CN103298782B - Oxime ester compound and a photopolymerization initiator containing the compound - Google Patents

Oxime ester compound and a photopolymerization initiator containing the compound Download PDF

Info

Publication number
CN103298782B
CN103298782B CN201280004665.9A CN201280004665A CN103298782B CN 103298782 B CN103298782 B CN 103298782B CN 201280004665 A CN201280004665 A CN 201280004665A CN 103298782 B CN103298782 B CN 103298782B
Authority
CN
China
Prior art keywords
acid
compound
vinegar
group
associative
Prior art date
Application number
CN201280004665.9A
Other languages
Chinese (zh)
Other versions
CN103298782A (en
Inventor
村田圣
大石武雄
君岛孝一
Original Assignee
株式会社艾迪科
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to JP2011067406 priority Critical
Priority to JP2011-067406 priority
Application filed by 株式会社艾迪科 filed Critical 株式会社艾迪科
Priority to PCT/JP2012/052775 priority patent/WO2012132558A1/en
Publication of CN103298782A publication Critical patent/CN103298782A/en
Application granted granted Critical
Publication of CN103298782B publication Critical patent/CN103298782B/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C391/00Compounds containing selenium
    • C07C391/02Compounds containing selenium having selenium atoms bound to carbon atoms of six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32Oximes
    • C07C251/62Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/65Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00Thiocarboxylic acids
    • C07C327/20Esters of monothiocarboxylic acids
    • C07C327/28Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D303/00Compounds containing three-membered rings having one oxygen atom as the only ring heteroatom
    • C07D303/02Compounds containing oxirane rings
    • C07D303/12Compounds containing oxirane rings with hydrocarbon radicals substituted by singly or doubly bound oxygen atoms
    • C07D303/18Compounds containing oxirane rings with hydrocarbon radicals substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C07D303/20Ethers with hydroxy compounds containing no oxirane rings
    • C07D303/22Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
    • C07D303/23Oxiranylmethyl ethers of compounds having one hydroxy group bound to a six-membered aromatic ring, the oxiranylmethyl radical not being further substituted, i.e.
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D307/00Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40Radicals substituted by oxygen atoms
    • C07D307/42Singly bound oxygen atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02Phosphorus compounds
    • C07F9/28Phosphorus compounds with one or more P—C bonds
    • C07F9/50Organo-phosphines
    • C07F9/5022Aromatic phosphines (P-C aromatic linkage)
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007Filters, e.g. additive colour filters; Components for display devices
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00Systems containing only non-condensed rings
    • C07C2601/12Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14The ring being saturated

Abstract

下述通式(1)表示的肟酯化合物。 Oxime ester compound of the following formula (1). 式中,R1~R4表示OR11、COOR11等,R11表示氢原子、C1~20的烷基、C6~30的芳基、C7~30的芳烷基或C2~20的杂环基,这些基团的氢原子还可以被-CR21=CR22R23、-CO-CR21=CR22R23、-O-CO-CR21=CR22R23等取代(R21~R23与R11相同);X表示硫原子、NR33(R33为氢原子、C1~20的烷基等)等;a表示0~4的整数;b表示1~5的整数,R4中的至少一个是具有-CR21=CR22R23、-CO-CR21=CR22R23、-O-CO-CR21=CR22R23等的基团。 Wherein, R1 ~ R4 represents OR11, COOR11 the like, R11 represents a hydrogen atom, an alkyl group of C1 ~ 20, C6 ~ 30 aryl group, an aralkyl group or a C7 ~ 30 heterocyclic group C2 ~ 20 of these groups the hydrogen atom also may be -CR21 = CR22R23, -CO-CR21 = CR22R23, -O-CO-CR21 = CR22R23 et substituted (R21 ~ R23 and R11 the same); X-represents a sulfur atom, NR33 (R33 is a hydrogen atom, C1- ~ 20 alkyl group, etc.) and the like; a represents an integer of 0 to 4; b. represents an integer of 1 to 5, R4 at least one is a -CR21 = CR22R23, -CO-CR21 = CR22R23, -O-CO-CR21 = CR22R23 groups or the like.

Description

巧醋化合物W及含有该化合物的光聚合引发剂 Compound W Qiao vinegar and a photopolymerization initiator containing the compound

技术领域 FIELD

[0001] 本发明设及作为感光性组合物中使用的光聚合引发剂有用的新型朽醋化合物、含有该化合物的光聚合引发剂、在具有締键式不饱和键的聚合性化合物中含有该光聚合引发剂而形成的感光性组合物W及该感光性组合物的固化物。 [0001] The present invention is provided as an optical and photosensitive composition using the novel polymeric initiator rotten vinegar useful compound, the compound contains a photopolymerization initiator, the polymerizable compound containing the associative unsaturated bond in having cured to form a photopolymerization initiator and a photosensitive composition W of the photosensitive composition.

背景技术 Background technique

[0002] 感光性组合物是在具有締键式不饱和键的聚合性化合物中加入光聚合引发剂而得到的,由于可W通过照射能量射线(光)而使其聚合固化,因而可用于光固化性油墨、感光性印刷版、各种光致抗蚀剂等。 [0002] In the photosensitive composition is a compound having a polymerizable unsaturated bond in association button photopolymerization initiator obtained, since W by energy ray (light) to polymerization and curing, and thus can be used for light curable inks, photosensitive printing plates, various photoresists.

[0003] 作为用于上述感光性组合物的光聚合引发剂,在专利文献1~3中提出了目亏醋化合物。 [0003] As for the photosensitive composition of the photopolymerization initiator, Patent Document 3 proposes mesh 1 to compound loss vinegar.

[0004] 但是,在专利文献1~3中记载的目亏醋化合物中,能够满足感光度的目亏醋化合物存在着可见光区域的透射率低、用滤色器无法获得所期望的颜色的问题(特别是,在用于保护膜等要求透明性的用途的感光性组合物、W及使用了蓝色的颜料或色素的滤色器用抗蚀剂中,如果混合了在380~450nm有吸收的化合物,则亮度、色纯度会下降),另外,可见光区域的透射率较高的目亏醋化合物存在着感光度不能充分满足要求的问题,需要有兼备两种特性的光聚合引发剂。 [0004] However, in the head loss vinegar compound described in Patent Documents 1 to 3, it is possible to meet the deficit of sensitivity mesh vinegar compound exists low transmittance of visible light region, a color filter can not be obtained a desired color problem (in particular, in the photosensitive composition for a protective film of applications requiring transparency, W, and the use of a blue dye or a pigment color filter resist, if the mixing in the absorption of 380 ~ 450nm compound, luminance, color purity drops), further, a high visible light transmittance loss goal area vinegar compound there is a problem of sensitivity are not fully satisfactory, both properties need both a photopolymerization initiator.

[0005] 另外,用于滤色器等的含有着色剂的着色碱显影性感光性树脂组合物要求具有高感光度,必须将抗蚀剂中的光聚合引发剂设置成高浓度。 [0005] Further, the colored alkali-developable photosensitive resin composition for a color filter containing a coloring agent or the like is required to have high sensitivity, the photoresist must be a polymerization initiator is set to a high concentration. 但是,高浓度的光聚合引发剂会引起因显影性的恶化而导致的残渣的发生、W及因升华物而导致的光掩模和加热炉的污染等。 However, a high concentration of the photopolymerization initiator can cause contamination occurs due to deterioration of the developability of the resulting residue, and W, and the furnace photomask was caused by sublimation and the like.

[0006] 现有技术文献 [0006] The prior art documents

[0007] 专利文献 [0007] Patent Document

[0008] 专利文献1 :日本特开2000 - 80068号公报 [0008] Patent Document 1: Japanese Patent Application Laid-Open 2000-- Publication No. 80068

[0009] 专利文献2 :日本特开2001 - 233842号公报 [0009] Patent Document 2: Japanese Patent Laid-Open 2001-- Publication No. 233842

[0010] 专利文献3 :专利第3860170号公报 [0010] Patent Document 3: JP Patent No. 3860170

发明内容 SUMMARY

[0011] 本发明所要解决的问题 [0011] The present invention solves the problem

[0012] 本发明所要解决的问题点是,迄今为止还没有具有能够满足要求的感光度,并且可见光区域的透射率较高、升华性较低的光聚合引发剂。 [0012] The invention solves this problem, so far has not yet meet the required sensitivity, and high transmittance of visible light region, low optical sublimable polymerization initiator.

[0013] 因此,本发明的目的是提供一种稳定性优良、低升华性、显影性优良、可见光区域的透射率较高、可高效吸收365nm等的近紫外光而被活化的高感光度的光聚合引发剂。 [0013] Accordingly, an object of the present invention is to provide an excellent stability, low sublimability, excellent developability, a high transmittance of visible light region, can efficiently absorb 365nm ultraviolet light such as near-activated high sensitivity a photopolymerization initiator.

[0014] 解决问题的手段 [0014] means to solve the problem

[0015] 本发明者们进行了深入研究,结果发现,如果使作为光聚合引发剂使用的化合物在制作树脂组合物时与树脂等反应,或者在能量射线(光)照射时与树脂等反应,则升华性变得比不与树脂等反应而W化合物本来的状态存在的情况低。 [0015] The present inventors have conducted intensive studies and found that, when the compound as the photopolymerization initiator used in the production of the resin composition and a resin, or energy ray (light) is irradiated with the reaction resin or the like, the sublimation becomes lower than the case of the reaction with a resin or the like is not the original state of the W compounds present.

[0016] 本发明是基于上述认识而完成的,提供一种由下述通式(1)表示的目亏醋化合物W 及含有该化合物而形成的光聚合引发剂。 [0016] The present invention is based on the above findings and accomplished, head loss W vinegar to provide a compound represented by the following formula (1) containing the compound and a light to form a polymerization initiator.

[0017] [0017]

Figure CN103298782BD00041

[001 引(式中,Ri、R2、R呀P R4分别独立地表示R 11、ORii、COORii、SRii、SOzRii、CONRi2R"或CN, [001 primer (wherein, Ri, R2, R die P R4 each independently represent R 11, ORii, COORii, SRii, SOzRii, CONRi2R "or CN,

[0019] Rii、R12和R "分别独立地表示氨原子或取代基,该取代基为碳原子数为1~20的烷基、碳原子数为6~30的芳基、碳原子数为7~30的芳烷基或碳原子数为2~20的杂环基, [0019] Rii, R12 and R "each independently represent an atom or a substituent amino group, which substituent is an alkyl group having a carbon number of 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, 7 aralkyl, or to 30 carbon atoms, heterocyclic group having 2 to 20,

[0020] Rii、Ri2和R "所表示的取代基的氨原子还可W进一步被0R2\ C0R2\ SR2\ NR22R23、 C0NR22r23、一nr22- OR 23、- nr22c〇- 0C0R23、一c(= N - 0R2i)- r22、一C(= N - 0C0R21)-R22、CN、面原子、一C00R21、一CR21= CR 22r23、- CO - CR21= CR 22r23、- 0 - CO - CR21 = CR22r23、一N = C = 0或环氧基取代, Substituted amino group [0020] Rii, Ri2 and R "represented by W may be further 0R2 \ C0R2 \ SR2 \ NR22R23, C0NR22r23, a nr22- OR 23, - nr22c〇- 0C0R23, a c (= N - 0R2i) - r22, a C (= N - 0C0R21) -R22, CN, surface atom, a C00R21, a CR21 = CR 22r23, - CO - CR21 = CR 22r23, - 0 - CO - CR21 = CR22r23, a N = C = 0 or an epoxy group,

[0021] R2\ R22和R 23分别独立地表示氨原子或取代基,该取代基为碳原子数为I~20的烷基、碳原子数为6~30的芳基、碳原子数为7~30的芳烷基或碳原子数为2~20的杂环基, [0021] R2 \ R22 and R 23 each independently represent a substituted amino group or atom, and the substituent is an alkyl carbon atoms, I ~ 20 carbon atoms, aryl group having 6 to 30 carbon atoms, 7 aralkyl, or to 30 carbon atoms, heterocyclic group having 2 to 20,

[0022] R2\R22和R 23所表示的取代基的氨原子还可W进一步被CN、面原子、径基或簇基取代, Substituted amino group [0022] R2 \ R22 R 23 and W may be further represented by the CN, the surface atoms, substituted or cluster path group,

[002引护、护、护、护1、护嘴323所表示的取代基的亚烷基部分还可^被一0-、一8-、一COO -、一OCO -、一NR24-、一NR2化00 -、一0C0NR24-、一SCO -、一COS -、一OCS -或一CSO -中断1~5次, [002 cited protection, protection, care, nursing 1, the nozzle guard 323 represents a substituent group of alkylene moiety may be a ^ 0-, a 8-, a COO -, a OCO -, a NR24-, a NR2 of 00 - a 0C0NR24-, a SCO -, a COS -, a OCS - or a CSO - interrupted 1 to 5 times,

[0024] RM表示氨原子、碳原子数为1~20的烷基、碳原子数为6~30的芳基、碳原子数为7~30的芳烷基或碳原子数为2~20的杂环基, [0024] RM represents ammonia atoms, carbon atoms, alkyl having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or 2 to 20 heterocyclyl,

[00巧]护、护、护、护1、护2和1?23所表示的取代基的烷基部分可^具有分支侧链、也可^为环状烷基,另外,Ri2与R "W及R22与R23也可W分别一起形成环, [00 Qiao] protection, protection, protection, a guard, and the guard 2 1? Alkyl moieties having substituents represented 23 may have a branched side chains ^, ^ may be a cyclic alkyl group, further, Ri2 of the R " W and W R22 and R23 may together form a ring, respectively,

[002引X表示氧原子、硫原子、砸原子、CRSIR32、C0、NR33或PR 34, [002 primer X represents an oxygen atom, a sulfur atom, smashing atoms, CRSIR32, C0, NR33 or PR 34,

[0027] R3i、r32、r33和RM分别独立地表示氨原子或取代基,该取代基为碳原子数为1~20 的烷基、碳原子数为6~30的芳基或碳原子数为7~30的芳烷基, [0027] R3i, r32, r33 and RM are each independently represent a substituted amino group or atom, a substituted aryl group the number of carbon atoms or carbon atoms of the alkyl group having 1 to 20 carbon atoms is 6 to 30 an aralkyl group having 7 to 30,

[0028] R3\ R32、R33和R34所表示的取代基的烷基部分可W具有分支侧链,也可W为环状烧基,护、R32、R3嘴R 34所表示的取代基的烷基末端也可W是不饱和键,R R32、R3嘴R34也可W分别独立地与邻接的任何一个苯环一起形成环, [0028] R3 \ alkyl moieties having substituents R32, R33 and R34 represented by W may have a branched side chain, a substituted alkyl group W may also be a cyclic group burned, care, R32, R3 represented by R 34 nozzle W is a terminal group may be an unsaturated bond, R R32, R3 R34 mouth W may each independently be a benzene ring with any adjacent form a ring,

[0029] a表示0~4的整数, [0029] a represents an integer of 0 to 4,

[0030] b表示1~5的整数, [0030] b represents an integer of 1 to 5,

[0031] r4中的至少一个是具有_ CR2i= CR22r23、_ CO _ CR2i= CR22r23、_ 0 _ CO _ CR21 =CR22r23、一N = C = 0或环氧基的基团。 The [0031] r4 having at least one _ CR2i = CR22r23, _ CO _ CR2i = CR22r23, _ 0 _ CO _ CR21 = CR22r23, a group N = C = 0 or an epoxy group. )

[0032] 另外,本发明提供一种感光性组合物,其是含有上述光聚合引发剂和具有締键式不饱和键的聚合性化合物而形成的。 [0032] Further, the present invention provides a photosensitive composition containing the photopolymerization initiator and a compound having a polymerizable unsaturated bond formed by the association button.

[0033] 另外,本发明提供一种碱显影性感光性树脂组合物,其是在上述感光性组合物中含有赋予碱显影性的化合物而形成的。 [0033] Further, the present invention provides an alkali-developable photosensitive resin composition, which is a compound containing impart alkali developability is formed in said photosensitive composition.

[0034] 另外,本发明提供一种着色碱显影性感光性树脂组合物,其是在上述碱显影性感光性树脂组合物中进一步含有着色剂而形成的。 [0034] Further, the present invention provides a colored alkali-developable photosensitive resin composition, which further comprises a colorant in the above-described alkali-developable photosensitive resin composition formed.

[0035] 另外,本发明提供一种固化物,其是通过对上述感光性组合物、上述碱显影性感光性树脂组合物或上述着色碱显影性感光性树脂组合物照射能量射线而形成的。 [0035] Further, the present invention provides a cured product which is obtained by the above-described photosensitive composition, the above-described alkali-developable photosensitive resin composition or the colored alkali-developable photosensitive resin composition formed by irradiating energy rays.

[003引发明的效果 [003 The effects of the initiator of

[0037] 本发明的朽醋化合物在可见光区域的透射率较高,对于365nm ( i线)等亮线可W 高效地产生自由基,作为光聚合引发剂是有用的。 [0037] The compounds of the invention rot vinegar in a higher transmittance of the visible light region, for 365nm (i-line) like bright lines W can efficiently generate a radical as a photopolymerization initiator is useful. 另外,本发明的目亏醋化合物当作为光聚合引发剂配合于树脂组合物中使用时,可W与具有聚合性基团的树脂反应,因而升华物较少, 进而能够提高固化物的耐热性。 Further, the compounds of the present invention vinegar head loss when fitted as the photopolymerization initiator in the resin composition is used, the reaction may be the resin having a polymerizable W group, thereby sublimate was less, and further possible to improve the heat resistance of the cured product sex.

具体实施方式 Detailed ways

[003引下面,对本发明的朽醋化合物和含有该化合物的光聚合引发剂进行详细说明。 [003 cited below, the compounds of the present invention rotten vinegar and a photopolymerization initiator containing the compound described in detail.

[0039] 本发明的目亏醋化合物是上述通式(1)所表示的新型化合物。 [0039] Deficit vinegar mesh compounds of the invention are novel compounds of the formula (1) represents. 该目亏醋化合物因目亏的双键而存在2种几何异构体,但本发明并不将它们区分。 The head loss due to head losses vinegar compounds exist two kinds of double bond geometric isomers, but the present invention does not distinguish between them.

[0040] 目P,在本说明书中,上述通式(1)、后述的表示上述通式(1)所表示的化合物的优选形态的通式(2)、W及例示化合物No. 1~No. 39的化学结构式仅表示了2种几何异构体中的1种,但本发明的目亏醋化合物不限定于运些化学式所表示的几何异构体,也可W是另一种几何异构体,也可W是2种几何异构体的混合物。 [0040] P mesh, in the present specification, the formula (1), represented by the above general formula (1) of the preferred embodiment of the compounds represented by the general formula (2) described below, W, and exemplified compound No. 1 ~ No. 39 chemical structural formulas represent only one kind of the two kinds of geometrical isomers, the head loss vinegar compound of the invention is not limited to these geometrical isomers operation represented by the formula, W may be another geometric isomers, W may also be a mixture of two geometric isomers.

[0041] 作为上述通式(1)中的Rii、护、R"、R2\ R22、R23、R24、护、R32、R 33、R34所表示的碳原子数为1~20的烷基,可W列举出例如甲基、乙基、丙基、异丙基、下基、异下基、仲下基、叔下基、戊基、异戊基、叔戊基、己基、庚基、辛基、异辛基、2-乙基己基、叔辛基、壬基、异壬基、 癸基、异癸基、十一烷基、十二烷基、十四烷基、十六烷基、十八烷基、二十烷基、环戊基、环己基、环己基甲基等。 [0041] Examples of the general formula (1) Rii, retaining, R ", R2 \ R22, R23, R24, nursing, R32, R 33, carbon atoms represented by R34 is an alkyl group having 1 to 20, may be W include methyl, ethyl, propyl, isopropyl, the group, the isobutyl group, sec-lower group, the tertiary, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl , iso-octyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, ten octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl and the like.

[004引作为上述通式(1)中的护、护、护、护1、护2、护3、护4、护、炒2、护、炒4所表示的碳原子数为6~30的芳基,可W列举出例如苯基、甲苯基、二甲苯基、乙基苯基、糞基、蔥基、菲基、 被1个W上的上述烷基取代后的苯基、联苯基、糞基、蔥基等。 [004 cited above general formula (1) in the protection, care, care, nursing 1, guard 2, 3 care, nursing 4, retaining, fried 2, retaining, fried indicated number of carbon atoms is 4 to 30 6 an aryl group, W may include e.g. phenyl, tolyl, xylyl, ethylphenyl, fecal group, onions, phenanthrenyl, the above-described alkyl group substituted with a W on the phenyl, biphenyl , manure-based, onions and the like.

[0043] 作为上述通式(1)中的Rii、护、R"、R2\ R22、R23、R24、护、R32、R 33、R34所表示的碳原子数为7~30的芳烷基,可W列举出例如苄基、a -甲基苄基、a,a -二甲基苄基、苯基乙基等。 [0043] Examples of the general formula (1) Rii, retaining, R ", R2 \ R22, R23, R24, nursing, R32, R 33, carbon atoms represented by R34 arylalkyl group having 7 to 30, W may include, for example, a benzyl group, a - methylbenzyl, A, a - dimethylbenzyl, phenylethyl and the like.

[0044] 作为上述通式(1)中的Rii、护、R"、R2\ R22、R23、R24所表示的可W被取代的碳原子数为2~20的杂环基,可W优选列举出例如化晚基、喀晚基、巧喃基、嚷嗯基、四氨巧喃基、 二氧杂环戊基、苯并嗯挫一2 -基、四氨化喃基、化咯烷基、咪挫烷基、化挫烷基、嚷挫烷基、 异嚷挫烷基、嗯挫烷基、异嗯挫烷基、赃晚基、赃嗦基、吗嘟基等5~7元杂环。 [0044] Examples of the general formula (1) Rii, retaining, R ", the number of carbon atoms in R2 \ R22, R23, R24 can be represented by W is a substituted heterocyclic group having 2 to 20, preferably, W may be an example of the later group, Ka late group, Qiao, tetrahydrothiopyranyl, cried ah group, tetrahydrothiopyranyl tetraammine Qiao, dioxolanyl, benzo ah a setback 2 - group, tetra amide, tetrahydrothiopyranyl, pyrrolidinyl of , imidazole fell alkyl, alkyl of frustration, cried setback alkyl, iso-alkyl cried setback, ah setback alkyl, iso-alkyl setback ah, stolen late group, stolen winded group, morpholinyl group beep 5 to 7-membered heteroaryl ring.

[0045] 上述通式(1)中,作为Ri2与R "、R22与R23可W-起形成的环W及R3\R32、R 33和R34 可W与邻接的苯环一起形成的环,可W优选列举出例如环戊烧环、环己烧环、环戊締环、苯环、赃晚环、吗嘟环、内醋环、内酷胺环等5~7元环。 [0045] The above formula (1), examples of Ri2 and R ", R22 and R23 may together form a ring W- W and R3 \ R32, R 33 and W may be and R34 together form a benzene ring adjacent to the ring may preferred W include e.g. cyclopentyl ring burn, burn cyclohexyl ring, cyclopentyl associative ring, a benzene ring, the ring later stolen, it beep 5 to 7-membered ring ring, vinegar ring, the ring amine cool.

[0046] 另外,上述通式(1)中,作为可W取代Rii、护、R"、R2\ R22、R23的面原子,可W列举出氣、氯、漠、舰。 [0046] Further, in the above general formula (1), as a W substituent Rii, retaining, R ", R2 \ R22, R23 faces atoms, W may be include air, chlorine, desert, ship.

[0047] 另外,护、护、R"、R2\ R22、R23所表示的取代基的亚烷基部分也可W被一0 -、一S -、一COO -、一OCO -、一NR24-、一NR 24〇00 -、一OCONR^^-、一SCO -、一COS -、一OCS -或一CSO -中断1~5次,此时中断的连结基团也可W是1种或2种W上的基团,在为能够连续中断的基团的情况下,也可W 2个W上的连结基团连续地中断。另外,上述取代基的烷基部分可W具有分支侧链,也可W是环状烷基。 [0047] Further, care, nursing, R ", a substituent of the alkylene moiety R2 \ R22, R23 may also be represented by W is a 0 -, a S - a COO -, a OCO - a NR24- , 24〇00 NR a -, a OCONR ^^ -, a SCO -, a COS -, the OCS a - a or the CSO - interrupt 1 to 5 times, the interrupt linking group may be one or two of W group on the W species, in the case where the group is continuously interrupted, W 2 may be two coupling groups on W continuously interrupted. Further, the alkyl portion of the substituent group W may have branched side chains, W may also be a cyclic alkyl group.

[0048] 本发明的目亏醋化合物中,上述通式(I)中,X是硫原子或NR33,并且R 33是可W具有分支侧链、可W为环状烷基的碳原子数为1~20的烷基的化合物;W及下述通式(2)表示的化合物由于感光度特别高,而且制造容易,所W是优选的。 [0048] Head loss vinegar compounds of the present invention, in the general formula (I), X is a sulfur atom or NR33, W and R 33 is a branched side chains having a number of carbon atoms may be cyclic alkyl group as W an alkyl group of 1 to 20; W, and the following compounds of formula (2) since a particularly high sensitivity, and ease of manufacture, the W is preferred.

[0049] [0049]

Figure CN103298782BD00061

[0050] (式中,1?1、护、炒、护^和3与上述通式(1)中的定义相同,护的定义与上述通式(1) 中的R4相同,至少R 5是具有至少一个选自一〇?21=〇?22护3、一〇)-〇?21=〇? 22护3、一0-CO - CR2i= CR 22r23、一N = C = 0和环氧基中的结构的基团,C表示0~4的整数。 [0050] (wherein, 1? 1, protection, fried, and 3 ^ retaining the general formula (Definition 1) are the same, the same retaining defined above general formula (1) R4, R 5 are at least having at least one selected ten billion = 21 3 22 nursing, ten) square -〇 21 = 22 guard 3, an 0-CO -???? CR2i = CR 22r23, a N = C = 0 and an epoxy group a group of the structure, C denotes an integer of 0 to 4. )

[0051] 上述通式(2)表示的化合物中,R5具有_0?21=0? 22护3、_0)_0?21=0?22护3或_ 0 - CO - CR2I= CR22R23的化合物由于反应性高,通过与具有不饱和双键的树脂组合物组合可W表现出高的耐热性,因而是更优选的,另外,R5具有一N = C = 0或环氧基的化合物通过与醇、胺、酷胺等具有活性氨的树脂组合可W表现出高的耐热性,因而同样是更优选的。 Compound [0051] the above formula (2) represented, R5 = 022 having a guard 21 _0 3 _0) _0 3 or guard 022 _ 0 21 = -???? CO - compound due CR2I = CR22R23 high reactivity, by having a combination of an unsaturated double bond W resin composition exhibits high heat resistance, and therefore is more preferable, further, R5 has a N = C = 0 group or an epoxy compound with alcohols, amines, amine cool resin composition having an active ammonia W can exhibit high heat resistance, and therefore the same is more preferable.

[0052] 另外,在更高地发挥本发明的效果方面,上述通式(1)和(2 )中的Ri和R 2优选为碳原子数为1~20 (特别优选为碳原子数为1~10,尤其优选为碳原子数为1~4)的烷基, 上述通式(1)和(2)中的a优选为0~1,上述通式(1)中的b优选为1~2,上述通式(2) 中的C优选为0~1。 [0052] Further, the higher effect of the present invention, the above general formula (1) and (2) Ri and R 2 is preferably a carbon number of 1 to 20 (more preferably 1 to carbon atoms 10, particularly preferably a carbon number of 1 to 4) alkyl group, the above general formula (1) and 2) to (a is preferably 0 to 1, the formula (1) is preferably 1 to 2 b the general formula (2) is preferably 0 to C 1.

[0053] 在更高地发挥本发明的效果方面,上述R3优选为氨原子。 [0053] In the higher effect of the present invention, the above-mentioned R3 is preferably ammonia atom. 由于同样的理由,上述X 优选为硫原子。 For the same reason, the above X is preferably a sulfur atom. 由于同样的理由,优选的是:上述R 4为OR 11或COOR 11,并且该Rii为碳原子数为1~20、特别是碳原子数为1~10、尤其是碳原子数为1~6的烷基,该Rii所具有的氨原子中的至少一个被一OCO - CR2I= CR 22R23取代,在该一OCO - CR2I= CR22R23中,R2I为氨原子或甲基,R22和R23为氨原子。 For the same reason, it is preferable that: the above-mentioned R 4 is OR 11 or COOR 11, and the Rii carbon atoms of 1 to 20, in particular the number of carbon atoms is 1 to 10, in particular the number of carbon atoms is 1 to 6 alkyl, Rii the ammonia has at least one atom is a OCO - CR2I = CR 22R23 substituted, in which a OCO - CR2I = CR22R23 in, R2I ammonia atom or a methyl group, R22 and R23 is ammonia atoms. 此时,当取代了OR 11的R 11所具有的氨原子时,一OCO -CR21= CR22r23优选与离该ORii的氧原子最远的位置的碳原子键合,当取代了COORii的Rii所具有的氨原子时,一OCO - CR21= CR 22r2优选与离该COOR 11的COO基最远的位置的碳原子键合。 At this time, when the substituent is OR R 11 11 atoms with ammonia, a OCO -CR21 = CR22r23 is preferably an oxygen atom from the farthest position ORii bonded to carbon atoms, as a substituent Rii has a COORii the ammonia atom, a OCO - carbon atom and preferably CR21 = CR 22r2 COOR COO group from the 11 position farthest engagement. 另外,优选的是:b为1,并且R4相对于X所键合的碳原子键合于对位。 Further, it is preferable that: b is 1, R4 and X with respect to the bonded carbon atom is bonded to the para position.

[0054] 作为上述通式(1)表示的本发明的目亏醋化合物的优选的具体例子,可W列举出W 下的化合物No. 1~No. 39的化合物。 [0054] Preferred compounds of vinegar loss goal of the present invention the above general formula (1) Specific examples of W include compounds under No. W 1 ~ No. 39 in. 不过,本发明不受W下化合物的任何限制。 However, the present invention is not restricted to any lower W compound.

[00 巧] [00 clever]

Figure CN103298782BD00071

Figure CN103298782BD00081

Figure CN103298782BD00091

Figure CN103298782BD00101

Figure CN103298782BD00111

[0060] 上述通式(I)表示的本发明的朽醋化合物没有特别限定,例如可W根据日本特开2000 - 80068号公報中记载的方法来制造。 [0060] The compounds of the present invention vinegar rotten by the general formula (I) is not particularly limited, for example, according to Japanese Patent Laid-Open W 2000-- manufacturing method described in Patent Publication No. 80,068. 作为方法之一,可W按照下述反应式1,使用W 下的方法来制造。 As one method, the W method according to following reaction formula 1, W manufactured. 首先,使酬体在路易斯酸存在下与(甲基)丙締酸反应,从而得到(甲基)丙締酸醋体。 First, the pay body and (meth) acrylic acid in the association of the presence of a Lewis acid, thereby obtaining (meth) acrylic associative vinegar thereof. 然后,在盐酸存在下使该(甲基)丙締酸醋体与亚硝酸醋反应,然后与酸酢或酷氯反应,得到上述通式(I)表示的本发明的朽醋化合物。 Then, in the presence of hydrochloric acid the (meth) acrylic associative vinegar vinegar body reaction with nitrous acid, followed by reaction with an acid chloride of Health or cool, to obtain the above general formula (I) is a compound of the invention rotten vinegar. 下述反应式I中记载了X为硫原子时的情况,但X为氧原子、砸原子、CRSIR32、NR33或PR34时的情况也可W按照上述的方法来制造。 Scheme I below describes a case when X is a sulfur atom, but X is an oxygen atom, smashing atoms, CRSIR32, NR33 or PR34 case when W may also be produced according to the method described above.

[00川反应式1 [00 Sichuan Scheme 1

Figure CN103298782BD00121

[006引(式中,R郝R2与上述通式(1)中的定义相同。) [006 primer (wherein R2 is the same as the above general formula R Hao (defined in 1).)

[0067] W上说明的本发明的新型目亏醋化合物作为光聚合引发剂是有用的。 [0067] The novel compounds of the present invention vinegar head loss of W as described in the photopolymerization initiator is useful.

[0068] 本发明的光聚合引发剂含有至少一种本发明的目亏醋化合物,特别是作为具有締键式不饱和键的聚合性化合物的光聚合引发剂是有用的。 [0068] The photopolymerization initiator of the present invention contains at least one compound vinegar head loss of the present invention, particularly a compound having a polymerizable unsaturated bond-button associated photopolymerization initiator is useful. 本发明的光聚合引发剂中的本发明的目亏醋化合物的含量优选为30~100质量%,更优选为50~100质量%。 Head loss vinegar content of the compounds of the present invention photopolymerization initiator agent of the present invention is preferably 30 to 100 mass%, more preferably 50 to 100 mass%. 本发明的光聚合引发剂除了含有本发明的朽醋化合物W外,还可W含有其它的光聚合引发剂。 The present invention is an optical polymerization initiator in addition to rot vinegar containing the inventive compound W, W may contain other photopolymerization initiator. 作为其它的光聚合引发剂,可W使用W往已知的化合物,可W列举出例如二苯甲酬、苯基联苯酬、 1- 径基-1-苯酷基环己烧、苯偶姻、苯偶酷双甲酸、1-苄基-1-二甲胺基-1- (4'-吗嘟代苯酷基)丙烷、2-吗嘟基-2- (4'-甲基琉基)苯酷基丙烷、嚷吨酬、1-氯-4-丙氧基嚷吨酬、 异丙基嚷吨酬、二乙基嚷吨酬、乙基蔥酿、4-苯酷基-4'-甲基二苯基硫化物、苯偶姻下酸、 As the other photopolymerization initiator, a known compound W to W may be used include, for example, W may be paid benzophenone, phenyl biphenyl paid, 1-phenyl-1-diameter cyclohexyl cool burning, benzoin benzoin, benzoin cool bis acid, 1-benzyl-1-dimethylamino-1- (4'-toluylene cool it beep yl) propane, 2-morpholin beep-2- (4'-methyl sulfur yl) phenyl propane cool, cried pay tons, 1-chloro-4-propoxy cried paid tons, isopropyl cried paid tons, diethyl cried paid tons, onions stuffed ethyl, 4-phenyl-4 cool '- methyl diphenyl sulfide, benzoin acid,

Figure CN103298782BD00122

[0070] 巧中,Ri、R2和R 33与上述通式(1)中的定义相同,Y 3表示面原子或烷基,n为0~ 2- 径基-2-苯酷基丙烷、2-径基-2- (4'-异丙基)苯酷基丙烷、4-下基苯酷基S氯甲烧、 4-苯氧基苯酷基二氯甲烧、苯酷基甲酸甲醋、1,7-双(9'-日丫晚基)庚烧、9-正下基-3, 6-双(2'-吗嘟代异下酷基)巧挫、2-甲基-4, 6-双(S氯甲基)-均S嗦、2-苯基-4, 6-双(S氯甲基)-均S嗦、2-糞基-4, 6-双(S氯甲基)-均S嗦、2, 2-双(2-氯苯基)-4, 5, 4',5' -四苯基-1-2'-联咪挫、4, 4-偶氮二异下腊、S苯基麟、精脑酿、N-1414、N-1717、N-1919、PZ-408、 NC I - 831、NC I - 930 (ADEKA 株式会社制造)、IRGACURE369、IRGACURE907、IRGACURE 0XE01、IRGACURE 0XE02 (BASF公司制造)、过氧化苯甲酯、下述通式(4)~(6)表示的化合物等。 [0070] In clever, Ri, R2, and R 33 defined above general formula (1) are the same, Y 3 represents a surface atom or alkyl, n is 0 ~ 2- phenyl-2-diameter cool propane, 2 - radial-2- (4'-isopropyl) benzene cool trimethylolpropane, 4-lower-yl S phenyl chloroformate cool burning, 4-phenoxybenzaldehyde cool methylene group burning, phenyl group cool acid methyl ester , 1,7-bis (9'-yl Night day Ah) heptyl burning, the 9-n-3, 6-bis (2'-isopropyl-generation beep it under cool-yl) clever setback, 2-methyl-4 , 4,6-bis (chloromethyl S) - S were winded, 2-phenyl-4,6-bis (chloromethyl S) - S were winded, 2 fecal group 4,6-bis (chloromethyl S yl) - S were winded, 2, 2-bis (2-chlorophenyl) -4, 5, 4 ', 5' - tetraphenyl -1-2'- setback associated microphone, 4,4-azobis under different wax, S Lin phenyl, brain fine wine, N-1414, N-1717, N-1919, PZ-408, NC I - 831, NC I - 930 (ADEKA Co., Ltd.), IRGACURE369, IRGACURE907, IRGACURE 0XE01, compound IRGACURE 0XE02 (BASF Corp.), benzoyl peroxide, methyl following general formula (4) to (6). 当使用运些本发明的除目亏醋化合物W外的光聚合引发剂时,可W使用一种或两种W 上组合使用。 When using op some other outer head losses vinegar compound W of the invention the photopolymerization initiator, W may be a combination of one or two W on use.

[0069] 5。 [0069] 5. )

[0071] [0071]

Figure CN103298782BD00131

[007引(式中,R\ R2和R33与上述通式(I)中的定义相同,Y郝n的定义与上述通式(4) 相同,Rl和R '2的定义与Rl和R 2相同,R '33的定义与R 33相同,Y '3的定义与Y 3相同,R 8表示二醇残基或二硫醇残基,Z5表示氧原子或硫原子。) [007 primer (in the formula, R \ R2, and R33 in the general formula (I) are the same as defined the same as defined Hao Y n in the general formula (. 4), Rl and R 'and R 2 are as defined Rl 2 identical, R '33 definition as R 33, Y define the 3 'and Y 3 is the same, R 8 represents a diol residue or a dithiol residue, Z5 represents an oxygen atom or a sulfur atom.)

[0073] [0073]

Figure CN103298782BD00132

[0074] 试中,Ri、r2和R33与上述通式(1)中的定义相同,Y郝n的定义与上述通式(4) 相同,Z6表示氧原子、硫原子或砸原子,A表示杂环基,t为0~5的整数,U为0或1。 [0074] Trials, Ri, r2, and R33 defined above general formula (1) are the same, the same definition Hao Y n in the general formula (4), Z6 represents an oxygen atom, a sulfur atom or a drop atom, A represents a heterocyclic group, t is an integer of 0 to 5, U is 0 or 1. )

[007引下面,对本发明的感光性组合物进行详细说明。 [007 cited below, the photosensitive composition of the invention will be described in detail.

[0076] 本发明的感光性组合物中,作为必要成分,含有(A)本发明的光聚合引发剂和(B) 具有締键式不饱和键的聚合性化合物,作为任意成分,组合含有(C)无机化合物、(D)着色剂、溶剂等成分。 [0076] The photosensitive composition of the present invention, as essential components, a photopolymerization (A) of the present invention, initiator and (B) a polymerizable compound having an unsaturated bond association button, as an optional component, a combination comprising ( C) is an inorganic compound, (D) a colorant, and a solvent.

[0077] 在本发明的感光性组合物中,(A)本发明的光聚合引发剂的含量没有特别限定,但本发明的感光性组合物中的本发明的朽醋化合物的含量相对于(B)具有締键式不饱和键的聚合性化合物100质量份优选为1~70质量份,更优选为1~50质量份,最优选为5~30 质量份。 [0077] In the photosensitive composition of the present invention, the light (A) of the present invention, the content of the polymerization initiator is not particularly limited, but the content of the compound rotten vinegar photosensitive composition of the present invention with respect to the present invention ( B) having a unsaturated bond association of 100 parts by mass of the polymerizable compound is preferably 1 to 70 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 5 to 30 parts by mass.

[007引作为上述(B)具有締键式不饱和键的聚合性化合物,没有特别限定,可W使用W往用于感光性组合物的化合物,可W列举出例如乙締、丙締、下締、异下締、氯乙締、偏氯乙締、 偏氣乙締、四氣乙締等不饱和脂肪族控;(甲基)丙締酸、a-氯代丙締酸、衣康酸、马来酸、 巧康酸、富马酸、纳迪克酸(himic acid)、己豆酸、异己豆酸、乙酸乙締醋、乙酸締丙醋、肉桂酸、山梨酸、中康酸、班巧酸单巧-(甲基)丙締酷氧基乙基]醋、邻苯二甲酸单巧-(甲基)丙締酷氧基乙基]醋、簇基聚己内醋单(甲基)丙締酸醋等在两末端具有簇基和径基的聚合物的单(甲基)丙締酸醋;径基乙基(甲基)丙締酸醋-苹果酸醋、径基丙基(甲基)丙締酸醋-苹果酸醋、二环戊二締-苹果酸醋或具有1个簇基和2个W上的(甲基)丙締酷基的多官能(甲基)丙締酸醋等不饱和多元酸;( [007 cited as a polymerizable unsaturated bond having the above formula associative bond (B), is not particularly limited, and W can be used for the photosensitive composition to the W compound may include, for example, W associative acetate, propionate association, the association, under different association, association chloride, vinylidene chloride association, association acetate gas partial, four gas b associative unsaturated aliphatic control; (meth) acrylic acid association, association A- chloro propionic acid, itaconic acid , maleic acid, mesaconic acid Qiao, fumaric acid, nadic acid (himic acid), hexanoic acid beans, beans isohexyl acid, ethyl acetate association acetate, propyl acetate association acetate, cinnamic acid, sorbic acid, mesaconic acid, ban Qiao Qiao acid mono - (meth) acrylic associative cool oxyethyl] acetate, phthalate Qiao - (meth) acrylic associative cool oxyethyl] vinegar, vinegar cluster group polycaprolactone mono (meth ) propan-like vinegar association with single diameter and the polymer clusters group-containing (meth) propan associated vinegar at both ends; diameter ethyl (meth) acrylic associative vinegar - apple vinegar, propyl diameter (meth) acrylic associative vinegar - apple vinegar, dicyclopentadiene association - apple vinegar or a polyfunctional (meth) acrylic group on the associative cool a cluster group, and 2 W (meth) acrylic vinegar association unsaturated polycarboxylic acids; ( 基)丙締酸-2-径基乙醋、(甲基)丙締酸-2-径基丙醋、(甲基)丙締酸缩水甘油醋、下述化合物No. Al~No. A4、(甲基)丙締酸甲醋、(甲基) 丙締酸下醋、(甲基)丙締酸异下醋、(甲基)丙締酸叔下醋、(甲基)丙締酸环己醋、(甲基)丙締酸正辛醋、(甲基)丙締酸异辛醋、(甲基)丙締酸异壬醋、(甲基)丙締酸硬脂醋、(甲基)丙締酸月桂醋、(甲基)丙締酸甲氧基乙醋、(甲基)丙締酸二甲基氨基甲醋、(甲基)丙締酸二甲基氨基乙醋、(甲基)丙締酸氨基丙醋、(甲基)丙締酸二甲基氨基丙醋、(甲基)丙締酸乙氧基乙醋、(甲基)丙締酸聚(乙氧基)乙醋、(甲基)丙締酸下氧基乙氧基乙醋、(甲基)丙締酸乙基己醋、(甲基)丙締酸苯氧基乙醋、(甲基)丙締酸四氨巧喃醋、(甲基)丙締酸乙締基醋、(甲基)丙締酸締丙醋、( Yl) propionic acid-2-associative diameter ethyl acetate, (meth) acrylic acid-2-associated path-yl propyl acetate, (meth) acrylic acid glycidyl associated vinegar, the following compound No. Al ~ No. A4, (meth) acrylic acid methyl ester association, (meth) acetate, (meth) acrylic acid isopropyl association associating the propionic acid under acetate, (meth) acetate, (meth) acrylic acid cyclic associated propan associated tert caprolactone, (meth) acrylic acid n-octyl associated vinegar, (meth) acrylic acid isooctyl associated vinegar, (meth) acrylic acid isononyl associated vinegar, (meth) acrylic acid stearyl associated vinegar, (meth ) propionic acid, lauryl association vinegar, (meth) acrylic acid methoxyethyl associative acetate, (meth) acrylic acid methylcarbamoyl associated vinegar, (meth) acrylic acid dimethyl amino ethyl acetate association, (A yl) propionic acid associated aminopropionate vinegar, (meth) acrylic acid dimethyl amino propyl associated vinegar, (meth) acrylic acid ethoxyethyl acetate association, (meth) acrylic acid associated poly (ethoxy) ethyl vinegar, (meth) propan-methoxyethoxy associated acid ethyl ester, (meth) acrylic associative ethylhexyl acetate, (meth) acrylic acid phenoxy ethyl ester associative, (meth) acrylic acid associated Qiao furans vinegar tetraamine, (meth) acrylic acid associative ethyl acetate associative group, (meth) acrylic acid associative associative propyl acetate, ( 基)丙締酸节醋、乙二醇二(甲基)丙締酸醋、二乙二醇二(甲基)丙締酸醋、S乙二醇二(甲基)丙締酸醋、聚乙二醇二(甲基)丙締酸醋、丙二醇二(甲基)丙締酸醋、1,4-下二醇二(甲基)丙締酸醋、1,6-己二醇二(甲基)丙締酸醋、S径甲基乙烧S (甲基) 丙締酸醋、=径甲基丙烷=(甲基)丙締酸醋、二季戊四醇六(甲基)丙締酸醋、二季戊四醇五(甲基)丙締酸醋、季戊四醇四(甲基)丙締酸醋、季戊四醇=(甲基)丙締酸醋、=环癸烧二径甲基二巧基)丙締酸醋、立[(甲基)丙締酷基乙基]异氯脈酸醋、聚醋巧基)丙締酸醋低聚物等不饱和一元酸和多元醇或多元酪的醋;(甲基)丙締酸锋、(甲基)丙締酸儀等不饱和多元酸的金属盐;马来酸酢、衣康酸酢、巧康酸酢、甲基四氨邻苯二甲酸酢、四氨邻苯二甲酸酢、=烷基四氨邻苯二甲酸酢、5- (2, 5-二氧代 Yl) propionic acid associated section vinegar, ethylene glycol di (meth) acrylic associative vinegar, diethylene glycol di (meth) acrylic associative vinegar, S ethylene glycol di (meth) acrylic associative vinegar, poly ethylene glycol di (meth) acrylic associative vinegar, propylene glycol di (meth) acrylic associative vinegar, the 1,4-hexanediol di (meth) acrylic associative vinegar, 1,6-hexanediol di ( meth) acrylic associative vinegar, S-methyl acetate diameter burning S (meth) acrylic associative vinegar, diameter = = methyl propane (meth) acrylic associative vinegar, dipentaerythritol hexa (meth) acrylic associative vinegar , dipentaerythritol penta (meth) acrylic associative vinegar, pentaerythritol tetra (meth) acrylic associative vinegar, = pentaerythritol (meth) acrylic associative vinegar, cyclodecyl = burnt skillfully dimethyl two diameter-yl) propionic acid associated unsaturated monocarboxylic acids and polyols or of casein vinegar, Li [(meth) acrylic associative cool ethyl] isobutyl chloro pulse vinegar, Qiao polyester-yl) propan-associative vinegar oligomer; (methyl metal salts of unsaturated polybasic acids) propionic acid associated front, (meth) acrylic acid, instrument, such association; Health maleic acid, itaconic acid Health, Health Qiao mesaconic acid, phthalic acid methyl tetraammine Health, tetraammine Health phthalic acid, phthalic = alkyl tetraammine of Health, 5- (2,5-dioxo 氨巧喃基)-3-甲基-3-环己締-1,2-二簇酸酢、=烷基四氨邻苯二甲酸酢-马来酸酢加成物、十二碳締基班巧酸酢、甲基纳迪克酸酢等不饱和多元酸的酸酢;(甲基)丙締酷胺、亚甲基双巧基)丙締酷胺、二乙S胺S巧基) 丙締酷胺、苯二甲基双(甲基)丙締酷胺、a -氯代丙締酷胺、N-2-径基乙基(甲基)丙締酷胺等不饱和一元酸和多元胺的酷胺;丙締醒等不饱和醒;(甲基)丙締腊、a -氯代丙締腊、 偏二氯乙締、締丙基氯等不饱和腊;苯乙締、4-甲基苯乙締、4-乙基苯乙締、4-甲氧基苯乙締、4-径基苯乙締、4-氯苯乙締、二乙締基苯、乙締基甲苯、乙締基苯甲酸、乙締基苯酪、乙締基横酸、4-乙締基苯横酸、乙締基苄基甲基酸、乙締基苄基缩水甘油酸等不饱和芳香族化合物;甲基乙締基酬等不饱和酬;乙締基胺、締丙基胺、N-乙締基化咯烧酬、乙締基赃晚等 Qiao Nan amino) -3-methyl-3-cyclohexene-1,2-associated cluster acid of Health, tetraammine = alkyl phthalates of Health - maleic acid adduct of Health, dodecene associative group Qiao acid class of Health, Health unsaturated polybasic acid, methanesulfonic acid, nadic acid, vinegar and the like; (meth) acrylic associative cool amines, methylene bis Qiao yl) propan-associative cool amine, diethyl amine S S Qiao-yl) propionic cool association amine, xylylene bis (meth) acrylic associative cool amine, a - chloropropionyl association cool amine, N-2- diameter ethyl (meth) acrylic associative cool amine unsaturated monocarboxylic and polycarboxylic acids cool amine amine; prop-unsaturated wake wake association; (meth) acrylic associative wax, a - chloro-propan association wax, associative vinylidene chloride, propyl chloride associative unsaturated wax; phenylethyl association, 4- association methylstyrene, 4-ethyl-phenethyl associative, 4-methoxy-phenethyl associative, 4- diameter phenethyl group association, 4-chloroacetophenone association, association diethyl benzene, toluene, ethyl associative group, b associative acid, ethyl benzene association casein, ethyl group cross-associative acid, 4-ethyl benzene cross-associative acid, ethanesulfonic acid associative benzyl methyl, benzyl ethyl associative unsaturated acid glycidyl aromatic compound; methyl ethyl associative unsaturated group paid pay; associative ethyl amine, propylamine association, N- ethyl associative group of paid slightly burned, b associative group and the like later stolen 饱和胺化合物;締丙醇、己豆醇等乙締基醇;乙締基甲基酸、乙締基乙基酸、正下基乙締基酸、异下基乙締基酸、締丙基缩水甘油酸等乙締基酸;马来酷亚胺、N-苯基马来酷亚胺、 N-环己基马来酷亚胺等不饱和酷亚胺类;巧、1-甲基巧等巧类;1,3-下二締、异戊二締、氯下二締等脂肪族共辆二締类;聚苯乙締、聚(甲基)丙締酸甲醋、聚(甲基)丙締酸正下醋、在聚硅氧烷等聚合物分子链的末端具有单(甲基)丙締酷基的大分子单体类;氯乙締、偏氯乙締、班巧酸二乙締基醋、邻苯二甲酸二締丙醋、憐酸=締丙醋、=締丙基异氯脈酸醋、乙締基硫酸、乙締基咪挫、乙締基嗯挫、乙締基巧挫、乙締基化咯烧酬、乙締基化晚、含径基的乙締基单体和聚异氯酸醋化合物的乙締基尿烧化合物、含径基的乙締基单体和聚环氧化合物的乙締基环氧化合物。 Unsaturated amine compound; associative propanol, ethyl hexyl alcohol beans associative alcohol; B-ylmethyl associative acid, ethanesulfonic acid associative ethyl, n-associative acid under ethyl, iso-associative acid under ethyl, propyl associated acetic acid glycidyl associative acid; cool maleic imide, N- phenylmaleimide cool imide, N- cyclohexylmaleimide unsaturated imide cool cool imines; Qiao, Qiao 1-methyl-like Qiao class; the two associative 1,3, isoprene association, the association aliphatic chlorodifluoromethane two vehicles were associated class; association polystyrene, poly (meth) acrylic acid methyl ester association, poly (meth) propionic acid, n-association under vinegar, macromonomer having a single class of (meth) acrylic group at the end associative cool polysiloxane polymer chains; chloroacetamide association, association vinylidene chloride, diethylammonium classes Qiao vinegar associative group, propyl acetate phthalate association, association pity acid = propyl acetate, iso-propyl chloride association = pulse vinegar, acetic acid associative group, ethyl group microphone associative setback, b associative group fell ah, associative group b Qiao setback, b group of the associative pay slightly burned, b associative group of late, ethyl diameter associative group-containing monomer and a polyisocyanate group acetic acid compound vinegar urinary burning compound associative group, ethyl group associative group-containing monomer diameter polyepoxides and epoxy compound b associative.

[0079] [0079]

Figure CN103298782BD00151

[0080] 另外,作为(B)具有締键式不饱和键的聚合性化合物,还可W使用丙締酸醋的共聚物、苯酪和/或甲酪酪醒清漆环氧树脂、具有多官能环氧基的聚苯基甲烧型环氧树脂、环氧丙締酸醋树脂、W及使不饱和一元酸与下述通式(3 )表示的环氧化合物等环氧化合物作用、 进而使多元酸酢与其作用而得到的树脂。 [0080] Further, as the (B) polymerizable compound having an unsaturated bond association button may also be used propan associative copolymer of vinegar W, benzene casein and / or caseinate caseinate wake A novolac epoxy resins, polyfunctional polyphenyl a type epoxy resin of epoxy group-burn, glycidoxy association vinegar resin, W, and an unsaturated monobasic acid and an epoxy compound on the following formula (3) epoxy compounds represented thereby enabling Health action polyacid resin obtained therewith. 其中,优选的是,使不饱和一元酸与下述通式(3) 表示的环氧化合物等环氧化合物作用、进而使多元酸酢与其作用而得到的树脂。 Among them, preferred is an epoxy compound effect (3) an epoxy compound represented by the unsaturated monocarboxylic acid with the following formula, and thus its action of Health polybasic acid resin obtained. 另外,上述化合物优选含有0. 2~1. 0当量的不饱和基团。 Further, the compound preferably contains 0.2 ~ 1.0 equivalents of unsaturated groups.

[0081] [0081]

Figure CN103298782BD00152

[0082] (式中,公表示直接键、亚甲基、碳原子数为1~4的烧叉基、碳原子数为3~20的脂环式控基、0、S、S化、SS、SO、C0、OCO或下述[i]、[ii]或[iii]表示的取代基,上述烧叉基也可W被面原子取代,RS1、R 52、R53和R54分别独立地表示氨原子、碳原子数为1~5的烧基、碳原子数为1~8的烷氧基、碳原子数为2~5的链締基或面原子,上述烷基、烷氧基和链締基也可W被面原子取代,m为0~10的整数,当m不为0时,存在的光学异构体可W是任何一种异构体。) [0082] (wherein, the public represents a direct bond, methylene, carbon atoms burning-group having 1 to 4 carbon atoms, 3 to 20 aliphatic cyclic control group, 0, S, S of, SS , SO, C0, OCO, or the following [i], [ii], or [III] represents a substituent group, the above-described burning-yl may be substituted with W atoms quilt, RS1, R 52, R53 and R54 each independently represent an ammonia atoms, carbon atoms fired group having 1 to 5 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a chain associated group having 2 to 5 atoms surface, said alkyl, alkoxy and associated chain W group may be substituted by the surface atoms, m is an integer of 0 to 10, and when m is not 0, the presence of optical isomers may be any of a W isomer.)

[0083] [0083]

Figure CN103298782BD00153

[0084] (式中,Z3表示氨原子、可W被碳原子数为I~10的烷基或碳原子数为I~10的烷氧基取代的苯基、或可W被碳原子数为1~10的烷基或碳原子数为1~10的烷氧基取代的碳原子数为3~10的环烷基,Yi表示碳原子数为1~10的烷基、碳原子数为1~10 的烷氧基、碳原子数为2~10的链締基或面原子,上述烷基、烷氧基和链締基也可W被面原子取代,d为0~5的整数。) [0084] (wherein, Z3 represents ammonia atom, W is an alkyl group having a carbon number or carbon atoms of I ~ 10 I ~ 10 alkoxy substituted phenyl, or W is the number of carbon atoms, carbon atoms, or an alkyl group having 1 to 10 carbon atoms, a substituted alkoxy group having 1 to 10, a cycloalkyl group having 3 to 10, Yi represents the number of carbon atoms, alkyl having 1 to 10 carbon atoms, 1 alkoxy ~ 10 carbon atoms or a chain associated group having 2 to 10 atoms surface, said alkyl, alkoxy and W chain associative groups may be substituted by the surface atoms, d is an integer of 0 to 5)

[0085] [0085]

Figure CN103298782BD00161

[0086] (式中,Y2和Z4分别独立地表示可W被面原子取代的碳原子数为1~10的烷基、可W被面原子取代的碳原子数为6~20的芳基、可W被面原子取代的碳原子数为6~20的芳氧基、可W被面原子取代的碳原子数为6~20的芳硫基、可W被面原子取代的碳原子数为6~20的芳链締基、可W被面原子取代的碳原子数为7~20的芳烷基、可W被面原子取代的碳原子数为2~20的杂环基、或面原子,上述烷基和芳烷基中的亚烷基部分也可W被不饱和键、一0 -或一S -中断,邻接的Z4之间也可W形成环,P表示0~4的整数,q表示0~8的整数,:T表示0~4的整数,S表示0~4的整数,:T与S的数的合计为2~4的整数。) [0086] (wherein, Y2 and Z4 each independently represent a substituted carbon atoms can quilt W atoms alkyl group having 1 to 10 carbon atoms may be substituted with W atoms quilt aryl group having 6 to 20, number of carbon atoms can be carbon atoms and W is quilt atoms substituted aryloxy group having 6 to 20, may be substituted quilt W atoms arylthio group having 6 to 20 carbon atoms may be substituted with W 6 atoms quilt ~ 20 aryl group associated chain of carbon atoms can quilt W atoms substituted aralkyl group having 7 to 20 carbon atoms may be substituted with W atoms quilt heterocyclic group having 2 to 20, or a surface atom, above alkyl and aralkyl alkylene moiety W may be an unsaturated bond, 10 -, or an S - interrupted between adjacent W Z4 may form a ring, P represents an integer of 0 to 4, q It represents an integer of 0 to 8,: T represents an integer of 0 to 4, and S represents an integer of 0 to 4: total number of S and T is an integer of 2 to 4).

[0087] 作为与上述环氧化合物作用的上述不饱和一元酸,可W列举出丙締酸、甲基丙締酸、己豆酸、肉桂酸、山梨酸、径基乙基甲基丙締酸醋-苹果酸醋、径基乙基丙締酸醋-苹果酸醋、径基丙基甲基丙締酸醋-苹果酸醋、径基丙基丙締酸醋-苹果酸醋、二环戊二締-苹果酸醋等。 [0087] The epoxy compound as the effect of the above unsaturated monobasic acid include propionic W may be associated acid, methacrylic acid association, beans hexanoic acid, cinnamic acid, sorbic acid, methyl ethyl diameter propionic acid associated vinegar - apple vinegar, vinegar associative diameter ethyl propionate - apple vinegar, propyl diameter methylpropanesulfonic associated vinegar - apple vinegar, vinegar associative diameter propyl propan - apple vinegar, dicyclopentadiene two association - apple vinegar and so on.

[0088] 另外,作为在使上述不饱和一元酸作用后使其作用的上述多元酸酢,可W列举出联苯基四簇酸二酢、四氨邻苯二甲酸酢、班巧酸酢、联苯四甲酸二酢、马来酸酢、偏苯=酸酢、均苯四酸酢、2, 2' -3, 3' -二苯甲酬四簇酸酢、乙二醇双偏苯=酸酢、丙=醇=偏苯= 酸酢、六氨邻苯二甲酸酢、甲基四氨邻苯二甲酸酢、纳迪克酸酢、甲基纳迪克酸酢、=烷基四氨邻苯二甲酸酢、六氨邻苯二甲酸酢、5- (2, 5-二氧代四氨巧喃基)-3-甲基-3-环己締-1,2-二簇酸酢、=烷基四氨邻苯二甲酸酢-马来酸酢加成物、十二碳締基班巧酸酢、甲基纳迪克酸酢等。 [0088] Examples of the polybasic acid in the vinegar so that the action of the unsaturated monobasic acid, the W may include biphenyltetracarboxylic acid clusters of Health, Health tetraammine phthalate, Qiao acid class of Health, Health-biphenyl tetracarboxylic acid, maleic acid Health, trimellitic acid = Health, Health pyromellitic acid, 2, 2 '-3, 3' - benzophenone pay four clusters of Health acid, ethylene glycol bis trimellitic = Health acid, propyl alcohol = = = trimellitic acid of Health, Health hexamine phthalate, methylcellulose phthalate, tetraammine of Health, Health nadic acid, methyl nadic acid of Health, phthalic = alkyl tetraammine Health-dicarboxylic acid, phthalic acid hexamine Health, 5- (2, 5-dioxo-thiopyran tetraamine clever) -3-methyl-3-cyclohexene-1,2-associated cluster acid Health, = alkyl phthalates tetraamine Health - maleic acid adduct of Health, dodecene-yl associative classes of Health clever acid, methyl nadic acid, vinegar and the like.

[0089] 上述环氧化合物、上述不饱和一元酸和上述多元酸酢的反应摩尔比优选如下设定。 [0089] the epoxy compound, the unsaturated monobasic acid and a molar ratio of the polybasic acid is preferably set as follows reaction of Health.

[0090] 目P,相对于上述环氧化合物的1个环氧基,上述不饱和一元酸的簇基为0. 1~1. 0 个,在具有W该比例加成后的结构的环氧加成物中,优选达到下述比例,相对于该环氧加成物的I个径基,上述多元酸酢的酸酢结构为0.1 ~1.0 个。 [0090] P mesh, with respect to one epoxy group of the epoxy compound, the unsaturated monobasic acid group is 0.1 ~ cluster 1.0, the ratio of the epoxy having the structure W after the addition adducts, preferably to the following proportions, with respect to the diameter of the I group of the epoxy adduct, the configuration of the acid of Health Health polybasic acid is 0.1 to 1.0.

[0091] 上述环氧化合物、上述不饱和一元酸和上述多元酸酢的反应可W按照常规方法来进行。 [0091] the epoxy compound, the unsaturated monobasic acid, and the polybasic acid W Health reaction can be carried out according to conventional methods.

[0092] 上述具有締键式不饱和键的聚合性化合物中,使用具有酸值的化合物时,可W赋予本发明的感光性组合物碱显影性。 [0092] The compound having a polymerizable unsaturated bond in association button, when using a compound having an acid value of W can be imparted to the present invention is alkali-developable photosensitive composition. 当使用上述具有酸值的化合物时,其使用量在(B)成分中优选设定为50~99质量%。 When the above compound having an acid value, which is used in an amount in the component (B) is preferably set to 50 to 99 mass%.

[0093] 另外,上述具有酸值的化合物还可W通过与单官能或多官能环氧化合物反应而调节酸值后来使用。 [0093] Further, the compound having an acid value of W may also be adjusted by an acid value of the reaction with a monofunctional or polyfunctional epoxy compound used later. 通过调节上述具有酸值的化合物的酸值,可W改善感光性树脂的碱显影性。 By adjusting the acid value of the compound having an acid value of W can improve alkali-developable photosensitive resin. 上述具有酸值的化合物(即可W赋予碱显影性的具有締键式不饱和键的聚合性化合物) 的固体成分的酸值优选为5~120m巧OH / g的范围,单官能或多官能环氧化合物的使用量优选按照满足上述酸值的方式来选择。 The acid value of the above compound having an acid value (W can impart alkali-developable compound having a polymerizable unsaturated bond association) of the solid component is 5 ~ 120m clever OH / g range, monofunctional or polyfunctional epoxy compound is preferably used in an amount so as to satisfy the above acid value is selected.

[0094] 作为上述单官能环氧化合物,可W列举出甲基丙締酸缩水甘油醋、甲基缩水甘油酸、乙基缩水甘油酸、丙基缩水甘油酸、异丙基缩水甘油酸、下基缩水甘油酸、异下基缩水甘油酸、叔下基缩水甘油酸、戊基缩水甘油酸、己基缩水甘油酸、庚基缩水甘油酸、辛基缩水甘油酸、壬基缩水甘油酸、癸基缩水甘油酸、十一烷基缩水甘油酸、十二烷基缩水甘油酸、十= 烷基缩水甘油酸、十四烷基缩水甘油酸、十五烷基缩水甘油酸、十六烷基缩水甘油酸、2-乙基己基缩水甘油酸、締丙基缩水甘油酸、烘丙基缩水甘油酸、对甲氧基乙基缩水甘油酸、苯基缩水甘油酸、对甲氧基缩水甘油酸、对下基苯酪缩水甘油酸、甲苯基缩水甘油酸、2-甲基甲苯基缩水甘油酸、4-壬基苯基缩水甘油酸、苄基缩水甘油酸、对枯基苯基缩水甘油酸、= 苯甲基缩水甘油酸、甲基丙締酸2, 3 [0094] Examples of the monofunctional epoxy compound, may be associated W-methylpropanesulfonic acid include glycidyl acetate, glycidyl methacrylic acid, ethacrylic acid, glycidyl, propyl glycidyl acid, glycidyl isopropyl acid, at glycidol acid, isostearic the group glycidic acid, tert-lower-yl glycidic acid, pentyl glycidyl acid, hexyl glycidyl acid, heptyl glycidyl acid, octyl glycidyl acid, nonyl glycidyl acid, decyl glycidic acid, glycidic undecyl, dodecyl glycidyl acid, glycidyl alkyl X = acid, tetradecyl glycidic acid, glycidic pentadecyl, hexadecyl glycidyl acid, 2-ethylhexyl glycidyl acid, glycidyl propyl associative acid, glycidyl propyl bake acid, p-methoxyethyl glycidyl acid, glycidyl phenyl acid, p-methoxy glycidyl acid, the phenyl glycidic acid casein, cresyl glycidyl acid, glycidyl 2-methyl glycerate tolyl, 4-nonylphenyl glycidyl acid, glycidyl acid benzyl group, p-cumyl phenyl glycidic acid, = benzyl glycidyl acid, 2-methylpropanesulfonic acid association, 3 -环氧丙醋、环氧化大豆油、环氧化亚麻仁油、下酸缩水甘油醋、乙締基环己烧一氧化物、1,2-环氧-4-乙締基环己烧、氧化苯乙締、氧化羡締、氧化甲基苯乙締、氧化环己締、氧化丙締、下述化合物No. EU No. E2等。 - epoxypropyl vinegar, epoxidized soybean oil, epoxidized linseed oil, vinegar acid glycidyl, cyclohexyl acetate associative burning monoxide, 1,2-epoxy-4-yl-cyclohexyl ethyl associative burn , styrene oxide associative oxide envy association, association methylstyrene oxide, cyclohexene oxide associative, oxypropylene association, the following compound No. EU No. E2 and the like.

[0095] [0095]

Figure CN103298782BD00171

[0096] 作为上述多官能环氧化合物,如果使用选自双酪型环氧化合物和缩水甘油酸类之中的一种W上的化合物,则可W得到特性更好的(着色)碱显影性感光性树脂组合物,因而是优选的。 [0096] Examples of the polyfunctional epoxy compound, if selected from casein bis type epoxy compound and compounds in a W acid glycidyl glycerol, better characteristics can be obtained W (colored) alkali developable photosensitive resin composition, which is preferable.

[0097] 作为上述双酪型环氧化合物,除了可W使用上述通式(3 )表示的环氧化合物之外, 还可W使用例如加氨双酪型环氧化合物等双酪型环氧化合物。 [0097] Examples of the casein-bis type epoxy compounds, in addition to the above general formula W (3) of the epoxy compound represented by, for example, W may also be a double-type epoxy compound ammoniated casein casein bis type epoxy compounds .

[0098] 另外,作为上述缩水甘油酸类,可W使用乙二醇二缩水甘油酸、丙二醇二缩水甘油酸、1,4-下二醇二缩水甘油酸、1,6-己二醇二缩水甘油酸、1,8-辛二醇二缩水甘油酸、 1,10-癸二醇二缩水甘油酸、2, 2-二甲基-1,3-丙二醇二缩水甘油酸、二乙二醇二缩水甘油酸、S乙二醇二缩水甘油酸、四乙二醇二缩水甘油酸、六乙二醇二缩水甘油酸、1,4-环己烧二甲醇二缩水甘油酸、1,1,IS(缩水甘油氧基甲基)丙烷、1,1,IS(缩水甘油氧基甲基) 乙烧、1, 1, 1-二(缩水甘油氧基甲基)甲烧、1, 1, 1, 1-四(缩水甘油氧基甲基)甲烧等。 [0098] Examples of the glycidyl acids, W may be acid ethylene glycol diglycidyl, propylene glycol diglycidyl acid, the 1,4-diol diglycidyl acid, 1,6-hexanediol diglycidyl glyceric acid, 1,8-octanediol diglycidyl acid, 1,10-decanediol diglycidyl acid, 2, 2-dimethyl-1,3-propanediol diglycidyl acid, diethylene glycol di glycidic acid, S acid diglycidyl glycol, tetraethylene glycol diglycidyl acid, hexaethylene glycol diglycidyl acid, 1,4-cyclohexane dimethanol diglycidyl burning acid, 1,1, IS (glycidyloxymethyl) propane, 1,1, IS (glycidyloxymethyl) ethane burning, 1, 1, 1-bis (glycidyloxymethyl) for methane, 1, 1, 1, 1- tetra (glycidyloxymethyl) for methane and the like.

[0099] 除此之外,还可W使用苯酪酪醒清漆型环氧化合物、联苯酪醒清漆型环氧化合物、 甲酪酪醒清漆型环氧化合物、双酪A酪醒清漆型环氧化合物、二环戊二締酪醒清漆型环氧化合物等酪醒清漆型环氧化合物;3, 4-环氧-6-甲基环己基甲基-3, 4-环氧-6-甲基环己烧簇酸醋、3, 4-环氧环己基甲基-3, 4-环氧环己烧簇酸醋、1-环氧乙基-3, 4-环氧环己烧等脂环式环氧化合物;邻苯二甲酸二缩水甘油醋、四氨化邻苯二甲酸二缩水甘油醋、二聚酸缩水甘油醋等缩水甘油醋类;四缩水甘油基二氨基二苯基甲烧、=缩水甘油基对氨基苯酪、 N,N-二缩水甘油基苯胺等缩水甘油基胺类;1,3-二缩水甘油基-5, 5-二甲基乙内酷脈、S 缩水甘油基异氯脈酸醋等杂环式环氧化合物;二氧化二环戊二締等二氧化物;糞型环氧化合物、=苯基甲烧型环氧化合物、二环戊二締型环氧化合物等。 [0099] In addition, also W YY wake benzene novolac epoxy compounds, biphenyl novolak type epoxy compound casein wake, wake YY A novolac-type epoxy compounds, novolak wake bis Casein casein A-ring oxygen compounds, dicyclopentadiene novolac type epoxy association casein wake wake casein compounds novolac epoxy compounds; 3,4-epoxy-6-methylcyclohexyl-3, 4-epoxy-6- cyclohexyl burn cluster vinegar, 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexyl burn cluster vinegar, 1-oxiranyl-3,4-epoxycyclohexyl fat burning and the like cyclic epoxy compounds; vinegar diglycidyl phthalate, diglycidyl phthalate, amides four glycerol vinegar, vinegar, dimeric acid glycidyl glycidyl vinegar; tetraglycidyl diaminodiphenyl A burn , = p-aminophenyl glycidyl casein, N, N- diglycidyl aniline, glycidyl amines; 1,3-diglycidyl -5, 5- dimethylhydantoin cool the vein, S glycidol isopropenyl chloro pulse heterocyclic epoxy compounds such as vinegar; bicyclic glutaric dioxide and other associative-dioxide; fecal type epoxy compounds, A = phenyl burning type epoxy compounds, dicyclopentadiene-type epoxy associative compound.

[0100] 作为本发明的感光性组合物中可W含有的上述(C)无机化合物,可W列举出例如氧化儀、氧化铁、氧化银、氧化铁、氧化锋、氧化儀、氧化巧、氧化钟、二氧化娃、氧化侣等金属氧化物;层状粘±矿物、米洛丽蓝、碳酸巧、碳酸儀、钻系、儘系、玻璃粉末(特别是玻璃料(glass化it))、云母、滑石、高岭±、亚铁氯化物、各种金属硫酸盐、硫化物、砸化物、娃酸侣、娃酸巧、氨氧化侣、销、金、银、铜等。 [0100] Examples of the (C) inorganic compound The photosensitive composition of the present invention may contain W, W may include apparatus such as oxidation, iron oxide, silver oxide, iron oxide, Feng oxide instrument oxide, Qiao oxide, bell, baby dioxide, metal oxides such as oxide, Lu; sticky ± layered mineral, Milori blue, Qiao carbonate, instrument, the drill system, make-based glass powder (especially glass frit (glass of IT)), mica, talc, kaolin ±, ferrous chloride, metal sulfates, sulfides, hit compounds, companion acid baby, baby clever acid, ammoxidation Lu, pin, gold, silver, copper and the like.

[0101] 其中,优选玻璃料、氧化铁、二氧化娃、层状粘±矿物、银等。 [0101] Among them, the glass frit, iron, baby dioxide, layered adhesive ± minerals, and silver. 本发明的感光性组合物中,(C)无机化合物的含量是,相对于(B)具有締键式不饱和键的聚合性化合物100质量份优选为0. 1~1000质量份,更优选为10~800质量份。 The photosensitive composition of the present invention, the content of (C) the inorganic compound is, with respect to the (B) polymerizable compound associative unsaturated bond having 100 parts by mass is preferably 0.1 to 1,000 parts by mass, more preferably 10 to 800 parts by mass. 此外,运些无机化合物可W使用1种或2种W上。 Further, these inorganic compounds may be transported using 1 W or two of W.

[0102] 上述无机化合物可W用作例如填充剂、防反射剂、导电剂、稳定剂、阻燃剂、机械强度提高剂、特殊波长吸收剂、防油墨剂等。 [0102] W may be used as the inorganic compound such as fillers, antireflection agents, electrically conductive agents, stabilizers, flame retardants, mechanical strength improving agents, specific wavelength absorbing agent, an ink and the like.

[0103] 另外,作为本发明的感光性组合物中可W含有的上述(D)着色剂,可W列举出颜料、染料、天然色素等。 [0103] Further, a photosensitive composition of the present invention may be above W (D) a colorant contained in W may include pigments, dyes, natural dyes. 运些着色剂可W单独使用或者2种W上混合使用。 These colorants may be transported W used alone or in combination on the W 2 thereof.

[0104] 作为上述颜料,可W使用例如亚硝基化合物;硝基化合物;偶氮化合物;重氮化合物;氧杂蔥化合物;哇嘟化合物;蔥酿化合物;香豆素化合物;献菁化合物;异吗I噪嘟酬化合物;异吗I噪嘟化合物;哇叮酬化合物;二并蔥酬化合物;紫环酬(perynone)化合物;巧化合物;二酬化咯并化咯化合物;硫說化合物;二嗯嗦化合物;=苯基甲烧化合物;哇献酬化合物;糞四簇酸;偶氮染料、菁染料的金属络合物;色淀颜料;用炉法、槽法、热裂解法得到的炭黑、或乙烘黑、科琴黑或灯黑等炭黑;将上述炭黑用环氧树脂进行调整或覆盖而得到的物质、将上述炭黑预先在溶剂中用树脂进行分散处理,并使其吸附20~200mg / g的树脂而得到的物质、将上述炭黑进行酸性或碱性表面处理而得到的物质、平均粒径为Snm W上且DBP吸油量为90ml / 100g W下的炭黑、由950°C下的挥 [0104] As the pigment, for example, W may be a nitroso compound; nitro compounds; azo compounds; diazo compounds; oxa compounds onions; wow beep compound; stuffed onions compound; coumarin compounds; cyanine compound offer; iso do I noise beep pay compound; heterologous do I noise beep compound; wow bite pay compound; two and onions pay compound; perinone pay (perynone) compound; Qiao compound; two pay of pyrrolo of slightly compounds; sulfur, said compound; two ah winded compound; = phenyl a compound burned; wow offer pay compound; fecal four cluster acid; azo dyes, metal complex cyanine dyes; lake pigments;, obtained by the channel furnace method, a thermal cracking process carbon black, or acetate bake black, ketjen black or carbon black, lamp black and the like; and the carbon black adjusted or covered with an epoxy resin material obtained by the treatment of the carbon black dispersed in advance with a resin in a solvent, and material, average particle diameter of the substance adsorbed 20 ~ 200mg / g of the resin obtained, the above-described acidic or basic carbon black surface is obtained on treatment Snm W and the DBP oil absorption of 90ml / 100g W char black, under the command of the 950 ° C 成分中的CO和C〇2算出的全氧量是每IOOm2表面积为9mg W上的炭黑雨墨、石墨化炭黑、活性炭、碳纤维、碳纳米管、螺旋状碳纤维、碳纳米突、碳气凝胶、富勒締;苯胺黑、颜料黑7、铁黑;氧化铭绿、米洛丽蓝、钻绿、钻蓝、儘系、亚铁氯化物、憐酸盐群青、普鲁±蓝、群青、钻天蓝、浓绿色颜料(viridian)、 悲翠绿、硫酸铅、铭黄、锋黄、氧化铁(红色氧化铁(III))、儒红、合成铁黑、栋±(amber)等有机或无机颜料。 C〇2 component CO and the total oxygen content was calculated per surface area of ​​carbon black is Yu Mo IOOm2 on 9mg W, graphitized carbon black, activated carbon, carbon fibers, carbon nanotubes, helical carbon fibers, carbon nanohorn, carbon gas gel, Fuller association; aniline black, pigment black 7, iron black; Ming oxide green, Milori blue, cobalt green, cobalt blue, make-based, iron chloride, salt pity ultramarine, Prussian blue ±, ultramarine, cobalt sky blue, dark green pigment (Viridian), sad green, lead sulfate, yellow Ming, Feng yellow, iron oxide (red iron oxide (III)), Ru red, synthetic iron black, Dong ± (amber) or organic inorganic pigment. 运些颜料可W单独使用或多种混合使用。 These pigments can be shipped W used alone or in combination of plural kinds.

[0105] 作为上述颜料,还可W使用市售的颜料,可W列举出例如颜料红1、2、3、9、10、14、 17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、 177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、 254 ;颜料澄13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71 ;颜料黄1、 3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、 120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、 185 ;颜料绿7、10、36 ;颜料蓝15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、56、60、61、62、 64 ;颜料紫1、19、23、27、29、30、32、37、40、50 等。 [0105] As the pigment, commercially available pigments may be W, W may include, for example, Pigment Red 1,2,3,9,10,14, 17,22,23,31,38,41,48,49 , 88,90,97,112,119,122,123,144,149,166,168,169,170,171, 177,179,180,184,185,192,200,202,209,215,216 , 217,220,223,224,226,227,228,240, 254; Cheng pigment 13,31,34,36,38,43,46,48,49,51,52,55,59,60,61 , 62,64,65,71; pigment yellow 1, 3,12,13,14,16,17,20,24,55,60,73,81,83,86,93,95,97,98,100 , 109,110,113,114,117, 120,125,126,127,129,137,138,139,147,148,150,151,152,153,154,166,168,175,180, 185 ; pigment green 7,10,36; pigment blue 15, 15: 1,15: 2,15: 3,15: 4,15: 5,15: 6,22,24,56,60,61,62, 64 ; pigment violet 1,19,23,27,29,30,32,37,40,50 and so on.

[0106] 作为上述染料,可W列举出偶氮染料、蔥酿染料、說类染料、=芳基甲烧染料、氧杂蔥染料、茜素染料、叮晚染料、巧染料、嚷挫染料、糞酪染料、哇嘟染料、硝基染料、吗I达胺染料、嗯嗦染料、献菁染料、菁染料等染料等,它们也可W多种混合使用。 [0106] Examples of the dyes include azo dyes may be W, onions stuffed dyes, said dyes, dyes burning A = aryl, oxa onions dyes, alizarin dyes, dyes late bite, Qiao dyes, dye cried setback, casein manure dyes, wow beep dyes, nitro dyes, amine dyes do I reach, ah winded dyes, cyanine dyes offer, dyes and other dyes, they may also be used in combination W variety.

[0107] 本发明的感光性组合物中含有(D)着色剂时,其含量相对于100质量份的(B)具有締键式不饱和键的聚合性化合物优选为50~350质量份,更优选为100~250质量份。 When the photosensitive composition [0107] of the present invention contains (D) a colorant, the content thereof with respect to 100 parts by mass of (B) having a unsaturated bond association polymerizable compound is preferably 50 to 350 parts by mass, more preferably 100 to 250 parts by mass. [010引另外,本发明的感光性组合物还可W含有不具有締键式不饱和键而赋予碱显影性的化合物,作为该化合物,只要是因具有酸值而可溶于碱水溶液的化合物,就没有特别限定,但作为代表性的化合物,可W列举出碱可溶性酪醒清漆树脂(W下仅称作"酪醒清漆树脂")。 [010 cited Further, the photosensitive composition of the present invention may further contain W no unsaturated bonds impart alkali developability with an association button, Examples of the compound having an acid value because as long as the aqueous alkali-soluble compound , is not particularly limited, but as a representative compound, W include alkali-soluble novolac resin wake casein (referred to as the W-only "wake casein novolak resin"). 酪醒清漆树脂可W在酸催化剂的存在下使酪类和醒类缩聚而得到。 W novolac resin may wake casein casein classes and class wake polycondensation in the presence of an acid catalyst to obtain.

[0109] 作为上述酪类,可W使用例如苯酪、邻甲酪、间甲酪、对甲酪、邻乙基苯酪、间乙基苯酪、对乙基苯酪、邻下基苯酪、间下基苯酪、对下基苯酪、2, 3 -二甲苯酪、2, 4-二甲苯酪、2, 5 -二甲苯酪、3, 4 -二甲苯酪、3, 5 -二甲苯酪、2, 3, 5 甲基苯酪、对苯基苯酪、氨酿、邻苯二酪、间苯二酪、2 -甲基间苯二酪、邻苯=酪、a -糞酪、双酪A、二径基苯甲酸醋、 没食子酸醋等,上述酪类中,优选苯酪、邻甲酪、间甲酪、对甲酪、2, 5 -二甲苯酪、3, 5 -二甲苯酪、2, 3, 5 甲基苯酪、间苯二酪、2 -甲基间苯二酪W及双酪A。 [0109] Examples of the casein-based, may be used, such as benzene casein W, o-tyrosine, m-tyrosine, para-tyrosine, o-ethylbenzene casein, caseinate between ethylbenzene, ethylbenzene of casein, casein benzene under o between the benzene casein, casein for the phenyl, 2, 3 - casein xylene, 2,4-xylene casein, 2, 5 - xylene casein, 3, 4 - xylene casein, 3, 5 - bis toluene casein, 2, 3, 5 methylbenzene casein, casein p-phenyl benzene, ammonia stuffed, phthalimido casein, casein isophthalic, 2 - casein-methylisophthalamide, phthalic = casein, a - casein dung , double-casein A, dicarboxylic acid diameter vinegar, vinegar and the like gallic the class casein, casein preferably benzene, o-tyrosine, m-tyrosine, para-tyrosine, 2, 5 - xylene casein, 3, 5 - xylene casein, 2, 3, 5 methylbenzene casein, casein isophthalic, 2 - W-methylisophthalamide casein and casein bis A. 上述酪类可W单独使用或两种W上混合使用。 Casein above class W alone or in combination using the two kinds of W.

[0110] 作为上述醒类,可W使用例如甲醒、多聚甲醒、乙醒、丙醒、苯甲醒、苯乙醒、a -苯丙醒、0 -苯丙醒、邻径基苯甲醒、间径基苯甲醒、对径基苯甲醒、邻氯苯甲醒、间氯苯甲醒、对氯苯甲醒、邻硝基苯甲醒、间硝基苯甲醒、对硝基苯甲醒、邻甲基苯甲醒、间甲基苯甲醒、对甲基苯甲醒、对乙基苯甲醒、对正下基苯甲醒等,上述化合物中,优选甲醒、乙醒W及苯甲醒。 [0110] Examples of the wake up type, for example, W can be A wake, paraformaldehyde wake, wake acetate, propionate wake, wake benzyl, phenethyl wake, a - benzenepropanoic awake, 0 - wake phenylpropyl, o-phenyl diameter A wake, wake benzyl group between the diameter, the diameter of the wake-yl benzoate, o-chlorobenzoic wake, wake A m-chlorophenyl, p-chlorophenyl A wake, wake o-nitrobenzoyl, m-nitrobenzoyl wake of wake-nitrobenzoyl, o-methylbenzoic wake, wake-methyl benzophenone, methyl benzophenone wake, wake-ethyl benzyl, p-n the wake benzyloxy group and the like, the above-mentioned compounds, A awake A, B and W benzoic wake up wake up. 上述醒类可W单独使用或两种W上混合使用。 W may be used to wake up the above-described type used alone or in combination on two kinds of W. 相对于每1摩尔的酪类,醒类优选W 0. 7~3摩尔、特别优选W 0. 7~2摩尔的比例来使用。 Per 1 mol of casein-based, wake preferred class W 0. 7 ~ 3 mol, particularly preferably W 0. 7 ~ 2 molar ratio used.

[0111] 作为上述酸催化剂,可W使用例如盐酸、硝酸、硫酸等无机酸、W及甲酸、草酸、乙酸等有机酸。 [0111] Examples of the acid catalyst, inorganic acids may be used, for example W as hydrochloric acid, nitric acid, sulfuric acid and the like, W, and formic acid, oxalic acid, acetic acid and the like. 上述酸催化剂的使用量是每1摩尔的酪类优选为1 X 10 4~5 X 10 1摩尔。 The amount of the acid catalyst per 1 mole of casein preferred class of 1 X 10 4 ~ 5 X 10 1 mol. 在缩合反应中,通常使用水作为反应介质,但如果缩合反应中使用的酪类不溶于醒类的水溶液, 反应初期就成为不均匀体系,则也可W使用亲水性溶剂作为反应介质。 In the condensation reaction, water is generally used as a reaction medium, but if the cheese-based condensation reaction is not soluble in aqueous solutions like awake, the initial reaction system becomes non-uniform, then W can be a hydrophilic solvent as the reaction medium. 作为上述的亲水性溶剂,可W列举出例如甲醇、乙醇、丙醇、下醇等醇类、或四氨巧喃、二嗯烧等环状酸类。 Examples of the hydrophilic solvent include, for example, W may be alcohols such as methanol, ethanol, propanol, lower alcohol, ammonia or tetra-thiopyran coincidence, two ah cyclic acid burn. 上述的反应介质的使用量通常是每100质量份的反应原料为20~1000质量份。 The amount of the reaction medium is generally above per 100 parts by mass of the reaction feed is from 20 to 1000 parts by mass. 缩合反应的反应溫度可W根据反应原料的反应性来适当调整,但通常为10~200°c,优选为70~150°C。 The reaction temperature of the condensation reaction may be appropriately adjusted W depending on the reactivity of the starting material, but is generally 10 ~ 200 ° c, preferably 70 ~ 150 ° C. 缩合反应结束后,为了除去体系内存在的未反应原料、酸催化剂和反应介质,一般要使内溫上升至130~230°C,并在减压下馈去挥发成分,然后将烙融的酪醒清漆树脂流延到不诱钢制的带上而进行回收。 After completion of the condensation reaction, the system memory in order to remove unreacted starting material, the acid catalyst and the reaction medium is generally increased to make the temperature of 130 ~ 230 ° C, under reduced pressure and feed off volatile components, and then baked into casein wake novolac resin cast onto the steel strip does not induce recovered.

[0112] 另外,缩合反应结束后,也可W将反应混合物溶解于前述的亲水性溶剂中,并添加到水、正己烧、正庚烧等沉淀剂中,由此使酪醒清漆树脂析出,分离析出物、加热干燥而进行回收。 [0112] Further, after the condensation reaction, the reaction mixture may be W is dissolved in the hydrophilic solvent and added to water, n-hexyl burning, n-heptyl and the like burning precipitant, whereby the casein precipitated novolak resin awake separating the precipitate was recovered and dried by heating.

[0113] 作为除上述酪醒清漆树脂W外的例子,可W列举出聚径基苯乙締或其衍生物、苯乙締一马来酸酢共聚物、聚乙締基径基苯甲酸等。 [0113] Examples of the addition to the novolac resin casein wake of W, W may include polyethylene or a derivative thereof associated path phenethyl group, a styrene maleic acid Health associative copolymer, polyvinyl acid and the like associated base diameter .

[0114] 本发明的感光性组合物中,根据需要还可W进一步添加溶剂。 [0114] The photosensitive composition of the present invention, if necessary, W may be further added a solvent. 作为该溶剂,通常是能够溶解或分散上述各成分((A)本发明的光聚合引发剂和(B)具有締键式不饱和键的聚合性化合物等)的溶剂,可W使用例如甲乙酬、甲基戊酬、二乙酬、丙酬、甲基异丙酬、甲基异下酬、环己酬、2-庚酬等酬类;乙酸、二嗯烧、四氨巧喃、1,2-二甲氧基乙烧、1,2 -二乙氧基乙烧、二丙二醇二甲酸等酸系溶剂;乙酸甲醋、乙酸乙醋、乙酸正丙醋、乙酸异丙醋、乙酸正下醋、乙酸环己醋、乳酸乙醋、班巧酸二甲醋、醇醋等醋系溶剂;乙二醇单甲酸、乙二醇单乙酸等溶纤剂系溶剂;甲醇、乙醇、异或正丙醇、异或正下醇、戊醇等醇系溶剂;乙二醇单甲基乙酸醋、乙二醇单乙基乙酸醋、丙二醇-1-单甲酸-2-乙酸醋、二丙二醇单甲酸乙酸醋、3-甲氧基下基乙酸醋、乙氧基乙基丙酸醋等酸醋系溶剂;苯、甲苯、二甲苯等BTX系溶剂;己烧、 庚烧 Examples of the solvent is generally capable of dissolving or dispersing the above respective components ((A) photopolymerization of the present invention, initiator and (B) a polymerizable compound having an unsaturated bond associative key type, etc.) of the solvent, may be W using e.g. methylethyl reward , methyl amyl paid, diethyl paid, propyl paid, methyl isopropyl paid, the pay methylisobutylketone, cyclohexanone paid, 2-heptanone, etc. paid pay type; acetic acid, burning ah, tetraammine clever furans, 1, b burn-dimethoxyethane, 1,2 - diethoxyethane burning, an acid-based solvent dipropylene glycol acid and the like; acid methyl acetate, acetic acid ethyl ester, acetic acid n-propyl acetate, isopropyl acetate, vinegar, the acetic acid n acetate, octyl acetate, cyclohexyl acetate, ethyl lactate acetate, dimethyl acid classes Qiao vinegar, vinegar, vinegar alcohol-based solvent; ethylene glycol mono-carboxylic acid, ethylene glycol monoethyl acetate cellosolve-based solvent; methanol, ethanol, isopropanol or n propanol, isopropyl alcohol or n the solvent, pentanol and the like; vinegar ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol 1-carboxylic acid 2-acetic acid acetate, dipropylene glycol monomethyl acid acetic acid, 3-acetic acid under methoxy, ethoxy ethyl propionate, vinegar, vinegar-based solvent; benzene, toluene, xylene, BTX solvents; burning hexyl, heptyl burn 辛烧、环己烧等脂肪族控系溶剂;松节油、D -巧樣締、羡締等祗締系控油;矿油精、 Swazol#310 (Cosmo松山石油株式会社)、Solvesso#100 (Exxon化学株式会社)等链烧控系溶剂;四氯化碳、氯仿、=氯乙締、二氯甲烧、1,2-二氯乙烧等面代脂肪族控系溶剂;氯苯等面代芳香族控系溶剂;卡必醇系溶剂;苯胺;S乙胺;化晚;乙酸;乙腊;二硫化碳;N,N-二甲基甲酯胺;N-甲基化咯烧酬;二甲亚讽;水等,运些溶剂可W使用1种,也可W使用2种W 上的混合溶剂。 Oct-burning, cyclohexyl burn control aliphatic solvents; turpentine, D - Oil-based associative Gion clever like association, association envy and the like; mineral spirits, Swazol # 310 (Cosmo Matsuyama Oil Corporation), Solvesso # 100 (Exxon Chemical Co., Ltd.) chain burn control based solvents; carbon tetrachloride, chloroform, ethylene chloride = association, burning dichloromethane, 1,2-dichloroethane and the like burn control surface-aliphatic solvents; chlorobenzene generation aromatase surface solvent control group; carbitol solvents; aniline; S ethylamine; lATE; acid; b December; carbon disulfide; N, N- dimethyl ester amine; N-methylation pay slightly burning; dimethylsulfoxide Bitterness; water, etc. these solvents may be shipped W used alone, the mixed solvent may be used on W W 2 thereof.

[0115] 其中酬类、酸醋系溶剂等特别是丙二醇-1-单甲酸-2-乙酸醋、环己酬等使得在感光性组合物中抗蚀剂和光聚合引发剂的相容性变得良好,因而优选。 [0115] wherein the reward category, solvents such as vinegar particularly propylene glycol 1-acetic acid-2- acetate, cyclohexyl and the like pay the photosensitive composition so that the resist and a photopolymerization initiator agent becomes compatible good, which is preferable.

[0116] 在本发明的感光性组合物中,溶剂的含量没有特别限制,只要是能够使各成分均匀分散或溶解、而且使本发明的感光性组合物呈现适合于各用途的液状或糊状的量就可W,通常优选按照使本发明的感光性组合物中的固体成分(除溶剂W外的全部成分)的量为10~50质量%的范围来含有溶剂。 [0116] In the photosensitive composition of the present invention, the content of the solvent is not particularly limited as long as the ingredients can be uniformly dispersed or dissolved, and the photosensitive composition of the invention is presented suitable for each use liquid or paste the amount can be W, preferably in an amount usually of the present invention, the solid content of the photosensitive composition (all components except solvent of W) to a solvent containing from 10 to 50% by mass.

[0117] 在本发明的感光性组合物中,还可W添加使(C)无机化合物和/或(D)着色剂分散的分散剂。 [0117] In the photosensitive composition of the present invention, may be added so that W (C) an inorganic compound and / or (D) a dispersant for dispersing a colorant. 作为该分散剂,只要是能够分散并稳定(C)无机化合物或(D)着色剂的分散剂,就没有限制,可W使用市售的分散剂、例如BYK公司制的BYK系列等。 Examples of the dispersing agent, and as long as it is possible to stabilize a dispersion (C) an inorganic compound or (D) a colorant dispersant, there is no limitation, W may be a commercially available dispersing agent, e.g. BYK series manufactured by BYK like. 特别是,由具有碱性官能团的聚醋、聚酸或聚氨醋构成的高分子分散剂、具有氮原子作为碱性官能团,并且具有氮原子的官能团是胺和/或其季锭盐,而且胺值为1~IOOm巧OH / g的分散剂可W优选使用。 In particular, a polyester having a basic functional group, or a polymeric polyacid dispersant formed of polyurethane vinegar, having a nitrogen atom as a basic functional group and a functional group having a nitrogen atom is an amine and / or quaternary salt spindle, and an amine value of 1 ~ IOOm clever OH / g of dispersant may be W is preferably used.

[0118] 此外,在本发明的感光性组合物中,通过在使用(B)具有締键式不饱和键的聚合性化合物的同时,使用其它的有机聚合物,还可W改善固化物的特性。 While [0118] Further, in the photosensitive composition of the present invention, by using the (B) polymerizable compound having an unsaturated bond of the associated button, other organic polymers, can also improve the properties of the cured product W . 作为该有机聚合物,可W列举出例如聚苯乙締、聚甲基丙締酸甲醋、甲基丙締酸甲醋一丙締酸乙醋共聚物、聚(甲基炳締酸、苯乙締一(甲基炳締酸共聚物、(甲基炳締酸一甲基丙締酸甲醋共聚物、乙締一氯乙締共聚物、乙締一乙締基共聚物、聚氯乙締树脂、ABS树脂、尼龙6、尼龙66、尼龙12、聚氨醋树脂、聚碳酸醋聚乙締醇缩下醒、纤维素醋、聚丙締酷胺、饱和聚醋、酪醒树脂、苯氧基树脂、聚酷胺酷亚胺树脂、聚酷胺酸树脂、环氧树脂等,其中优选聚苯乙締、(甲基)丙締酸一甲基丙締酸甲醋共聚物、环氧树脂。 Examples of the organic polymer, e.g. polystyrene W include associative, polymethyl methacrylate associative acid methyl ester, methacrylic acid methyl ester associating a propionic acid ethyl ester associative copolymer, poly (meth Jibing associative acid, benzene associating a b (a Jibing associative acid copolymer, (a carboxylic acid Jibing association methylpropanesulfonic acid methyl ester associative copolymer, a vinyl chloride acetate associative associative copolymer, monoethyl acetate associative associative based copolymers, polyvinyl chloride associating resins, ABS resins, nylon 6, nylon 66, nylon 12, polyurethane resin vinegar, polycarbonate polyvinyl alcohol association under reduced wake, cellulose acetate, polypropylene amine associative cool, saturated polyester, casein wake resins, phenoxy based resins, polyethylene amine cool cool imide resin, a poly lysine cool and epoxy resins, wherein the polystyrene is preferably associated, (meth) acrylic acid-methylpropanesulfonic associative associative acid methyl ester copolymer, an epoxy resin .

[0119] 在使用其它有机聚合物时,其使用量相对于100质量份的(B)具有締键式不饱和键的上述聚合性化合物,优选为10~500质量份。 [0119] When other organic polymer, its amount with respect to 100 parts by mass of (B) the polymerizable compound having an unsaturated bond association button, preferably 10 to 500 parts by mass.

[0120] 本发明的感光性组合物中可W进一步并用链转移剂、增感剂、表面活性剂、硅烷偶联剂、=聚氯胺化合物等。 [0120] The photosensitive composition of the present invention may be W, and further chain transfer agents, sensitizers, surface active agents, silane coupling agent, poly = chloramine compounds.

[0121] 作为上述链转移剂、增感剂,一般使用含硫原子的化合物。 [0121] Examples of the chain transfer agents, sensitizers, sulfur atoms, the compound is generally used. 可W列举出例如琉基乙酸、硫代苹果酸、硫代水杨酸、2-琉基丙酸、3-琉基丙酸、3-琉基下酸、N- (2-琉基丙酷基) 甘氨酸、2-琉基烟酸、3-阳-(2-琉基乙基)氨基甲酯基]丙酸、3-阳-(2-琉基乙基)氨基] 丙酸、N- (3-琉基丙酷基)丙氨酸、2-琉基乙横酸、3-琉基丙横酸、4-琉基下横酸、十二烷基(4-甲硫基)苯基酸、2-琉基乙醇、3-琉基-1, 2-丙二醇、1-琉基-2-丙醇、3-琉基-2-下醇、琉基苯酪、2-琉基乙胺、2-琉基咪挫、2-琉基苯并咪挫、2-琉基-3-化晚酪、2-琉基苯并嚷挫、琉基乙酸、=径甲基丙烷=(3-琉基丙酸醋)、季戊四醇四(3-琉基丙酸醋)等琉基化合物、将该琉基化合物氧化而得到的二硫化物、舰乙酸、舰丙酸、2-舰乙醇、2-舰乙横酸、 3-舰丙横酸等舰代烷基化合物、=径甲基丙烷=(3 -琉基异下酸醋)、下二醇双(3 -琉基异下酸醋)、己二硫醇、癸二硫醇、1,4 -二甲基琉基苯、 W may include, for example, sulfur acid, thiomalic acid, thiosalicylic acid, 2-thiol acid, 3 thiol acid, 3 thiol acid, N- (2- propyl-SH cool yl) glycine, 2-thiol acid, 3- male - (2-ethyl-SH) methyl amino] propionic acid, 3- male - (2-thiol ethyl) amino] propionic acid, N- (3-propyl thiol cool yl) alanine, 2-SH cross-acetic acid, 3-SH cross-propionic acid, an acid cross-4- thiol, dodecyl (4-methylthio) phenyl acid, 2-thiol ethanol, 3-thiol-1,2-propanediol, 1-thiol-2-propanol, 3-2 sulfur an alcohol, benzene casein sulfur, sulfur 2- amine 2-thiol microphone setback, benzene and sulfur 2- microphone setback, 2-3 lATE casein sulfur, benzene and sulfur 2- cried setback, sulfur acid, methyl propane diameter = = (3- thiol acetic acid), pentaerythritol tetrakis (3-thiol acetic acid) and other sulfur compounds, and the compound oxide obtained by thiol disulfide, acetic acid ship, ship acid, 2 ship ethanol, 2- ship ship substituted alkyl compound b cross acid, 3-ship cross-propionic acid, methyl propane diameter = = (3 - iso thiol under Suancu), the glycol-bis (3 - iso thiol under vinegar), -hexanedithiol, decanedithiol, 1,4 - dimethyl benzene sulfur, 下二醇二硫丙酸醋、下二醇二硫乙醇酸醋、乙二醇二硫乙醇酸醋、=径甲基丙烷=硫乙醇酸醋、下二醇二硫丙酸醋、=径甲基丙烷=硫丙酸醋、=径甲基丙烷=硫乙醇酸醋、季戊四醇四硫丙酸醋、季戊四醇四硫乙醇酸醋、=径基乙基=硫丙酸醋、二乙基嚷吨酬、二异丙基嚷吨酬、下述化合物No. CU =琉基丙酸^(2-径基乙基)异氯脈酸醋等脂肪族多官能硫醇化合物、昭和电工公司制的Karenz MT 抓1、阳UNRl等。 Acetic acid under disulfide diol, a diol under acid disulfide vinegar, vinegar acid disulfide glycol, methyl propane = diameter = sulfur acid vinegar, vinegar acid under disulfide diol, A = diameter acetic acid = sulfur, trimethylolpropane, diameter = methylpropanesulfonic acid vinegar = sulfur, sulfur acid pentaerythritol tetrakis vinegar, vinegar acid pentaerythritol tetrakis sulfur, sulfur = diameter = ethyl acetate propionate, diethyl cried ton payload , diisopropyl cried tons pay, following compound No. CU = ^ thiol acid (2-ethyl-diameter-yl) iso-chloro pulse vinegar and other aliphatic polyfunctional thiol compounds, manufactured by Showa Denko Karenz MT 1 catch, Yang UNRl and so on.

[0122] [0122]

Figure CN103298782BD00211

[0123] 作为上述表面活性剂,可W使用全氣烷基憐酸醋、全氣烷基簇酸盐等含氣表面活性剂;高级脂肪酸碱盐、烷基横酸盐、烷基硫酸盐等阴离子系表面活性剂;高级胺面酸盐、 季锭盐等阳离子系表面活性剂;聚乙二醇烷基酸、聚乙二醇脂肪酸醋、山梨糖醇酢脂肪酸醋、脂肪酸单甘油醋等非离子表面活性剂;两性表面活性剂;娃酬系表面活性剂等表面活性剂,它们也可W组合起来使用。 [0123] Examples of the surface active agent, using a full W vinegar gas pity alkyl, alkyl full gas cluster acid salt surfactant containing gas; higher fatty acid salts, alkyl horizontal salts, alkyl sulfate other anionic surfactant; surface higher amine salts, quaternary salts ingot cationic surfactant; alkyl acid, polyethylene glycol, polyethylene glycol fatty acid vinegar, vinegar sorbitan fatty acid vinegar, vinegar fatty acid monoglyceride nonionic surfactants; amphoteric surfactants; baby pay-based surfactant surfactants are used in combination may be W.

[0124] 作为上述硅烷偶联剂,可W使用例如信越化学公司制的硅烷偶联剂,其中,邸E -9007、邸M - 502、邸E - 403等具有异氯酸醋基、甲基丙締酷基、环氧基的硅烷偶联剂可W 优选使用。 [0124] Examples of the silane coupling agent, for example, W manufactured by Shin-Etsu Chemical Co., a silane coupling agent, wherein Di E -9007, Di M - 502, Di E - 403 acetic acid and the like having a different group, methyl cool propan associative group, epoxy group silane coupling agents may be W is preferably used.

[0125] 作为上述=聚氯胺化合物,可W列举出(聚)径甲基=聚氯胺、(聚)径甲基甘脈、 (聚)径甲基鸟粪胺、(聚)径甲基脈等氮化合物中的活性径甲基(CHzOH基)的全部或一部分(至少两个)被烷基酸化后的化合物等。 [0125] Examples of the polyethylene = chloramine compounds, W may include (poly) methyl diameter = poly chloramine, (poly) methyl Gan-diameter veins, (poly) methyl guanamine diameter, (poly) Diameter A yl-methyl-diameter veins and other active nitrogen compound (CHzOH yl) all or part of (at least two) after acidification a compound is an alkyl group and the like.

[0126] 其中,作为构成烷基酸的烷基,可W列举出甲基、乙基或下基,相互可W相同,也可W不同。 [0126] wherein the alkyl group constituting the acid group, W may include methyl, ethyl or the group, each W may be the same as or different from W. 另外,未烷基酸化的径甲基可W在一个分子内进行自缩合,也可W二个分子间进行缩合,结果形成低聚物成分。 Further, non-methyl alkyl acidified diameter W can be performed in one molecule self-condensation, W may be between two molecules condensation, resulting in the formation oligomer component.

[0127] 具体地,可W使用六甲氧基甲基=聚氯胺、六下氧基甲基=聚氯胺、四甲氧基甲基甘脈、四下氧基甲基甘脈等。 [0127] Specifically, using hexamethoxymethylmelamine W = polyethylene chloride, polyethylene = a methyl group at six chloramine, pulse tetramethoxymethyl glycoluril, methyl glycoluril pulse looked like.

[0128] 其中,优选六甲氧基甲基S聚氯胺、六下氧基甲基S聚氯胺等烷基酸化后的S聚氯胺。 [0128] wherein the alkyl group is acidified, preferably hexamethoxymethylmelamine S polyethylene chloride, polyethylene six lower oxymethyl S S chloramine poly chloramine.

[0129] 此外,在本发明的感光性组合物中,根据需要可W加入对苯甲酸、氨酿、焦儿茶酪、 叔下基儿茶酪、吩嚷嗦等热聚合抑制剂;增塑剂;粘接促进剂;填充剂;消泡剂;流平剂;表面调整剂;抗氧化剂;紫外线吸收剂;分散助剂;抗凝剂;催化剂;效果促进剂;交联剂;增粘剂等惯用的添加物。 [0129] Further, in the photosensitive composition of the present invention, W may be added as needed to the acid, ammonia stuffed, coke catechu casein, casein tert lower base catechu, thiophene cried winded thermal polymerization inhibitor and the like; plasticizing agents; adhesion promoters; fillers; defoamer; leveling agent; surface modifiers; antioxidants; ultraviolet absorbers; dispersing aid; anticoagulants; catalyst; effect accelerators; crosslinking agent; a thickener and other conventional additives.

[0130] 在本发明的感光性组合物中,除(A)本发明的光聚合引发剂和(B)具有締键式不饱和键的聚合性化合物W外的任意成分(其中,(C)无机化合物、(D)着色剂和溶剂除外)的使用量可W根据其使用目的来适当选择,没有特别限制,但优选的是,相对于(B)具有締键式不饱和键的聚合性化合物100质量份,将任意成分的总量设定为50质量份W下。 [0130] In the photosensitive composition of the present invention, in addition to the photopolymerization (A) of the present invention, and initiator (B) component associated with any button outer polymerizable compound W unsaturated bond (wherein, (C) inorganic compounds, (D) a colorant and a solvent excluded) the use of an amount W be appropriately selected depending on its purpose, it is not particularly limited, but is preferably, with respect to the polymerizable compound associative unsaturated bond (B) having 100 parts by mass, the total amount of any component is set to 50 parts by mass of W.

[0131] 本发明的感光性组合物可W通过照射能量射线而制成固化物。 The photosensitive composition [0131] The present invention W may be made by irradiation of an energy ray cured. 该固化物可W根据用途而形成为适当的形状。 The cured product W may be formed depending on the use of an appropriate shape. 例如在形成膜状的固化物时,本发明的感光性组合物可W通过旋涂器、漉涂器、棒涂器、模涂器、帘式涂布器、各种印刷、浸溃等公知的手段应用于钢玻璃、 石英玻璃、半导体基板、金属、纸、塑料等支撑基体上。 For example, when a film is formed of a cured product, a photosensitive composition of the invention may be W by a spin coater, Luk coater, bar coater, a die coater, a curtain coater, various printing, dipping a known It means applied on the steel, glass, quartz glass, semiconductor substrates, metals, paper, plastic and other support base. 此外,也可W暂时在薄膜等支撑基体上实施后,转印到其它支撑基体上,其应用方法没有限制。 Furthermore, W may be temporarily carried out on the support base film or the like, transferred onto another support base, the application method is not limited.

[0132] 作为在使本发明的感光性组合物固化时使用的能量射线的光源,可W利用从超高压隶灯、高压隶灯、中压隶灯、低压隶灯、隶蒸气弧灯、氣弧灯、碳弧灯、金属面化物灯、巧光灯、鹤灯、准分子灯、杀菌灯、发光二极管、CRT光源等获得的具有2000A至7000A的波长的电磁波能量或电子束、X射线、放射线等高能量射线,发出波长为300~450nm的光的超高压隶灯、隶蒸气弧灯、碳弧灯、氣弧灯等可W优选使用。 [0132] As the energy usage of the present invention in the photosensitive composition to curing radiation source, available from the use of EHV Li W lamp, high-pressure lamps Li, Li medium pressure lamps, low light Li, Li vapor arc lamps, gas electromagnetic energy or electron beam having a wavelength of 2000A to 7000A of the arc lamp, a carbon arc lamp, a metal surface of the lamp, a clever light, crane lamp, excimer lamp, germicidal lamp, light emitting diodes, CRT light source obtained, X-rays, high energy ray radiation, W is preferably emit light of a wavelength of 300 ~ 450nm UHP lamp Li, Li vapor arc lamp, a carbon arc lamp, a gas arc lamp or the like.

[0133] 另外,曝光光源使用激光时,不使用掩模而从计算机等数字信息直接形成图像的激光直接描画法不仅从生产率的观点出发,而且从提高分辨力和位置精度等的观点出发也是有用的,作为该激光,优选使用340~430nm的波长的光,但准分子激光、氮激光、氣离子激光、氮儒激光、氮氛激光、氯离子激光、各种半导体激光W及YAG激光等发出从可见至红外区域的光的激光也可W使用。 [0133] Further, exposure using a laser light source, a laser without using a mask to form an image directly from the computer digital information directly from the drawing method is not only the viewpoint of productivity, but also in terms of improving resolution and accuracy of the viewpoint position may also be useful as the laser light, preferably light having a wavelength of 340 ~ 430nm is used but an excimer laser, a nitrogen laser, gas ion laser, a nitrogen laser Ru, nitrogen atmosphere laser, chloride ion lasers, various semiconductor laser and a YAG laser emits W visible light from the laser to the infrared region W may also be used. 当使用上述激光时,优选加入可吸收从可见至红外的该区域光的增感色素。 When using the laser, it can be preferably added from a sensitizing dye absorbing the visible region to the infrared light.

[0134] 本发明的感光性组合物可W用于光固化性涂料或清漆;光固化性粘接剂;印刷基板;彩色电视机、PC监视器、便携信息终端、数码相机等彩色显示的液晶显示元件中的滤色器;CCD图像传感器的滤色器;等离子体显示面板用的电极材料;粉末涂料;印刷油墨;印刷版;粘接剂;牙科用组合物;凝胶涂层;电工学用的光致抗蚀剂;电锻抗蚀剂;蚀刻抗蚀剂;干膜;焊锡抗蚀剂;用于制造各种显示用途用的滤色器或在等离子体显示面板、电发光显示装置W及LCD的制造工序中用于形成运些结构的抗蚀剂;用于密封电气或电子部件的组合物;焊料抗蚀剂;磁记录材料;微小机械部件;波导;光学开关;锻覆用掩模;蚀刻掩模;彩色试验系;玻璃纤维电缆涂层;丝网印刷用模版;用于通过立体平版印刷制造=维物体的材料;全息照相记录用材料;图像记录材料 Liquid crystal color TV, PC monitor, a portable information terminal, a digital camera, a color display; [0134] The photosensitive composition of the invention may be used for W photocurable coating or varnish; photocurable adhesive; printed circuit board display device a color filter; CCD image sensor, a color filter; plasma display panel with an electrode material; powder coating; printing inks; printing plate; an adhesive; dental composition; gelcoat; electrotechnics means for producing a color filter use with various displays or plasma display panels, electroluminescent display; photoresist used; electrically resist forging; etch resist; dry film; solder resist W and LCD manufacturing process for forming these transport resist structure; a composition for sealing electrical and electronic components; a solder resist; magnetic materials; micro-mechanical parts; waveguide; optical switches; forging coated with mask; etching mask; color-based test; glass fiber cable coatings; screen-printing stencil; for the manufacture of materials by stereolithography = 3D object; holographic recording material; an image recording material 微细电路;脱色材料;用于图像记录材料的脱色材料;使用微囊的图像记录材料用的脱色材料;印刷布线板用光致抗蚀剂材料;UV 和可见激光直接图像系用的光致抗蚀剂材料;用于形成印刷电路基板的逐次叠层中的电介体层的光致抗蚀剂材料或保护膜等各种用途中,其用途并没有特别限制。 Fine circuit; decolorizing materials; decolorizing materials for image recording materials; decolorizing materials for image recording materials using microcapsules used; printed wiring board with a photoresist material; the UV and visible laser direct image with a photo-based anti corrosion inhibitor material; a dielectric layer formed sequentially laminated printed circuit board in the photoresist material or a protective film for various applications, their use is not particularly limited.

[0135] 本发明的感光性组合物也可W是用于形成液晶显示面板用间隔物的目的W及用于形成垂直取向型液晶显示元件用突起的目的。 The photosensitive composition [0135] W of the present invention can also be used to form a liquid crystal display panel is the object W with the spacers and means for forming a vertical alignment type liquid crystal display element projection purposes. 特别是作为用于同时形成垂直取向型液晶显示元件用的突起和间隔物的感光性组合物而有用。 Particularly as for simultaneously forming a vertical alignment type liquid crystal display element for photosensitive composition and the spacer projections is useful.

[0136] 上述的液晶显示面板用间隔物优选通过下述工序来形成:(1)在基板上形成本发明的感光性组合物的涂膜的工序、(2)隔着具有规定的图案形状的掩模对该涂膜照射能量射线(光)的工序、(3)曝光后的烘烤工序、(4)将曝光后的覆盖膜进行显影的工序、(5)对显影后的该覆盖膜进行加热的工序。 [0136] The liquid crystal display panel spacer is preferably formed by the following steps: (1) forming a coating film of the photosensitive composition of the present invention on a substrate, (2) therebetween having a predetermined pattern shape of the coat was irradiated mask process energy ray (light), (3) post-exposure baking step, (4) the coating film after developing the exposed step (5) of the cover film the developed heating step.

[0137] 添加了(D)着色剂的本发明的感光性组合物适合用作构成滤色器中的RGB等各像素的抗蚀剂、或形成各像素的隔壁的黑色矩阵用抗蚀剂。 The photosensitive composition [0137] added (D) a colorant of the present invention is suitable as a constituent such as RGB color filters for each pixel of a resist, or formation of the partition walls of each pixel black matrix resist. 进而,添加防油墨剂的黑色矩阵用抗蚀剂的情况,优选用于齿形角(profile angle)为50° W上的喷墨方式滤色器用隔壁。 Further, the ink repellent agent is added in the case of a black matrix resist, preferably a profile angle (profile angle) of an inkjet method on a color filter partition 50 ° W. 作为该防油墨剂,优选使用氣系表面活性剂和含有氣系表面活性剂的组合物。 Examples of the ink repellent agent, preferably using an air-based surfactant and gas-based composition containing a surfactant.

[013引当用于上述喷墨方式滤色器用隔壁时,由本发明的感光性组合物形成的隔壁在被转印体上进行划分,向划分后的被转印体上的凹部通过喷墨法赋予液滴,从而形成像素区域,通过该方法来制造光学元件。 [013 cited above when used in ink-jet color filter walls embodiment, the partition walls formed from the photosensitive composition of the invention will be divided over the transfer body, the recess on the transfer-receiving material after imparting divided by an ink jet method droplets, thereby forming a pixel region, an optical element manufactured by this method. 此时,优选上述液滴含有着色剂,上述像素区域被着色,在运种情况下,通过上述的制造方法制作的光学元件成为在基板上至少具有由多个着色区域构成的像素群和隔离该像素群的各着色区域的隔壁的元件。 In this case, the droplet preferably contain a colorant, the pixel region is colored in the transport case, the optical element manufactured by the above manufacturing method and the pixel group having at least be made of a plurality of isolation regions on the substrate which coloring the partition wall element in each pixel group colored region.

[0139] 本发明的感光性组合物还可W用作保护膜或绝缘膜用组合物。 [0139] The photosensitive composition of the present invention may also be used as a W film or insulating protective film composition. 此时,可W含有紫外线吸收剂、烷基化改性=聚氯胺和/或丙締酸改性=聚氯胺、分子中含有醇性径基的1 或2官能的(甲基)丙締酸醋单体和/或硅胶。 In this case, W may contain an ultraviolet absorber, alkylated modified chloramine = polyethylene and / or propionic acid-modified associative = polyethylene chloride, molecules containing alcoholic group of 1 or 2 diameter functional (meth) acrylic vinegar associative monomer and / or silica gel.

[0140] 作为上述保护膜、绝缘膜用的感光性组合物,是W下述成分为主成分的树脂组合物: [0140] As the protective film, an insulating film with the photosensitive composition, W is the following main components, the resin composition:

[0141] (A)本发明的光聚合引发剂、 [0141] (A) according to the present invention, a photopolymerization initiator,

[0142] (B)具有締键式不饱和键的聚合性化合物(优选含有重均分子量为2, 000~ 40, 000、酸值为50~200m巧OH / g的含簇基的聚合性化合物)、W及 [0142] polymerizable compound (B) a polymerizable unsaturated bond has an association button (preferably having a weight average molecular weight of from 2, 000 to 40, 000, an acid value of 50 ~ 200m clever OH / g group-containing clusters ), W and

[0143] (X)环氧化合物, [0143] (X) an epoxy compound,

[0144] 优选的是,相对于(B)成分100重量份,(A)成分换算为本发明的目亏醋化合物量为0.0 l~2. 0重量份,(X)成分为10~40重量份。 [0144] Preferably, with respect to (B) 100 parts by weight of component, (A) the component in terms of the amount of vinegar compound of the present invention is deficient mesh 0.0 l ~ 2. 0 parts by weight, (X) component of 10 to 40 wt. copies.

[0145] 上述绝缘膜可W用于在能够剥离的支撑基材上设置有绝缘树脂层的层叠体中的该绝缘树脂层,该层叠体可W用碱水溶液显影,绝缘树脂层的膜厚优选为10~100 ym。 [0145] W may be used for the insulating film of the insulating resin layer provided with a laminate insulating resin layer on the supporting substrate can be peeled off, the laminate may be a film thickness of W is preferably an alkaline aqueous solution developer, the insulating resin layer of 10 ~ 100 ym.

[0146] 本发明的感光性组合物通过含有(C)无机化合物,可W用作感光性糊状组合物。 The photosensitive composition [0146] of the present invention contains (C) an inorganic compound may be used as a photosensitive paste composition W. 该感光性糊状组合物可W用于形成等离子体显示面板的隔壁图案、电介体图案、电极图案和黑色矩阵图案等烧成物图案。 The photosensitive paste composition may be used to form the plasma display panel W partition wall patterns, dielectric patterns, electrode patterns, and black matrix pattern was baked like pattern. 实施例 Example

[0147] 下面通过列举实施例和比较例来对本发明进行更详细的说明,但是本发明并不限定于运些实施例等。 [0147] in more detail below with the present invention is described by Examples and Comparative Examples, but the present invention is not limited to these examples and the like operation.

[014引〔实施例1)化合物No. 1的制造 [Example 1 Primer 014) for producing the compound No. 1

[0149] <步骤1 >甲基丙締酸醋化 [0149] <Step 1> methylpropanamide association of vinegar

[0150] 将含有1 - (4 - (4 - (2 ―径基乙氧基)苯硫基)苯基)丙烷一1 -酬(W下也称作酬体a) 19. Sg (65mmol)、甲基丙締酸56. 2g (653mmol)、对甲苯横酸一水合物5. Og (26mmol)、BHTl. 2g (5. 6mmol) W及二氯乙烧121g的溶液揽拌回流10. 5小时。 [0150] The containing 1 - (4 - (4 - (2 - ethoxy diameter yl) phenylthio) phenyl) propane a 1-- paid (also referred to as the payload body W a) 19. Sg (65mmol) , association methylpropanesulfonic acid 56. 2g (653mmol), p-toluenesulfonic acid monohydrate cross 5. Og (26mmol), BHTl. 2g (5. 6mmol) W and dichloro acetate solution 121g stirred at reflux for burning embrace 10.5 hour. 冷却后,加入乙酸乙醋和水进行油水分离。 After cooling, water was added acetic acid ethyl ester and water separation. 按照水、碳酸氨钢水溶液、水的顺序洗涂有机层。 The organic layer was in the order of water, an aqueous solution of ammonium carbonate steel, water wash coating. 将有机层用无水硫酸儀干燥后,进行脱溶剂,得到26. 3g下述甲基丙締酸醋体a。 The organic layer was dried over anhydrous sulfate meter, carried out with removing the solvent, to give 26. 3g vinegar following methylpropanesulfonic associated body a.

[0151] [0151]

Figure CN103298782BD00241

[0152] <步骤2 >月亏化 [0152] <Step 2> of waning

[0153] 将含有步骤1中得到的甲基丙締酸醋体a的26.0g (70mmol)、浓盐酸7.3g (70mmol)和二甲基甲酯胺70g的溶液冷却至5°C,加入亚硝酸异下醋10. Sg (105mmol),在室溫下揽拌3小时。 [0153] Step 1 obtained containing methylpropanesulfonic vinegar association of a body 26.0g (70mmol), concentrated hydrochloric acid 7.3g (70mmol) and dimethyl amine ester 70g was cooled to 5 ° C, Jiaru Ya isosorbide the vinegar 10. Sg (105mmol), embrace stirred at room temperature for 3 hours. 加入乙酸乙醋和水进行油水分离,按照水、碳酸氨钢水溶液、水的顺序洗涂有机层。 Acetic acid ethyl ester and water, oil-water separation, the organic layer was in the order of water, an aqueous solution of ammonium carbonate steel, water wash coating. 将有机层用无水硫酸儀干燥后,进行脱溶剂,得到23. Sg下述朽体a。 The organic layer was dried over anhydrous sulfate meter, carried out with removal of the solvent gave 23. Sg following rotten body a.

[0154] [0154]

Figure CN103298782BD00242

[0155] <步骤3 >朽醋化 [0155] <Step 3> rot of vinegar

[0156] 将含有步骤2中得到的朽体a的23. Sg (eOmmol)、乙酸酢9. Ig (90mmol)和乙酸乙醋79g的溶液在70°C下揽拌4小时。 [0156] The containing body obtained in the step a 2 of rotten 23. Sg (eOmmol), acetic acid Health 9. Ig (90mmol) and acetic acid ethyl ester 79g of olive stirred at 70 ° C 4 hours. 冷却后,加入水进行油水分离。 After cooling, water was added oil-water separation. 按照水、碳酸氨钢水溶液、水的顺序洗涂有机层。 The organic layer was in the order of water, an aqueous solution of ammonium carbonate steel, water wash coating. 将有机层用无水硫酸儀干燥后,进行脱溶剂。 The organic layer was dried over anhydrous sulfate instrument, removing the solvent. 将得到的粗产物27. 2g用柱色谱进行精制,得到2. 3g化合物No. 1。 The resulting crude product 27. 2g was purified by column chromatography to give compound 2. 3g No. 1. 通过分析确认了得到的化合物是目标物。 By analysis confirmed that the obtained compound is a target product. 分析结果示于〔表1)~〔表3)中。 The results are shown in [Table 1) [Table 3).

[0157] 〔实施例2~4)化合物No. 2、化合物No. 3、化合物No. 4的制造 [0157] [Examples 2 to 4) Compound No. 2, compound No. 3, Compound No. 4 is manufactured

[015引使用对应的酬体代替酬体a(并且对于化合物No. 3,使用丙締酸代替甲基丙締酸), 除此W外,按照实施例1中记载的方法分别制造化合物No. 2、化合物No. 3和化合物No. 4。 [015 using corresponding primers paid pay member body in place a (and the compound No. 3, using propionic acid in place of methyl propionate association associative acid), addition to this W, according to the method described in Example 1, respectively, for producing a compound of Embodiment No. 2, compound No. 3 and compound No. 4. 分析结果示于〔表1)~〔表3)中。 The results are shown in [Table 1) [Table 3). 入[0159]表1 The [0159] TABLE 1

Figure CN103298782BD00251

[0161] *1:溶剂使用CHCls [0161] * 1: The solvent used CHCls

Figure CN103298782BD00252

[0167] 〔实施例引碱显影性感光性树脂组合物No. 1的制造 [0167] Example primers alkali-developable photosensitive resin composition No. 1 for producing

[0168] <步骤1 >碱显影性树脂〔赋予碱显影性的(B)成分)的制备 Preparation of [0168] <Step 1> [imparting alkali-developable resin alkali-developable of component (B)) of

[0169] 在反应容器中加入双酪巧型环氧树脂(环氧当量为231,上述通式(3)所表示的环氧化合物)184g、丙締酸58g、2, 6 -二叔下基一对甲酪0. 26g、四正下基漠化锭0.1 lg W及丙二醇一I -单甲酸一2 -乙酸醋23g,在120°C下揽拌16小时。 [0169] added to the reaction vessel in a double casein Qiao type epoxy resin (epoxy equivalent of 231, the general formula (3) an epoxy compound represented by) 184g, propionic acid association 58g, 2, 6 - di-lower-yl toluenesulfonic a casein 0. 26g, tetra-n-lower-yl desertification ingot glycol and 0.1 lg W I - a mono-carboxylic acid 2 - acetate acetate 23g, embrace stirred at 120 ° C 16 h. 将反应液冷却至室溫,加入丙二醇一1 -单甲酸一2 -乙酸醋35g、联苯四甲酸酢59g和四正下基漠化锭0.24g,在120°C下揽拌4小时。 The reaction was cooled to room temperature, propylene glycol 1 - Single-carboxylic acid a 2 - acetate acetate 35g, 59g of Health biphenyltetracarboxylic acid and tetra-n the group of Mo ingots 0.24g, embrace stirred at 120 ° C 4 hours. 进而,加入四氨邻苯二甲酸酢20g,在120°C下揽拌4小时、在100°C下揽拌3小时、在80°C下揽拌4小时、在60°C下揽拌6小时、在40°C下揽拌11小时,然后加入丙二醇_ 1 _单甲酸_ 2 _乙酸醋90g,得到作为丙二醇_ 1 _单甲酸_ 2 _乙酸醋溶液的目标物的碱显影性树脂No. 1 (MW = 5000,Mn = 2100,酸值(固体成分)为92.加巧OH / g)。 Further, phthalic acid ammonium tetrakis Health 20g, embrace stirred at 120 ° C 4 hours embrace stirred at 100 ° C 3 hours embrace stirred at 80 ° C 4 hours at 60 ° C for 6 embrace mix hours, at 40 ° C for football stirred for 11 hours, followed by addition of propylene glycol _ 1 _ single acid _ 2 _ acid vinegar 90g, to give propylene glycol _ 1 _ single acid _ object 2 _ acid acetate solution of alkali developable resin No . 1 (MW = 5000, Mn = 2100, acid value (solid content) was added to 92. Qiao OH / g).

[0170] <步骤2 >碱显影性感光性树脂组合物No. 1的制备 [0170] alkali-developable photosensitive resin composition No. prepared in <Step 2> 1

[0171] 将作为赋予碱显影性的(B)成分的<步骤1 >中得到的碱显影性树脂No. 1的14. 7g、作为(B)成分的二季戊四醇五和六丙締酸醋(AR0NIX M-402 ;东亚合成株式会社制) 3. Og、表面活性剂FZ - 2122 (日本化icar株式会社制)的环己酬1 %溶液1. 8g、丙二醇一1 -单甲酸一2-乙酸醋10.0 g、W及环己酬20. 2g进行混合,添加作为(A)成分的实施例1中得到的化合物No. 10. 3g并充分揽拌,得到作为本发明的感光性组合物的碱显影性感光性树脂组合物No. 1。 [0171] As the alkali developing property imparting component (B) of <Step 1> alkali-developable resin No. obtained 14. 7g 1, and (B) is dipentaerythritol pentaacrylate, and vinegar hexapropyl associated component ( AR0NIX M-402; manufactured by Toagosei Co.) 3. Og, surfactants FZ - 2122 (Nippon icar Co., Ltd.) 1% solution paid cyclohexyl 1. 8g, propylene glycol 1 - single 2-acetic acid a vinegar 10.0 g, W and cyclohexanone were mixed payload 20. 2g, the compound No. as component (a) obtained in Example 1 and 10. 3g embrace fully stirred to obtain a photosensitive composition of the present invention bases developable photosensitive resin composition No. 1.

[0172] 〔实施例6)碱显影性感光性树脂组合物No. 2的制造 [0172] [6) Production Example alkali-developable photosensitive resin composition No. 2 of

[0173] 除了将实施例1中得到的化合物No. 1替换为实施例2中得到的化合物No. 2 W外, 用与实施例5的<步骤2 >同样的方法得到作为本发明的感光性组合物的碱显影性感光性树脂组合物No. 2。 [0173] The procedure of Example 1 was replaced with the compound No. 1 obtained in Embodiment Compound No. 2 W 2 exceptions, in Example 5 <step 2> obtained in the same manner as a photosensitive present invention alkali-developable photosensitive resin composition No. 2 composition.

[0174] 〔实施例7)碱显影性感光性树脂组合物No. 3的制造 [0174] [7) alkali developable photosensitive resin composition No. 3 of Manufacturing Example

[0175] 除了将实施例1中得到的化合物No. 1替换为实施例3中得到的化合物No. 3 W外, 用与实施例5的<步骤2 >同样的方法得到作为本发明的感光性组合物的碱显影性感光性树脂组合物No. 3。 [0175] The procedure of Example 1 was replaced with Compound No. 1 Compound No. 3 obtained in Example 3 W, the use of Example <Step 2> obtained in the same manner as the present invention, a photosensitive 5 alkali-developable photosensitive resin composition No. 3 compositions.

[0176] 〔比较例1)碱显影性感光性树脂组合物No. 4的制造 [0176] [Comparative Example 1) alkali developable photosensitive resin composition No. 4 manufactured

[0177] 除了将实施例1中得到的化合物No. 1替换为2 -苄基一2 -二甲基氨基一1 -(4 -吗嘟代苯基)一1 -下酬W外,用与实施例5的<步骤2 >同样的方法得到作为比较品的碱显影性感光性树脂组合物No. 4。 [0177] In addition to replacing compound No. 1 obtained in Example 1 of the embodiment 2 - benzyl-2 - dimethylamino - 1 - (4 - it beep substituted phenyl) - 1 - W outside the paid, and with same manner as in Example 5 <step 2> was obtained as a comparative product alkali-developable photosensitive resin composition No. 4.

[017引〔比较例2)碱显影性感光性树脂组合物No. 5的制造 [017 Comparative Example 2 [Production primer) alkali developable photosensitive resin composition No. 5 is

[0179] 除了将实施例1中得到的化合物No. 1替换为乙酬,1 - [9 -乙基一6 - (2 -甲基苯酷基)一9H-巧挫一3 -基]一,1 - (0-乙酷朽)W外,用与实施例5的<步骤2 > 同样的方法得到作为比较品的碱显影性感光性树脂组合物No. 5。 [0179] The procedure of Example 1 was replaced with Compound No. 1 paid B, 1 - [9 - ethyl - 6 - (2 - methylphenyl Cool yl) 9H- a setback a clever 3 - yl] a 1 - external (0- cool rot b) W is, as in Example 5 of the embodiment <step 2> obtained in the same manner as the alkali-developable photosensitive resin composition No. 5 comparative product.

[0180] <透射性> [0180] <transmissive>

[0181] 如下所述地将得到的碱显影性感光性树脂组合物No. 1~No. 5进行透射性试验。 [0181] obtained as described below alkali-developable photosensitive resin composition No. 1 ~ No. 5 transmissive test.

[0182] 目P,在玻璃基板上旋涂碱显影性感光性树脂组合物(W 50化pm旋涂2秒钟、W 80化pm旋涂6秒钟),使用加热板在90°C下进行90秒钟的预烘烤。 [0182] P mesh, was spin-coated on a glass substrate, alkali-developable photosensitive resin composition (W 50 pm spin coating of 2 seconds, W 80 6 seconds of spin coating pm), using a hot plate at 90 ° C for pre-baked for 90 seconds. 然后,使用高压隶灯作为光源,进行150mJ / cm2的曝光后,使用烘箱在230°C下进行30分钟的后烘烤,得到固化膜。 Then, using a high-pressure lamp as a light source Li, exposed 150mJ / cm2 using an oven for 30 minutes post-baking at 230 ° C, to obtain a cured film. 对得到的固化膜,使用吸光光度计测定380nm处的透射率。 Cured film obtained was measured using absorptiometer transmittance at 380nm. 结果示于〔表4)中。 The results are shown in [Table 4).

[0183] 表4 [0183] TABLE 4

[0184] [0184]

Figure CN103298782BD00271

阳1财如表4所记载的,使用本发明的目亏醋化合物作为光聚合引发剂的本发明的感光性组合物与使用了比较化合物的比较例1和2的感光性组合物相比,透射率较高。 1 male Choi described in Table 4, the present invention is the use of compounds as vinegar purpose loss photopolymerizable photosensitive composition of the present invention as compared initiator and a photosensitive composition using 2 Comparative Example 1 Comparative compound, high transmittance.

[0186] 〔实施例8)导电性组合物No. 1的制造 [0186] [Production Example 8) conductive composition No. 1 of the embodiment

[0187] 将作为赋予碱显影性的(B)成分的实施例5的<步骤1 >中得到的碱显影性树脂No. 114. Ig、作为(B)成分的二季戊四醇五和六丙締酸醋(AR0NIX M-402 ;东亚合成株式会社制)7. Ig、表面活性剂BYK - 323(BYK Japan株式会社制)0. 05g、醇醋(2, 2, 4 -S甲基一1,3 -戊二醇单异下酸醋)11. 3g、作为(A)成分的实施例1中得到的化合物No. 1的0. 7邑、 W及作为(C)成分的玻璃料3. Ig和银粉63. 7g进行混合揽拌,然后使用3漉磨机进行混炼, 得到作为本发明的感光性组合物的导电性组合物No. 1。 [0187] As the component (B) to impart alkali developability of Example 5 <step 1> alkali-developable resin No. 114. Ig obtained, as component (B) is dipentaerythritol pentaacrylate and hexapropyl associated acid vinegar (AR0NIX M-402; manufactured by Toagosei Co.).. 7 Ig, surfactants BYK - 323 (BYK Japan KK) 0 05g, alcohol vinegar (2, 2, 4 -S-methyl-1,3 - pentanediol iso under Suancu) 11 3g, as component (a) obtained in Example 1 compound No. 1 of 0.7 eup, glass frit and 3. Ig W as component (C) and. 63. 7g silver embrace stirred and mixed, and then kneaded using a 3 Luk mill to obtain a photosensitive composition of the present invention is a conductive composition No. 1.

[0188] 〔实施例9)着色碱显影性感光性树脂组合物No. 1的制造 [0188] [9) colored alkali-developable photosensitive resin composition No. 1 of Production Example

[0189] <步骤1 >蓝色分散液的制造 Manufacturing [0189] <Step 1> blue dispersion

[0190] 在500ml聚乙締制容器中加入57. 6g蓝色颜料的颜料蓝15 :6、分散剂AJIS阳RP B821 (Ajinomoto Fine-Techno 株式会社制)20.0 g、分散助剂SOLS阳RSE5000 (Avecia 株式会社制)2. 4g、W及丙二醇一1 -单甲酸一2 -乙酸醋320.0 g,使用粒径为0. 5mm的氧化错珠350g,在化int conditioner中振动10小时后,过滤氧化错珠,得到蓝色分散液。 [0190] 57. 6g blue pigment is added in a 500ml polyethylene container in association Pigment Blue 15: 6, dispersants AJIS male RP B821 (Ajinomoto Fine-Techno Co., Ltd.) 20.0 g, dispersing aids SOLS male RSE5000 ( Avecia Ltd.) 2 4g, W, and propylene glycol 1 - a single-carboxylic acid 2 - acetic acid 320.0 g, a particle diameter of 0. 5mm fault oxide 350 g of beads, the vibration of int conditioner after 10 hours, filtered oxide wrong beads, to obtain a blue dispersion.

[0191] <步骤2 >着色碱显影性感光性树脂组合物No. 1的制造 [0191] <Step 2> The colored alkali-developable photosensitive resin composition No. 1 for producing

[0192] 将作为(D)成分的<步骤1 >中得到的蓝色分散液10. 63g、赋予碱显影性的作为(B)成分的实施例5的<步骤1 >中得到的碱显影性树脂No. 12. 98g、作为(B)成分的二季戊四醇五和六丙締酸醋(AR0NIX M-402 ;东亚合成株式会社制)0. 31g、作为(B)成分的尿烧丙締酸醋UN3320服(根上工业株式会社制)0. 31g、表面活性剂BYK - 323 (BYK Japan株式会社制)的环己酬1%溶液0. 30g、丙二醇一1 -单甲酸一2 -乙酸醋4. 70g、W及环己酬10. 36g进行混合,添加作为(A)成分的实施例1中得到的化合物No. 10. 41g并进行揽拌,得到作为本发明的感光性组合物的着色碱显影性感光性树脂组合物No. 1。 [0192] The obtained blue dispersion 10. 63g as <Step 1> (D) component, to impart alkali developability alkali-developable embodiment as component (B) of <Step 1> 5 is obtained resin No. 12. 98g, (B) is dipentaerythritol pentaacrylate, and vinegar hexapropyl associated component (AR0NIX M-402; manufactured by Toagosei Co.). 0 31g, vinegar associated urine as prop-burning component (B) is UN3320 service (the root industries, Ltd.) 0 31g, surfactants BYK -. 323 (BYK Japan KK) cyclohexyl pay a 1% solution of 0. 30g, propylene glycol 1 - single-carboxylic acid a 2 - acetic acid 4. 70g, W and cyclohexyl paid mixing 10. 36g, added as a component (a) obtained in Example 1 and compound No. 10. 41g embrace stirred to obtain a colored alkali-developable photosensitive composition of the present invention photosensitive resin composition No. 1.

[0193] 〔比较例3)着色碱显影性感光性树脂组合物No. 2的制造 [0193] [Comparative Example 3) colored alkali-developable photosensitive resin composition No. 2 in the manufacture

[0194] 除了将实施例1中得到的化合物No. 1替换为乙酬,1 - [9 -乙基一6 - (2 -甲基苯酷基)一9H-巧挫一3 -基]一,1 - (0-乙酷朽)W外,用与实施例9的<步骤2 > 同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 2。 [0194] The procedure of Example 1 was replaced with Compound No. 1 paid B, 1 - [9 - ethyl - 6 - (2 - methylphenyl Cool yl) 9H- a setback a clever 3 - yl] a 1 - the same <step 2> outer (0- cool rot b) W is, Example 9 and using the product obtained as a comparative colored alkali-developable photosensitive resin composition No. 2.

[0195] 〔比较例4)着色碱显影性感光性树脂组合物No. 3的制造 [0195] [Comparative Example 4) colored alkali-developable photosensitive resin composition No. 3 of Manufacturing

[0196] 除了将实施例1中得到的化合物No. 1替换为2 -甲基一1 -(4 -甲硫基苯基)一2 -吗嘟代丙烷一I -酬W外,用与实施例9的<步骤2 >同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 3。 [0196] The procedure of Example 1 was replaced with Compound No. 1 2 - methyl - 1 - (4 - methylthiophenyl) - 2 - morpholin a beep iodopropane I - W paid outside, and in the embodiment Example <step 2> 9 obtained in the same manner as the comparative product colored alkali-developable photosensitive resin composition No. 3.

[0197]〔比较例引着色碱显影性感光性树脂组合物No. 4的制造[019引除了将实施例1中得到的化合物No. 1替换为1,2 -辛二酬,1 - [4 -(苯硫基) 苯基]一,2 - (0-苯酷基目亏)W外,用与实施例9的<步骤2 >同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 4。 [0197] [Comparative Example primers colored alkali-developable photosensitive resin composition No. 4 manufactured [019 except that compound No. 1 alternative primers obtained in Example 1 of the embodiment 1, 2 - pay suberic, 1 - [4 - (phenylthio) phenyl] a, 2 - the same manner as the outer (0- yl phenyl cool loss mesh) W is, in Example 9 <step 2> to give the product as a comparative colored alkali-developable photosensitive resin The composition No. 4.

[0199] 〔比较例6)着色碱显影性感光性树脂组合物No. 5的制造 [0199] [Comparative Example 6) colored alkali-developable photosensitive resin composition No. 5 manufactured

[0200] 除了将实施例1中得到的化合物No. 1替换为2 -苄基一2 -二甲基氨基一1 -(4 -吗嘟代苯基)一1 -下酬W外,用与实施例9的<步骤2 >同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 5。 [0200] In addition to replacing compound No. 1 obtained in Example 1 of the embodiment 2 - benzyl-2 - dimethylamino - 1 - (4 - it beep substituted phenyl) - 1 - W outside the paid, and with same manner as in Example 9 <step 2> to give the product as a comparative colored alkali-developable photosensitive resin composition No. 5.

[0201] <透射性> [0201] <transmissive>

[0202] 如下所述地将得到的着色碱显影性感光性树脂组合物No. 1~No. 3进行透射性试验。 [0202] obtained as described below colored alkali-developable photosensitive resin composition No. 1 ~ No. 3 transmissive test.

[0203] 在玻璃基板上旋涂着色碱显影性感光性树脂组合物50化pm旋涂7秒钟),使用加热板在90°C下进行90秒钟的预烘烤。 [0203] spin-on glass substrate painted color alkali-developable photosensitive resin composition was spin coated 7 pm of 50 seconds), pre-baked using a hot plate for 90 seconds at 90 ° C. 然后,使用高压隶灯作为光源进行150mJ / cm2的曝光后,使用烘箱在23(TC下进行30分钟的后烘烤,得到固化膜。作为耐热性试验,将得到的固化膜进一步在260°C下加热1小时。对耐热性试验后的固化膜,使用吸光光度计测定420nm处的透射率。结果示于〔表引中。 Then, after the high-pressure lamp as a light source Li exposed 150mJ / cm2 using an oven for 30 minutes after baking (the TC 23, to give a cured film as a heat resistance test, the cured film obtained further 260 ° heated at C 1 hour. the cured film after the heat resistance test, was measured using an absorptiometer transmittance at 420nm. the results are shown in [table primers.

[0204] 表5 [0204] TABLE 5

[0205] [0205]

Figure CN103298782BD00281

[0206] 如表5所记载的,使用本发明的朽醋化合物作为光聚合引发剂的本发明的着色碱显影性感光性组合物与使用了比较化合物的比较例3和4的着色碱显影性感光性组合物相比,透射率较高。 [0206] As described in Table 5, using the compound of the present invention rotten vinegar as a photopolymerization initiator of the present invention, a colored base colored alkali-developable photosensitive composition used in Comparative Example 3 and Comparative Compound 4 developable photosensitive composition as compared to higher transmittance.

[0207] <排气性> [0207] <outgassing>

[020引作为得到的着色碱显影性感光性树脂组合物No. 1、No. 3~No. 5的排气性试验,如下所述地进行固化物的重量减少率的测定。 [020 cited as colored alkali-developable photosensitive resin composition obtained in No. 1, No. Exhaust Test 3 ~ No. 5, as the measured weight reduction rate is cured.

[0209]目P,在玻璃基板上旋涂着色碱显影性感光性树脂组合物(500rpm,7秒钟),使用加热板在90°C下进行90秒钟的预烘烤。 [0209] P mesh, painted in color on the glass substrate spin alkali-developable photosensitive resin composition (500rpm, 7 seconds), pre-baked using a hot plate for 90 seconds at 90 ° C. 然后,使用高压隶灯作为光源进行IOOmJ / cm2的曝光,得到固化膜。 Then, using a high-pressure lamp as a light source for an exposure Li IOOmJ / cm2 to obtain a cured film. 削下约3mg的该固化膜,使用削下的固化膜作为试样,通过TG - DTA (Seiko Instruments株式会社制)测定在230°C下保持了30分钟时的重量减少率。 The cured film is cut at approximately 3mg, the cured film is used as a sample cutting, TG by - DTA (Seiko Instruments Inc.) was measured weight reduction rate kept for 30 minutes at 230 ° C. 结果示于巧6)中。 The results are shown in 6) in coincidence.

[0引0] 表6 [Cited 0 0] TABLE 6

[0211] [0211]

[0212] 从表6可知,使用本发明的朽醋化合物作为光聚合引发剂的本发明的感光性组合物即着色碱显影性感光性树脂组合物与使用了比较化合物的比较例4~6的着色碱显影性感光性树脂组合物相比,耐热性更优良,排气较少。 [0212] As apparent from Table 6, the present invention is used as the photopolymerizable compound rotten vinegar photosensitive composition of the present invention, i.e. initiator colored alkali-developable photosensitive resin composition used in Comparative Example Comparative Compound 4-6 compared superior in heat resistance colored alkali-developable photosensitive resin composition, less exhaust gas. 此外,从该结果推测,作为光聚合引发剂的本发明的目亏醋化合物与树脂成分反应,由此,本发明的目亏醋化合物和/或树脂成分的升华性变低。 Further, from the result of estimation as a loss of head of the present invention photopolymerization initiator compound with vinegar resin component, whereby, head loss vinegar compound of the invention and / or sublimation of the resin component becomes low.

[0213] 〔实施例10)着色碱显影性感光性树脂组合物No. 6的制造 [0213] [Production Example 10) colored alkali-developable photosensitive resin composition No. 6 is

[0214] 将作为(D)成分的实施例9的<步骤1 >中得到的蓝色分散液的10. 63g、赋予碱显影性的作为(B)成分的实施例5的<步骤1 >中得到的碱显影性树脂No. 1的2. 93g、作为(B)成分的二季戊四醇五和六丙締酸醋(AR0NIX M-402 ;东亚合成株式会社制)0. 30g、作为(B)成分的尿烧丙締酸醋UN3320服(根上工業株式会社制)0. 30g、增感剂DETX - S (日本化药株式会社制)0. 05g、表面活性剂BYK - 323 (BYK Japan株式会社制)的环己酬1% 溶液0.30g、丙二醇一1 -单甲酸一2 -乙酸醋4.72g、W及环己酬10.36g进行混合,添加作为(A)成分的实施例1中得到的化合物No. 1的0.41g并充分揽拌,得到作为本发明的感光性组合物的着色碱显影性感光性树脂组合物No. 6。 [0214] As the component (D) in Example <Step 1> 9 blue dispersion liquid obtained in 10. 63g, impart alkali developability as Example (B) component <Step 1> 5 the resulting alkali-developable resin No. 1 of 2. 93g, (B) is dipentaerythritol pentaacrylate, and vinegar hexapropyl associated component (AR0NIX M-402; manufactured by Toagosei Co.). 0 30g, as component (B) prop-burning urine vinegar UN3320 associated service (the root industry Co., Ltd.) 0 30g, sensitizer DETX -. S (Nippon Kayaku Co., Ltd.) 0 05g, surfactants BYK -. 323 (BYK Japan KK ) cyclohexyl pay 0.30 g 1% solution, propylene glycol 1 - single-carboxylic acid a 2 - acetic acid 4.72g, W and cyclohexanone were mixed 10.36g pay added as component (a) in Example 1 to give compound No 0.41g. 1 and fully embrace mixed to obtain a photosensitive composition of the present invention, the colored alkali-developable photosensitive resin composition No. 6.

[0215] 〔比较例7)着色碱显影性感光性树脂组合物No. 7的制造 [0215] [Comparative Example 7) colored alkali-developable photosensitive resin composition No. 7 for producing

[0216] 除了将实施例1中得到的化合物No. 1替换为乙酬,1 - [9 -乙基一6 - (2 -甲基苯酷基)一9H -巧挫一3 -基]-,1 - (0-乙酷朽)W外,用与实施例10同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 7。 [0216] In addition to the compounds No. 1 obtained in Example 1 was replaced with the embodiment paid acetate, 1 - [9 - ethyl - 6 - (2 - methylphenyl cool-yl) a 9H - a clever fell 3 - yl] - 1 - external (0- cool rot b) W is, with the same manner as in Example 10 to give a colored alkali-developable photosensitive resin composition No. 7 of the comparative products.

[0217] 〔比较例8)着色碱显影性感光性树脂组合物No. 8的制造 [0217] [Comparative Example 8) colored alkali-developable photosensitive resin composition No. 8 in the manufacture

[021引除了将实施例1中得到的化合物No. 1替换为2 -甲基一1 -(4 -甲硫基苯基)一2 -吗嘟代丙烷一1 -酬W外,用与实施例10同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 8。 [021 except that compound No. 1 cited in Example 1 was alternatively be implemented as 2 - methyl - 1 - (4 - methylthiophenyl) - 2 - morpholin a beep iodopropane 1-- W paid, the embodiment with the same manner as in Example 10 to give a comparative article colored alkali-developable photosensitive resin composition No. 8.

[0219] 〔比较例9)着色碱显影性感光性树脂组合物No. 9的制造 [0219] [Comparative Example 9) A colored alkali-developable photosensitive resin composition No. 9 of

[0220] 除了将实施例1中得到的化合物No. 1替换为1,2 -辛二酬,1 - [4 -(苯硫基) 苯基]一,2 - (0-苯酷朽)W外,用与实施例10同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 9。 [0220] except that the compound No. 1 obtained in Example 1, replacing 1,2 - pay suberic, 1 - [4 - (phenylthio) phenyl] a, 2 - (O-benzyl cool rot) W in addition, in the same manner as in Example 10 to give the product as a comparative colored alkali-developable photosensitive resin composition No. 9.

[0221] 〔比较例10)着色碱显影性感光性树脂组合物No. 10的制造 [0221] [Comparative Example 10) producing a colored alkali-developable photosensitive resin composition. No. 10 is

[0222] 除了将实施例1中得到的化合物No. 1替换为2 -苄基一2 -二甲基氨基一1 -(4 -吗嘟代苯基)一1 -下酬W外,用与实施例10同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 10。 [0222] In addition to replacing compound No. 1 obtained in Example 1 of the embodiment 2 - benzyl-2 - dimethylamino - 1 - (4 - it beep substituted phenyl) - 1 - W outside the paid, and with the method of Example 10 of the same embodiment as a comparative product obtained colored alkali-developable photosensitive resin composition No. 10.

[0223] <光刻性> [0223] <lithographic properties>

[0224] 作为得到的着色碱显影性感光性树脂组合物No. 6~10的光刻性的评价,对W下顺序中的感光度、粘附性和残渣,分别使用W下方法进行评价。 [0224] As the colored alkali-developable photosensitive resin composition No. of obtained evaluation photolithography 6 to 10, the sequence of W sensitivity, adhesion and the residue were evaluated using the method in W. 结果示于〔表7)中。 The results are shown in [Table 7).

[0225] 在玻璃基板上旋涂着色碱显影性感光性树脂组合物(500rpm、7秒钟),使用加热板在9(TC下进行90秒钟的预烘烤。然后,使用高压隶灯作为光源,隔着掩模进行规定量(50、 100或150mJ / cm2)的曝光。使用2. 5质量%碳酸钢水溶液作为显影液,用旋转显影机显影45秒钟后,充分水洗,然后使用烘箱在23(TC下进行30分钟的后烘烤,使图案定影。 [0225] spin-on glass substrate painted color alkali-developable photosensitive resin composition (500rpm, 7 seconds), pre-baked using a hot plate at 90 seconds (at 9 TC. Then, using a high-pressure lamp as Li a light source, a predetermined amount through a mask (50, 100 or 150mJ / cm2) exposed using an aqueous solution of 2.5 mass% steels carbonate as the developer, a rotary developing machine after 45 seconds and thoroughly rinsed with water, and then oven after baking for 30 minutes at 23 (TC, the fixing of the pattern.

[0226] (感光度) [0226] (sensitivity)

[0227] 用下述的4个等级评价着色碱显影性感光性树脂组合物的感光度。 [0227] Evaluation of sensitivity with four ranks colored alkali-developable photosensitive resin composition is described below.

[022引旨P,将形成的图案的线宽超过掩模开口线宽时的曝光量为50mJ / cm2的情况设定为曰,将曝光量为IOOmJ / cm2的情况设定为b,将曝光量为150mJ / cm 2的情况设定为C, 将曝光量即使为150mJ / cm2也无法形成图案的情况设定为d。 [022 P cited purpose, the line width of the pattern to be formed over the mask at the exposure amount where the opening width is 50mJ / cm2 of said set, the exposure amount IOOmJ / cm2 in the case of setting is b, the exposed where an amount of 150mJ / cm 2 is set as C, even when the exposure amount d is set to 150mJ / cm2 can not pattern formation.

[022引(粘附性) [022 primers (adhesion)

[0230] 用下述的4个等级评价着色碱显影性感光性树脂组合物的粘附性。 [0230] adhesion evaluation by four ranks colored alkali-developable photosensitive resin composition is described below.

[0231] 旨P,将在IOOmJ / cm2的条件下曝光、显影后残留的图案的最细的掩模线宽为3ym W下的情况设定为A,将超过3 ym但为10 ym W下的情况设定为B,将超过10 ym但为15 ym W下的情况设定为C,将超过15 ym超的情况设定为D。 [0231] purpose by P, and the exposure at IOOmJ / cm2, the line width of the thinnest mask pattern remaining after development is the case 3ym W is set to A, but more than 3 ym for the next 10 ym W the case is set as B, but more than 10 ym as the case where the set 15 ym W is C, over more than 15 ym case is set to D.

[0232] (残渣) [0232] (residue)

[0233] 显影后,将非曝光部的玻璃面上完全观察不到残渣的情况设定为0,将在一面上观察到残渣的情况设定为X。 [0233] After developing, the situation was not observed at the non-glass surface of the exposed portion of the residue is set to 0, in the case where one side of residue was observed was set to X.

Figure CN103298782BD00301

[0236] 由表7可知,本发明的朽醋化合物与比较例7中使用的化合物相比,由于未确认到残渣,所W显影性更加优良。 [0236] As apparent from Table 7, compared with Comparative Compound rot vinegar compound of Example 7 of the present invention is used, since no residue was confirmed, the W further excellent developability. 另外,使用本发明的目亏醋化合物时,与比较例8~10中使用的化合物相比,感光度和粘附性更加优良。 Further, the use of mesh Deficit vinegar compound of the invention, as compared to compounds used in Comparative Examples 10 ~ 8, more excellent sensitivity and adhesion.

[0237] 〔实施例11)着色碱显影性感光性树脂组合物No. 11的制造 [0237] Example 11) colored alkali-developable photosensitive resin composition No. 11 manufactured

[023引将作为(D)成分的实施例9的<步骤1 >中的颜料蓝15 :6变更为炭黑而制作的炭黑分散液7. 06g、赋予碱显影性的作为(B)成分的实施例5的<步骤1 >中得到的碱显影性树脂No. 13. 07g、作为(B)成分的二季戊四醇五和六丙締酸醋(AR0NIX M-402 ;东亚合成株式会社制)0. 53g、表面活性剂BYK - 323 (BYK Japan株式会社制)的环己酬1 %溶液0.30g、丙二醇一1 -单甲酸一2 -乙酸醋8. 16g、W及环己酬10.69g进行混合,添加作为(A)成分的实施例1中得到的化合物No. 1的0. 19g并充分揽拌,得到作为本发明的感光性组合物的着色碱显影性感光性树脂组合物No. 11。 [Example 023 as a primer component (D) 9 <Step 1> Pigment Blue 15: 6 is changed to carbon black dispersion of the carbon black produced 7. 06g, impart alkali developability as component (B) of Example 5 <step 1> obtained in the alkali-developable resin No. 13. 07g, as dipentaerythritol pentaacrylate and hexapropyl associated vinegar (B) component (AR0NIX M-402; manufactured by Toagosei Co.) 0 . 53g, surfactants BYK - 323 (BYK Japan KK) cyclohexyl pay a 1% solution 0.30g, propylene glycol 1 - single-carboxylic acid a 2 - acetic acid 8. 16g, W and cyclohexanone were mixed 10.69g pay added as component (a) obtained in Example 1 compound No. 1 of 0. 19g fully embrace and stirred to obtain a photosensitive composition of the present invention, the colored alkali-developable photosensitive resin composition No. 11.

[0239] 〔实施例12)着色碱显影性感光性树脂组合物No. 12的制造 [0239] [12 manufactured embodiment) colored alkali-developable photosensitive resin composition of Example No. 12

[0240] 除了将实施例1中得到的化合物No. 1替换为实施例2中得到的化合物No. 2 W外, 用与实施例11同样的方法得到作为本发明的感光性组合物即着色碱显影性感光性树脂组合物No. 12。 [0240] Example 1 except that the compound obtained in place of Compound No. 1 to No. 2 W obtained in Example 2, the same method as in Example 11 to obtain a photosensitive composition of the present invention, i.e., colored base developable photosensitive resin composition No. 12.

[0241] 〔实施例13)着色碱显影性感光性树脂组合物No. 13的制造 [0241] [13) Production Example colored alkali-developable photosensitive resin composition. No. 13 is

[0242] 除了将实施例1中得到的化合物No. 1替换为实施例3中得到的化合物No. 3 W外, 用与实施例11同样的方法得到作为本发明的感光性组合物即着色碱显影性感光性树脂组合物No. 13。 [0242] The procedure of Example 1 was replaced with Compound No. 1 Compound No. 3 obtained in Example 3 W, the same method using 11 obtained in Example as a photosensitive composition of the invention, i.e. the colored base developable photosensitive resin composition No. 13.

[0243] 〔比较例11)着色碱显影性感光性树脂组合物No. 14的制造 [0243] [Comparative Example 11) producing a colored alkali-developable photosensitive resin composition No. 14 of the

[0244] 除了将实施例1中得到的化合物No. 1替换为乙酬,1 - [9 -乙基一6 - (2 -甲基苯酷基)一9H -巧挫一3 -基]-,1 - (0-乙酷朽)W外,用与实施例11同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 14。 [0244] In addition to the compounds No. 1 obtained in Example 1 was replaced with the embodiment paid acetate, 1 - [9 - ethyl - 6 - (2 - methylphenyl cool-yl) a 9H - a clever fell 3 - yl] - 1 - external (0- cool rot b) W is, using the same method as in Example 11 to give a colored alkali-developable photosensitive resin composition No. 14 comparative product.

[0245] 〔比较例12)着色碱显影性感光性树脂组合物No. 15的制造 [0245] [Comparative Example 12) colored alkali-developable photosensitive resin composition No. 15 manufactured

[0246] 除了将实施例1中得到的化合物No. 1替换为1,2 -辛二酬,1 - [4 -(苯硫基) 苯基]-,2 - (0-苯酷朽)W外,用与实施例11同样的方法得到作为比较品的着色碱显影性感光性树脂组合物No. 15。 [0246] except that the compound No. 1 obtained in Example 1, replacing 1,2 - pay suberic, 1 - [4 - (phenylthio) phenyl] - 2 - (O-benzyl cool rot) W in addition, using the same method as in Example 11 to give the product as a comparative colored alkali-developable photosensitive resin composition No. 15.

[0247] <光刻性> [0247] <lithographic properties>

[024引作为得到的着色碱显影性感光性树脂组合物No. 11~15的光刻性的评价,对W下顺序中的感光度、粘附性和显影性,分别使用W下方法进行评价。 [024 cited as colored alkali-developable photosensitive resin composition No. of obtained evaluation lithographic 11 to 15, the order of the W, sensitivity, developability and adhesion were evaluated using the method of the W . 结果示于〔表8)中。 The results are shown in [Table 8).

[0249] 在玻璃基板上旋涂着色碱显影性感光性树脂组合物(500rpm、7秒钟),使用加热板在9(TC下进行90秒钟的预烘烤。然后,使用高压隶灯作为光源,隔着掩模进行规定量(100 或120mJ / cm2)的曝光。使用2. 5质量%碳酸钢水溶液作为显影液,用旋转显影机显影45 秒钟后,充分水洗,然后使用烘箱在23(TC下进行30分钟的后烘烤,使图案定影。 [0249] spin-on glass substrate painted color alkali-developable photosensitive resin composition (500rpm, 7 seconds), pre-baked using a hot plate at 90 seconds (at 9 TC. Then, using a high-pressure lamp as Li a light source through the mask by a predetermined amount (100 or 120mJ / cm2) exposed using an aqueous solution of 2.5 mass% steels carbonate as the developer, a rotary developing machine after 45 seconds and thoroughly rinsed with water, and then using an oven at 23 after baking for 30 minutes (at TC, the fixing of the pattern.

[0250] (感光度) [0250] (sensitivity)

[0251] 用下述的3个等级评价着色碱显影性感光性树脂组合物的感光度。 [0251] Evaluation of sensitivity levels with three colored alkali-developable photosensitive resin composition is described below.

[025引旨M尋形成的图案的线宽超过掩模开口线宽时的曝光量为IOOmJ / cm2的情况设定为曰,将曝光量为12011^/01112的情况设定为13,将曝光量即使为12011^/01112也无法形成图案的情况设定为C。 [Purpose primer linewidth of a pattern 025 is formed over mask M to find the exposure amount at a line width of the opening IOOmJ / cm2 was set to said case, an amount of exposure ^ 12011/01112 is set to a case 13, the exposed even in a case where the amount of ^ 12011/01112 can not be set to be patterned C.

[0巧引(粘附性) [0 Qiao primers (adhesion)

[0巧4] 用下述的3个等级评价着色碱显影性感光性树脂组合物的粘附性。 [Qiao 4 0] adhesion with three grade evaluation colored alkali-developable photosensitive resin composition is described below.

[0255]旨M尋在IOOmJ / cm2的条件下曝光、显影后残留的图案的最细的掩模线宽为3ym W下的情况设定为A,将超过3 ym但为5 ym W下的情况设定为B,将超过5 ym超的情况设定为C。 [0255] M aimed at finding IOOmJ / cm2 exposure line width of the thinnest mask pattern remaining after development is the case 3ym W is set to A, but more than 3 ym is at the 5 ym W the case where is set as B, more than 5 ym super set to C.

[0巧引(显影性) [0 Qiao primer (developing property)

[0257] 显影后,将在非曝光部的玻璃面上完全观察不到残渣的情况设定为0,将在整面上都观察到残渣的情况设定为X。 [0257] After developing, the situation observed at residue not set to 0 in the non-exposed portion of the glass surface, the residue was observed on the entire surface of the case is set to X.

[0巧8] 表8 [Qiao 0 8] Table 8

Figure CN103298782BD00321

[0260] 由表8可知,使用本发明的目亏醋化合物时,与比较例12中使用的化合物相比,感光度和粘附性更加良好。 [0260] apparent from Table 8, when using the head loss vinegar compound of the invention, as compared with the compound used in Comparative Example 12, a more excellent adhesion and sensitivity. 另外,与感光度和粘附性良好的比较例11相比,如果使用本发明的月亏醋化合物,则显影性更加优良。 Further, compared with the sensitivity and good adhesion to Comparative Example 11, if the waning vinegar compounds of the invention, the developing property is more excellent.

[0261] 由W上的结果可知W下的事实。 The fact that the W [0261] From the results on W.

[0262] 使用本发明的目亏醋化合物时,与比较例2、3、7和11中使用的化合物相比,可见光区域的透射性和显影性更加优良。 [0262] When the compound of vinegar head loss, compared to the use of compounds 3, 7 and Comparative Example 11, the visible light transmittance and the developing region using the present invention is more excellent.

[0263] 另外,使用本发明的目亏醋化合物时,与比较例4和8中使用的化合物相比,可见光区域的透射性、耐热性、感光度和粘附性更加优良。 [0263] Further, when the head loss vinegar compound, the compound as compared with Comparative Examples 4 and 8 are used, the transmittance, heat resistance, sensitivity, and adhesion more excellent visible light region using the present invention.

[0264] 另外,使用本发明的目亏醋化合物时,与比较例5、9和12中使用的化合物相比,耐热性、感光度和粘附性更加优良。 [0264] Further, when using the head loss vinegar compound of the invention, as compared with Examples 5, 9 and 12 used in the comparative compound, heat resistance, sensitivity and more excellent adhesion.

[0265] 另外,使用本发明的目亏醋化合物时,与比较例1、6和10中使用的化合物相比,可见光区域的透射性、耐热性、感光度和粘附性更加优良。 [0265] Further, when the head loss vinegar compound, and the compound as compared with Comparative Example 10 using 1,6, transmittance, heat resistance, sensitivity, and adhesion more excellent visible light region using the present invention.

[0266] 如上所述,使用本发明的朽醋化合物时,可见光区域的透射性较高,耐热性优良, 光刻性优良,本发明的朽醋化合物作为光聚合引发剂是有用的。 [0266] As described above, when using the compounds of the invention rotten vinegar, high transmittance of visible light region, excellent heat resistance, excellent lithography, rotten vinegar compound of the invention as a photopolymerization initiator is useful.

Claims (9)

1. 一种朽醋化合物,其由下述通式(1)表示, A rotten vinegar compound represented by the following general formula (1),
Figure CN103298782BC00021
式(1)中,ri、r2和r3分别独立地表示氨原子或烷基, r4 表示〇1?11或〇)〇尺11, R"表不烷基, Rii所表示的烷基的氨原子进一步被一0 - C0 - CR21= CR22r23取代, R21、R22和R 23分别独立地表示氨原子或烷基, Rii所表示的烷基的亚烷基部分可W被一nr24coo -中断, R24表示氨原子或烷基, 所述烷基为甲基、乙基、丙基、异丙基、下基、异下基、仲下基、叔下基、戊基、异戊基、叔戊基或己基, X表示氧原子、硫原子或砸原子, a表示1的整数, b表示1的整数。 Formula (1), ri, r2 and r3 are each independently represent amino or alkyl, r4 represents 〇1? Or 11 billion) square foot 11, R "table is not alkyl, the amino alkyl group represented Rii a further 0 - C0 - CR21 = CR22r23 substituted, R21, R22 and R 23 each independently represent an alkylene moiety or alkyl amino group, Rii represented by W may be a nr24coo - interrupt, R24 represents amino atom or an alkyl group, said alkyl is methyl, ethyl, propyl, isopropyl, the group, the isobutyl group, sec-lower group, the tertiary, pentyl, isopentyl, tert-pentyl or hexyl , X represents an oxygen atom, a sulfur atom or a drop atom, a represents an integer of 1, b represents an integer of 1.
2. -种光聚合引发剂,其是含有权利要求1所述的朽醋化合物而形成的。 2. - seed light polymerization initiator which is a compound containing vinegar rot claim 1 is formed.
3. -种感光性组合物,其是含有(A)权利要求2所述的光聚合引发剂和度)具有締键式不饱和键的聚合性化合物而形成的。 3 - Species photosensitive composition which contains a photopolymerization initiator and of the 2) a polymerizable compound having an unsaturated bond formed by the association button (A) as claimed in claim.
4. 根据权利要求3所述的感光性组合物,其中,所述度)具有締键式不饱和键的聚合性化合物中的至少一种是赋予碱显影性的化合物。 4. The photosensitive composition according to claim 3, wherein said degree) is at least one compound having imparting alkali-developable compound polymerizable unsaturated bond in the associated button.
5. 根据权利要求3或4所述的感光性组合物,其是进一步含有(C)无机化合物而形成的。 5. The photosensitive composition according to claim 3 or claim 4, which further comprises (C) an inorganic compound formed.
6. 根据权利要求3或4所述的感光性组合物,其是进一步含有(D)着色剂而形成的。 6. A photosensitive composition according to claim 3 or claim 4, which further comprises (D) a colorant is formed.
7. 根据权利要求5所述的感光性组合物,其是进一步含有(D)着色剂而形成的。 7. The photosensitive composition as claimed in claim 5, which further comprises (D) a colorant is formed.
8. -种固化物,其是通过对权利要求3~7中任一项所述的感光性组合物照射能量射线而形成的。 8. - cured species, which is by 3 to 7 as claimed in claim any one of the photosensitive composition formed by irradiating energy rays.
9. 一种滤色器,其使用了权利要求8所述的固化物。 A color filter, which uses the cured product according to claim 8.
CN201280004665.9A 2011-03-25 2012-02-07 Oxime ester compound and a photopolymerization initiator containing the compound CN103298782B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2011067406 2011-03-25
JP2011-067406 2011-03-25
PCT/JP2012/052775 WO2012132558A1 (en) 2011-03-25 2012-02-07 Oxime ester compound and photoinitiator containing said compound

Publications (2)

Publication Number Publication Date
CN103298782A CN103298782A (en) 2013-09-11
CN103298782B true CN103298782B (en) 2016-04-06

Family

ID=46930324

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280004665.9A CN103298782B (en) 2011-03-25 2012-02-07 Oxime ester compound and a photopolymerization initiator containing the compound

Country Status (5)

Country Link
JP (1) JP6000942B2 (en)
KR (1) KR101930099B1 (en)
CN (1) CN103298782B (en)
TW (1) TWI541221B (en)
WO (1) WO2012132558A1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6333727B2 (en) * 2012-11-01 2018-05-30 株式会社Adeka Alkali developable photosensitive composition
JP5337293B1 (en) * 2012-11-13 2013-11-06 積水化学工業株式会社 Sealant for a liquid crystal display element, vertically conducting material and a liquid crystal display device
WO2015029846A1 (en) * 2013-08-29 2015-03-05 積水化学工業株式会社 Sealant for display element, and oxime ester initiator
WO2017200354A1 (en) * 2016-05-19 2017-11-23 주식회사 삼양사 Oxime ester derivative compound, photopolymerization initiator comprising same, and photosensitive composition
KR101892086B1 (en) * 2016-05-19 2018-08-27 주식회사 삼양사 Oxime ester derivative compounds, photopolymerization initiator, and photosensitive composition containing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007310317A (en) * 2006-05-22 2007-11-29 Fujifilm Corp Photopolymerization composition, color filter, and manufacturing method therefor
JP2009047871A (en) * 2007-08-20 2009-03-05 Fujifilm Corp Composition for holographic recording, holographic recording medium, information recording method and new compound
CN101528682A (en) * 2006-12-27 2009-09-09 株式会社艾迪科 Oxime ester compound and photopolymerization initiator comprising the compound
CN102086171A (en) * 2009-11-27 2011-06-08 株式会社艾迪科 Oxime ester compound and photopolymerization initiator containing the same

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG77689A1 (en) * 1998-06-26 2001-01-16 Ciba Sc Holding Ag New o-acyloxime photoinitiators
JP5507054B2 (en) * 2008-03-28 2014-05-28 富士フイルム株式会社 Polymerizable composition, a color filter, a method of manufacturing a color filter, and a solid-state imaging device
JP2011099974A (en) * 2009-11-05 2011-05-19 Fujifilm Corp Colored photosensitive composition, color filter, and liquid crystal display device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007310317A (en) * 2006-05-22 2007-11-29 Fujifilm Corp Photopolymerization composition, color filter, and manufacturing method therefor
CN101528682A (en) * 2006-12-27 2009-09-09 株式会社艾迪科 Oxime ester compound and photopolymerization initiator comprising the compound
JP2009047871A (en) * 2007-08-20 2009-03-05 Fujifilm Corp Composition for holographic recording, holographic recording medium, information recording method and new compound
CN102086171A (en) * 2009-11-27 2011-06-08 株式会社艾迪科 Oxime ester compound and photopolymerization initiator containing the same

Also Published As

Publication number Publication date
WO2012132558A1 (en) 2012-10-04
TW201242931A (en) 2012-11-01
JPWO2012132558A1 (en) 2014-07-24
TWI541221B (en) 2016-07-11
CN103298782A (en) 2013-09-11
JP6000942B2 (en) 2016-10-05
KR20130140096A (en) 2013-12-23
KR101930099B1 (en) 2018-12-17

Similar Documents

Publication Publication Date Title
JP4223071B2 (en) Photopolymerization initiator containing the oxime ester compound and the compound
JP5354863B2 (en) Oxime derivatives, photopolymerisable compositions, color filters, and a manufacturing method thereof
CN101024624B (en) Oxime derivative, photopolymerisable composition, colour filter and process for producing the same
JP5919657B2 (en) Colored composition, color filters and display devices
EP2327689B1 (en) Oxime ester compound and photopolymerization initiator containing the same
CN102112497B (en) Photoinitiator mixtures
JP2004198542A (en) Color filter black matrix resist composition and photosensitive composition used for same composition
CN102459171A (en) Oxime ester compound, radical polymerization initiator, polymerizable composition, negative resist and image pattern
JP2010015025A (en) Photosensitive composition containing specific photopolymerization initiator
CN101528682A (en) Oxime ester compound and photopolymerization initiator comprising the compound
JP4633582B2 (en) Photosensitive composition
JP5096153B2 (en) Use of pyrimido [5,4-g] pteridines as shading components of a color filter colorant composition
CN102203136B (en) Photoinitiator mixtures
CN1223576C (en) Compound with (methyl) acrylyl radical and its preparation process
JP5744528B2 (en) The colored photosensitive resin composition for a touch panel, a touch panel, and a display device
CN101542392B (en) Photocurable resin composition, dry film, cured product, and printed wiring board
CN102636954B (en) Photocurable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using the same
CN102770495B (en) Polyester base resin composition, and the dry film using the same printed circuit board
CN101855201B (en) Oxime esters and photopolymerization initiators containing the same
CN101546122A (en) Color resist composition and a color filter using the same
CN101553549A (en) Photobase generator and photocurable resin composition
JP6057892B2 (en) Color filters for low temperature applications
WO2006030631A1 (en) Colored alkali developable photosensitive resin composition, and color filter using said colored alkali developable photosensitive resin composition
CN101183217A (en) Photosensitive composition
JP2007212654A (en) Photosensitive coloring composition and a color filter

Legal Events

Date Code Title Description
C06 Publication
C14 Grant of patent or utility model