CN109188865A - The photosensitive covering film composition of one kind and application - Google Patents

The photosensitive covering film composition of one kind and application Download PDF

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Publication number
CN109188865A
CN109188865A CN201811018276.7A CN201811018276A CN109188865A CN 109188865 A CN109188865 A CN 109188865A CN 201811018276 A CN201811018276 A CN 201811018276A CN 109188865 A CN109188865 A CN 109188865A
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resin binder
photosensitive
meth
composition
film
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CN109188865B (en
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朱霞月
李志强
李伟杰
周光大
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Hangzhou Foster Electronic Materials Co ltd
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Zhejiang Forster New Material Research Institute Co Ltd
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    • 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
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

It include 40-70 parts by weight resin binder, 25-50 parts by weight optical polymerism composition, 1-10 parts by weight photoinitiator and 1-3 parts by weight additive the invention discloses a kind of photosensitive covering film composition and application, the photosensitive covering film composition；Wherein, the resinoid bond is made of the resinoid bond containing epoxy construction of 15-50wt% and (methyl) acrylic compounds alkali soluble resin binder of 50-85wt%.Compared with traditional photosensitive cover film of ink and polyimide, the present invention have the characteristics that weak alkaline aqueous solution development, raw material are easy to get and film directly fits, therefore, have the advantages that it is environmental-friendly, reduce cost, be easy to operate.

Description

Photosensitive covering film composition and application thereof
Technical Field
The invention relates to a photovoltaic material, in particular to a photosensitive covering film composition and application thereof.
Background
In general, solder resist materials used for FPCs (flexible circuit boards) mainly have the functions of "three prevention" and "one resistance": the bridging between conductors or wires is prevented during welding to form a short circuit; the moisture-proof and corrosion-proof function prevents the scratch of the outer surface of the circuit board and the like. Solder resist ink and polyimide cover films are two types of conventional solder resist materials, and are covered on a circuit by a screen printing technology and other technologies, so that the operation is troublesome, and flexible circuit boards are increasingly miniaturized and thinned, which causes a problem of bonding precision during bonding, and therefore, research and development of photosensitive cover films are currently focused. Among them, a dry photosensitive coating film is expected from the viewpoint of reducing environmental load, simplifying production processes, and improving dimensional accuracy.
Patent CN102015835A discloses a polyimide precursor, a photosensitive polyimide precursor composition, a photosensitive dry film and a flexible printed wiring board using the same, which have excellent bending property, but have certain warpage and relatively high cost, and are uneconomical and affect the later assembly of the FPC board. Patent US0178448a1 discloses resin compositions containing carboxylic acid and acrylic acid, but the heat and chemical resistance thereof has certain limitations. Patents US7335460B2 and US7670752B2 disclose photosensitive dry film compositions in which epoxy resin and urethane acrylate are blended, but the heat resistance of the composition is still under consideration because the epoxy resin contains a relatively large amount of rigid structure and the urethane acrylate is easily phase-separated, the film is not uniform and is not subsequently thermally cured.
Disclosure of Invention
The invention aims to provide a photosensitive cover film composition and application thereof aiming at the defects of the prior art, the photosensitive cover film composition can be used as a photosensitive cover solder resist material to be applied to the field of high-precision and micronized FPC flexible circuit boards, has better resolution and excellent folding resistance, and meanwhile, the solder resist film is basically free of warping, resistant to high temperature and relatively low in production cost.
The purpose of the invention is realized by the following technical scheme: a photosensitive coverlay composition comprising: 40-70 parts of resin binder, 25-50 parts of photopolymerizable composition, 1-10 parts of photoinitiator and 1-3 parts of additive. Wherein the resin binder consists of 15-50 wt% of resin binder containing epoxy structure and 50-85 wt% of (meth) acrylic alkali-soluble resin binder.
The resin binder containing an epoxy structure has a structure represented by the general structural formula (I):
wherein,R1、R2、R3each independently selected from H atom, methyl, R4、R5Each independently selected from alkyl chain with 1-7 carbon atoms, R6The epoxy resin binder is characterized by comprising 10-40% of structural units of a, b, c, d and e, 25-60% of structural units of c, d and e, 2-8% of structural units of c, d and e, and 3-12% of structural units of c, d and e.
The (meth) acrylic alkali-soluble resin binder has a structure represented by the general structural formula (II):
wherein R is7、R8、R9、R10Each independently selected from H atom, methyl, R11Selected from alkyl chain with 1-15 carbon atoms, R12The resin binder is selected from methylene chain segments with 1-4 carbon atoms, and the mass contents of the structural units f, g, h and i in the (meth) acrylic acid alkali-soluble resin binder are respectively 15-40%, 30-70%, 2-15% and 5-15%.
Furthermore, in the resin binder, the weight average molecular weight of the resin binder containing the epoxy structure is 60000-80000, and the weight average molecular weight of the (meth) acrylic alkali-soluble resin binder is 80000-120000.
Further, the photopolymerizable composition is composed of 2 or more than 2 of ethoxylated or propoxylated or ethoxylated (meth) acrylate, ethoxylated di (meth) acrylate, ethoxylated propoxylated di (meth) acrylate, ethoxylated bisphenol a diacrylate monomer, propoxylated bisphenol a diacrylate monomer, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, glycerol triacrylate, mixed in an arbitrary ratio.
Further, the photoinitiator is formed by mixing one or more of benzoin ether, benzophenone and derivatives thereof, thioxanthone series compounds, anthraquinone and derivatives thereof, thioxanthone series compounds and hexaarylbisimidazole series compounds according to any proportion, and preferably hexaarylbisimidazole series compounds.
Furthermore, the additive is formed by mixing one or more of dye, pigment, light-induced color coupler, stabilizer, flatting agent and perfume according to any proportion.
Further, the photosensitive covering film composition not only has photosensitive developability, but also has the characteristics of a covering film which is high-temperature resistant, bending resistant and basically free of warping.
Further, the photosensitive covering film composition can be used for obtaining a photosensitive covering film through a known glue solution coating process flow, and is applied to the FPC industry and the like as a protective film.
The invention also provides an application of the photosensitive covering film composition, which comprises the following specific steps: sequentially adding the components of the photosensitive covering film composition into a container, uniformly stirring, coating the composition on a PET film, and drying at 75 ℃ for 20 min; flatly pasting the film on a copper-clad plate, exposing the copper-clad plate by a parallel light exposure machine, developing and washing the copper-clad plate in a sodium carbonate aqueous solution with the mass concentration of 1%, and drying the copper-clad plate at 50 ℃; soaking the copper-clad plate in 3-5% hydrochloric acid aqueous solution for 1-5min, washing with water for 2min, and drying at 50 deg.C to expose carboxyl on (meth) acrylic resin to the outside as much as possible; and finally, thermally curing at the high temperature of about 170-230 ℃ for about 25-35min to ensure that the epoxy group can be thoroughly crosslinked with the carboxyl group to form a high-temperature-resistant covering film, wherein the covering film is a circuit pattern protective layer.
The photosensitive developable covering film composition has the advantages of weak alkaline aqueous solution development, easily obtained raw materials and direct film lamination, so that compared with the traditional printing ink and polyimide photosensitive covering films, the photosensitive developable covering film composition is more cost-saving, convenient to operate and environment-friendly. Particularly, an alkyl acrylic acid structural unit containing 1-6 carbons and an alkyl acrylate structural unit containing 8-15 carbons are properly added in the epoxy resin structure, mainly used for adjusting the flexibility of the resin, wherein the alkyl acrylate structural unit containing 8-15 carbons is particularly preferably 2-ethylhexyl (meth) acrylate, so that the adhesion and the resolution of a finished film can be improved while the flexibility is adjusted, and in addition, a structural unit of a benzene ring is embedded in the structure, so that the high temperature resistance of the epoxy resin is improved. In conclusion, the epoxy resin related to the invention introduces an alkyl ester structure and a benzene ring structure with certain flexibility according to a proper proportion, so that the problem of phase separation generated when the conventional epoxy resin is mixed with other resins due to excessive rigid structures is weakened to a certain extent, the conventional epoxy resin is more uniformly mixed with the acrylic resin containing hydroxyalkyl acrylate structural units, and the developing, pickling and curing can obtain the covering film which is basically free of warpage, high-temperature resistant and good in flexibility.
Detailed Description
The invention is further illustrated below.
The invention discloses a resin binder involved in a photosensitive developing covering film composition. One part is an epoxy resin adhesive containing the structural general formula (I) and consists of five basic structural units. The first unit is 10-40 wt% of glycidyl (meth) acrylate, incorporating an epoxy structure. The second and third units are alkyl acrylate and alkyl methacrylate, respectively, the alkyl group has a carbon number of 1-7, and accounts for 25-60 wt%, and mainly adjusts the flexibility of the whole epoxy resin, including but not limited to methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, and the like. The component containing the alkyl (meth) acrylate having a carbon number of 8 to 15 in the fourth unit of 2 to 8 wt% may be exemplified by, but not limited to, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, etc., and among them, 2-ethylhexyl (meth) acrylate is particularly preferred, mainly for assisting improvement of the overall flexibility of the resin while adjusting the adhesion and resolution. The fifth unit is 3-12 wt% methyl substituted styrene or styrene, and adds certain rigid structure to improve the high temperature resistance of the epoxy resin. The epoxy resin accounts for 15-50 wt% of the total amount of the resin binder, and the weight average molecular weight is controlled to be about 60000-80000.
The other part is (methyl) acrylic acid alkali soluble resin binder containing the structural general formula (II) and containing a carboxyl structure, on one hand, the carboxyl structure is favorable for development under weak alkaline conditions after exposure, and on the other hand, the carboxyl structure participates in the high-temperature ring opening curing process of the epoxy resin to form a final high-temperature resistant covering film, and the high-temperature resistant covering film accounts for 50-85 wt% of the total amount of the resin binder. The resin is acrylic resin, and particularly, the structural unit of the resin needs to contain (methyl) acrylic acid, alkyl (methyl) acrylate, hydroxyalkyl (methyl) acrylate and (methyl substituted) styrene, wherein the hydroxyalkyl (methyl) acrylate comprises hydroxymethyl (methyl) acrylate, hydroxyethyl (methyl) acrylate, hydroxypropyl (methyl) acrylate and hydroxybutyl (methyl) acrylate, and preferably the hydroxyethyl (methyl) acrylate is used as a comonomer, so that the compatibility among the resins can be improved, and the adhesion to a copper foil can be improved, and the mass percent of the hydroxyalkyl (methyl) acrylate in the alkali-soluble resin composition is 2-15%, preferably 3.5-8%. The alkyl (meth) acrylate is not particularly limited as long as the number of carbon atoms in the alkyl chain is in the range of 1 to 15, and the alkyl (meth) acrylate accounts for 30 to 70 mass%. The mass percentage of the (methyl substituted) styrene structural unit in the alkali soluble resin structure is 5-15%, and the mass percentage of the (methyl) acrylic acid structural unit in the alkali soluble resin structure is 15-40%. From the viewpoint of resolution and adhesion, the weight-average molecular weight of the alkali-soluble acrylic resin is controlled to about 80000-120000, and preferably not to exceed 120000.
The photopolymerizable compositions described herein comprise structures comprising at least one ethylenically unsaturated acrylate, including but not limited to ethoxylated propylene oxide or ethoxylated (meth) acrylates, ethoxylated di (meth) acrylates, ethoxylated propylene oxide di (meth) acrylates, ethoxylated bisphenol A diacrylate monomers, propoxylated bisphenol A diacrylate monomers, ethoxylated propoxylated bisphenol A diacrylate monomers, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, ethylene, At least 2 or more than 2 monomers of polypropylene glycol diacrylate and glyceryl tripropionate, accounting for 25-50% of the weight portion. The compound containing alkoxy in the molecular structure adjusts the hydrophilic-hydrophobic water balance of the covering film composition, thereby being beneficial to obtaining good side appearance of an image, improving the resolution and reducing development residues. The combination of compounds with different functionalities can adjust the photosensitive speed and the crosslinking strength, and properly control the flexibility of the film.
The photoinitiator is formed by mixing one or more of benzoin ether, benzophenone and derivatives thereof, thioxanthone series compounds, anthraquinone and derivatives thereof, thioxanthone series compounds, benzoin phenyl ether compounds, acridine series compounds and hexaaryl bisimidazole series compounds according to any proportion, wherein the photoinitiator can be benzoin dimethyl ether, benzoin diethyl ether, benzophenone, Michler copper, 4' -bis (diethylamino) benzophenone, 2-ethylanthraquinone, octaethylanthraquinone, 1, 2-benzoanthraquinone, 2, 3-benzoanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone and 1, 4-naphthoquinone, and the photoinitiator is prepared by mixing 1 to 10 weight parts, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, 2, 3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, diethylthiazolone, chlorothiazolone, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, ethylbenzoin, 9-phenylacridine, 9- (p-methylphenyl) acridine, 9- (p-ethylphenyl) acridine, 9- (p-isopropylphenyl) acridine, 9- (p-tert-butylphenyl) acridine, 9- (p-methoxyphenyl) acridine, 9- (p-ethoxyphenyl) acridine, 9- (p-acetylamino) acridine, 9- (p-dimethylaminophenyl) acridine, 9- (p-cyanophenyl) acridine, 2-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, diethylthiazolone, benzoin ethyl-benzoin, 9-phenylacridine, 9- (p-methylphenyl, 9- (p-chlorophenyl) acridine, 9- (p-bromophenyl) acridine, 9-hydroxyethylacridine, 9-pyridylacridine, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer, hexaarylbisimidazole compound being preferred, 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer being particularly preferred.
The additive is prepared by mixing one or more of dye, pigment, light-induced color coupler, stabilizer, leveling agent, perfume and the like according to any proportion.
The photo-coupler mainly includes leucomalachite green (LMG), victoria blue, diamond green and leucocrystal violet (LCV) or fluoran dyes such as 3-diethylamino-6-methyl-7-anilinofluoran, 2-N, N-dibenzylamino-6-diethylaminofluoran, 2-bromo-3-methyl-6-dibutylaminofluoran, and the like.
The stabilizer includes phenols, hydroquinones, benzotriazoles, aromatic nitro compounds and the like, and conventionally used are tribromomethylphenol, p-hydroxyanisole, hydroquinone, t-butylcatechol, 2, 6-di-t-butyl-p-methylphenol, [ tris (N-nitroso-N-phenylhydroxylamine) aluminum salt ], diphenylnitrosamine, 1, 2, 3-benzotriazole, 1-chloro-1, 2, 3-benzotriazole, bis (N-2-hydroxyethyl) aminomethylene-1, 2, 3-benzotriazole, 4-carboxy-1, 2, 3-benzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.
The leveling agent mainly comprises three types of polyacrylate, organic silicon resin and fluorine surfactant.
The perfume mainly comprises natural perfume and artificially synthesized perfume, including hydrocarbon compounds, alcohol compounds, aldehyde compounds, ketone compounds, aliphatic carboxylic acid and the like.
In addition, the solvent used in the present invention is a conventional ketone and alcohol solvent, and is usually butanone, acetone, ethanol, isopropanol, etc.
The photosensitive covering film composition not only has photosensitive developing property, but also has the characteristics of high temperature resistance, bending resistance and basically no warping of the covering film, and is realized by the following modes: sequentially adding all components of the photosensitive covering film composition into a container, uniformly stirring, coating the composition on a PET film, drying at 75 ℃ for 20min, flatly pasting the film on a copper-clad plate, exposing by a parallel light exposure machine, developing by a 1% sodium carbonate aqueous solution, washing by water, drying at 50 ℃ at low temperature, soaking the copper-clad plate in a 3-5 wt% hydrochloric acid aqueous solution for 1-5min, washing by water for 2min, drying at 50 ℃ at low temperature to expose carboxyl on (methyl) acrylic resin as far as possible, and finally, thermally curing at about 170-230 ℃ for about 25-35min to ensure that epoxy groups can be thoroughly crosslinked with the carboxyl to form a high-temperature resistant covering film, wherein the covering film is a circuit pattern protective layer.
The present invention will be further described with reference to the following examples. The following are examples specifically illustrating embodiments of the present invention, but the present invention is not limited to these examples.
The synthesis of the resin binder having an epoxy structure is referred to the following method:
under the protection of nitrogen, 120mL of butanone is added into a 500mL four-neck flask equipped with a heating device, a stirring paddle, a serpentine condenser tube, a constant-pressure dropping funnel and a thermometer, all monomers used in the resin formula are added, stirring is started, and the temperature of the heating device is raised to 80 ℃; then, under the protection of nitrogen, 30mL of butanone solution containing 0.7g of azobisisobutyronitrile was slowly added dropwise into the reaction flask at a rate of 1.5 hours, and after the addition, the temperature was maintained for 4 hours. Then, 0.3g of azobisisobutyronitrile was dissolved in butanone and added dropwise to the reaction mixture in two portions, each dropwise addition took 15min, and the mixture was subjected to the second dropwise addition after heat preservation for 1 hour after the first dropwise addition. After the dropwise addition, the heat preservation is continued for 2 hours. The heating and stirring were stopped, and the reaction solution was cooled to room temperature and taken out to obtain an alkali-soluble copolymer resin solution.
Synthetic acrylic binders were made with reference to the following method:
under the protection of nitrogen, 120mL of butanone is added into a 500mL four-neck flask equipped with a heating device, a stirring paddle, a serpentine condenser tube, a constant-pressure dropping funnel and a thermometer, all monomers used in the resin formula are added, stirring is started, and the temperature of the heating device is raised to 80 ℃; then, under the protection of nitrogen, 30mL of butanone solution containing 0.4g of azobisisobutyronitrile is slowly dropped into the reaction flask, the dropping speed is controlled at 1.5 hours, and the temperature is kept for 4 hours after the dropping is finished. Then, 0.3g of azobisisobutyronitrile was dissolved in butanone and added dropwise to the reaction mixture in two portions, each dropwise addition took 15min, and the mixture was subjected to the second dropwise addition after heat preservation for 1 hour after the first dropwise addition. After the dropwise addition, the heat preservation is continued for 2 hours. The heating and stirring were stopped, and the reaction solution was cooled to room temperature and taken out to obtain an alkali-soluble copolymer resin solution.
The components were mixed in the mixing ratio shown in Table 1 below, sufficiently stirred until completely dissolved, vacuum-filtered to remove insoluble matter, and the photosensitive resin composition solution was uniformly coated on a 15 μm-thick PET film as a support using a wire bar coater, dried in a 75 ℃ forced air drying oven for 15 minutes, and then taken out to form a photosensitive dry film having a thickness of about 30 μm. Then, an 18 μm thick PE film was laminated on the surface thereof as a protective layer.
Table 1: resist formulation tables for different examples and comparative examples
In table 1 above:
the proportion of each polymerization monomer in the A-1 epoxy resin binder is as follows:
glycidyl methacrylate, butyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and styrene are as follows:
12\27\44\7\10
the proportion of each polymerization monomer in the A-2 epoxy resin binder is as follows:
glycidyl methacrylate, butyl acrylate, ethyl methacrylate, acrylic acid-2-ethylhexyl ester and styrene are as follows:
12\27\54\3\4
the proportion of each polymerization monomer in the A-3 epoxy resin binder is as follows:
glycidyl methacrylate, butyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and styrene are as follows:
38\30\25\3\4
the proportion of each polymerization monomer in the A-4 epoxy resin binder is as follows:
glycidyl methacrylate, butyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and styrene are as follows:
12\56\25\3\4
the proportion of each polymerization monomer in the A-5 epoxy resin binder is as follows:
glycidyl methacrylate, n-heptyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate and styrene are as follows:
18\25\41\6\10
the proportion of each polymerization monomer in the A-6 epoxy resin adhesive is as follows:
glycidyl methacrylate, butyl acrylate, ethyl methacrylate, 2-ethylhexyl methacrylate and styrene are as follows:
5\45\40\8\2
b-1 methacrylic acid \ ethyl methacrylate \ hydroxyethyl methacrylate \ styrene is:
17\65\13\5
b-2 methacrylic acid \ ethyl methacrylate \ hydroxyethyl methacrylate \ styrene are:
40\35\10\15
b-3, the methacrylic acid \ ethyl methacrylate \ hydroxyethyl methacrylate \ styrene is as follows:
35\55\4\6
b-4 methacrylic acid \ ethyl methacrylate \ hydroxyethyl methacrylate \ styrene are:
35\60\2\3。
the sample preparation methods, sample evaluation methods, and evaluation results of examples 1 to 4 and comparative examples 1 to 3 will be described below.
[ METHOD FOR MAKING SAMPLE ]
And (3) carrying out surface microetching treatment on the surface of the copper foil with the polyimide film on the reverse side, washing with water and drying. Then, a 30um thick photosensitive coating film formed by coating the photosensitive resin composition was applied to a copper-clad laminate subjected to surface processing and preheating to 60 ℃ by a hot-roll laminator while peeling the protective film on the surface of the composition at a roll temperature of 100 ℃. The pressure is controlled at 0.4Mpa, and the film sticking speed is 1.5 m/min. Thus, an imaging element having a dry film resist layer formed on a test substrate on which a copper foil was deposited was obtained.
[ Exposure ] to light
The exposure was carried out at 365nm using a Shisansan parallel light exposure machine C SUN UVE-M552.
[ DEVELOPING ]
And developing the exposed sample by using a sodium carbonate aqueous solution with the mass concentration of 1% at the temperature of 30 ℃, wherein the developing pressure is 1.5bar, and the developing time is 2 times of the shortest developing time. And drying the test substrate at 50 ℃ after the development is finished.
[ Pickling ] with acid
Soaking the dried test substrate in 3-5% hydrochloric acid aqueous solution for 1-2min, taking out, washing with water for 1min, and drying at low temperature of 50 deg.C.
[ HEAT-CURING ]
And placing the dried test substrate in an oven which is heated to 200 +/-30 ℃ in advance for thermal curing for 30 min.
[ evaluation method ]
[ evaluation of photospeed ]
Measured using a 41-grid exposure ruler from Stouffer Graphic Arts instruments as a reference. And adjusting the exposure energy until the number of the photosensitive grids after the substrate is developed is 14-17 grids, wherein the lower the required exposure energy is, the higher the photosensitive speed of the photosensitive dry film is and the higher the sensitivity is.
[ evaluation of resolution ]
The resolution was evaluated using a film RP-4 um, L/S ═ n/400, and after development, observation was performed using an optical microscope, and the minimum line width with good side morphology and complete development clarity was evaluated.
[ HIGH-TEMPERATURE RESISTANCE ]
The resist pattern was placed on a hot plate at 150 ℃ and heated for 2 minutes, and then observed with an optical microscope to evaluate the state of the resist pattern as follows: when the variation in the shape and surface of the resist pattern is not more than 3% with respect to the thickness of the pattern, it is evaluated as "good"; the evaluation was "normal" when the variation ranged from 3% to 5%; changes greater than 10% were evaluated as "poor".
[ pliability ]
The photosensitive dry film is attached to a double-sided soft copper plate with the thickness of 18um or 12um copper under the pressure of 4kg, the temperature of 100 ℃ hot roller and the transmission speed of 1.5m/min, laser is directly subjected to whole plate exposure, and a 41-step photosensitive ruler is used for displaying 14-17 grids. And rubbing the membrane for multiple times by using a 2mm round bar to observe the damage condition of the membrane surface, folding the flexible plate for 3 times if the membrane is basically not damaged, and observing the damage condition of the crease position. The following pattern is used to show the failure.
◎ the round bar is basically unbroken after kneading, and the fold is intact after folding for 3 times
△ the round bar is broken after kneading, and the fold is broken
[ CALLING ]
After coating a 15um thick PET film with a suitable wire bar, drying at 75 ℃/15min in an oven, heat-curing the obtained photosensitive cover film at a high temperature of 200 ± 30 ℃, cutting the coated portion into 20cm × 20cm, and evaluating the warpage as a test sample film by a visual method.
No warpage is noted ◎;
☉, when slight warping has occurred;
the film was warped and rolled into a roll form, and was designated as △.
Table 2: evaluation results of examples and comparative examples
As shown in Table 2 above, the evaluation results of examples 1 to 6 and comparative examples 1 to 3 show that the dry film of the photoresist of the present invention has good resolution, heat resistance and flexibility, and is substantially free from warpage, and can be used as a photosensitive developing cover film.
In the above examples 1 to 6, the resin binder composition ratios were varied but within the scope of the claims, and thus the high temperature resistance, warpage and flexibility were not substantially affected. The functionality of examples 2 and 3 is slightly reduced compared with example 1, thereby causing a slight decrease in exposure speed, while the proportion of the epoxy resin in the resin binder is increased in examples 2 and 3 compared with example 1, resulting in further improvement in flexibility and high temperature resistance, but the resolution is also slightly reduced, thereby not affecting the whole. In example 3, the photoinitiator system was changed from the chlorine-containing bisimidazole compound and thioxanthone system to the pure chlorine-containing bisimidazole compound system, and the exposure rate was slightly decreased, but the other properties were not substantially affected. In example 5, the addition of n-heptyl acrylate to the epoxy resin structure can balance the flexibility of the film better, compared with example 6, when the photoinitiator is replaced by a fluorine-containing bisimidazole compound, the polymerization of the monomers in the resin composition can be initiated better, but the exposure speed is reduced by about 5 mj.
Compared with the example 5, the epoxy resin of A-6 is used for replacing A-5 in the comparative example 1, and the monomer structures of glycidyl methacrylate and styrene in the resin structure are greatly reduced, so that the final flexibility, high temperature resistance and warping condition of the covering film are obviously deteriorated. In comparative example 2, in which the acrylic resin of B-4 was used instead of B-3, the monomer structures of hydroxyethyl methacrylate and styrene were both significantly reduced in the resin structure, and thus the adhesion was reduced to deteriorate the analysis and the high temperature resistance was also reduced. Comparative example 3 excessively decreases the proportion of the epoxy resin, excessively uses the acrylic resin, resulting in poor final thermosetting effect, deterioration in heat resistance, flexibility and warpage, and excessively increases the proportion of the resin in the resin composition, resulting in a decrease in the proportion of the photopolymerizable monomer, deterioration in adhesion and finally deterioration in resolution.
Therefore, the resin composition has the characteristics of high resolution, good flexibility, good high temperature resistance and basically no warpage, can be better used as a photosensitive developing covering film to be applied to the fine circuit manufacturing industry, has a simple preparation process, and can save a large amount of manpower and material cost.

Claims (8)

1. A photosensitive coverlay composition, comprising: 40-70 parts of resin binder, 25-50 parts of photopolymerizable composition, 1-10 parts of photoinitiator and 1-3 parts of additive. Wherein the resin binder consists of 15-50 wt% of resin binder containing epoxy structure and 50-85 wt% of (meth) acrylic alkali-soluble resin binder.
The resin binder containing an epoxy structure has a structure represented by the general structural formula (I):
wherein R is1、R2、R3Each independently selected from H atom, methyl, R4、R5Each independently selected from alkyl chain with 1-7 carbon atoms, R6The epoxy resin binder is characterized by comprising 10-40% of structural units of a, b, c, d and e, 25-60% of structural units of c, d and e, 2-8% of structural units of c, d and e, and 3-12% of structural units of c, d and e.
The (meth) acrylic alkali-soluble resin binder has a structure represented by the general structural formula (II):
wherein R is7、R8、R9、R10Each independently selected from H atom, methyl, R11Selected from alkyl chain with 1-15 carbon atoms, R12The resin binder is selected from methylene chain segments with 1-4 carbon atoms, and the mass contents of the structural units f, g, h and i in the (meth) acrylic acid alkali-soluble resin binder are respectively 15-40%, 30-70%, 2-15% and 5-15%.
2. The photosensitive coverlay composition of claim 1, wherein the weight average molecular weight of the resin binder containing an epoxy structure is 60000-80000, and the weight average molecular weight of the (meth) acrylic alkali-soluble resin binder is 80000-120000.
3. A photosensitive coverlay composition according to claim 1, wherein the photopolymerizable composition is selected from the group consisting of ethoxylated or propoxylated or ethoxylated (meth) acrylates, ethoxylated di (meth) acrylates, ethoxylated propoxylated di (meth) acrylates, ethoxylated bisphenol A diacrylate monomers, propoxylated bisphenol A diacrylate monomers, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate and glycerol tripropionate in any proportion.
4. A photosensitive coverlay composition according to claim 1, wherein the photoinitiator is formed by mixing one or more of benzoin ether, benzophenone and derivatives thereof, thioxanthone compounds, anthraquinone and derivatives thereof, thioxanthone compounds and hexaarylbisimidazole compounds according to any ratio, preferably hexaarylbisimidazole compounds.
5. A photosensitive coverlay composition according to claim 1, wherein the additive is composed of one or more of a dye, a pigment, a photo-coupler, a stabilizer, a leveling agent, and a perfume, which are mixed in any ratio.
6. The photosensitive coverlay composition of claim 1, wherein the photosensitive coverlay composition has not only photosensitive developability but also high temperature, bending, and substantially warp-free coverlay characteristics.
7. The photosensitive coverlay composition according to claim 1, wherein the photosensitive coverlay composition can be obtained by a known glue solution coating process, and can be used as a protective film in the FPC industry and the like.
8. The application of the photosensitive coverlay composition of claim 1, which is characterized in that the application specifically comprises: sequentially adding the components of the photosensitive covering film composition into a container, uniformly stirring, coating the composition on a PET film, and drying at 75 ℃ for 20 min; flatly pasting the film on a copper-clad plate, exposing the copper-clad plate by a parallel light exposure machine, developing and washing the copper-clad plate in a sodium carbonate aqueous solution with the mass concentration of 1%, and drying the copper-clad plate at 50 ℃; soaking the copper-clad plate in 3-5% hydrochloric acid aqueous solution for 1-5min, washing with water for 2min, and drying at 50 deg.C to expose carboxyl on (meth) acrylic resin to the outside as much as possible; and finally, thermally curing at the high temperature of about 170-230 ℃ for about 25-35min to ensure that the epoxy group can be thoroughly crosslinked with the carboxyl group to form a high-temperature-resistant covering film, wherein the covering film is a circuit pattern protective layer.
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