CN112824973A - Dry film resist laminate - Google Patents
Dry film resist laminate Download PDFInfo
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- CN112824973A CN112824973A CN201911144334.5A CN201911144334A CN112824973A CN 112824973 A CN112824973 A CN 112824973A CN 201911144334 A CN201911144334 A CN 201911144334A CN 112824973 A CN112824973 A CN 112824973A
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- photoinitiator
- phenylglycine
- chlorophenyl
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
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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
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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
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Abstract
The invention provides a dry film resist laminate. The dry film resist laminate includes a support layer, a first resist layer coated on one side surface of the support layer, and a second resist layer; the second resist layer is coated on the surface of one side of the first resist layer, which is far away from the support layer; wherein the exposure rate of the second resist layer is greater than the exposure rate of the first resist layer. A dry film resist is divided into two layers to be superposed, and the two layers absorb the same light source to carry out exposure at different speeds at the same time, so that the problem of poor exposure phenomenon which is easy to occur due to weak photocuring of the bottom of the resist after the dry film thickness is larger, particularly more than 50 mu m, can be solved. Therefore, the dry film resist laminated body is used as a dry film resist laminated body material for etching or plating in the fields of printed circuit boards, lead frames, metal precision processing, semiconductor packaging, IC carrier plate manufacturing and the like, and after pattern exposure and development, a pattern with excellent side appearance and clear water caltrops can be obtained.
Description
Technical Field
The invention relates to the technical field of semiconductor manufacturing, in particular to a dry film resist laminated body.
Background
Dry film resists are widely used as key materials for pattern transfer in printed circuit boards, lead frames, solar cells, conductor packages, bga (ball Grid array), cps (chip Size package) packages. As electronic devices become thinner, smaller, and integrated electronic devices become more dense, wafer level packaging technology and stacked packaging technology become more important, and they have smaller size, better heat dissipation performance and electrical performance than conventional pin-based mounting and mounting. The core of the two packaging technologies is to realize high-performance packaging by utilizing wafer salient points or copper column structures for interconnection and reducing resistivity to accurately transmit signals at high speed. At present, copper columns and wafer bumps are generally manufactured in a mode of 'pattern windowing of an ultra-thick dry film (or photoresist), -blind hole filling, electroplating, window filling and film removing', namely the ultra-thick dry film is the basis for realizing high-performance packaging. However, the thicker the resist layer of the dry film, the more likely the incomplete bottom curing occurs, which eventually results in plating and diffusion or over-plating, and the like, and the short circuit or open circuit of the finished product.
Patents CN106711096A and CN109326575A disclose a copper pillar package substrate, a method for fabricating the same, and a method for fabricating a low-cost redistribution bump package structure, respectively, and do not specifically teach the performance of ultra-thick dry film. Patent CN104536266A describes a dry film resist laminate provided with a dry film resist layer with inconsistent acid value to solve the problem of incomplete development, but fails to solve the problem of incomplete bottom curing of thick dry films. Patent CN106462067A relates to a resist with a high aspect ratio, but unfortunately, the presence of too much sensitizing dye pyrazoline species in the resist tends to deteriorate the side profile of the dry film with a thickness of more than 50 um. The method for reinforcing the thick copper circuit board with the dry film corrosion resistance of patent CN102695367A mainly uses a secondary film pasting and secondary exposure method, but this method may cause overexposure of the bottom and affect the circuit analysis.
Disclosure of Invention
The invention mainly aims to provide a dry film resist laminated body to solve the problems of poor dry film appearance and defects of finished products of corresponding products caused by incomplete curing of the bottom of a resist layer in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a dry film resist laminate comprising: a support layer; the first resist layer is coated on one side surface of the supporting layer; the second resist layer is coated on the surface of one side, far away from the support layer, of the first resist layer; wherein the exposure rate of the second resist layer is greater than the exposure rate of the first resist layer.
Further, the first resist layer contains a first photoinitiator, the second resist layer contains a second photoinitiator, and the first photoinitiator is the same as or different from the second photoinitiator; wherein the first photoinitiator is the same as the second photoinitiator, and the weight percentage of the first photoinitiator in the first resist layer is less than the weight percentage of the second photoinitiator in the second resist layer; or the first photoinitiator is different from the second photoinitiator, the initiation rate of the first photoinitiator is less than the initiation rate of the second photoinitiator, and the weight percentage of the first photoinitiator in the first resist layer and the weight percentage of the second photoinitiator in the second resist layer are the same or different.
Further, the weight percentage of the first photoinitiator in the first resist layer is 0.5-10%, and the weight percentage of the second photoinitiator in the second resist layer is 1-20%.
Further, the first photoinitiator and the second photoinitiator are respectively and independently selected from one or more of 2,4, 5-triaryl imidazole dimer and derivatives thereof, benzoin ether, benzophenone and derivatives thereof, thioxanthone compounds, anthraquinone and derivatives thereof, thioxanthone compounds, pyrazoline compounds, acridine compounds, coumarin compounds and diphenyl phosphine oxide compounds; preferably, the first photoinitiator and the second photoinitiator are respectively and independently selected from one or more of 2,4, 5-triaryl imidazole dimer and derivatives thereof, and acridine series compounds.
Further, the first photoinitiator and the second photoinitiator are each independently selected from one of the following photoinitiator systems: 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/tetraethyl-misonide/N-phenylglycine, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/tetraethyl-misonide/2-mercaptobenzoxazole, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2-isopropylthioxanthone/N-phenylglycine, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-isopropylthioxanthone/N-phenylglycine, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-isopropylthioxanthone/2-mercaptobenzoxazole, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/tetraethyl-mienone/N-phenylglycine, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/tetraethylmikrylon, 9-phenylacridine/N-phenylglycine, 9- (p-methylphenyl) -acridine/N-phenylglycine, 9-phenylacridine/2-mercaptobenzoxazole, 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone, 1, 7-bis (9,9' -acridinyl) heptane/N, N ' -tetraethyl-4, 4' -diaminobenzophenone, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene/7-diethyl-4-methylcoumarin, 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole/1-phenyl-3- (4-methoxystyryl) -5- (4-methoxybenzene) Phenyl) -pyrazoline, 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide.
Further, the first photoinitiator was 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, and the second photoinitiator was 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/tetraethyl-milone and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine; or the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine; or the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/2-isopropylthioxanthone and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropylthioxanthone; or the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/tetraethyl mikrolone/N-phenylglycine; alternatively, the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone; or the first photoinitiator is 9-phenylacridine/2-mercaptobenzoxazole, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 9-phenylacridine/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropyl thioxanthone; or the first photoinitiator 9- (p-methylphenyl) -acridine/N-phenylglycine and the second photoinitiator 9-phenylacridine/N-phenylglycine, or the first photoinitiator 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropylthioxanthone and the second photoinitiator 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone; or the first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene/7-diethyl-4-methylcoumarin; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline; alternatively, the first photoinitiator is 1, 7-bis (9,9' -acridinyl) heptane/N, N ' -tetraethyl-4, 4' -diaminobenzophenone; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator was 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide.
Further, the thickness of the first resist layer is greater than or equal to the thickness of the second resist layer, and preferably, the thickness of the first resist layer is 1.2 to 2.0 times the thickness of the second resist layer.
Further, the first resist layer comprises, by weight, 40-75% of a first carboxyl-containing alkali-soluble copolymer, 20-50% of a first monomer containing at least one polymerizable unsaturated bond, 0.5-10% of a first photoinitiator and 0.01-5% of a first auxiliary agent; the second resist layer comprises, by weight, 40-75% of a second type of alkali-soluble copolymer containing carboxyl groups, 20-50% of a second type of monomer containing at least one polymerizable unsaturated bond, 1-20% of a second photoinitiator, and 0.01-5% of a second type of auxiliary agent.
Further, the first and second carboxyl group-containing alkali-soluble copolymers are obtained by copolymerizing one or more carboxyl group-containing comonomer units and one or more comonomer units not containing carboxyl groups, wherein the carboxyl group-containing comonomer units are itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid half ester, maleic acid, fumaric acid or vinyl acetic acid and anhydrides thereof, and the comonomer units not containing carboxyl groups are methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, methyl acrylate, styrene, alpha-methylstyrene, glycidyl (meth) acrylate, ethyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, butyl N, N-dimethyl (meth) acrylate, butyl N, N-diethyl (meth) acrylate, (meth) acrylamide, N-methylolacrylamide, N-butoxymethyl-acrylamide, phenoxyethyl (meth) acrylate or (alkoxylated) nonylphenol (meth) acrylate.
Further, the acid value of the first type of alkali-soluble copolymer containing carboxyl and the acid value of the second type of alkali-soluble copolymer containing carboxyl are respectively 80-300 mgKOH/g, and the weight average molecular weight is respectively 30000-150000.
Further, the first type of monomer having at least one polymerizable unsaturated bond and the second type of monomer having at least one polymerizable unsaturated bond are each independently selected from the group consisting of ethoxylated (meth) acrylates, propoxylated (meth) acrylates, ethoxylated di (meth) acrylates, ethoxylated propoxylated (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, ethylene glycol diacrylate, propylene glycol, At least two of polypropylene glycol diacrylate, glyceryl tripropionate, lauryl acrylate, isodecyl acrylate, and tetrahydrofuryl methyl acrylate.
Further, the first auxiliary agent and the second auxiliary agent are respectively and independently selected from one or more of dyes, light couplers, color-forming heat stabilizers, plasticizers, pigments, fillers, defoaming agents, flame retardants, stabilizers, flatting agents, peeling promoters, antioxidants, perfumes, imaging agents and thermal crosslinking agents.
The dry film resist laminated body provided by the invention comprises the resist bodies with double-layer structures with different exposure speeds, the exposure speed of the second layer is higher than that of the first layer, one dry film resist body is divided into two layers to be superposed, and the same light source is absorbed to carry out exposure with different speeds at the same time, so that the problem of poor exposure phenomenon which is easy to occur due to the fact that the photo-curing of the bottom of the resist is weak after the dry film thickness is larger and particularly exceeds 50 mu m can be solved. In a word, the dry film resist laminated body provided by the invention has the advantage of thorough bottom curing, and can be used as a dry film resist laminated body material for etching or plating in the fields of printed circuit boards, lead frames, metal precision processing, semiconductor packaging, IC carrier plate manufacturing and the like, and after pattern exposure and development, patterns with excellent side appearance and clear water caltrops can be obtained. The ultra-thick dry film is particularly suitable for manufacturing wafer bumps in wafer level packaging and copper column structures in semiconductor packaging, and high-performance packaging is realized.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the problems of poor dry film appearance and defects of finished products of corresponding products caused by incomplete bottom curing of the resist layer in the prior art are solved.
In order to solve the above problems, the present invention provides a dry film resist laminate comprising a support layer, a first resist layer coated on one side surface of the support layer, and a second resist layer coated on one side surface of the first resist layer remote from the support layer; wherein the exposure rate of the second resist layer is greater than the exposure rate of the first resist layer.
The dry film resist laminated body comprises the resist bodies with the double-layer structures with different exposure speeds, the exposure speed of the second layer is higher than that of the first layer, one dry film resist body is divided into two layers which are overlapped with different thicknesses, the same light source is absorbed, and the exposure with different speeds is carried out at the same time, so that the problem of poor exposure phenomenon which is easy to occur due to the fact that the photo-curing of the bottom of the resist is weak after the dry film thickness is larger and particularly exceeds 50 mu m can be solved. In a word, the dry film resist laminated body provided by the invention has the advantage of thorough bottom curing, and can be used as a dry film resist laminated body material for etching or plating in the fields of printed circuit boards, lead frames, metal precision processing, semiconductor packaging, IC carrier plate manufacturing and the like, and after pattern exposure and development, patterns with excellent side appearance and clear water caltrops can be obtained. The ultra-thick dry film is particularly suitable for manufacturing wafer bumps in wafer level packaging and copper column structures in semiconductor packaging, and high-performance packaging is realized.
During the specific operation, the exposure speed relationship of the first resist layer and the second resist layer is preferably adjusted in the following manner. In a preferred embodiment, the first resist layer contains a first photoinitiator, the second resist layer contains a second photoinitiator, and the first photoinitiator is the same as or different from the second photoinitiator; wherein the first photoinitiator is the same as the second photoinitiator, and the weight percentage of the first photoinitiator in the first resist layer is less than the weight percentage of the second photoinitiator in the second resist layer (manner one); alternatively, the first photoinitiator is different from the second photoinitiator, the initiation rate of the first photoinitiator is less than the initiation rate of the second photoinitiator, and the weight percentage of the first photoinitiator in the first resist layer and the weight percentage of the second photoinitiator in the second resist layer are the same or different (manner two).
In the first mode, due to the fact that the dosage of the photoinitiator contained in the first resist layer and the dosage of the photoinitiator contained in the second resist layer are different, the initiation rates of the first resist layer and the second resist layer are different, the exposure speeds are different, and the curing degree in the same time is different. The second way is to use different photoinitiators or initiating systems to adjust. In the above two modes, the exposure rate relationship between the first resist layer and the second resist layer can be more effectively adjusted, and the exposure rate of the second resist layer can be made higher than the exposure rate of the first resist layer.
The dosage of the photoinitiator is preferably 0.5-20% of the total weight of the resist; preferably, the weight percentage of the first photoinitiator in the first resist layer is 0.5-10%, and the weight percentage of the second photoinitiator in the second resist layer is 1-20%.
In a preferred embodiment, the first photoinitiator and the second photoinitiator are each independently selected from one or more of 2,4, 5-triarylimidazole dimer and derivatives thereof, benzoin ether, benzophenone and derivatives thereof, thioxanthone-based compounds, anthraquinone and derivatives thereof, thioxanthone-based compounds, pyrazoline-based compounds, acridine-based compounds, coumarin-based compounds, diphenylphosphine oxide compounds; preferably, the first photoinitiator and the second photoinitiator are respectively and independently selected from one or more of 2,4, 5-triaryl imidazole dimer and derivatives thereof, and acridine series compounds.
The following groups of photo-initiation systems are exemplified, but not limited thereto, as long as the photo-initiation system satisfying the condition of the exposure speed relationship satisfies the requirements of the present invention: the first photoinitiator and the second photoinitiator are each independently selected from one of the following photoinitiator systems:
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/tetraethyl-mirtaeone/N-phenylglycine,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/tetraethyl-MILdone/2-mercaptobenzoxazole,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2-isopropylthioxanthone/N-phenylglycine,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-isopropylthioxanthone/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-isopropylthioxanthone/2-mercaptobenzoxazole,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/tetraethyl-mikrolone/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/tetraethyl-michelson,
9-phenylacridine/N-phenylglycine,
9- (p-methylphenyl) -acridine/N-phenylglycine,
9-phenylacridine/2-mercaptobenzoxazole,
9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone,
1, 7-bis (9,9' -acridinyl) heptane/N, N ' -tetraethyl-4, 4' -diaminobenzophenone,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene/7-diethyl-4-methylcoumarin,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide.
More preferably, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/tetraethyl-milone and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine; or the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine; or the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/2-isopropylthioxanthone and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropylthioxanthone; or the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/tetraethyl mikrolone/N-phenylglycine; alternatively, the first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone; or the first photoinitiator is 9-phenylacridine/2-mercaptobenzoxazole, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 9-phenylacridine/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropyl thioxanthone; or, the first photoinitiator 9- (p-methylphenyl) -acridine/N-phenylglycine and the second photoinitiator 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropyl thioxanthone, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropyl thioxanthone; or the first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9.10-dibutoxyanthracene and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9.10-dibutoxyanthracene/7-diethyl-4-methylcoumarin; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline; alternatively, the first photoinitiator is 1, 7-bis (9,9' -acridinyl) heptane/N, N ' -tetraethyl-4, 4' -diaminobenzophenone and the second photoinitiator is 2,2' -bis (2-chlorophenyl) -4,4',5,5' -tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; alternatively, the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator was 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide. Of course, the above is a preferred combination but not limited to the above combination.
The thickness of the first resist layer may be an integer of 10 to 100um, and the thickness of the second resist layer may be an integer of 10 to 100 um. Preferably, the first resist layer has a thickness greater than or equal to the second resist layer. Preferably, the first resist layer has a thickness greater than the second resist layer, most preferably the first resist layer has a thickness 1.2 to 2.0 times the thickness of the second resist layer. On the premise of meeting the requirement of sufficient exposure of the second resist layer, the first resist layer can not generate the phenomena of overexposure, so that the conditions of brittleness and fragility of a surface film or poor analysis and the like can be generated, the patterns with excellent side appearance and clear edges and corners can be further obtained, the problem of low yield caused by unqualified image transfer materials in PCB production can be further reduced, and the production quality is improved.
The first resist layer and the second resist layer may contain other components commonly used in the art in addition to the photoinitiator. Certainly, in order to further improve the curing effect of the resist layer and the morphology after pattern transfer, thereby further improving the product yield, in a preferred embodiment, the first resist layer comprises, by weight, 40 to 75% of a first type of alkali-soluble copolymer containing a carboxyl group, 20 to 50% of a first type of monomer containing at least one polymerizable unsaturated bond, 0.5 to 10% of a first photoinitiator, and 0.01 to 5% of a first type of auxiliary agent; the second resist layer comprises, by weight, 40-75% of a second type of alkali-soluble copolymer containing carboxyl groups, 20-50% of a second type of monomer containing at least one polymerizable unsaturated bond, 1-20% of a second photoinitiator, and 0.01-5% of a second type of auxiliary agent.
Preferably, the first and second carboxyl-containing alkali-soluble copolymers are each independently prepared by copolymerizing one or more carboxyl-containing comonomer units and one or more carboxyl-free comonomer units in any ratio, and the preparation method can be well-known preparation methods, such as solution polymerization, suspension polymerization, etc.
Wherein the carboxyl group containing comonomer includes, but is not limited to, itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid half ester, maleic acid, fumaric acid, or vinyl acetic acid and anhydrides thereof, and the comonomer free of carboxyl groups includes, but is not limited to, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, styrene, alpha-methylstyrene, glycidyl (meth) acrylate, ethyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, butyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl 2-acrylate, hydroxypropyl methacrylate, benzyl acrylate, styrene, alpha-methylstyrene, glycidyl (meth) acrylate, n, N-dimethyl (meth) acrylate, N-diethyl (meth) acrylate, (meth) acrylamide, N-methylol-acrylamide, N-butoxymethyl-acrylamide, phenoxyethyl (meth) acrylate or (alkoxylated) nonylphenol (meth) acrylate.
Methacrylic acid, styrene or a derivative thereof, and benzyl methacrylate are preferable as a copolymerization unit of the first type of alkali-soluble copolymer having a carboxyl group and the second type of alkali-soluble copolymer having a carboxyl group in view of improving the adhesion, the image-resolving property, the developing property, and the peelability. From the viewpoint of developing property and improvement of edge and side corrosion resistance, it is more preferable that the acid values of the two types of carboxyl group-containing alkali-soluble polymers are 80 to 300mgKOH/g, preferably 120 to 230mgKOH/g, and the weight average molecular weights are 30000 to 120000, more preferably 50000 to 100000, respectively.
The first and second types of monomers having at least one polymerizable unsaturated bond are not particularly limited as long as they have at least 1 ethylenically unsaturated bond in the molecule, and may be independently selected from the group consisting of, but are not limited to, ethoxylated (meth) acrylate, propoxylated (meth) acrylate, ethoxylated di (meth) acrylate, ethoxylated propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated propylene glycol diacrylate, ethoxylated bisphenol A diacrylate monomer, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, mixtures thereof, and mixtures thereof, At least two of dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, glyceryl tripropionate, lauryl acrylate, isodecyl acrylate, and tetrahydrofurfuryl acrylate. Alternative commercial monomers may be exemplified by sartomer numbers SR454, SR349, SR602, SR541, SR480, SR252, SR644, and the like. The kind and amount of the monomer having at least one polymerizable unsaturated bond used in the first resist layer and the second resist layer may be the same or different.
In addition to the above-mentioned components, an auxiliary may be added as needed. In a preferred embodiment, the first auxiliary and the second auxiliary are each independently selected from one or more of dyes, light couplers, color-forming heat stabilizers, plasticizers, pigments, fillers, defoamers, flame retardants, stabilizers, leveling agents, peeling promoters, antioxidants, fragrances, image forming agents, thermal crosslinking agents. The specific type of use may be that commonly used in the art, for example, the dye may be malachite green or the like, and the color former may be leuco crystal violet or the like.
The dry film resist laminate of the present invention can be used in a solution state with a solid content of 10 to 80% by dissolving a carboxyl group-containing alkali-soluble polymer, a monomer having at least one polymerizable unsaturated bond, a photoinitiator, and an additive in a solvent such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl cellosolve, toluene, N-dimethylformamide, propylene glycol methyl ether acetate, or a mixed solvent of these solvents, as required.
The dry film resist laminate of the present invention can be obtained by: for example, a solution of the first resist layer and a solution of the second resist layer are prepared separately, and the solution of the first resist layer is applied to a colorless support having a certain thickness and dried. After drying, the solution of the second resist layer is continuously applied to the first resist layer and dried (the solution of the first resist layer and the solution of the second resist layer may be applied at a time by multi-stage slide extrusion coating). Then, a polymer cover film for protecting the dry film resist laminate is laminated on the coated dry film resist laminate to finally obtain a dry film.
The support may be a colorless transparent support, and may be a film of, for example, low-density polyethylene, high-density polyethylene, polypropylene, polyester, polyethylene terephthalate, polycarbonate, polyarylate, or the like. In order to avoid the influence of moisture on the physical properties and coating conditions of the dry film resist laminate, the support is preferably a polyethylene terephthalate, polyethylene, or polypropylene film, and the thickness thereof may be 10 to 100. mu.m, preferably 15 to 80 μm.
The polymer cover film is preferably a resin film having low moisture permeability and easy peeling, as well as a transparent support film, but may be transparent or opaque. The cover film is preferably a resin film such as polyethylene terephthalate, polyethylene, or polypropylene having a thickness of 5 to 100 μm.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
The synthesis of the carboxyl group-containing alkali-soluble polymer (a) was carried out by 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, and then vacuum filtered to remove insoluble matter, and the resist laminate having a two-layer structure was formed by coating in the above coating operation.
(1) The following A-1 resin was synthesized according to the above method
Methacrylic acid \ ethyl methacrylate \ hydroxyethyl methacrylate \ benzyl methacrylate \ styrene (32 \43\12\8\5 by weight)
(2) The following monomer (B) containing at least one polymerizable unsaturated monomer is prepared
B-1: (3) ethoxylated trimethylolpropane triacrylate (Saedoma monomer SR454)
B-2 (10) ethoxylated bisphenol A dimethacrylate (Saedoma monomer SR480)
B-3 polyethylene glycol (400) diacrylate (Saedoma monomer SR344)
(3) The following photoinitiators (C) were prepared
C-1:2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole (Changzhou strong electron)
C-2:2, 2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole (Changzhou strong electron)
C-3: 9-phenylacridine (Shanghai Dingwei Gao)
C-4: N-phenylglycine (Shanghai Daiwei)
C-5: 2-mercaptobenzoxazole
C-6: 2-Isopropylthioxanthone (Shanghai Dingwei Gao)
(4) The following other additives (D) were prepared
D-1 alkaline green 1 (Shanghai ladder love chemical)
D-2 tribromomethylphenyl sulfone (Shanghai ladder love chemical industry)
D-3 invisible crystal violet (Shanghai ladder xi ai chemical)
D-4: 5-Carboxybenzotriazole (Shanghai Bailingwei chemical technology Co., Ltd.)
(5) The following solvents (E) were prepared
E-1: butanone
Table 1 formulation table of solutions for different resist layers
(6) After being uniformly mixed according to the proportion in table 1, the mixture was fully stirred, mixed and defoamed, and then coated according to the coating method in table 2.
TABLE 2 Dry film laminate composition and thickness
Remarking: the first layer of resist is a and the second layer of resist is B.
The sample preparation methods, sample evaluation methods, and evaluation results of examples 1 to 12 and comparative examples 1 to 3 will be described below.
[ METHOD FOR MAKING SAMPLE ]
Coating the surface of a 18 μm-thick polyethylene terephthalate film as a support was uniformly coated with the first resist layer solution using a bar coater, dried in a 90 ℃ forced air drying oven for 3 minutes, then taken out to form a first resist layer having a thickness of about 20 μm, and the coating surface of the resist composition 1 was continuously uniformly coated with the second resist layer solution using a bar coater, and dried in a 90 ℃ forced air drying oven for 5 minutes to finally form a second resist layer. The coating composition and thickness of the first and second layers of dry film resist were as per table 2 above.
[ LAMINATION ] to obtain a laminate
While peeling the protective film of the dry film resist laminate at a roll temperature of 105 ℃, the resist was laminated on a copper-clad laminate subjected to surface processing and preheating to 60 ℃ by a hot-roll laminator. The pressure was controlled at 0.3MPa and the lamination speed was 1.5 m/min.
[ 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.
[ evaluation method ]
[ resolution and adhesion evaluation ]
After removing the PE film of the manufactured photosensitive dry film resist laminate, a dry film was laminated on the copper plate by a heating press roller. Then, exposure was performed using a mask having a wiring pattern with a width of 1:1 of an exposed portion and an unexposed portion, and after development with 2 times of the minimum development time, the minimum mask width where a cured resist line was normally formed was taken as a value of resolution. Exposure was performed using a mask having wiring patterns in which different-sized circles were formed in exposed portions and unexposed portions, and after development with 2 times the minimum development time, the minimum circle of cured resist was normally formed as a value of adhesion.
Very good: the resolution value is less than or equal to 35 mu m;
o: resolution value is greater than 35 μm and less than or equal to 45 μm
And (delta): resolution value greater than 45 μm
Very good: the adhesion value is less than or equal to 2 mil;
o: the adhesion value is more than 2mil and less than or equal to 3mil
And (delta): the adhesion value is more than 3mil
[ evaluation of side morphology ]
Evaluating the side feature of the graph: after normal photosensitive development according to the above procedure, whether the unexposed portion of the lines was removed was observed. The shape of the end face of the formed line or the shape of the end face of the formed cylinder after being cut along the diameter vertical side is evaluated, and the rectangular shape of the end face shows that the side appearance is excellent.
Very good: the end face is rectangular;
o: the end faces are substantially rectangular
And (delta): the end surface presents an inverted trapezoid shape;
table 3 evaluation results
Compared with comparative examples 1 to 3, in examples 1 to 12, the exposure speeds of the first resist layer and the second resist layer were controlled by adjusting the initiator system or the amount of the initiator used, due to the adoption of the dry film laminate structure, the obtained lines had a higher degree of curing at the bottom, excellent profile at the sides, improved adhesion, and improved resolution. In comparison with example 13, the film thickness of the first layer is greater than that of the second layer in example 1, and the curing effect is superior to that of example 13. The thickness ratio of the two resist layers in examples 1, 8 and 11 was more preferable and the curing effect was better than that in example 12. In contrast, in comparative examples 2 and 3, a single-layer structure is adopted, and the film is thick, so that the bottom curing is not sufficient, an inverted trapezoidal structure is formed, and the adhesion is weakened. In comparative example 1, since the exposure speed of the first layer was faster than that of the second layer, the intended effect was not achieved as well.
Therefore, as can be seen from table 3 above, the resist laminate provided by the present invention, as a resist material in the fields of printed circuit boards, lead frames, semiconductor packages, precision processing of metals, etc., has the characteristics of good resolution, complete bottom curing, excellent side profile, etc., and is particularly suitable for being used as an ultra-thick dry film for manufacturing wafer bumps in wafer level packaging and copper pillar structures in semiconductor packaging, thereby realizing high performance packaging.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A dry film resist laminate, comprising:
a support layer;
the first resist layer is coated on one side surface of the supporting layer;
the second resist layer is coated on the surface of one side, far away from the support layer, of the first resist layer;
wherein an exposure rate of the second resist layer is greater than an exposure rate of the first resist layer.
2. The dry film resist laminate according to claim 1, wherein the first resist layer contains a first photoinitiator therein, and the second resist layer contains a second photoinitiator therein, the first photoinitiator being the same as or different from the second photoinitiator; wherein the content of the first and second substances,
the first photoinitiator is the same as the second photoinitiator, and the weight percentage of the first photoinitiator in the first resist layer is less than the weight percentage of the second photoinitiator in the second resist layer; or
The first photoinitiator is different from the second photoinitiator, the initiation rate of the first photoinitiator is less than the initiation rate of the second photoinitiator, and the weight percentage of the first photoinitiator in the first resist layer and the weight percentage of the second photoinitiator in the second resist layer are the same or different.
3. The dry film resist laminate according to claim 2, wherein the weight percentage of the first photoinitiator in the first resist layer is 0.5 to 10%, and the weight percentage of the second photoinitiator in the second resist layer is 1 to 20%.
4. The dry film resist laminate according to claim 2 or 3, wherein the first photoinitiator and the second photoinitiator are each independently selected from one or more of 2,4, 5-triarylimidazole dimer and derivatives thereof, benzoin ether, benzophenone and derivatives thereof, thioxanthone-based compounds, anthraquinone and derivatives thereof, thioxanthone-based compounds, pyrazoline-based compounds, acridine-based compounds, coumarin-based compounds, diphenylphosphine oxide compounds; preferably, the first photoinitiator and the second photoinitiator are respectively and independently selected from one or more of 2,4, 5-triaryl imidazole dimer and derivatives thereof, and acridine series compounds.
5. The dry film resist laminate of claim 4, wherein the first photoinitiator and the second photoinitiator are each independently selected from one of the following photoinitiator systems:
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/tetraethyl-mirtaeone/N-phenylglycine,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/tetraethyl-MILdone/2-mercaptobenzoxazole,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2-isopropylthioxanthone/N-phenylglycine,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-isopropylthioxanthone/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-isopropylthioxanthone/2-mercaptobenzoxazole,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/tetraethyl-mikrolone/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine,
2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/tetraethyl-michelson,
9-phenylacridine/N-phenylglycine,
9- (p-methylphenyl) -acridine/N-phenylglycine,
9-phenylacridine/2-mercaptobenzoxazole,
9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone,
1, 7-bis (9,9' -acridinyl) heptane/N, N ' -tetraethyl-4, 4' -diaminobenzophenone,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene/7-diethyl-4-methylcoumarin,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline,
2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide.
6. The dry film resist laminate according to claim 2 or 3,
the first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine/2-isopropylthioxanthone; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine, and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/tetraethyl-milone, and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine, and the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine; or
The first photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine; or
The first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/2-isopropyl thioxanthone, and the second photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropyl thioxanthone; or
The first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/2-mercaptobenzoxazole/2-isopropylthioxanthone; or
The first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/tetraethyl mikrolone/N-phenylglycine; or
The first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole, and the second photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine; or
The first photoinitiator is 2,2 '-bis (2-chlorphenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or
The first photoinitiator is 2,2 '-bis (2-chlorphenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropyl thioxanthone, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropyl thioxanthone; or
The first photoinitiator is 9-phenylacridine/2-mercaptobenzoxazole, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or
The first photoinitiator is 9-phenylacridine/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropyl thioxanthone; or
The first photoinitiator is 9- (p-methylphenyl) -acridine/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine, or
The first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine/2-isopropyl thioxanthone, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropyl thioxanthone; or
The first photoinitiator is 2,2', 4-tri (2-chlorphenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -diimidazole/N-phenylglycine, and the second photoinitiator is 9-phenylacridine/N-phenylglycine; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, 2,2', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4', 5 '-diphenyl-1, 1' -biimidazole/N-phenylglycine/2-isopropylthioxanthone, and the second photoinitiator is 9-phenylacridine/N-phenylglycine/2-isopropylthioxanthone; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene/7-diethyl-4-methylcoumarin; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline; or
The first photoinitiator is 1, 7-bis (9,9' -acridinyl) heptane/N, N ' -tetraethyl-4, 4' -diaminobenzophenone; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; or
The first photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/9, 10-dibutoxyanthracene; the second photoinitiator is 2,2 '-bis (2-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole/2, 4, 6-trimethylbenzoyl-diphenylphosphine oxide.
7. The dry film resist laminate according to any one of claims 1 to 6, wherein a thickness of the first resist layer is greater than or equal to a thickness of the second resist layer, preferably the thickness of the first resist layer is 1.2 to 2.0 times the thickness of the second resist layer.
8. The dry film resist laminate according to any one of claims 2 to 7, wherein the first resist layer comprises, in weight percent, 40 to 75% of a first type of alkali-soluble copolymer containing a carboxyl group, 20 to 50% of a first type of monomer containing at least one polymerizable unsaturated bond, 0.5 to 10% of the first photoinitiator, and 0.01 to 5% of a first type of auxiliary agent;
the second resist layer comprises, by weight, 40-75% of a second type of alkali-soluble copolymer containing a carboxyl group, 20-50% of a second type of monomer containing at least one polymerizable unsaturated bond, 1-20% of a second photoinitiator, and 0.01-5% of a second type of auxiliary agent.
9. The dry film resist laminate of claim 8, wherein the first and second carboxyl-containing alkali-soluble copolymers are each independently copolymerized from one or more carboxyl-containing comonomer units and one or more comonomer units free of carboxyl groups, wherein the carboxyl-containing comonomer units are itaconic acid, crotonic acid, acrylic acid, methacrylic acid, maleic acid half ester, maleic acid, fumaric acid, or vinyl acetic acid and anhydrides thereof, and the carboxyl-free comonomer units are methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, benzyl acrylate, styrene, alpha-methylstyrene, glycidyl (meth) acrylate, ethyl N, N-dimethyl (meth) acrylate, propyl N, N-diethyl (meth) acrylate, butyl N, N-dimethyl (meth) acrylate, butyl N, N-diethyl (meth) acrylate, (meth) acrylamide, N-hydroxymethyl-acrylamide, N-butoxymethyl-acrylamide, phenoxyethyl (meth) acrylate or (alkoxylated) nonylphenol (meth) acrylate.
10. The dry film resist laminate according to claim 8, wherein the first and second carboxyl group-containing alkali-soluble copolymers each have an acid value of 80 to 300mgKOH/g and a weight average molecular weight of 30000 to 150000.
11. The dry film resist laminate of claim 8, wherein the first type of monomer comprising at least one polymerizable unsaturated bond and the second type of monomer comprising at least one polymerizable unsaturated bond are each independently selected from the group consisting of ethoxylated (meth) acrylates, propoxylated (meth) acrylates, ethoxylated di (meth) acrylates, ethoxylated propoxylated (meth) acrylates, ethoxylated bisphenol A diacrylate monomers, propoxylated bisphenol A diacrylate monomers, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and mixtures thereof, At least two of dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, glyceryl tripropionate, lauryl acrylate, isodecyl acrylate, and tetrahydrofurfuryl acrylate.
12. The dry film resist laminate of claim 8, wherein the first type of auxiliary agent and the second type of auxiliary agent are each independently selected from one or more of dyes, photo-couplers, color-forming heat stabilizers, plasticizers, pigments, fillers, defoamers, flame retardants, stabilizers, leveling agents, stripping accelerators, antioxidants, fragrances, imaging agents, thermal crosslinkers.
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| CN201911144334.5A CN112824973A (en) | 2019-11-20 | 2019-11-20 | Dry film resist laminate |
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| CN201911144334.5A CN112824973A (en) | 2019-11-20 | 2019-11-20 | Dry film resist laminate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1039503A (en) * | 1996-07-23 | 1998-02-13 | Mitsubishi Chem Corp | Color resist composition |
| JPH10110008A (en) * | 1996-10-08 | 1998-04-28 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition and dry film resist using the same |
| JP2000321767A (en) * | 1999-05-07 | 2000-11-24 | Nichigo Morton Co Ltd | Photosensitive resin composition and dry film resist using the same |
| CN104536266A (en) * | 2015-01-30 | 2015-04-22 | 杭州福斯特光伏材料股份有限公司 | Dry film photoresist lamination body |
| CN105511227A (en) * | 2015-12-26 | 2016-04-20 | 杭州福斯特光伏材料股份有限公司 | Dry film resist with good hole shielding function and laminated body thereof |
-
2019
- 2019-11-20 CN CN201911144334.5A patent/CN112824973A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1039503A (en) * | 1996-07-23 | 1998-02-13 | Mitsubishi Chem Corp | Color resist composition |
| JPH10110008A (en) * | 1996-10-08 | 1998-04-28 | Nippon Synthetic Chem Ind Co Ltd:The | Photosensitive resin composition and dry film resist using the same |
| JP2000321767A (en) * | 1999-05-07 | 2000-11-24 | Nichigo Morton Co Ltd | Photosensitive resin composition and dry film resist using the same |
| CN104536266A (en) * | 2015-01-30 | 2015-04-22 | 杭州福斯特光伏材料股份有限公司 | Dry film photoresist lamination body |
| CN105511227A (en) * | 2015-12-26 | 2016-04-20 | 杭州福斯特光伏材料股份有限公司 | Dry film resist with good hole shielding function and laminated body thereof |
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