WO2021036538A1 - 一种感光性树脂组合物及其应用 - Google Patents

一种感光性树脂组合物及其应用 Download PDF

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WO2021036538A1
WO2021036538A1 PCT/CN2020/101205 CN2020101205W WO2021036538A1 WO 2021036538 A1 WO2021036538 A1 WO 2021036538A1 CN 2020101205 W CN2020101205 W CN 2020101205W WO 2021036538 A1 WO2021036538 A1 WO 2021036538A1
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Prior art keywords
resin composition
photosensitive resin
weight
parts
carbonate
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PCT/CN2020/101205
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English (en)
French (fr)
Inventor
朱高华
李伟杰
童荣柏
钱伟强
周光大
林建华
Original Assignee
浙江福斯特新材料研究院有限公司
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Priority claimed from CN201910805259.6A external-priority patent/CN110488570B/zh
Priority claimed from CN201910805266.6A external-priority patent/CN110515271B/zh
Application filed by 浙江福斯特新材料研究院有限公司 filed Critical 浙江福斯特新材料研究院有限公司
Priority to US17/436,628 priority Critical patent/US11827781B2/en
Priority to EP20856265.2A priority patent/EP4024133A4/en
Publication of WO2021036538A1 publication Critical patent/WO2021036538A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0291—Aliphatic polycarbonates unsaturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
    • 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
    • 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
    • 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
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the invention belongs to the technical field of printed circuit boards, and particularly relates to a photosensitive resin composition and its application.
  • photosensitive resin compositions are widely used.
  • the photosensitive resin composition can produce a polymerization reaction after ultraviolet irradiation to form a stable substance to adhere to the plate surface, thereby becoming a resist material in the electroplating and etching processes.
  • PCB functions are correspondingly increased, component sizes are getting smaller and smaller, and the update frequency of a new generation of intelligent electronic products is also becoming more frequent.
  • Film stripping is an indispensable process in the production of printed circuit boards. After the circuit is formed, the photosensitive resist layer is peeled off from the board surface with an alkaline solution. The cleanliness and speed of the film removal on the board directly affect the production efficiency and product yield of the subsequent processes.
  • amine organic stripping liquid can increase the stripping time and reduce the stripping residue, but the production cost will increase correspondingly and it is harmful to the environment; increasing the stripping spray pressure is beneficial to improve the stripping efficiency, but because the FPC is thin and easy to bend , Increasing the spray pressure of the film will cause it to fold, deform, or even jam and cause it to be scrapped.
  • the film removal performance of dry film resists In order to improve the film removal performance of dry film resists, researchers have done a lot of research. Generally, the film removal performance can be improved by increasing the acid value and the content of the hydrophilic group in the photosensitive resin.
  • the patent document CN108490737A regulates the amount of ethylene oxide-propylene oxide block copolymer and the molar amount of ethylenically unsaturated double bonds in the photopolymerizable monomer to prepare a dry film with the characteristics of easy breakage and fast film removal. Film resist, but there is still room for improvement in adhesion.
  • Patent document CN102144189B provides a photosensitive resin composition, which is modified by adding ethylene oxide to polyoxyethylene (tris(1-phenylethyl)) phenyl ether, its resolution, adhesion, and hole capping performance Excellent, but there is still room for improvement in peeling performance.
  • the present invention has developed a photosensitive resin composition in view of the above-mentioned defects of the existing dry film resist and market demand.
  • the resin composition is used as a dry film resist, the film is easy to break and degrade.
  • the film has the advantages of small fragments, fast film removal speed, and excellent flexibility.
  • the purpose of the present invention is to provide a photosensitive resin composition and its application.
  • the photosensitive resin composition of the present invention contains a carbonate structure monomer. After the monomer reacts with light, a long polymer chain with a carbonate structure can be generated. The carbonate structure in the long chain can be quickly combined with a strong Alkaline sodium hydroxide or potassium hydroxide reacts with the stripping solution to realize the cleavage of the long polymer chain of the carbonate structure to generate carbon dioxide. Therefore, when the photosensitive resin composition of the present invention is used as a dry film resist, it has the characteristics of easy breakage of film removal, small film removal fragments, fast film removal speed, etc., and does not affect line resolution and adhesion.
  • a plasticizer containing a carbonate structure is added to the photosensitive resin composition, so that the prepared resin composition has excellent flexibility when used as a dry film resist.
  • the functional group of the carbonate structure can react with the strong alkaline sodium hydroxide or potassium hydroxide removal solution, and the carbonate structure reacts with hydroxide ions to decompose to generate carbon dioxide and small molecules, which makes the dry film resist swell It cracks and peels off quickly from the copper plate. Therefore, when the photosensitive resin composition of the present invention is used as a dry film resist, it has the characteristics of easy breakage of film removal, small film removal fragments, and fast film removal speed. Effectively improve production efficiency and product yield.
  • a photosensitive resin composition comprising 40-70 parts by weight of alkali-soluble resin, 20-50 parts by weight of photopolymerizable monomer, 0.5-10.0 parts by weight of photoinitiator, and 0.1-10.0 parts by weight of additives;
  • the photopolymerizable monomer includes 0.5-15.0 parts by weight of a carbonate structure-containing monomer and/or the additive includes 0.1-8.0 parts by weight of a carbonate structure-containing plasticizer.
  • the monomer containing a carbonate structure is one or more of the following three general structures:
  • R1 is hydrogen or phenyl
  • R2 is hydrogen or methyl
  • R3 is 1,4-phenylene, or one with 1 to 10 carbon atoms Alkylene
  • R4 is a straight or branched chain alkyl group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms
  • R5 is a straight or branched chain alkylene group with 1 to 10 carbon atoms, C6-10 arylene group, or C1-C10 linear or branched alkylene group, C6-10 arylene group in which non-cyclic -CH2- is optionally -O -, -S- or 1,4-phenylene substituted groups.
  • R4 is more preferably methyl, ethyl, or tert-butyl
  • R5 is more preferably methyl, ethyl, 1,4-phenylene.
  • the weight part of the monomer containing the carbonate structure is preferably 0.5-15.0 parts by weight, more preferably 1.0-12.0 parts by weight in consideration of the film removal time and the size of the film. If the weight part is less than 0.5, it will obviously affect the film removal time; if the weight part is higher than 15.0, the size of the membrane is too small, which is not conducive to the collection and treatment of waste membrane debris.
  • the monomer containing a carbonate structure is selected from the group consisting of cinnamyl methyl carbonate, tert-butyl allyl formate, tert-butyl 4-vinylphenyl carbonate, allyl methyl carbonate, double One or more of (2-methylallyl) carbonate and allyl diethylene glycol dicarbonate.
  • R1 and R2 are independently selected from C1-C10 linear or branched alkyl, C3-C10 cycloalkyl, C4-C10 alkylcycloalkyl or cycloalkylalkyl, phenyl, benzyl Groups, C6-C10 aryl groups, C4-C10 heteroaryl groups, C2-C10 heterocyclic groups, or C2-C20 ester-containing groups; and the non-cyclic -CH2- in the above groups can be any Optionally substituted by -O-, -CO-, -NH-, -S- or 1,4-phenylene.
  • R1 and R2 are independently preferably phenyl, benzyl, C6-C10 aryl, C4-C10 heteroaryl, C4-C10 straight chain or
  • the acyclic -CH2- in these groups may be optionally substituted with -O-, -CO-, -NH-, -S- or 1,4-phenylene.
  • the plasticizer containing carbonate structure is selected from diphenyl carbonate, dibutyl carbonate, dibenzyl carbonate, bis(2-methoxyphenyl) carbonate, benzyl phenyl carbonate , One or more of benzyl methyl carbonate and tert-butyl phenyl carbonate.
  • the plasticizer containing a carbonate structure is preferably 0.1-8.0 parts by weight, more preferably 1.0-6.0 parts by weight from the viewpoint of film removal effect. If the weight part is less than 0.1, it will obviously affect the film removal time; if the weight part is higher than 8.0, the size of the membrane is too small, which is not conducive to the collection and treatment of waste membrane debris.
  • the alkali-soluble resin is composed of methacrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, It is formed by copolymerization of two or more of 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, styrene, and styrene derivatives.
  • the alkali-soluble resin is prepared by solution polymerization or suspension polymerization.
  • the weight average molecular weight of the alkali-soluble resin is 20,000-150,000, and the acid value of the resin is 100-350 mg KOH/g; preferably, the weight average molecular weight of the alkali-soluble resin is 30,000- 120,000, the resin acid value is 120-250mg KOH/g.
  • the acid value of the resin is less than 100mg KOH/g, there is a tendency for alkali solubility to become poor and the film stripping time to be longer. When it exceeds 400mg In the case of KOH/g, there is a tendency for the resolution to deteriorate.
  • the weight part of the alkali-soluble resin is preferably 40-70 parts by weight. If the weight part is less than 40 parts, the photosensitive resin composition is likely to overflow and is difficult to store; if the weight part is higher than 70 parts, it will affect the low sensitivity and The risk of poor resolution.
  • the photopolymerizable monomer includes an ethylenically unsaturated double bond monomer.
  • the photopolymerization monomer comprises lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, isobornyl ester , Tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethyl Oxidized (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, One or more of pentaerythri
  • the weight part of the above-mentioned photopolymerizable monomer is preferably 20-50 parts by weight. If the weight part is less than 20 parts, the photosensitive resin composition is likely to cause problems of low sensitivity and low resolution; if the weight part is more than 50 parts, then The photosensitive layer will easily overflow.
  • the photopolymerization initiator is selected from the group consisting of benzoin ether, benzophenone and its derivatives, thioxanthone series compounds, anthraquinone and its derivatives, thioxanthone series compounds, and hexaarylbisimidazole series One or more of the compounds.
  • the photopolymerization initiator is selected from 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxy) Phenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer dimer Compounds, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, etc., preferably 2,2',4-tris(2-chlorophenyl)-5-(3,4- Dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.
  • thioxanthone benzoin phenyl ether, benzophenone, benzoin methyl ether, N,N'-tetramethyl-4,4'-diaminobenzophenone, N ,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino- 1-(4-morpholinylphenyl)-butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone
  • the additives include one or more of plasticizers, defoamers, and polymerization inhibitors.
  • the present invention also provides a use of the above-mentioned photosensitive resin composition as a dry film resist.
  • the photosensitive resin composition of the present invention contains a carbonate structure monomer and/or a carbonate structure plasticizer, the photopolymerization of which has a carbonate structure polymer long chain, and the resin composition is used as a dry film resist It has excellent flexibility when removing the film, and can quickly react with the strong alkaline sodium hydroxide or potassium hydroxide removing liquid to realize the carbonate structure of the polymer long chain or the carbonate structure of the plasticizer The rupture, decomposition and generation of carbon dioxide and small molecules, so that the dry film resist swells and breaks, and quickly peel off from the copper plate.
  • the photosensitive resin composition of the present invention when used as a dry film resist, it has the characteristics of easy breakage of film removal, small film removal fragments, fast film removal speed, excellent flexibility, etc., and good line resolution and adhesion. , Thereby effectively improving production efficiency and product yield.
  • B-6 Bis(2-methylallyl) carbonate, (Hubei Guangao Biological Technology Co., Ltd.).
  • C-2 N-Phenylglycine (West Asia Chemistry).
  • D-4 N,N-Diethylhydroxylamine (Shanghai Bailingwei Chemical Technology Co., Ltd.);
  • a polyethylene film protective layer with a thickness of 20 ⁇ m is attached to the surface of the dry film resist layer to obtain a photosensitive dry film with a three-layer structure.
  • Sample preparation methods including filming, exposure, development, etching, and film removal), sample evaluation methods and evaluation results of the examples and comparative examples.
  • the copper clad plate is polished on its copper surface by a grinder, washed with water, and wiped dry to obtain a bright and fresh copper surface.
  • the sample After the film is attached, the sample is allowed to stand for more than 15 minutes, and use the Zhisheng Technology M-552 parallel light exposure machine for exposure, and use the stouffer 41-step exposure ruler for the photosensitivity test.
  • the number of exposure grids is controlled at 16-22 grids, and the exposure energy is 25-60mJ. /cm2.
  • the sample After exposure, the sample is allowed to stand for more than 15 minutes, the developing temperature is 30°C, the pressure is 1.2Kg/cm2, the developing solution is 1%wt sodium carbonate aqueous solution, and the developing time is 1.5-2.0 times the minimum developing time. After developing, it is washed with water and dried.
  • the etching solution is a copper chloride (CuCl2)/hydrochloric acid (HCL) system
  • the etching temperature is 50°C
  • the pressure is 1.2Kg/cm2
  • the specific gravity of the etching solution is 1.20-1.30g/mL
  • the concentration of hydrochloric acid is 1.5mol/L
  • the concentration of copper ion 120-160g/L is a copper chloride (CuCl2)/hydrochloric acid (HCL) system
  • CuCl2 copper chloride
  • HCL hydrochloric acid
  • the stripping liquid is NaOH, the concentration is 3.0wt%, the temperature is 50°C, the pressure is 1.2Kg/cm2, and the stripping time is 1.5-2.0 times the minimum stripping time. After the stripping, it is washed with water and dried.
  • the film removal speed is evaluated by testing the film removal time. The shorter the film removal time, the faster the film removal speed.
  • the photosensitive dry film resist is laminated on the copper plate by hot pressing film, and the exposed part and the unexposed part are exposed by a mask with a wiring pattern of n:400 in width. After developing at 1.5 times the minimum development time, it will be normal The minimum mask width where the cured resist line is formed is used as the value of adhesion, and observation is performed with a magnifying glass.
  • Example 1-9 The weight part of the carbonate structure monomer in the photopolymerization monomer in Example 1-9 is in the range of 0.1-15.0. From the comparison of Example 1-9 and Comparative Example 1-2 in Table 3, it can be found that: Example 1- 7 The unwinding film breaks cleanly, the unwinding speed is fast, the size of the unwinding film fragments is moderate, and the resolution and adhesion are good. The adhesion and resolution of Examples 8-9 are better, but the film-removing fragments are average.
  • Comparative Example 1 the addition amount of the carbonate structure monomer was 0, which resulted in unclean rupture of the film removal, reduced film removal speed, larger size of the film removal fragments, and decreased adhesion; in Comparative Example 2, the weight of the carbonate structure monomer More than 15.0, although it has no obvious impact on the resolution and adhesion performance, the size of the film removal fragments is too small, which is not conducive to the recovery of the film removal sheet, and it is easy to block the pipes and nozzles.
  • Comparative Example 3 the addition amount of the carbonate structure plasticizer was 0, resulting in unclean film removal, reduced film removal speed, larger size of the film removal fragments, and poor flexibility; in Comparative Example 4, the carbonate structure increased If the weight of the plasticizer exceeds 8.0, although it has no effect on the resolution and adhesion, the size of the film stripping fragments is too small, which is not conducive to the recovery and treatment of the film stripping sheet, and it is easy to block the pipes and nozzles.
  • the photosensitive resin composition of the invention comprises a monomer with a carbonate structure and/or a plasticizer with a carbonate structure, and a long polymer chain with a carbonate structure is obtained by photopolymerization, and the resin composition is used as a dry film resist It has excellent flexibility and can quickly react with the strong alkaline sodium hydroxide or potassium hydroxide removal liquid when removing the film, so as to realize the long chain of the carbonate structure of the polymer or the carbonate structure of the plasticizer. Fracture, decomposition to generate carbon dioxide and small molecules, so that the dry film resist swells and breaks, and quickly peels off from the copper plate.
  • the photosensitive resin composition of the present invention when used as a dry film resist, it has the characteristics of easy breakage of film removal, small film removal fragments, fast film removal speed, excellent flexibility, and good line resolution and adhesion. , Thereby effectively improving production efficiency and product yield.

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Abstract

一种感光性树脂组合物及其应用。树脂组合物包括40-70重量份的碱可溶性树脂、20-50重量份的光聚合单体、0.5-10.0重量份光引发剂和0.1-10.0重量份添加剂；光聚合单体包括0.5-15.0重量份的含有碳酸酯结构的单体。感光性树脂组合物用作干膜抗蚀剂，具有退膜易断裂、退膜碎片较小、退膜速度快等特性，同时线路分辨率、附着力、柔韧性良好，从而有效地提高生产效率和产品良率。

Description

一种感光性树脂组合物及其应用 技术领域
本发明属于印刷线路板技术领域，特别是涉及一种感光性树脂组合物及其应用。
 背景技术
在印刷电路板的制造过程中，广泛使用感光性树脂组合物。感光性树脂组合物在紫外线的照射后能够产生聚合反应形成稳定的物质附着于板面，从而成为电镀和蚀刻制程中的抗蚀剂材料。随着信息传输的数据量不断增加，PCB功能相应增加，部件尺寸越来越小减小，新一代智能电子产品的更新频率也越来越频繁。这就对印刷电路板的高精细化、高密度化、高效生产性均提出更高要求。这就对用作线路图形转移的感光抗蚀层的分辨率、附着力、显影时间和退膜速率等性能方面提出了更高的要求。退膜是印刷电路板制作中必不可少的一道工序。在线路形成后，用碱溶液将感光抗蚀层从板面剥离。板面退膜干净程度和速度直接影响后续工序的生产效率和产品良率。
为了提高生产效率，需要改善退膜时间和效率。退膜时间过长会直接影响生产性和下一步制程工序，导致效率低下；退膜不干净，退膜后即有部分抗蚀层残留在板面上，导致蚀刻不净、报废率增加。较快的退膜时间和退膜无残留有助于缩短产品生产周期，降低生产成本。使用胺类有机去膜液可以提高去膜时间、减少退膜残留，但生产成本相应增加且对环境危害大；提高退膜喷淋压力有利于提高退膜效率，但因FPC厚度薄、易弯曲，提高退膜喷淋压力会导致其折叠，变形、甚至卡板而造成报废。
为了改善干膜抗蚀剂的退膜性能，研究工作者们做了很多研究。一般可通过提高感光性树脂中的酸值和亲水性基团的含量来提高退膜性能。专利文献CN108490737A通过调控环氧乙烷-环氧丙烷嵌段共聚物的用量以及光聚合单体中烯属不饱和双键摩尔量，制得具有退膜易断裂、退膜速度快等特性的干膜抗蚀剂，但附着力仍有提升空间。专利文献CN102144189B提供一种感光性树脂组合物，通过添加环氧乙烷修饰的聚氧亚乙基(三(1-苯基乙基))苯基醚，其分辨率、附着力、盖孔性能优异，但剥离性能仍有改善余地。
综上，本发明针对上述现有干膜抗蚀剂的缺陷及市场需求，开发出一种感光性树脂组合物，该树脂组合物用作干膜抗蚀剂时，具有退膜易断裂、退膜碎片较小、退膜速度快、柔韧性优异等优点。
 技术解决方案
为了解决现有技术中存在的缺陷，本发明的目的在于提供一种感光性树脂组合物及其应用。
本发明的感光性树脂组合物中含有碳酸酯结构的单体，单体在光照反应后能够生成具有碳酸酯结构的高分子长链，在退膜时长链中的碳酸酯结构可快速地与强碱性的氢氧化钠或氢氧化钾退膜液反应，从而实现碳酸酯结构的高分子长链断裂生成二氧化碳。因此，本发明的感光性树脂组合物用作干膜抗蚀剂时，具有退膜易断裂、退膜碎片较小、退膜速度快等特性，同时不影响线路分辨率、附着力。
此外，本发明的另一种技术方案中，感光性树脂组合物中加入含有碳酸酯结构的增塑剂，使得所制得的树脂组合物用作干膜抗蚀剂时拥有优异的柔韧性，在退膜时碳酸酯结构的官能团可与强碱性的氢氧化钠或氢氧化钾退膜液反应，碳酸酯结构与氢氧根离子反应分解生成二氧化碳和小分子，使干膜抗蚀剂膨胀碎裂，快速地从铜板上剥离脱落，因此，本发明的感光性树脂组合物用作干膜抗蚀剂时，具有退膜易断裂、退膜碎片较小、退膜速度快等特性，从而有效地提高生产效率和产品良率。
为了达到上述的目的，本发明采取以下技术方案：
一种感光性树脂组合物，该树脂组合物包括40-70重量份的碱可溶性树脂、20-50重量份的光聚合单体、0.5-10.0重量份光引发剂和0.1-10.0重量份添加剂；该感光性树脂组合物中，所述光聚合单体包括0.5-15.0重量份的含有碳酸酯结构的单体和/或所述添加剂包括0.1-8.0重量份的含有碳酸酯结构的增塑剂。
进一步地，所述含有碳酸酯结构的单体为以下三种通式结构中的一种或多种：
Figure 252584dest_path_image001
，
Figure 750561dest_path_image002
，
Figure 522208dest_path_image003
；
其中，上述通式（1）、（2）和（3）中，R1为氢或者苯基；R2为氢或者甲基；R3为1,4-亚苯基、或碳原子数1~10的亚烷基；R4为碳原子数1~10的直链或支链烷基、或碳原子数2~10的烯基；R5为碳原子数1~10的直链或支链亚烷基、碳原子数6~10的亚芳基、或者碳原子数1～10的直链或支链亚烷基、碳原子数6-10的亚芳基中非环-CH2-任选地被-O-、-S-或1 ,4-亚苯基取代得到的基团。
进一步地，所述通式（1）R4进一步优选甲基，乙基，叔丁基；R5进一步优选甲基，乙基，1 ,4-亚苯基。
进一步地，所述含有碳酸酯结构的单体的重量份，从退膜时间和膜片尺寸考虑，优选0.5-15.0重量份，更优选1.0-12.0重量份。如果重量份低于0.5，会明显影响退膜的时间；如果重量份高于15.0，膜片尺寸太小，不利于废膜屑的收集处理。
进一步地，所述含有碳酸酯结构的单体选自甲基碳酸肉桂酯，甲酸叔丁基烯丙基酯，叔丁基4-乙烯基苯基碳酸酯，烯丙基甲基碳酸酯，双(2-甲基烯丙基)碳酸酯，烯丙基二甘醇二碳酸酯中的一种或多种。
进一步地，所述含有碳酸酯结构的增塑剂的结构式如通式（4）所示：
Figure 909065dest_path_image004
，
其中，R1和R2分别独立地选自C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的烷基环烷基或环烷基烷基、苯基、苄基、C6-C10的芳基、C4-C10的杂芳基、C2-C10的杂环基、或C2-C20的含酯基基团；并且，上述基团中的非环-CH2-可任选地被-O-、-CO-、-NH-、-S-或1 ,4-亚苯基所取代。
进一步地，所述通式（4）中R1和R2分别独立地优选苯基、苄基、C6-C10的芳基、C4-C10的杂芳基、碳原子数为C4-C10的直链或支链烷基，这些基团中的非环-CH2-可任选地被-O-、-CO-、-NH-、-S-或1 ,4-亚苯基所取代。
进一步地，所述含有碳酸酯结构的增塑剂选自碳酸二苯酯，碳酸二丁酯，碳酸二苄酯，双(2-甲氧基苯基)碳酸盐，苄基苯基碳酸酯，苄基甲基碳酸酯，叔丁基苯基碳酸酯中的一种或多种。
进一步地，所述含有碳酸酯结构的增塑剂，从退膜效果考虑，优选0.1-8.0重量份，更优选1.0-6.0重量份。如果重量份低于0.1，会明显影响退膜的时间；如果重量份高于8.0，膜片尺寸太小，不利于废膜屑的收集处理。
进一步地，所述碱可溶性树脂由甲基丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-乙基已酯、（甲基）丙烯酸-2-羟乙酯、(甲基)丙烯酸苄酯、苯乙烯、苯乙烯衍生物中的两种或两种以上的共聚而成。
进一步地，所述碱可溶性树脂通过溶液聚合或悬浮聚合制备而成。
进一步地，所述碱可溶性树脂的重均分子量为20000-150000，树脂酸值为100-350mg KOH/g；优选地，所述碱溶性树脂的重均分子量为30000- 120000，树脂酸值为120-250mg KOH/g。树脂酸值小于100mg KOH/g，存在有碱溶解性变差，退膜时间变长的倾向，当其超过400mg KOH/g时，存在有分辨率变差的倾向。
上述碱可溶性树脂的重量份优选40-70重量份，如果重量份低于40份，则感光性树脂组合物容易溢胶，不易保存；如果重量份高于70份，则会影响存在感度低下和分辨率差的风险。
进一步地，所述光聚合单体包含烯属不饱和双键单体。优选的，所述光聚合单体包含(甲基)丙烯酸月桂酯、(甲基)丙烯酸十八烷基酯、壬基苯酚丙烯酸酯，乙氧化(丙氧化)壬基苯酚丙烯酸酯、异冰片酯、丙烯酸四氢呋喃甲酯、双酚A二(甲基)丙烯酸酯、乙氧化(丙氧化)双酚A二(甲基) 丙烯酸酯、聚乙二醇(丙二醇)二(甲基)丙烯酸酯、乙氧化(丙氧化)新戊二醇二丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、乙氧化(丙氧化)三羟甲基丙烷三(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯中的一种或多种。
上述光聚合单体的重量份，优选20-50重量份，如果重量份低于20份，则感光性树脂组合物容易产生低感度和低分辨率的问题；如果重量份高于50份，则感光层会容易溢胶。
进一步地，所述光聚合引发剂选自安息香醚、二苯甲酮及其衍生物、硫杂蒽酮系类化合物、蒽醌及其衍生物、噻吨酮系列化合物、六芳基双咪唑系列化合物中的一种或多种。
进一步地，所述光聚合引发剂选自2-(邻氯苯基)-4,5-二苯基咪唑二聚物、2-(邻氯苯基)-4,5-二(甲氧基苯基)咪唑二聚物、2-(邻氟苯基)-4,5-二苯基咪唑二聚物、2-(邻甲氧基苯基)-4,5-二苯基咪唑二聚物、2-(对甲氧基苯基)-4,5-二苯基咪唑二聚物等，优选2,2’,4-三(2-氯苯基)-5-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,1’-二咪唑。此外，还可以用噻吨酮、苯偶姻苯基醚、二苯甲酮、苯偶姻甲基醚、N,N'-四甲基-4,4'-二氨基二苯甲酮、N,N'-四乙基-4,4'-二氨基二苯甲酮、4-甲氧基-4'-二甲基氨基二苯甲酮、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)-丁酮、2-乙基蒽醌、菲醌、2-叔丁基蒽醌、八甲基蒽醌、1,2-苯并蒽醌、2,3-苯并蒽醌、2,3-二苯基蒽醌、1-氯蒽醌、2-甲基蒽醌、1,4-萘醌、9,10-菲醌、2,3-二甲基蒽醌、安息香甲醚、安息香乙醚、安息香苯基醚、苯偶酰二甲基缩酮等苯偶酰衍生物、9-苯基吖啶、1,7-二(9,9'-吖啶基)庚烷等吖啶衍生物、N-苯基甘氨酸、香豆素系化合物、恶唑系化合物等中的一种或多种。
进一步地，所述添加剂包括增塑剂、消泡剂、阻聚剂中的一种或者多种。
本发明还提供一种上述感光性树脂组合物用作干膜抗蚀剂的用途。
本发明具有以下技术特点：
本发明的感光树脂组合物包含碳酸酯结构的单体和/或含有碳酸酯结构的增塑剂，其光聚合得到的具有碳酸酯结构的高分子长链，树脂组合物用作干膜抗蚀剂时拥有优异的柔韧性，在退膜时可快速地与强碱性的氢氧化钠或氢氧化钾退膜液反应，从而实现碳酸酯结构的高分子长链或者碳酸酯结构的增塑剂的断裂，分解生成二氧化碳和小分子，使干膜抗蚀剂膨胀碎裂，快速地从铜板上剥离脱落。因此，本发明的感光性树脂组合物用作干膜抗蚀剂时，具有退膜易断裂、退膜碎片较小、退膜速度快、柔韧性优异等特性，同时线路分辨率、附着力良好，从而有效地提高生产效率和产品良率。
 本发明的实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例的技术方案进行清楚、完整的描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明的保护范围。
除非另作定义，本公开所使用的技术术语或者科学术语应当为本发明所属领域内有一般技能的人士所理解的通常意义。
一、实施例1-18和比较例1-4感光性树脂组合物中具体成分及其重量配比（参见表1和表2）
（1）碱溶性树脂A：利用溶液聚合制备，主要成分为甲基丙烯酸/甲基丙烯酸甲酯/甲基丙烯酸正丁酯/丙烯酸月桂酯/苯乙烯＝22/40/15/5/18（Mw＝80,000）。
（2）光聚合单体B：
B-1：(8)乙氧化壬基苯酚丙烯酸酯，分子量626(沙多玛)；
B-2：(9)乙氧化二甲基丙烯酸酯，分子量598(美源)；
B-3：(3)乙氧化三羟甲基丙烷三丙烯酸酯，分子量428(沙多玛)；
B-4：烯丙基二甘醇二碳酸酯，(湖北广奥生物科技有限公司)；
B-5：烯丙基甲基碳酸酯，(湖北广奥生物科技有限公司)；
B-6：双(2-甲基烯丙基)碳酸酯，(湖北广奥生物科技有限公司)。
（3）光引发剂C：
C-1：2,2’,4-三(2-氯苯基)-5-(3,4-二甲氧基苯基)-4’,5’-二苯基-1,1’-二咪唑 (常州强力电子新材料)；
C-2：N-苯基甘氨酸(西亚化学)。
（4）添加剂D：
D-1：灿烂绿颜料(上海百灵威化学技术有限公司)；
D-2：隐色结晶紫(上海百灵威化学技术有限公司)；
D-3：三溴甲基苯基砜(上海梯希爱化工)；
D-4：N，N-二乙基羟胺(上海百灵威化学技术有限公司)；
D-5：碳酸二苄酯(湖北广奥生物科技有限公司)；
D-6：苄基苯基碳酸酯(湖北广奥生物科技有限公司)；
D-7：叔丁基苯基碳酸酯(湖北广奥生物科技有限公司)。
Figure 791570dest_path_image005
Figure 144054dest_path_image006
二、实施例和比较例感光干膜的制备
具体制备步骤如下：
（1）按照表1和表2中感光性树脂组合物各组分的配比，将各组分混合，然后加入丙酮，充分搅拌至完全溶解，得到固含量为40%的树脂组合物溶液；
（2）利用涂布机将上述树脂组合物溶液均匀涂布在厚度15μm的PET支撑膜表面，放在85℃烘箱中烘10min，形成厚度为35μm的干膜抗蚀剂层，在黄光灯下呈现蓝绿色；
（3）在干膜抗蚀剂层表面贴合厚度为20μm的聚乙烯薄膜保护层，即得到了3层结构的感光干膜。
三、实施例和比较例的样品制作方法(包括贴膜、曝光、显影、蚀刻、退膜)、样品评价方法以及评价结果。
（1）样品制作方法
【贴膜】
将覆铜板经打磨机对其铜表面进行抛光处理，水洗，擦干，得到光亮新鲜的铜表面。设置贴膜机压辊温度为110℃，输送速度为1.5m/min，标准压力下热贴合。
【曝光】
贴膜后样品静置15min以上，使用志圣科技M-552型平行光曝光机进行曝光，使用stouffer 41阶曝光尺进行光敏性测试，曝光格数控制在16-22格，曝光能量为25-60mJ/cm2。
【显影】
曝光后样品静置15min以上，显影温度30℃，压力1.2Kg/cm2，显影液为1％wt的碳酸钠水溶液，显影时间为最小显影时间的1.5-2.0倍，显影后水洗、烘干。
【蚀刻】
酸性蚀刻，蚀刻液为氯化铜(CuCl2)/盐酸(HCL)体系，蚀刻温度50℃，压力1.2Kg/cm2，蚀刻液比重1.20-1.30g/mL，盐酸浓度1.5mol/L，铜离子浓度120-160g/L。
【退膜】
退膜液为NaOH，浓度3.0wt％，温度50℃，压力1.2Kg/cm2，退膜时间为最小退膜时间的1.5-2.0倍，退膜后水洗、烘干。
（2）评价方法
【退膜速度评价】
通过测试退膜时间来评价退膜速度，退膜时间越短，退膜速度越快。
【退膜碎片大小评价】
取贴膜、曝光、显影后的基板1块，裁剪成5*5cm的正方形，放入盛有100mL退膜液(浓度3wt％，温度50℃)的烧杯中，磁力搅拌1min后，观察退膜碎片大小。
好：碎片大小10-20mm；一般：碎片大小20-30mm；差：碎片大小30mm以上或5mm以下。
【分辨率的评价】
利用具有曝光部分和未曝光部分的宽度为1:1的布线图案的掩模进行曝光，用最小显影时间的1.5倍显影后，将正常形成了固化抗蚀剂线的最小掩模宽度作为分辨率的值，利用放大镜进行观察。
【附着力的评价】
通过热压贴膜在铜板上层叠感光干膜抗蚀剂，利用具有曝光部分和未曝光部分的宽度为n:400的布线图案的掩模进行曝光，用最小显影时间的1.5倍显影后，将正常形成了固化抗蚀剂线的最小掩模宽度作为附着力的值，利用放大镜进行观察。
【柔韧性的评价】
贴膜、曝光、显影后，将柔性基材从不同角度对折20次，观察干膜是否开裂，统计开裂次数，用数字表示结果，数值越小说明干膜柔韧性越好。
好：对折后干膜开裂0次；一般：对折后干膜开裂1-5次；差：对折后干膜开裂5次以上。
（3）附着力、分辨率、退膜速度、退膜碎片大小的评价结果见表3和表4
Figure 86602dest_path_image007
实施例1-9中光聚合单体中碳酸酯结构单体的重量份在0.1-15.0范围内，由表3中实施例1-9与比较例1-2的对比可以发现：实施例1-7退膜断裂干净、退膜速度快、退膜碎片大小适中，并且分辨率、附着力较好。实施例8-9的附着力、分辨率较好，但退膜碎片一般。比较例1中，碳酸酯结构单体加入量为0，导致退膜断裂不干净，退膜速度下降，退膜碎片尺寸较大，附着力下降；比较例2中，碳酸酯结构单体重量份超过15.0，虽对分辨率、附着力性能无明显影响，但退膜碎片尺寸过小，不利于退膜片的回收处理，易堵塞管道、喷嘴。
Figure 524537dest_path_image008
通过实施例10-18与比较例3-4的对比可以发现：实施例10-18添加剂中的含碳酸酯结构的增塑剂重量份在0.1-8.0范围内，退膜断裂干净、退膜速度快、退膜碎片大小适中，并且分辨率、附着力性能稳定，柔韧性优异。比较例3中，碳酸酯结构的增塑剂加入量为0，导致退膜不干净、退膜速度下降、退膜碎片尺寸较大、柔韧性较差；比较例4中，碳酸酯结构的增塑剂重量份超过8.0，虽对分辨率、附着力无影响，但退膜碎片尺寸过小，不利于退膜片的回收处理，易堵塞管道、喷嘴。
发明的感光树脂组合物包含碳酸酯结构的单体和/或含有碳酸酯结构的增塑剂，其光聚合得到的具有碳酸酯结构的高分子长链，树脂组合物用作干膜抗蚀剂时拥有优异的柔韧性，在退膜时可快速地与强碱性的氢氧化钠或氢氧化钾退膜液反应，从而实现碳酸酯结构的高分子长链或者碳酸酯结构的增塑剂的断裂，分解生成二氧化碳和小分子，使干膜抗蚀剂膨胀碎裂，快速地从铜板上剥离脱落。因此，本发明的感光性树脂组合物用作干膜抗蚀剂时，具有退膜易断裂、退膜碎片较小、退膜速度快、柔韧性优异等特性，同时线路分辨率、附着力良好，从而有效地提高生产效率和产品良率。
以上实施例的说明只是用于帮助理解本发明方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求保护范围内。

Claims (10)

  1. 一种感光性树脂组合物，其特征在于，该树脂组合物包括40-70重量份的碱可溶性树脂、20-50重量份的光聚合单体、0.5-10.0重量份光引发剂和0.1-10.0重量份添加剂；该感光性树脂组合物中，所述光聚合单体包括0.5-15.0重量份的含有碳酸酯结构的单体和/或所述添加剂包括0.1-8.0重量份的含有碳酸酯结构的增塑剂。
  2. 根据权利要求1所述的感光性树脂组合物，其特征在于，所述含有碳酸酯结构的单体为以下三种通式结构中的一种或多种：
    Figure 931696dest_path_image001
    ，
    Figure 404265dest_path_image002
    ，
    Figure 517715dest_path_image003
    ；
    其中，上述通式（1）、（2）和（3）中，R1为氢或者苯基；R2为氢或者甲基；R3为1,4-亚苯基、或碳原子数1~10的亚烷基；R4为碳原子数1~10的直链或支链烷基、或碳原子数2~10的烯基；R5为碳原子数1~10的直链或支链亚烷基、碳原子数6~10的亚芳基、或者碳原子数1～10的直链或支链亚烷基、碳原子数6-10的亚芳基中非环-CH2-任选地被-O-、-S-或1 ,4-亚苯基取代得到的基团。
  3. 根据权利要求1所述的感光性树脂组合物，其特征在于，所述含有碳酸酯结构的单体选自甲基碳酸肉桂酯，甲酸叔丁基烯丙基酯，叔丁基4-乙烯基苯基碳酸酯，烯丙基甲基碳酸酯，双(2-甲基烯丙基)碳酸酯，烯丙基二甘醇二碳酸酯中的一种或多种。
  4. 根据权利要求1所述的感光性树脂组合物，其特征在于，所述含有碳酸酯结构的增塑剂的结构式如通式（4）所示：
    Figure 442946dest_path_image004
    ，
    其中，R1和R2分别独立地选自C1-C10的直链或支链烷基、C3-C10的环烷基、C4-C10的烷基环烷基或环烷基烷基、苯基、苄基、C6-C10的芳基、C4-C10的杂芳基、C2-C10的杂环基、或C2-C20的含酯基基团；并且，上述基团中的非环-CH2-可任选地被-O-、-CO-、-NH-、-S-或1 ,4-亚苯基所取代。
  5. 权利要求1所述的感光性树脂组合物，其特征在于，所述光聚合单体包含烯属不饱和双键单体。
  6. 根据权利要求1所述的感光性树脂组合物，其特征在于，所述碱可溶性树脂由甲基丙烯酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-乙基已酯、（甲基）丙烯酸-2-羟乙酯、(甲基)丙烯酸苄酯、苯乙烯、苯乙烯衍生物中的两种或两种以上的共聚而成。
  7.   根据权利要求1所述的感光性树脂组合物，其特征在于，所述碱可溶性树脂的重均分子量为20000-150000，树脂酸值为100-350mg KOH/g。
  8. 根据权利要求1所述的感光性树脂组合物，其特征在于，所述光聚合引发剂选自安息香醚、二苯甲酮及其衍生物、硫杂蒽酮系类化合物、蒽醌及其衍生物、噻吨酮系列化合物、六芳基双咪唑系列化合物中的一种或多种。
  9. 根据权利要求1所述的感光性树脂组合物，其特征在于，所述添加剂包括增塑剂、消泡剂、阻聚剂中的一种或者多种。
  10. 一种权利要求1-9中任一项所述的感光性树脂组合物用作干膜抗蚀剂的用途。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114456425A (zh) * 2021-12-23 2022-05-10 河源诚展科技有限公司 一种感光干膜及其制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1026826A (ja) * 1996-07-12 1998-01-27 Mitsubishi Chem Corp レーザーダイレクト画像形成材料及びレーザーダイレクト湿し水不要感光性平版印刷版
CN101201543A (zh) * 2006-12-15 2008-06-18 北京化工大学 一种用于印刷电路板的光固化喷墨抗蚀剂及其制备方法
CN101379434A (zh) * 2006-02-08 2009-03-04 日合·莫顿株式会社 感光性树脂组合物及使用该组合物的光刻胶膜
CN102144189A (zh) 2008-09-04 2011-08-03 旭化成电子材料株式会社 感光性树脂组合物、感光性树脂层压体、抗蚀图案形成方法以及导体图案、印刷电路板、引线框、基材和半导体封装的制造方法
CN104497272A (zh) * 2008-10-02 2015-04-08 株式会社钟化 光固化性组合物以及固化物
CN106200266A (zh) * 2015-07-21 2016-12-07 太阳油墨制造株式会社 固化性树脂组合物、干膜、固化物及印刷电路板
CN108027563A (zh) * 2015-04-21 2018-05-11 富士胶片电子材料美国有限公司 光敏性聚酰亚胺组合物
CN108490737A (zh) 2018-03-14 2018-09-04 浙江福斯特新材料研究院有限公司 一种感光性树脂组合物及其用途
CN110488570A (zh) * 2019-08-29 2019-11-22 浙江福斯特新材料研究院有限公司 一种感光性树脂组合物及其用途
CN110515271A (zh) * 2019-08-29 2019-11-29 浙江福斯特新材料研究院有限公司 一种感光性树脂组合物及其应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6855480B2 (en) 2001-04-19 2005-02-15 Shipley Company, L.L.C. Photoresist composition
JP4315892B2 (ja) * 2004-11-25 2009-08-19 東京応化工業株式会社 感光性樹脂組成物、およびこれを用いた感光性ドライフィルム
TWI456346B (zh) * 2008-07-11 2014-10-11 Sumitomo Chemical Co 感光性樹脂組成物
US11635688B2 (en) * 2012-03-08 2023-04-25 Kayaku Advanced Materials, Inc. Photoimageable compositions and processes for fabrication of relief patterns on low surface energy substrates
CN105152710A (zh) 2015-08-05 2015-12-16 马鞍山科邦生态肥有限公司 一种牛奶发酵制备粉叶面肥料及其制备方法
KR102027935B1 (ko) * 2017-01-20 2019-11-04 한화케미칼 주식회사 알칼리 수용성 수지, 이의 제조 방법 및 알칼리 수용성 수지를 포함하는 에멀젼 중합체

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1026826A (ja) * 1996-07-12 1998-01-27 Mitsubishi Chem Corp レーザーダイレクト画像形成材料及びレーザーダイレクト湿し水不要感光性平版印刷版
CN101379434A (zh) * 2006-02-08 2009-03-04 日合·莫顿株式会社 感光性树脂组合物及使用该组合物的光刻胶膜
CN101201543A (zh) * 2006-12-15 2008-06-18 北京化工大学 一种用于印刷电路板的光固化喷墨抗蚀剂及其制备方法
CN102144189A (zh) 2008-09-04 2011-08-03 旭化成电子材料株式会社 感光性树脂组合物、感光性树脂层压体、抗蚀图案形成方法以及导体图案、印刷电路板、引线框、基材和半导体封装的制造方法
CN104497272A (zh) * 2008-10-02 2015-04-08 株式会社钟化 光固化性组合物以及固化物
CN108027563A (zh) * 2015-04-21 2018-05-11 富士胶片电子材料美国有限公司 光敏性聚酰亚胺组合物
CN106200266A (zh) * 2015-07-21 2016-12-07 太阳油墨制造株式会社 固化性树脂组合物、干膜、固化物及印刷电路板
CN108490737A (zh) 2018-03-14 2018-09-04 浙江福斯特新材料研究院有限公司 一种感光性树脂组合物及其用途
CN110488570A (zh) * 2019-08-29 2019-11-22 浙江福斯特新材料研究院有限公司 一种感光性树脂组合物及其用途
CN110515271A (zh) * 2019-08-29 2019-11-29 浙江福斯特新材料研究院有限公司 一种感光性树脂组合物及其应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4024133A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114456425A (zh) * 2021-12-23 2022-05-10 河源诚展科技有限公司 一种感光干膜及其制备方法

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