CN105694582B - 一种光固化阻焊油墨 - Google Patents

一种光固化阻焊油墨 Download PDF

Info

Publication number
CN105694582B
CN105694582B CN201410708692.5A CN201410708692A CN105694582B CN 105694582 B CN105694582 B CN 105694582B CN 201410708692 A CN201410708692 A CN 201410708692A CN 105694582 B CN105694582 B CN 105694582B
Authority
CN
China
Prior art keywords
photo
solder resist
resist ink
phenyl
substituted
Prior art date
Legal status (The legal status 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 status listed.)
Active
Application number
CN201410708692.5A
Other languages
English (en)
Other versions
CN105694582A (zh
Inventor
赵文超
王辰龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yingli Science And Technology Development Co Ltd Beijing
Original Assignee
Yingli Science And Technology Development Co Ltd Beijing
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
Application filed by Yingli Science And Technology Development Co Ltd Beijing filed Critical Yingli Science And Technology Development Co Ltd Beijing
Priority to PCT/CN2015/000825 priority Critical patent/WO2016082304A1/zh
Publication of CN105694582A publication Critical patent/CN105694582A/zh
Application granted granted Critical
Publication of CN105694582B publication Critical patent/CN105694582B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
    • C07D295/135—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/83—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/88—Benzo [c] furans; Hydrogenated benzo [c] furans with one oxygen atom directly attached in position 1 or 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
    • C07D307/935—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans
    • C07D307/937—Not further condensed cyclopenta [b] furans or hydrogenated cyclopenta [b] furans with hydrocarbon or substituted hydrocarbon radicals directly attached in position 2, e.g. prostacyclins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
    • C07D333/66—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B55/00—Azomethine dyes
    • C09B55/009—Azomethine dyes, the C-atom of the group -C=N- being part of a ring (Image)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Indole Compounds (AREA)
  • Materials For Photolithography (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Furan Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Optical Filters (AREA)

Abstract

本发明涉及一种光固化阻焊油墨，其含有：(A)碱溶性树脂，(B)至少一种式(Ⅰ)的光引发剂化合物，(C)分子中具有烯键式不饱和基团的化合物，(D)颜料

Description

一种光固化阻焊油墨
技术领域
本发明涉及一种光固化阻焊油墨的组成及阻焊膜的形成方法，将光固化组合物涂布到基材上使其干燥后，通过掩膜板对该干燥涂膜照射紫外光后，通过碱性水溶液显影而形成阻焊膜图案。
背景技术
在印刷线路板中，电子元件安装在其上预先形成有导电电路图案的印刷电路基材的焊接区上，而焊接区外的所有电路区域都被作为永久保护膜的阻焊膜覆盖。这样，在将电子元件焊接到印刷电路板上时，就可避免焊料粘在无需被焊料覆盖的区域上，并防止构成电路图案的导体因直接暴露于空气中而氧化。
目前，阻焊膜中应用较多的是光固化阻焊油墨。光固化阻焊油墨的使用方法一般为首先将涂膜层在较低温度下烘烤以使溶剂挥发，再利用紫外光照射使其预固化，然后通过稀的碱性水溶液显影，形成图案，之后对涂膜进行高温热固化，最终形成阻焊膜。
现有阻焊油墨中普遍使用的光引发剂如：907、DETX、IRGACURE OXE02或其组合物，它们在图案尺寸的精准度和图案边缘的齐整度方面仍存在欠缺，需要改进。
发明内容
本发明的目的在于，提供一种光固化阻焊油墨，涂布后经曝光和显影得到了图案尺寸更精准、图案边缘更加齐整的阻焊膜。
本发明的光固化阻焊油墨，含有：
(A)碱溶性树脂
(B)光引发剂
(C)分子中具有烯键式不饱和基团的化合物
(D)颜料，
另外可含有(E)溶剂及(F)表面活性剂和(G)填料等非特征性的常规组分。
碱溶性树脂是具有一定酸值特性的树脂，酸值范围一般是30-300mg/gKOH，重均分子量范围在2000-150000。在组合物中质量份数为100份。
一种碱溶性树脂的制备：将甲基丙烯酸苄酯180g、甲基丙烯酸60g、甲基丙烯酸羟乙酯60g、偶氮二异丁腈15g、十二硫醇6g与甲苯1000ml混匀并放入恒压滴液漏斗中；将1000ml甲苯放入三口烧瓶，安装搅拌、恒压滴液漏斗和温度计，开启搅拌，用氮气置换烧瓶中气体；加热烧瓶使溶剂温度达到80‐85℃，保温，开始滴加引发剂溶液，约1h滴完；继续反应6h；自然冷却降温，停止搅拌，等树脂沉降后，吸取上部澄清溶液，过滤下部含溶剂的树脂，并用500ml甲苯淋洗树脂滤饼；减压烘干滤饼，得到白色粉末状固体树脂250g。
光引发剂是吸收光能引起膜层固化的关键组分，其中至少含有一种选自式(Ⅰ)所示的环戊二酮肟酯光引发剂，
其中，
Ar1为取代的邻亚芳基或邻亚杂芳基，该邻亚芳基或邻亚杂芳基以相邻的两个原子与Y1和羰基相连构成并环结构，除R18X取代基外其余原子上的取代基各自独立地为：
氢原子，卤素原子，C1‐C12烷基，C5‐C7环烷基，被C5‐C7环烷基取代的C1‐C4烷基，苯基，任意被一个或多个C1‐C4烷基、羧基、C1‐C12烷基酰基、芳基甲酰基、杂芳基甲酰基、苯基、卤素原子、CN取代的苯基，C1‐C4烷基苄氧基，R1C(O)O取代的C1‐C4烷氧基，C1‐C3亚烷基二氧基，R1C(O)O，C1‐C12烷基硫基，C1‐C4烷基苯硫基，R1C(O)O取代的C1‐C4烷基硫基，CN，羧基，C1‐C12烷氧基甲酰基，芳基甲酰基，杂芳基甲酰基，XR18；
或Ar1的上述取代基中相邻的两个取代基之间或者取代基与Ar1之间通过直键、碳原子、羰基相连构成环状结构；
X为O，S或NR19；
Y1为O，S，NR20，BR20，CR15R16，SiR15R16；
R1为氢原子，C1‐C18烷基或C1‐C18烷氧基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17***的C2‐C18烷基，C2‐C18烯基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代和/或被C5‐C7环亚烷基、亚苯基、O、S、NR17***的C2‐C18烯基；
或R1为C5‐C7环烷基，任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；或R1为苯基，任意被一个或多个C1‐C4烷基、C1‐C4烷氧基、苯基、卤素原子、CN取代的苯基；或R1为萘基；或R1为苯甲酰基，苯氧基羰基，其中苯基任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；
R17为C1‐C4烷基；
R18为氢原子，C1‐C18烷基，C1‐C4烷氧基酰基取代的C1‐C5烷基，R1C(O)O取代的C1‐C4烷基，任意被一个或多个卤素原子、C1‐C4烷基、C5‐C7环烷基、杂环烷基、苯基、杂芳基、CN、C1‐C4烷酰氧基、芳酰氧基取代或被C5‐C7亚环烷基、亚苯基、O、S、NR17***的C2‐C18烷基；或R18为C5‐C7环烷基，或任意被一个或多个C1‐C4烷基、苯基、卤素原子、CN取代的C5‐C7环烷基；或R18为苯基，任意被一个或多个C1‐C12烷基、羧基、C1‐C12烷基酰基、有亚苯基、O、S、NR17***的C2‐C12烷基酰基、C5‐C6环烷基甲酰基、C5‐C6环烷基取代的C2‐C4烷基酰基、芳基甲酰基、杂芳基甲酰基、XR17、苯基、卤素原子、CN、NO2取代的苯基；
或R18为C1‐C4烷基酰基、C1‐C4共轭烯酰基、苯甲酰基、苯氧基羰基，其中苯基任意被一个或两个以上卤素原子、R17、C5或C6环烷基、CN、OH、XR17取代；
或上述R18通过直键、碳原子、羰基与Ar1或Ar2中的芳环相连构成新的环。
上述式(Ⅰ)所示环戊二酮肟酯光引发剂具体为式(Ⅱ)或式(Ⅲ)化合物。
该光固化阻焊油墨中还可以含有作为共引发剂的其他市售产品，例如选自α‐氨基酮类、硫杂蒽酮类、酰基氧化膦类、二苯甲酮类、咔唑肟酯类、芳基‐1,2‐二酮‐2‐肟酯类光引发剂；这些类光引发剂具体的化合物可以为：
2‐甲基‐2‐(4‐吗啉基)‐1‐[4‐(甲硫基)苯基]‐1‐丙酮，2‐二甲基氨基‐2‐苄基‐1‐(4‐吗啉基苯基)‐1‐丁酮，2‐异丙基噻吨酮，2,4‐二乙基噻吨酮，2,4,6‐三甲基苯甲酰基二苯基氧化膦，二(2,4,6‐三甲基苯甲酰基)苯基氧化膦，4,4’‐二(二甲氨基)二苯甲酮，9‐乙基‐6‐(2‐甲基苯甲酰基)咔唑‐3‐乙酮肟‐O‐乙酸酯，9‐乙基‐6‐(2‐甲基苯甲酰基)咔唑‐3‐(3‐环戊基)丙酮肟‐O‐乙酸酯，1‐(4‐苯硫基)苯基‐1,2‐辛二酮‐2‐肟‐O‐苯甲酸酯，
该光固化阻焊油墨中还含有成分(C)，即分子中具有烯键式不饱和基团的化合物，例如丙烯酸酯类化合物，具体的例子有新戊二醇二丙烯酸酯，二季戊四醇六丙烯酸酯，季戊四醇三丙烯酸酯，季戊四醇四丙烯酸酯，三羟甲基丙烷三丙烯酸酯，乙氧基化三羟甲基丙烷三丙烯酸酯，丙氧基化三羟甲基丙烷三丙烯酸酯，三甘醇二丙烯酸酯，二缩三丙二醇二丙烯酸酯，1,6‐己二醇二丙烯酸酯，新戊二醇二丙烯酸酯，1,4‐丁二醇二丙烯酸酯及环氧丙烯酸酯等。
该光固化阻焊油墨中的成分还有：
(D)颜料，例如酞青绿等颜料及颜料分散体；
(E)溶剂，例如丙二醇甲醚醋酸酯，二丙二醇甲醚醋酸酯，乙二醇***醋酸酯，甲苯，二甲苯，四甲基苯，甲基异丁酮，环己酮，乙酸乙酯，乙酸丁酯，γ‐丁内酯，丙二醇单甲醚，二丙二醇二***等；
(F)表面活性剂，例如含硅消泡剂，颜料分散剂。
(G)填料，例如碳酸钡，硫酸钡，滑石粉，高岭土，石英粉，碳酸镁，碳酸钙，氢氧化铝，钛酸钡，
硅酸铝，硅酸钙，锌白，二氧化钛等。
光固化阻焊油墨中组分(A)碱溶性树脂用量100份质量；(B)光引发剂用量10‐50份质量；(C)分子中具有烯键式不饱和基团的化合物用量40‐200份质量；(D)颜料，用量2‐50份质量。
其他成分(E)溶剂，用量100‐300份质量；(F)表面活性剂和(G)填料用量为适合组合物应用的常规用量。
光固化阻焊油墨适合用作厚度为15‐100μm的干燥涂膜。还可以制成一种干膜，即是将光固化阻焊油墨涂布到基材上后进行干燥而得到的。
干燥的涂膜上覆盖掩膜板，经紫外光曝光后，在碱性显影液中显影，洗去未曝光部分，得到保留的阻焊膜。
紫外线光源一般的是高压汞灯，常用具有365nm发射波长的汞灯或经过光栅过滤的365nm光线。
具体的碱性显影液是氨水、氢氧化钠溶液、氢氧化钾溶液、碳酸钠溶液或碳酸钾溶液等，可以将未曝光的膜层溶解清洗掉。
采用本发明阻焊油墨得到的阻焊膜，具有如下优点：图案尺寸更精准，显影后图案边缘更洁净整齐。
具体实施方式
实施例1
1)阻焊油墨配制：
用表1所示的量(质量份)配合表1所示的成分，并搅拌，混合使其分散，分别得到光固化阻焊油墨配方A-E。
表1
2)阻焊膜成膜过程：
将各个光固化阻焊油墨配方丝网印刷至经去氧化处理的覆铜板上，使用热风循环干燥箱，在75℃下干燥40min，干燥后，缓慢冷却至室温，在其上固定描绘有线宽为20μm及150μm线宽图案的光掩膜，用汞灯以150mJ/cm2的曝光量进行正面曝光，利用1wt％的Na2CO3水溶液以喷压0.25MPa、温度30℃显影90s后，水洗吹干。
3)阻焊膜性能评价：
边缘整齐度评价：
用100倍体式显微镜观察样板图案边缘整齐度。其结果示于表2。判定基准如下：
◎边缘整齐、无破损及多余物、清晰；
○边缘较整齐、边缘有少量锯齿；
△边缘较不整齐、边缘有较多锯齿；
×边缘不整齐或边缘不清晰。
图案精准度评价
用100倍体式显微下测量样板显影图像线宽，并与掩膜图案线宽进行比较。其结果示于表2。判定基准如下：
150μm图案精准度评价：
◎图像尺寸在掩膜尺寸±10％之内；
○图像尺寸在掩膜尺寸±15％之内；
△图像尺寸在掩膜尺寸±20％之内；
×图像尺寸<掩膜尺寸-20％或图像尺寸>掩膜尺寸+20％。20μm图案精准度评价：
◎图像尺寸在掩膜尺寸±5％之内；
○图像尺寸在掩膜尺寸±10％之内；
△图像尺寸在掩膜尺寸±15％之内；
×图像尺寸<掩膜尺寸-15％或图像尺寸>掩膜尺寸+15％。
表2
结论：使用了5-(4-异丙基苯硫基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方A及5-(正丁氧基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方B，边缘齐整度和图案精准度是最优的。
实施例2
更换曝光光源为365nmLED灯，其他过程与实施例1相同，结果列于表3
表3
结论：使用了5-(4-异丙基苯硫基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方A及5-(正丁氧基)茚满-1,2-二酮-2-肟-O-乙酸酯的配方B，在测试中的综合效果较配方C、D、E更好。

Claims (7)

1.一种光固化阻焊油墨，含有：
(A)碱溶性树脂，重量比例是100份；
(B)光引发剂，重量比例是10-50份；
(C)分子中具有烯键式不饱和基团的化合物，重量比例是40-200份；
(D)颜料，重量比例是2-50份；
其特征在于，光引发剂(B)至少含有一种选自式(Ⅰ)所示的环戊二酮肟酯光引发剂，
其中，
Ar1为取代的邻亚苯基，该邻亚苯基以相邻的两个原子与Y1和羰基相连构成并环结构，R18X处于羰基对位，除R18X取代基外其余原子上的取代基为氢原子；
X为S；
Y1为CH2、CHCH3、或C(CH3)2；
R1为甲基，乙基，苯基，2-甲基苯基，3-甲基苯基，2,4,6-三甲基苯基或2,6-二甲氧基苯基；
R18为C1-C18烷基，R1C(O)O取代的C1-C4烷基，或R18为苯基，被一个C1-C12烷基、C1-C8烷基酰基、C5-C6环烷基甲酰基、C5-C6环烷基取代的C2-C4烷基酰基取代的苯基。
2.根据权利要求1所述的光固化阻焊油墨，其特征在于，所述式(Ⅰ)环戊二酮肟酯光引发剂为式(Ⅱ)化合物。
3.根据权利要求1所述的光固化阻焊油墨，其中组分B还含其他光引发剂作为共同引发剂，其他光引发剂选自α-氨基酮类、硫杂蒽酮类、酰基氧化膦类、二苯甲酮类、咔唑肟酯类或芳基-1,2-二酮-2-肟酯。
4.根据权利要求3所述的光固化阻焊油墨，其他光引发剂的具体化合物为：
2-甲基-2-(4-吗啉基)-1-[4-(甲硫基)苯基]-1-丙酮，2-二甲基氨基-2-苄基-1-(4-吗啉基苯基)-1-丁酮，2-异丙基噻吨酮，2,4-二乙基噻吨酮，2,4,6-三甲基苯甲酰基二苯基氧化膦，二(2,4,6-三甲基苯甲酰基)苯基氧化膦，4,4’-二(二甲氨基)二苯甲酮，9-乙基-6-(2-甲基苯甲酰基)咔唑-3-乙酮肟-O-乙酸酯，9-乙基-6-(2-甲基苯甲酰基)咔唑-3-(3-环戊基)丙酮肟-O-乙酸酯或1-(4-苯硫基)苯基-1,2-辛二酮-2-肟-O-苯甲酸酯。
5.根据权利要求1-4任一项所述的光固化阻焊油墨，其特征在于，还含有：
(E)溶剂，用量100-300份质量。
6.根据权利要求1所述的光固化阻焊油墨，用作干燥后厚度为15～100μm的涂膜，该涂膜在经过掩膜曝光后通过稀碱溶液显影形成图案。
7.一种干膜，其是将权利要求1所述的光固化阻焊油墨涂布到基材上后进行干燥而得到的。
CN201410708692.5A 2013-09-02 2014-11-28 一种光固化阻焊油墨 Active CN105694582B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/000825 WO2016082304A1 (zh) 2014-11-28 2015-11-27 一种光固化阻焊油墨

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN201310390911 2013-09-02
CNPCT/CN2014/084541 2014-08-15
PCT/CN2014/084541 WO2015027833A1 (zh) 2013-09-02 2014-08-15 环戊二酮肟酯及其应用

Publications (2)

Publication Number Publication Date
CN105694582A CN105694582A (zh) 2016-06-22
CN105694582B true CN105694582B (zh) 2019-12-31

Family

ID=52585496

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201480000154.9A Active CN103998422B (zh) 2013-09-02 2014-03-19 环戊二酮肟酯及其应用
CN201410708692.5A Active CN105694582B (zh) 2013-09-02 2014-11-28 一种光固化阻焊油墨

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201480000154.9A Active CN103998422B (zh) 2013-09-02 2014-03-19 环戊二酮肟酯及其应用

Country Status (5)

Country Link
JP (1) JP6328642B2 (zh)
KR (1) KR101985054B1 (zh)
CN (2) CN103998422B (zh)
TW (1) TWI617539B (zh)
WO (2) WO2015027702A1 (zh)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103998422B (zh) * 2013-09-02 2016-11-30 北京英力科技发展有限公司 环戊二酮肟酯及其应用
CN104910053B (zh) * 2014-06-09 2017-09-12 北京英力科技发展有限公司 不对称二肟酯化合物及其制造方法与应用
WO2016082304A1 (zh) * 2014-11-28 2016-06-02 北京英力科技发展有限公司 一种光固化阻焊油墨
CN105237383A (zh) * 2015-11-12 2016-01-13 黑龙江大学 一种茚酮衍生物5,6-二羟基-2,3-二氢-1h-茚-1-酮及其制备方法
TWI630460B (zh) * 2015-12-30 2018-07-21 奇美實業股份有限公司 感光性樹脂組成物、彩色濾光片及其液晶顯示元件
TWI664499B (zh) * 2016-06-04 2019-07-01 奇美實業股份有限公司 黑色感光性樹脂組成物及其應用
CN106243635A (zh) * 2016-07-29 2016-12-21 华蓥友达精密模具制造有限公司 一种具有防霉变抗菌功能的3d打印材料
TWI671363B (zh) * 2016-11-30 2019-09-11 奇美實業股份有限公司 感光性樹脂組成物及其應用
TWI671593B (zh) * 2016-12-07 2019-09-11 奇美實業股份有限公司 感光性樹脂組成物及其應用
TWI731033B (zh) * 2017-02-10 2021-06-21 奇美實業股份有限公司 感光性樹脂組成物及其應用
CN107573443B (zh) * 2017-08-15 2022-07-01 宁波七诺新材料科技有限公司 用于3d打印技术由可见光引发的光引发剂组合物及应用
CN109666088A (zh) * 2017-10-16 2019-04-23 北京英力科技发展有限公司 一种双酮肟酯化合物及其制造方法与应用
CN109957350B (zh) * 2017-12-14 2021-08-17 常州强力电子新材料股份有限公司 各向异性导电膜、用于形成其的组合物及其应用
US20220121113A1 (en) 2019-01-23 2022-04-21 Basf Se Oxime ester photoinitiators having a special aroyl chromophore
CN112746138B (zh) * 2019-05-16 2022-01-21 烟台大学 防污超低总碳散发耐磨耗牛皮汽车坐垫革抑制烟雾材料
CN114149517B (zh) * 2020-09-07 2022-12-30 常州强力电子新材料股份有限公司 含噻吩结构的肟酯光引发剂、制备方法及光敏树脂组合物
CN116444460A (zh) * 2022-01-07 2023-07-18 常州强力先端电子材料有限公司 肟酯类化合物、含其光引发剂、光固化树脂组合物及应用
WO2024070695A1 (ja) * 2022-09-26 2024-04-04 富士フイルム株式会社 着色組成物、膜、光学フィルタ、固体撮像素子および画像表示装置
CN115650886A (zh) * 2022-10-15 2023-01-31 瑞红(苏州)电子化学品股份有限公司 肟磺酸酯类光产酸剂及其抗蚀剂组合物应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011033793A (ja) * 2009-07-31 2011-02-17 Fujifilm Corp 新規化合物、重合性組成物、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、並びに、平版印刷版原版

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1180846A (en) * 1967-08-08 1970-02-11 Agfa Gevaert Nv Photopolymerisation of Ethylenically Unsaturated Organic Compounds
US5223506A (en) * 1991-06-04 1993-06-29 Glaxo Inc. Cyclic antitumor compounds
ATE133939T1 (de) * 1992-04-03 1996-02-15 Innothera Lab Sa Indan-1,3-dion und indan-1,2,3-trionderivate, verfahren zu ihrer herstellung und ihrer therapeutische verwendung
CN101111472A (zh) * 2004-12-21 2008-01-23 弗·哈夫曼-拉罗切有限公司 1,2,3,4-四氢化萘和茚满衍生物及其作为5-ht拮抗剂的用途
JP5669386B2 (ja) * 2009-01-15 2015-02-12 富士フイルム株式会社 新規化合物、重合性組成物、カラーフィルタ、及びその製造方法、固体撮像素子、並びに、平版印刷版原版
CN103998422B (zh) * 2013-09-02 2016-11-30 北京英力科技发展有限公司 环戊二酮肟酯及其应用

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011033793A (ja) * 2009-07-31 2011-02-17 Fujifilm Corp 新規化合物、重合性組成物、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子、並びに、平版印刷版原版

Also Published As

Publication number Publication date
JP6328642B2 (ja) 2018-05-23
WO2015027702A1 (zh) 2015-03-05
KR20160096233A (ko) 2016-08-16
TWI617539B (zh) 2018-03-11
CN103998422A (zh) 2014-08-20
TW201509888A (zh) 2015-03-16
WO2015027833A1 (zh) 2015-03-05
KR101985054B1 (ko) 2019-05-31
JP2016500710A (ja) 2016-01-14
CN105694582A (zh) 2016-06-22
CN103998422B (zh) 2016-11-30

Similar Documents

Publication Publication Date Title
CN105694582B (zh) 一种光固化阻焊油墨
JP2008509967A5 (zh)
KR101583538B1 (ko) 다관능 티올 화합물을 함유한 블랙 레지스트용 감광성 수지조성물, 그것을 이용한 컬러필터용 블랙 매트릭스, 및 컬러필터
WO2018196619A1 (zh) 含有可聚合基团的芴肟酯类光引发剂、制备方法及其应用
KR101883164B1 (ko) 비대칭 디옥심에테르 화합물 및 그 제조 방법과 응용
JP4218828B2 (ja) チオール化合物、光重合開始剤組成物および感光性組成物
TWI480696B (zh) A photosensitive resin composition, and a photosensitive member using the same, a method for forming a photoresist pattern, and a method of manufacturing the printed circuit board
KR20200068722A (ko) 트랜스, 트랜스-디케톡심에스테르 이성질체 및 이의 제조 방법과 용도
JP6037708B2 (ja) 感光性樹脂組成物、パターン形成方法、カラーフィルタ、及び表示装置
CN113412289A (zh) 感光性树脂组合物、感光性元件、抗蚀剂图案的形成方法及印刷线路板的制造方法
JP6216133B2 (ja) ２液混合型の主剤及び硬化剤、並びにプリント配線板の製造方法
WO2005029188A1 (ja) 感光性エレメント、レジストパターンの形成方法及びプリント配線板の製造方法
KR20170141708A (ko) 피라졸린계 증감제 및 그 제조방법과 응용
JP2002082428A (ja) アルカリ現像型感光性ペースト組成物
WO2021193232A1 (ja) 感光性樹脂組成物、感光性エレメント、及び配線基板の製造方法
JP2003252918A (ja) 光重合開始剤および感光性組成物
WO2016082304A1 (zh) 一种光固化阻焊油墨
WO2021166082A1 (ja) 感光性樹脂組成物、感光性エレメント、及び配線基板の製造方法
JP3632868B2 (ja) 樹脂組成物及びその硬化物
JP5315909B2 (ja) 重合性組成物およびそれを用いたネガ型レジストおよびそれを用いた画像パターン形成方法。
JP5916482B2 (ja) 感光性導電ペーストおよび導電回路
JP6697125B2 (ja) ９−フェニルアクリジン大分子類光増感剤及びその製造方法、ならびに使用
JPH06348013A (ja) 感光性樹脂組成物
JP2007304542A (ja) 感光性樹脂組成物及び感光性エレメント
JPH04116558A (ja) 螢光体パターンを形成する方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant