross-linked polymer. 箭头105代表通过用溶剂冲洗除去组合物未曝光区域的步骤。 Arrow 105 denotes the step of removing the composition by the unexposed areas with a solvent rinse. 图3C代表交联聚合物106和常规晶片加工过程107，如蚀刻或掺杂。 Figure 3C representative conventional cross-linked polymer 106 and the wafer 107 during processing, such as etching or doping.

图4为根据本发明实施例61显影的图象的光学显微照片。 Figure 4 is a picture of Example 61 according to the present invention is an optical micrograph of the developing. 暗区为聚合/交联区域，其宽度为约140微米。 Dark areas of the polymerization / crosslinking region having a width of about 140 microns. 发明详述本发明组合物包括五部分：(1)反应性单体，(2)多官能团交联剂，(3)射线增感剂，(4)聚合物粘合剂，和(5)填料。 DETAILED DESCRIPTION The compositions of the present invention comprises five parts: (1) a reactive monomer, (2) a polyfunctional cross-linking agent, (3) radiation sensitizers, (4) a polymeric binder, and (5) a filler . 必须组分为反应性单体和多官能团交联剂。 Must component reactive monomers and polyfunctional crosslinking agents. 这两种组分必须协同联用以形成有效的组合物。 The two components must be linked to form an effective synergistic compositions. 缺少任何一种都是不能被接受的。 The lack of any kind is unacceptable. 射线增感剂、聚合物粘合剂和填料在某些情况下及对某些应用是需要的。 Radiation sensitizers, polymeric binders and fillers in some cases and for some applications is required. 有效的组合物在经过电离辐射如X射线、高能电子束或γ射线辐照后必须显示在所选溶剂中足够的溶解度变化。 Effective compositions must exhibit sufficient solubility in the selected solvent change after X-rays, high energy electron beam or γ-ray irradiation, such as through the ionizing radiation. 这种溶解度变化只能限定在接受电离辐射的区域(即具有良好的空间分辨力)。 This change can only be limited solubility of ionizing radiation in a region (i.e., having good spatial resolution). 出于实用的目的，足够的溶解度变化必须由较低强度的辐射如实验室X射线仪器产生者获得，而不是由较昂贵的同步辐射产生。 For practical purposes, sufficient solubility must change as the instrument produced by laboratory X-ray obtained from a lower radiation intensity, rather than the more expensive to produce synchrotron radiation. 应该在相当短的持续时间内获得，优选在约1hr或更短的时间内。 Should be within a relatively short duration to obtain, preferably within about 1hr or less.

为了获得可X射线成象的感光聚合物组合物，需要许多性能。 In order to obtain an X-ray imaging of the photosensitive polymer composition, requires a lot of performance. 组合物必须能够在较低强度X射线束如通常用于X射线衍射、医学诊断和检测者下聚合/交联。 The composition must be able to lower the intensity of the X-ray beam is typically used as an X-ray diffraction, medical diagnosis and detection by polymerization / crosslinking. 一些单体/聚合物(例如PMMA)可由高强度同步辐射聚合/交联而不能在较低强度的实验室X射线仪器辐照下完成。 Some monomer / polymer (eg PMMA) by high-intensity synchrotron radiation polymerization / crosslinking can not be completed in a laboratory X-ray irradiation apparatus lower intensity. 聚合/交联所需的曝射时间应该尽可能短，优选在1小时以内或更短。 Polymerization / crosslinking required exposure time should be as short shot, preferably within one hour or less. 聚合/交联区域应该在某些溶剂中显示出大的溶解度差别以便只通过简单地溶去未曝光区域就可使图象显影。 Polymerization / crosslinking area should show some solvent so that only the large solubility difference by simply dissolve the unexposed areas can make image development. 为了保持所需的空间分辨力，曝光和未曝光区域间溶解度的差别必须显著。 Space in order to maintain the desired resolution, exposure, and the difference between the solubility of the unexposed regions to be significant. 此外，聚合/交联反应必须限定在成象区以保持良好的空间分辨力。 Further, the polymerization / crosslinking reaction zone must be limited in order to maintain good image forming spatial resolution.

组合物应该具有热稳定性和长使用寿命并且优选应该是对光稳定的以易于处理。 The composition should have thermal stability and long service life, and preferably should be light stable for ease of handling. 对于要求使用薄膜的应用，组合物应该具有诸如为了流铸出良好品质薄膜的最佳粘度等性能。 For film applications require the use of, such as for the composition should have good flow properties of the cast film quality of the best viscosity. 对于涉及加入填料如陶瓷和金属颗粒的应用，必须优化组合物以保持图象显影及在高温烧结后的结构完整性。 For applications involving adding a filler such as ceramic and metal particles, the composition must be optimized in order to maintain the structural integrity of the image developing and after the high temperature sintering.

本发明的一个目的是研制可在短持续时间内由较低强度电离辐射如X射线、电子束或γ射线成象聚合/交联的材料。 An object of the present invention is to develop in a short duration can be from a lower intensity of ionizing radiation such as X-rays, electron beams or γ-ray imaging polymerized / cross-linked material. 另一个目的是研制用于显微制造陶瓷、立体平版印刷和X射线(电子束)平版印刷的材料和工艺方法。 Another object is to develop materials and process for producing a ceramic microstructure, stereo lithography and X-ray (electron beam) lithography is used. (A)单体有效的单体具有下列通式结构： (A) a monomer effective monomer having the general structure: 其中R1、R2、R3、R4和R5选自：氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；带有酰胺或丙烯酰胺取代基的脂族基团、或带有R'O-取代基的脂族基团，其中R'代表脂族基团CnH2n+1和CnH2n-1(n=1-20)。 Wherein R1, R2, R3, R4 and R5 is selected from: hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20) ; with or acrylamide substituted aliphatic group, or a substituent having R'O- aliphatic group, wherein R 'represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1- 20).

另外的有效单体具有通式结构： Another effective monomer having the general structure: 其中R1和R2选自：氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；或乙酰胺。 Wherein R1 and R2 are selected from: hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic radicals CnH2n-1 (n = 1-20); or acetamide.

另外的有效单体具有通式结构： Another effective monomer having the general structure:

其中R1和R2选自：氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；或不饱和脂族基团CnH2n-1(n=1-20)。 Wherein R1 and R2 are selected from: hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); or an unsaturated aliphatic group CnH2n-1 (n = 1-20).

另外的有效单体具有通式结构： Another effective monomer having the general structure: 其中R1和R2选自：氢；脂族基团CnH2n+1和CnH2n-1(n=1-20)；不饱和脂族基团CnH2n-1(n=1-20)；或氨基取代的脂族基团CnH2n+1和CnH2n-1(n=1-20)。 Wherein R1 and R2 are selected from: hydrogen; an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); unsaturated aliphatic group (n = 1-20) CnH2n-1; or substituted aliphatic amino aromatic group CnH2n + 1 and CnH2n-1 (n = 1-20).

最优选的单体为：丙烯酰胺 脲CH2=CH-CO-NH2 The most preferred monomers are: acrylamide urea CH2 = CH-CO-NH2 甲基丙烯酰胺 氨基甲酸乙酯 Methacrylamide urethane N-(叔丁基)丙烯酰胺 氨基甲酸丁酯 N- (t-butyl) acrylamide, butyl carbamate

乙酰胺 N,N'-亚甲基双丙烯酰胺CH3CO-NH2 Acetamide N, N'- methylene-bis-acrylamide CH3CO-NH2 N-环己基丙烯酰胺 N-烯丙基丙烯酰胺 N- cyclohexyl acrylamide N- diallylacrylamide N-(3-氨基丙基)甲基丙烯酰胺 N-(异丁氧基甲基)甲基丙烯酰胺 N- (3- aminopropyl) methacrylamide N- (isobutoxymethyl) methacrylamide 丙二酰胺 Propanediamide (B)多官能团交联剂有效的交联剂由与至少2个、优选2-4个、最优选2-3个官能团相连的骨架(BB)组成。 (B) a polyfunctional crosslinking agent effective crosslinker by at least two, preferably 2 to 4, the skeleton (BB) and most preferably 2-3 functional groups attached to the composition. 其图示如下： Its illustrated as follows: 骨架的选择影响组合物的机械性能、溶解性能、及涂膜性能。 Select affect the mechanical properties of the composition skeleton, solubility, and film properties. 优选的骨架为(1)线型或支化脂族链-(CRH)n-,n=1-1000，其中R代表脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)乙二醇链-(CH2GH2O)n-,其中n=1-1000；(3)丙二醇链-(CH(CH3)CH2O)n-，其中n=1-1000；(4)饱和环烃如环己基；和(5)下式的异氰脲酸酯C3N3O3： The skeleton is preferably (1) a linear or branched aliphatic chain - (CRH) n-, n = 1-1000, wherein R represents an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2) glycol chain - (CH2GH2O) n-, where n = 1-1000; (3) Propylene glycol chain - (CH (CH3) CH2O) n-, where n = 1-1000; (4) saturated cyclic hydrocarbon such as cyclohexyl; and (5) the formula isocyanurate C3N3O3: 官能团X的选择决定着组合物的反应性和辐射产物中聚合/交联的程度。 Functional group X selection determines the reactivity of the product composition and radiation polymerization / cross-linking degree. 反应性不能太高以便热聚合在不存在X射线时进行。 Reactivity is not too high for the thermal polymerization in the absence of X-rays. 一般进行有效的交联和快速聚合需要一个以上的官能团。 Generally effective crosslinking and rapid polymerization need more than one functional group. 交联剂可包含相同的官能团或有效官能团的不同组合。 Crosslinking agent may contain different combinations of the same functional group or effective functional groups. 优选的官能团为：(1)丙烯酸酯 Preferred functional groups are: (1) acrylates 其中R1、R2和R3选自氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；(2)羧酸-COOH；(3)环氧化物 Wherein R1, R2 and R3 are selected from hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); (2) a carboxylic acid -COOH; (3) epoxide 其中R1、R2和R3选自：氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)；和(4)乙烯基 Wherein R1, R2 and R3 is selected from: a hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20); and (4) vinyl 其中R1、R2和R3选自：氢或脂族基团CnH2n+1和CnH2n-1(n=1-20)。 Wherein R1, R2 and R3 is selected from: a hydrogen or an aliphatic group CnH2n + 1 and CnH2n-1 (n = 1-20). 最优选的交联剂为：PEG(1000)二甲基丙烯酸酯 衣康酸 The most preferred crosslinking agents are: PEG (1000) dimethacrylate itaconic acid 丙二酸 聚丙烯酸HOOC-CH2-COOH Malonic polyacrylic acid HOOC-CH2-COOH PEG(4000)二丙烯酸酯 1,4-环己二醇二甲基丙烯酸酯 PEG (4000) diacrylate, 1,4-cyclohexanediol dimethacrylate

PEG(600)二环氧甘油醚 甲基丙烯酸烯丙酯 PEG (600) diglycidyl ether, allyl methacrylate 3-丁烯-1,2,3-三羧酸 三甘醇二丙烯酸酯 3-buten-1,2,3-tricarboxylic acid triethylene glycol diacrylate 1,1,1-三羟甲基丙烷三甲基丙烯酸酯 Trimethylolpropane trimethacrylate 甲基-2-异氰酸根合-3-甲基丁酸酯 Methyl-2-isocyanato-3-butyrate 异氰脲酸三烯丙酯 Triallyl isocyanurate

异氰脲酸三(2-丙烯酰氧基乙基)酯 Isocyanurate, tris (2-acryloyloxyethyl) ester 异氰脲酸三(2,3-环氧丙基)酯(异氰脲酸三缩水甘油酯)。 Isocyanuric acid tris (2,3-epoxypropyl) ester (isocyanurate triglycidyl). (C)射线增感剂由于X射线、电子束和γ射线在有机介质中的低吸收横截面，用于引发聚合反应产生的每单位体积的反应性物种的数目少。 Small number of (C) due to radiation sensitizer X-rays, electron beams and γ-rays in the organic medium of low absorption cross section, is used to initiate the polymerization reaction per unit volume of the reactive species. 组合物对X射线的吸收效率可通过加入无机物得到改进。 The composition of the X-ray absorption efficiency can be improved by the addition of an inorganic substance. 如果无机物的粒度太大，例如在微米尺寸状态，则开始时产生的电子和空穴将在无机颗粒内再结合并消失。 If the inorganic particle size is too large, e.g., in micronized state, electrons and holes are generated at the beginning of the combined and disappear within the inorganic particles. 因此，无机颗粒必须足够小，以使电子和空穴可以逃逸到周围的介质中并引发化学反应。 Therefore, the inorganic particles must be small enough so that electrons and holes can escape to the surrounding medium and initiating a chemical reaction. 制备纳米尺寸无机颗粒的方法已由在此引入作为参考的US5,556,716(1996年9月17日，Herron和Wang)；US5,132,051(1992年7月21日，Herron和Wang)；US5,238,607(1993年8月24日，Herron和Wang)；Res.Chem.Interm.,15,17-29(1991),Y.Wang和N.Herron；J.Phys.Chem.,95,525(1991),Y.Wang和N.Herron公开。 Preparation of nano-sized particles of inorganic methods are hereby incorporated by reference in US5,556,716 (1996 年 9 月 17 日, Herron and Wang); US5,132,051 (1992 年 7 月 21 日, Herron and Wang); US5,238,607 (August 24, 1993, Herron and Wang);. Res.Chem.Interm, 15,17-29 (1991), Y.Wang and N.Herron;. J.Phys.Chem, 95,525 (1991), Y .Wang and N.Herron public.

加入无机射线增感剂增强了组合物对X射线的吸收效率。 Adding an inorganic ray sensitizer enhances the composition of X-ray absorption efficiency. 它还可以影响聚合/交联动力学、全部反应速率、和被辐照区的交联密度。 It can also affect the polymerization / cross-linking kinetics, the overall reaction rate, and the crosslinking density of the irradiated area. 优选无机物应该包含强辐射吸收的重原子如Bi、Pb、Hg、Au、Pt和I并且应该能够很容易地分散到组合物中，优选在0.1-80wt.％范围。 Should preferably contain inorganic strong radiation absorbing heavy atoms such as Bi, Pb, Hg, Au, Pt, and I and should be able to be easily dispersed in the composition, preferably 0.1-80wt.% Range. 优选其尺寸应该为1-1000nm。 Preferred size should 1-1000nm. 最优选尺寸范围为1-100nm。 The most preferred size range 1-100nm.

无机微粒选自ⅤB-ⅥB半导体、ⅤB-ⅦB半导体、ⅡB-ⅥB半导体、ⅡB-ⅤB半导体、ⅢB-ⅤB半导体、ⅢB-ⅥB半导体、ⅠB-ⅥB半导体和ⅣB-ⅦB半导体。 Inorganic particles selected from ⅤB-ⅥB semiconductors, ⅤB-ⅦB semiconductors, ⅡB-ⅥB semiconductors, ⅡB-ⅤB semiconductors, ⅢB-ⅤB semiconductors, ⅢB-ⅥB semiconductors, ⅠB-ⅥB ⅣB-ⅦB semiconductors and semiconductor. 优选的无机微粒选自Bi2S3、Bi2Se3、BiI3、BiBr3、HgS、PbI2、PbI4-2和Pb2I7-3。 Preferred inorganic particles are selected from Bi2S3, Bi2Se3, BiI3, BiBr3, HgS, PbI2, PbI4-2 and Pb2I7-3. 最优选的无机微粒为BiI3。 The most preferred inorganic particulates BiI3. (D)粘合剂此处规定粘合剂为高分子量(＞1000)聚合物。 (D) a binder where the binder is a predetermined high molecular weight (> 1000) polymer. 在配方中使用粘合剂出于多种目的。 Using an adhesive for various purposes in the formulation. 某些单体如丙烯酰胺具有结晶的倾向，这不仅降低了组合物对X射线的感光度而且影响了X射线成象区的空间分辨力。 Some monomers such as acrylamide has a tendency to crystallize, which not only reduces the composition of X-ray sensitivity and influence the spatial resolution of the X-ray imaging area. 加入粘合剂可防止这种单体结晶问题。 The monomer is added to prevent crystallization of the adhesive problems. 某些单体和交联剂的组合物如丙烯酰胺和丙二酸，尽管可被X射线辐射聚合，但聚合不可控制并且不能保留X射线图象。 The composition of some of the monomers and crosslinking agents such as acrylamide and malonic acid, although the polymerization can be X-ray radiation, but the polymerization can not be controlled and it can not retain an X-ray image. 加入适当的粘合剂可将聚合限制在辐照区，由此形成有用的X射线图象。 Addition of a suitable polymeric binder may restrict irradiation zone, thereby forming a useful X-ray image. 加入粘合剂还可增加薄膜的流延和加工性能，这使得薄膜制备更容易。 Adding a binder can also increase the casting and machining properties of the film, which makes it easier for film preparation. 粘合剂还能控制聚合/交联产品的机械和化学性能。 Adhesives can control the polymerization / cross-linking of mechanical and chemical properties of the product.

粘合剂的选择依赖于所用单体和交联剂的组合物及应用目的。 The choice of binder depends on the composition of the monomer and crosslinking agent and the application purpose use. 粘合剂应该是与单体、交联剂、以及如果使用的射线增感剂混溶的。 The binder should be with the monomers, crosslinking agent, radiation sensitizers and, if used miscible. 对于涉及陶瓷的显微制造如等离子体显示器的阻挡凸缘制造的应用，所用粘合剂应该在烧结步骤中很容易地被烧掉。 For microfabricated relates to a ceramic, such as a plasma display barrier flange manufacturing applications, the binder should be easily burned off during the sintering step. 丙烯酸酯基聚合物和聚乙烯粘合剂可用于此目的。 Acrylate-based polymers and polyethylene binder used for this purpose. 当应用为立体平版印刷时，聚合材料的机械强度和尺寸稳定性是重要的。 When applied as stereolithography, mechanical strength and dimensional stability of the polymeric material is important. 丙烯酸酯和环氧基聚合物以及聚酰胺是这种应用的有效粘合剂。 Acrylate and epoxy polymers, and polyamide adhesive is effective for this application. 当应用为平版印刷时，所选粘合剂在制造半导体的蚀刻步骤期间于等离子体环境下必须是稳定的。 When applied to a lithographic printing, the selected adhesive during the etching step of manufacturing a semiconductor in a plasma environment must be stable. 环氧基聚合物以及聚酰胺对这种应用是有效的。 Epoxy polymers and polyamides for this application is effective. 当使用水基组合物时，例如当环境因素很重要时，水溶性聚合物如聚酰胺、聚乙烯醇和聚乙二醇是适宜的。 When using water-based compositions, e.g., when the environmental factors are important, the water-soluble polymer such as polyamides, polyvinyl alcohol and polyethylene glycol are suitable.

优选的粘合剂为丙烯酸酯聚合物、丙烯酸酯-丙烯酸聚合物如由BF Goodrich Specialty Chemicals,Cleveland,Ohil市售的CARBOSET xpd2470及相关聚合物、环氧聚合物、聚酰胺、聚丙烯酰胺、聚乙烯醇、聚乙二醇、聚丙二醇、聚乙烯和聚乙酸乙烯酯。 Preferred adhesives are acrylate polymers, acrylate - acrylic polymers such as from BF Goodrich Specialty Chemicals, Cleveland, Ohil commercially available CARBOSET xpd2470 and related polymers, epoxy polymers, polyamides, polyacrylamide, poly vinyl alcohol, polyethylene glycol, polypropylene glycol, polyethylene and polyvinyl acetate. (E)填料以上公开的组合物可与陶瓷颗粒或金属颗粒混合以形成辐射感光组合物。 (E) a filler composition disclosed above may be mixed with ceramic particles or metal particles to form a radiation sensitive composition. 使用辐射(X射线、电子束或γ射线)成象技术，可随后将这些组合物在烧去有机物后制成陶瓷或金属物品。 Using radiation (X-rays, electron beams or γ-ray) imaging technology, these compositions may then go after the burning of organic matter is made of ceramic or metal objects. 所用填料应该不强烈吸收辐射，否则它们将降低感光性。 The filler should not strongly absorb radiation, which would otherwise reduce the sensitivity. 填料的表面与组合物中所用单体和交联剂应该是不反应的以避免热聚合。 The filler and the surface of the composition of the monomers and the crosslinking agent should be non-reactive to prevent thermal polymerization. 适宜的金属颗粒填料由Al、Ti、V、Cu、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、In和Sb组成。 Suitable metal particulate filler from Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In and Sb. 优选的金属颗粒填料为Al、Cu、Fe、Co、Ni和Cu。 Preferred metal particulate filler is Al, Cu, Fe, Co, Ni and Cu. 最优选的填料为Al。 The most preferred filler is Al. 适宜的陶瓷颗粒填料由Al、Ti、V、Cu、Mn、Fe、Co、Ni、Cu、Zn、Y、Zr、Nb、Mo、In、Sb、Ta、W和Si的氧化物组成。 Suitable ceramic particulate filler from Al, Ti, V, Cu, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, In, Sb, Ta, W and Si oxide. 优选的陶瓷颗粒填料为Al、Ti、Fe、Ni、Zn、Ta、W和Si的氧化物。 The preferred ceramic particles filler is Al, Ti, Fe, Ni, Zn, Ta, W and Si oxides. 最优选的为氧化铝和氧化硅。 Most preferably alumina and silica. (F)可辐射成象感光聚合物组合物的制备：可X射线成象组合物可由熔融路线或溶解路线制备。 Preparation of (F) a radiation imaging photopolymer composition: X-ray imaging compositions may be melted or dissolved route route to prepare. 某些单体、交联剂和射线增感剂如丙烯酰胺、聚(乙二醇)n二甲基丙烯酸酯和BiI3可以共同熔融。 Some of the monomers, crosslinking agent and radiation sensitizers such as acrylamide, poly (ethylene glycol) n dimethacrylate and BiI3 can be melted together. 随后可通过铸塑或挤塑由熔体形成固体薄膜。 May then be formed by casting or extrusion from the melt solid film. 更灵活的方法是使用共同溶剂将全部组分溶解在一起。 More flexible approach is to use a common solvent to dissolve all the components together. 例如，二甲基甲酰胺可有效地将丙烯酰胺、聚(乙二醇)n二甲基丙烯酸酯、BiI3和CARBOSETxpd2470粘合剂溶解在一起。 For example, dimethylformamide effective to acrylamide, poly (ethylene glycol) n dimethacrylate, BiI3 and CARBOSETxpd2470 binder dissolved together. 该溶液可直接用于诸如立体平版印刷等应用；或者固体薄膜可通过旋涂或网印技术由溶液制备。 This solution can be used directly in applications such as stereo lithography; spin coating or screen printing technique by preparing a solution or solid film through. (G)辐射源本发明中所用辐射源限定为电离辐射，一般由γ射线、X射线、电子束和离子束组成。 (G) a radiation source in the present invention as defined by the radiation source of ionizing radiation, generally composed of γ-rays, X-rays, electron beam and ion beam composition. γ射线可由放射性同位素如60Co便利地产生。 γ-rays may be conveniently produced radioisotopes such as 60Co. X射线束可通过电子轰击金属靶或由同步仪器产生。 X-ray beam can be a metal target bombarded by electrons generated by the synchronization or instrument. 常用的靶为W、Mo和Cu。 Commonly used target for W, Mo and Cu. 电子束可由电子加速器产生。 Electron beam generated by an electron accelerator. 因为本发明中公开的应用要求要进行的辐射引发的聚合反应具有高空间分辨力，所以通常需要一个面罩。 The polymerization of the present invention, because the radiation application requirements to be disclosed in the initiation of a high spatial resolution, it typically requires a mask. 当选择辐射源时，面罩材料的选择是一个重要的考虑因素。 When selecting a radiation source, select the mask material is an important consideration. 面罩材料的厚度必须增加以补偿较高能量电离辐射如γ射线的较低吸收效率。 The thickness of the mask material must be increased to compensate for the high energy ionizing radiation such as γ-ray absorption efficiency is low. 优选的辐射源为X射线和电子束。 The preferred radiation source for X-rays and electron beams. 最优选的源为X射线。 The most preferred source of X-rays.

(1)陶瓷的显微制造：陶瓷的显微制造是诸如压电体和等离子体显示器等应用所要求的。 Microfabrication (1) Ceramics: microfabricated piezoelectric ceramic such as a plasma display and the like required by the application. 由于陶瓷膏体的不透明性能，传统的显微制造技术如照相平版印刷术是不适用的。 Since the properties of ceramic opaque paste, conventional microfabrication techniques such as photolithography are not applicable. 使用X射线敏感聚合物/陶瓷组合物可以解决这一问题。 X-ray sensitive polymer / ceramic composition can solve this problem. 这在下面制造等离子体平板显示器的阻挡凸缘中加以详述。 This is to be described in detail below plasma flat panel display manufacturing barrier flange.

在典型的等离子体显示器设备中，将含有Xe或Ar的特殊气体混合物密封在一个单元中，代表显示器设备中的一个象素(pixel)，壁是由陶瓷如氧化硅和氧化铝制成的。 In a typical plasma display device, a special gas mixture containing Xe or Ar is sealed in a cell, on behalf of the display device in a pixel (pixel), the wall is made of a ceramic such as silica and alumina. 单元壁用显示性磷光剂涂布，在两端装有电极。 Cell wall with a display of the phosphor coating on both ends with electrodes. 施加足够大的电压通过电极击穿气体，放射UV光，并激发磷光剂产生需要的蓝、绿或红光。 Applying a sufficiently large voltage breakdown gas, UV light radiation through the electrode, and excite phosphors to produce the desired blue, green or red light. 制造典型尺寸为宽50-75微米、高150-200微米的陶瓷元件壁(或阻挡凸缘)是具有挑战性的。 Typical dimensions for the manufacture of a wide 50-75 microns, 150-200 microns high ceramic element wall (or barrier flange) is challenging. 目前优选的方法包括使用照相平版印刷术将非常薄的感光聚合物/陶瓷混合物薄膜反复曝光一层一层地构造厚度。 A presently preferred method involves the use of photolithography would be very thin photosensitive polymer / ceramic mixture is repeatedly exposed layer by layer film structure thickness. 该反复是大量生产不能接受的，因为它太慢且昂贵。 This is repeated for mass production unacceptable, because it is too slow and expensive. 使用本发明公开的X射线敏感感光聚合物/陶瓷组合物使用一次X射线曝光可形成更厚的层。 The present invention discloses the use of an X-ray sensitive photopolymer / ceramic composition of the primary X-ray exposure can be used to form a thicker layer. 基本原理在下面的图1中进行了示意性说明。 In the following basic principles of Figure 1 has been schematically described. 本发明可以许多不同的方式实践并且不限于此处所述的构造。 The present invention may be practice in many different ways and is not limited to the configuration described herein.

本申请的可行性在实施例中通过使用混有氧化铝和氧化硅的X射线感光组合物进行了示例性说明。 Feasibility of the present application in an embodiment by using mixed with X-ray sensitive composition is aluminum oxide and silicon oxide were illustrative. 混合物可通过X射线成象聚合/交联。 The mixture can be polymerized by X-ray imaging / crosslinking. 未曝光区域易于用溶剂洗去以露出由聚合物/陶瓷复合物组成的交联立体图象。 Unexposed area easy to wash with a solvent to expose the cross-linked three-dimensional images from a polymer / ceramic composites thereof. 这一技术，如图1所示，可用于制造等离子体平板显示器的阻挡凸缘。 This technique, shown in Figure 1, can be used to manufacture plasma flat-panel display of the barrier flange. (2)立体平版印刷：由计算机辅助设计程序快速得到三维(3D)物体原型的需要日益增长。 (2) stereolithography: computer-aided design program from the growing need to quickly get a three-dimensional (3D) object prototypes. 这种立体物体是目视、设计修改、功能检查等所需要的。 Such three-dimensional object is visual, design modification, function tests required. 目前的技术包括使用扫描激光器使感光聚合物曝光形成交联固体层并随后通过图2所示的跳返基材一层一层地构造立体物体层。 Current techniques include the use of laser scanning exposure of the photosensitive polymer layer and form a crosslinked solid is then constructed layer by layer by layer jump back stereoscopic object substrate 2 shown in Fig. 感光聚合物薄膜必须相当薄，一般厚度为100-150微米且最终物体尺寸可最高达1/2米。 Photopolymer film must be quite thin, the general thickness of 100-150 microns and the final body size can be up to 1/2 meters. 市场上需要制造基于光学感光聚合物技术难以提供的陶瓷和金属物品。 On the market need to manufacture ceramic and metal objects based on the optical photopolymer technology is difficult to provide. 本发明公开的可电离辐射成象的感光聚合物/陶瓷和感光聚合物/金属组合物可以解决该问题。 The present invention disclosed may be ionizing radiation imaging photopolymer / photopolymer and ceramic / metal composition can solve the problem. 基本原理在下面的图2中进行了示意性说明。 The basic principle in Figure 2 below were described schematically. 本发明可以许多不同的方式实践并且不限于此处所述的构造。 The present invention may be practice in many different ways and is not limited to the configuration described herein.

本申请的可行性在本发明给出的实施例中通过使用混有氧化铝、氧化硅或铝金属粉末的X射线感光组合物得到了证明。 Example feasibility of the present application in the present invention given by using mixed with aluminum oxide, silicon oxide, or X-ray sensitive composition of aluminum metal powder was demonstrated. 混合物可通过X射线成象聚合/交联。 The mixture can be polymerized by X-ray imaging / crosslinking. 未曝光区域易于用溶剂洗去以露出由聚合物/陶瓷复合物或聚合物/金属复合物组成的交联立体图象。 Unexposed area easy to wash with a solvent to expose the cross-linked three-dimensional images from a polymer / ceramic composite or polymer / metal composite thereof. (3)X射线平版印刷术：X射线平版印刷术是为制造形体尺寸小至30nm(0.03微米)的后代半导体器件而开发的。 (3) X-ray lithography: X-ray lithography for manufacture of small feature size to 30nm (0.03 microns) and the development of future generations of semiconductor devices. 目前，尚无适合X射线平版印刷术的理想光刻胶。 Currently, there is no ideal photoresist for X-ray lithography. 例如，PMMA薄膜可用于此目的但书写图象必须使用高强度同步辐射(通过薄膜消融)。 For example, PMMA film used for this purpose, but the image must be written using a high intensity synchrotron radiation (ablation through the film). 这适用于研究目的，但不实用。 This applies to research purposes, but not practical. 本发明公开的X射线感光组合物可用于此目的。 X-ray photosensitive compositions of the present disclosure can be used for this purpose. 图3示意性说明了负片光刻胶的工作原理。 Figure 3 schematically illustrates a negative photoresist works. 本发明可以许多不同的方式实践并且不限于此处所述的构造。 The present invention may be practice in many different ways and is not limited to the configuration described herein. 实验仪器X射线曝光实验是使用配有广焦Mo管在40KV和40mA下运行的Siemens X射线发生器进行的。 Experimental apparatus is the use of X-ray exposure experiments with a wide focal Mo tube at 40KV and 40mA operation of Siemens X-ray generator. 测定的入射X射线剂量率为6.1×104伦琴/分钟。 Determination of the incident X-ray dose was 6.1 × 104 Roentgen / min. 定义空气曝光1伦琴(R)释放的总电荷为每千克空气2.58×10-4库仑。 The definition of an air exposure Roentgen (R) released the total charge per kilogram of air 2.58 × 10-4 coulomb. 当1cm3空气接受1伦琴X射线时，吸收剂量为0.87rad(“辐射化学”，AJSwallow,Wiley,New York,1973)。 When accepting a 1cm3 air Roentgen X-ray absorbed dose 0.87rad ("Radiation Chemistry", AJSwallow, Wiley, New York, 1973). 对比例A将3.496g丙烯酰胺在～85℃熔融。 Comparative Example A The 3.496g of acrylamide at ~ 85 ℃ melted. 用该熔体在玻璃基底上流延薄膜。 Cast film in the glass substrate with the melt. 用来自Mo靶的X射线束辐照薄膜10和30分钟。 With from Mo target X-ray beam irradiating the film 10 and 30 minutes. 然后水洗使薄膜显影。 Then wash the film developed. 被辐射区显示溶解度下降但不能显影出不溶的图象。 Solubility decreased radiation zone is displayed but not insoluble developing image. 这一实例证明只含有反应性单体如丙烯酰胺的组合物是无效的。 This example shows only contains a reactive monomer composition of acrylamide is invalid. 对比例B在40分钟内将总共4.543g丙烯酰胺缓慢加入到2.0g蒸馏水中并在室温搅拌过夜。 Comparative Example B in 40 minutes A total 4.543g of acrylamide was added slowly to 2.0g distilled water and stirred at room temperature overnight. 然后用3.603g蒸馏水稀释透明的均相溶液使丙烯酰胺的浓度为39.6％。 Clear homogeneous solution was then diluted with 3.603g distilled water so that the concentration of acrylamide was 39.6%. 在玻璃小瓶(直径1.5cm)中装入一些溶液。 Some solution was charged in a glass vial (diameter 1.5cm) in. 用来自Mo靶的X射线束辐照小瓶30分钟。 With from Mo target X-ray beam irradiation vial 30 minutes. 可观察到形成不规则形状的凝胶但不能得到明确的不溶图象。 Gel formation can be observed irregularly shaped but can not get a clear picture insoluble. 这一实例证明虽然与固态相比丙烯酰胺在水溶液中的聚合增强了，但还是不能在空间上控制聚合反应并且聚合产物不是完全不溶的，因此不适用于本发明所考虑的应用。 This example demonstrates Although compared with the solid state polymerization of acrylamide in aqueous solution increased, but still can not control the polymerization reaction and the polymerization product in space is not completely insoluble, therefore not suitable for applications of the present invention is contemplated. 对比例C用来自Mo靶的X射线束辐照小瓶中的3.881g聚丙烯酰胺/水溶液(50/50)30分钟。 Comparative Example C with from Mo target X-ray beam irradiation vial 3.881g polyacrylamide / water (50/50) for 30 minutes. 辐照后溶液中未发生变化。 After irradiation the solution does not change. 这一实例证明聚丙烯酰胺单独时是无效的。 This example demonstrates polyacrylamide alone is ineffective.

将0.998g Carboset XPD2470和5ml DMF混合在一起并在室温搅拌1小时。 The 0.998g Carboset XPD2470 and 5ml DMF were mixed together and stirred at room temperature for 1 hour. 然后加入3.008g丙烯酰胺和2.000g PEGDMA并将该混合物在室温搅拌3小时。 Was then added 3.008g and 2.000g PEGDMA acrylamide and the mixture was stirred at room temperature for 3 hours. 在一个直径1.5cm的玻璃小瓶中装入一些这种溶液并在玻璃基底上流延薄膜。 Some of this solution was loaded film is cast on a glass substrate in a 1.5cm diameter glass vial. 用来自Mo靶的X射线束辐照两者30分钟。 With a Mo target from the two X-ray beams irradiated for 30 minutes. 在小瓶样品中形成固体白色塞-一种X射线束的复制品，而薄膜样品在经丙酮显影后在X射线束辐照处给出不溶的斑点。 To form a solid plug in the white sample vial - an X-ray beam reproductions, and film samples were developed with acetone after the X-ray beam irradiation at the given spot insoluble.

制备62.501g Carboset XPD2470和250ml DMF的备用溶液并在制备实施例36-48时使用。 Preparation 62.501g Carboset XPD2470 and alternate solution 250ml DMF and patients when used in the preparation of the implementation of 36-48.

将3.002g丙烯酰胺和2.999g聚丙烯酸混合在一起并在～85℃熔融。 2.999g to 3.002g of acrylamide and polyacrylic acid were mixed together and melted at ~ 85 ℃. 在小瓶(直径1.5cm)中装入该熔体。 Mount the melt in a vial (diameter 1.5cm) in. 用来自Mo靶的X射线束辐照小瓶60分钟。 With from Mo target X-ray beam irradiation vial 60 minutes. 用丙酮洗涤显影小瓶中的物料。 Vial was washed with acetone and the developing materials. 在小瓶样品中形成固体白色塞-一种X射线束的复制品。 To form a solid plug in the white sample vial - an X-ray beam reproductions.