Photosensitive resin composition, resist ink, resist laminate and use thereof

Abstract

The invention provides a photosensitive resin composition, a resist ink, a resist laminate, and an application thereof. The photosensitive resin composition is prepared from the following components in parts by weight: 50 to 70 parts of alkali soluble resin, 30 to 50 parts of photopolymerizable monomer and 0.1 to 4.0 parts of photoinitiator, wherein the photopolymerizable monomer comprises an allyl compound and a sulfhydryl compound, and the mass content of the sulfhydryl compound in the photopolymerizable monomer is 7 wt%-22 wt%. According to the photosensitive resin composition, the allyl compound and the sulfhydryl compound are introduced into the photosensitive resin composition, and the alkenyl in the allyl compound and the sulfhydryl in the sulfhydryl compound can be subjected to addition polymerization reaction, so that the prepared photosensitive resin has relatively uniform crosslinking after exposure, and the photosensitive resin with low polymerization shrinkage stress is obtained; the adhesive has good adhesive force in the attaching process of the copper substrate.

Description

Technical Field

[0001] The present invention relates to the technical field of printed circuit boards, and in particular to a photosensitive resin composition, an anti-etching ink, an anti-etching laminate and applications thereof. Background Art

[0002] Dry film resist is widely used as a key material for pattern transfer in products such as printed circuit boards, lead frames, solar cells, conductor packages, ball grid arrays (BGA), and chip-scale (CPS) packages. For example, in printed circuit boards, a dry film resist laminate is bonded to a copper substrate using laser direct imaging (LDI) for pattern exposure, then developed to remove the unexposed areas, then etched or electroplated, and finally the cured parts are removed to achieve pattern transfer.

[0003] For the production of high-density and high-integration printed circuit (PCB) products such as high-density interconnect (HDI) boards and packaging substrates, the accuracy is generally required to be around 15μm or even lower. This requires the dry film resist layer used for pattern transfer to have a higher resolution and excellent adhesion to the copper substrate to ensure that the dry film remains intact on the copper-clad laminate substrate after harsh processes such as development, electroplating or etching, which involve high-pressure spraying and long-term contact with corrosive chemicals.

[0004] The Chinese patent with the patent authorization announcement number CN102385253B discloses that a photosensitive resin composition with excellent resolution and stripping properties is obtained by using an adhesive polymer with a specific structure, that is, a polymer having a (meth) acrylate benzyl ester and a styrene structure; the Chinese patent application with the patent application publication number CN110531583A discloses that the addition of a (meth) acrylate hydroxyethyl structure to an alkali-soluble resin significantly enhances the resistance to acid etching and electroplating solutions and the stripping performance; the Chinese patent application with the patent application publication number CN117008417A discloses that the synthesis of an alkali-soluble resin using a comonomer with an alicyclic structure exhibits good flexibility and hydrophobicity. However, the stripping time disclosed in these patents is relatively long, and there is still room for improvement in the stripping performance. Summary of the invention

[0005] The main purpose of the present invention is to provide a photosensitive resin composition, a resist ink, a resist laminate and their use, so as to solve the problem that the photosensitive resin used in the resist laminate in the prior art has poor resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability.

[0006] In order to achieve the above-mentioned object, according to one aspect of the present invention, there is provided a photosensitive resin composition, which comprises, in parts by weight: 50 to 70 parts of an alkali-soluble resin, 30 to 50 parts of a photopolymerizable monomer and 0.1 to 4.0 parts of a photoinitiator; wherein the photopolymerizable monomer comprises an allyl compound and a mercapto compound, and the mass content of the mercapto compound in the photopolymerizable monomer is 7 wt % to 22 wt %.

[0007] Furthermore, the mass proportion of the above-mentioned allyl compound in the photopolymerizable monomer is 5wt% to 14wt%; and / or the mass proportion of the thiol compound in the photopolymerizable monomer is 8wt% to 22wt%; preferably, the mass ratio of the allyl compound to the thiol compound is 0.625 to 1:1.

[0008] Further, the allyl compound is selected from any one or more of allyl (meth)acrylate, diallyl carbonate, allyl benzyl ether, 2,4,6-triallyloxy-1,3,5-triazine, tert-butoxy N-propenecarbamate, diethyl allylmalonate, eugenol and its derivatives, safrole and its derivatives, estragole and its derivatives; and / or the thiol compound is selected from methyl mercaptan, ethyl mercaptan, 1-propanethiol, n-butyl mercaptan, dodecanethiol , ethanedithiol, 1,3-propanedithiol, 2,3-dimercaptopropanol, hexanedithiol, 1,4-dimethylthiophenol, tris(2-hydroxyethyl)isocyanurate tris(mercaptopropionate), diethanolamine tris(mercaptopropionate), bis(3-mercaptopropionic acid)ethylene glycol, hydroxymethylpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), benzylmercaptopropionate, cysteine, and any one or more of bis(3-mercaptopropionic acid)ethylene glycol.

[0009] Furthermore, the above-mentioned photopolymerizable monomer includes an acrylate compound; preferably, the mass proportion of the acrylate compound in the photopolymerizable monomer is 65wt% to 86wt%; and / or, the photopolymerizable monomer includes an unsaturated fatty acid; preferably, the mass proportion of the unsaturated fatty acid in the photopolymerizable monomer is 1wt% to 5wt%; further preferably, the photopolymerizable monomer includes an acrylate compound and an unsaturated fatty acid, and the mass ratio of the acrylate compound to the unsaturated fatty acid is 12.5 to 26:1.

[0010] Furthermore, the acrylate compound is selected from lauryl (meth)acrylate, octadecyl (meth)acrylate, nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol Any one or more of tetraol hexaacrylates; preferably, the acrylate compound is a combination of ethoxylated (propoxylated) bisphenol A di(meth)acrylate and ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, and the mass ratio of ethoxylated (propoxylated) bisphenol A di(meth)acrylate to ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate is 12 to 20:5 to 16; and / or, the unsaturated fatty acid is selected from any one or more of 9-octadecenoic acid, 9,12-octadecadienoic acid, 9,12,15-octadecatrienoic acid, 9,11,13-octadecattrienoic acid, and 12-hydroxy-9-octadecenoic acid.

[0011] Further, the acid value of the alkali-soluble resin is 120-250 mg KOH / g; and / or, the weight average molecular weight of the alkali-soluble resin is 20,000-120,000; and / or, the polydispersity index of the alkali-soluble resin is 1.3-2.5; and / or, the alkali-soluble resin is prepared from a polymerized monomer, and the polymerized monomer is selected from (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, isooctyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl methacrylate , any one or more of allyl (meth)acrylate, polyethylene (or propylene) glycol (meth)acrylate, styrene and its derivatives, benzyl (meth)acrylate, p-oxyphenyl benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, adamantyl (meth)acrylate, cyclopentadienyl (meth)acrylate, and isobornene (meth)acrylate; preferably, the polymerizable monomer is selected from any one or more of methacrylic acid, methyl methacrylate, butyl acrylate, styrene and butyl methacrylate.

[0012] Further, the above-mentioned photoinitiator is selected from any one or more of azo compounds, peroxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, α-oxyacyloxime ester compounds, hexaarylbisimidazole derivatives, acridine derivatives, benzoin ethers, benzophenone and its derivatives, thioxanthone derivatives, anthraquinone and its derivatives, aromatic diazonium salts, iodonium salts, sulfonium salts, aromatic ferrocenium salt compounds, titanocene photoinitiators and non-ionic acid generators; preferably, the photoinitiator is selected from 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycin any one or more of amino acids; further preferably, the photoinitiator is a combination of 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycine, and the mass ratio of 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycine is 1.5-1.8:0.4-0.7:0.05-0.1:0.05:0.1.

[0013] According to another aspect of the present invention, a resist ink is provided, wherein the resist ink contains the aforementioned photosensitive resin composition.

[0014] According to another aspect of the present invention, there is provided a resist laminate, comprising a support layer, a photosensitive resin layer and a protective layer stacked in sequence, wherein the photosensitive resin layer is prepared from the aforementioned photosensitive resin composition or the aforementioned resist ink.

[0015] According to another aspect of the present invention, there is provided application of the aforementioned resist laminate on a circuit board.

[0016] The technical solution of the present application is applied. The present application introduces an allyl compound and a mercapto compound into a photosensitive resin composition. The alkenyl group in the allyl compound can undergo addition polymerization with the mercapto group in the mercapto compound. Since the polymerization reaction of the mercapto-ene reaction system lasts longer than the free radical double bond copolymerization reaction of other photopolymerizable monomers, it is helpful to make the prepared photosensitive resin have a more uniform cross-linking after exposure, and the shrinkage stress of the polymerization process is alleviated to obtain a photosensitive resin with low polymerization shrinkage stress. The photosensitive resin with low polymerization shrinkage stress exhibits good adhesion during the bonding process of the copper substrate. Since the introduction of the mercapto-ene reaction system makes the photosensitive resin have a good bonding force with the copper substrate, it is helpful to reduce the risk of abnormalities such as infiltration plating in the pattern electroplating process, thereby helping to improve the yield of the product. The photosensitive resin composition of the present invention adds an initiator that can be decomposed by light or heat to trigger the mercapto-ene reaction system to partially react during the drying process, which helps to make the photosensitive resin have a slightly cross-linked network support, thereby helping to reduce the risk of glue flow and overflow, and then helping to improve the storage stability of the photosensitive resin. Among them, if the mass proportion of the thiol compound in the photopolymerizable monomer is too low, it is not conducive to improving the film stripping performance, electroplating resistance and storage stability of the photosensitive resin; if the mass proportion of the thiol compound in the photopolymerizable monomer is too high, it is not conducive to improving the resolution performance and adhesion performance of the photosensitive resin. It is preferred to control the mass proportion of the thiol compound in the photopolymerizable monomer within the above-mentioned range, which will help improve the comprehensive performance of the photosensitive resin such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability. DETAILED DESCRIPTION

[0017] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0018] As analyzed in the background technology of this application, the photosensitive resin used in the resist laminate in the prior art has the problems of poor resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability. In order to solve this problem, this application provides a photosensitive resin composition, resist ink, resist laminate and its application.

[0019] In a typical embodiment of the present application, a photosensitive resin composition is provided, which includes, by weight: 50 to 70 parts of an alkali-soluble resin; 30 to 50 parts of a photopolymerizable monomer; and 0.1 to 4.0 parts of a photoinitiator; wherein the photopolymerizable monomer includes an allyl compound and a mercapto compound, and the mass content of the mercapto compound in the photopolymerizable monomer is 7 wt % to 22 wt %.

[0020] The present application introduces an allyl compound and a mercapto compound into a photosensitive resin composition, and the alkenyl group in the allyl compound can undergo an addition polymerization reaction with the mercapto group in the mercapto compound. Since the polymerization reaction of the mercapto-ene reaction system lasts longer than the free radical double bond copolymerization reaction of other photopolymerizable monomers, it is helpful to make the prepared photosensitive resin have a more uniform cross-linking after exposure, and the shrinkage stress of the polymerization process is alleviated to obtain a photosensitive resin with low polymerization shrinkage stress. The photosensitive resin with low polymerization shrinkage stress shows good adhesion during the bonding process of the copper substrate. Since the introduction of the mercapto-ene reaction system makes the photosensitive resin have a good bonding force with the copper substrate, it is helpful to reduce the risk of abnormalities such as infiltration plating in the graphic electroplating process, thereby helping to improve the yield of the product. The photosensitive resin composition of the present invention adds an initiator that can be decomposed by light or heat to trigger the mercapto-ene reaction system to partially react during the drying process, which helps to make the photosensitive resin have a slightly cross-linked network support, thereby helping to reduce the risk of glue flow and overflow, and then helping to improve the storage stability of the photosensitive resin. Among them, if the mass proportion of the thiol compound in the photopolymerizable monomer is too low, it is not conducive to improving the film stripping performance, electroplating resistance and storage stability of the photosensitive resin; if the mass proportion of the thiol compound in the photopolymerizable monomer is too high, it is not conducive to improving the resolution performance and adhesion performance of the photosensitive resin. It is preferred to control the mass proportion of the thiol compound in the photopolymerizable monomer within the above-mentioned range, which will help improve the comprehensive performance of the photosensitive resin such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability.

[0021] In one embodiment of the present application, the mass proportion of the above-mentioned allyl compound in the photopolymerizable monomer is 5wt% to 14wt%; and / or, the mass proportion of the thiol compound in the photopolymerizable monomer is 8wt% to 22wt%; preferably, the mass ratio of the allyl compound to the thiol compound is 0.625 to 1:1.

[0022] It is preferred to control the mass proportion of the allyl compound in the photopolymerizable monomer and the mass proportion of the mercapto compound in the photopolymerizable monomer within the above-mentioned range, which helps to fully exert the synergistic effect between the two, so that the alkenyl group in the allyl compound and the mercapto group in the mercapto compound undergo addition polymerization reaction, thereby helping to improve the comprehensive performance of the photosensitive resin, such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability.

[0023] In one embodiment of the present application, the allyl compound is selected from any one or more of allyl (meth)acrylate, diallyl carbonate, allyl benzyl ether, 2,4,6-triallyloxy-1,3,5-triazine, tert-butoxy N-propenecarbamate, allylmalonate, eugenol and its derivatives, safrole and its derivatives, estragole and its derivatives; and / or the thiol compound is selected from methyl mercaptan, ethyl mercaptan, 1-propanethiol, n-butyl mercaptan , dodecanethiol, ethanedithiol, 1,3-propanedithiol, 2,3-dimercaptopropanol, hexanedithiol, 1,4-dimethylthiophenol, tris(2-hydroxyethyl)isocyanurate tris(mercaptopropionate), diethanolamine tris(mercaptopropionate), bis(3-mercaptopropionic acid)ethylene glycol, hydroxymethylpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), benzylmercaptopropionate, cysteine, bis(3-mercaptopropionic acid)ethylene glycol, any one or more thereof.

[0024] It is preferred to control the types of allyl compounds and mercapto compounds within the above range, which helps to enrich the selectivity of the types of allyl compounds and mercapto compounds and further improve the compatibility between allyl compounds and mercapto compounds, thereby helping to further improve the comprehensive properties of the photosensitive resin, such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability.

[0025] In one embodiment of the present application, the above-mentioned photopolymerizable monomer includes an acrylate compound; preferably, the mass proportion of the acrylate compound in the photopolymerizable monomer is 65wt% to 86wt%; and / or, the photopolymerizable monomer includes an unsaturated fatty acid; preferably, the mass proportion of the unsaturated fatty acid in the photopolymerizable monomer is 1wt% to 5wt%; further preferably, the photopolymerizable monomer includes an acrylate compound and an unsaturated fatty acid, and the mass ratio of the acrylate compound to the unsaturated fatty acid is 12.5 to 26:1.

[0026] It is preferred to control the mass of the acrylate compound in the photopolymerizable monomer to be within the above range, which helps to further improve the resolution, adhesion and film stripping properties of the photosensitive resin. The addition of unsaturated fatty acids helps to make the cross-linked network of the photosensitive resin after exposure to carboxyl groups, thereby helping to improve the film stripping properties of the photosensitive resin; at the same time, unsaturated fatty acids are bio-renewable resources, and the mercapto-ene reaction system can therefore achieve the introduction and use of more renewable resource monomers, which is more environmentally friendly. It is preferred to control the mass of the unsaturated fatty acid in the photopolymerizable monomer to be within the above range, which helps to further improve the film stripping properties of the photosensitive resin.

[0027] In order to further improve the resolution performance, adhesion performance and film stripping performance of the photosensitive resin, in one embodiment of the present application, the above-mentioned acrylate compound is preferably selected from lauryl (meth) acrylate, octadecyl (meth) acrylate, nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, tetrahydrofuran methyl acrylate, bisphenol A di(meth) acrylate, ethoxylated (propoxylated) bisphenol A di(meth) acrylate, polyethylene glycol (propylene glycol) di(meth) acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth) acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetrapropylene glycol di ... Any one or more of ethoxylated (propoxylated) bisphenol A di(meth)acrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; preferably, the acrylate compound is a combination of ethoxylated (propoxylated) bisphenol A di(meth)acrylate and ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, and the mass ratio of ethoxylated (propoxylated) bisphenol A di(meth)acrylate to ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate is 12 to 20:5 to 16; and / or, the unsaturated fatty acid is selected from any one or more of 9-octadecenoic acid, 9,12-octadecadienoic acid, 9,12,15-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, and 12-hydroxy-9-octadecenoic acid.

[0028] It should be noted that, in the above-mentioned acrylate compounds, "(methyl)" means substituted with a methyl group or not; "(propoxy)" means substituted with a propoxy group or not.

[0029] In one embodiment of the present application, the acid value of the alkali-soluble resin is 120-250 mg KOH / g; and / or, the weight average molecular weight of the alkali-soluble resin is 20,000-120,000; and / or, the polydispersity index of the alkali-soluble resin is 1.3-2.5; and / or, the alkali-soluble resin is prepared from a polymerized monomer, and the polymerized monomer is selected from (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, isooctyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl methacrylate , any one or more of allyl (meth)acrylate, polyethylene (or propylene) glycol (meth)acrylate, styrene and its derivatives, benzyl (meth)acrylate, p-oxyphenyl benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, adamantyl (meth)acrylate, cyclopentadienyl (meth)acrylate, and isobornene (meth)acrylate; preferably, the polymerizable monomer is selected from any one or more of methacrylic acid, methyl methacrylate, butyl acrylate, styrene and butyl methacrylate.

[0030] It should be noted that "(methyl)" in the above-mentioned polymerizable monomers means being substituted with a methyl group or being unsubstituted.

[0031] The alkali-soluble resin is prepared by solution polymerization, the initiator is azobisisobutyronitrile, the solvent is acetone, and the reaction is carried out in a closed reactor at 80° C. for a period of time.

[0032] In order to control the polymerization rate of the photopolymerizable monomer, thereby improving the comprehensive performance of the photosensitive resin such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability, in one embodiment of the present application, the above-mentioned photoinitiator is preferably selected from any one or more of azo compounds, peroxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, α-oxyacyloxime ester compounds, hexaarylbisimidazole derivatives, acridine derivatives, benzoin ether, benzophenone and its derivatives, thioxanthone derivatives, anthraquinone and its derivatives, aromatic diazonium salts, iodonium salts, sulfonium salts, aromatic ferrocenium salt compounds, titanocene photoinitiators and non-ionic acid generators; the photoinitiator is preferably selected from 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenyl oxide any one or more of phosphorus, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycine; further preferably, the photoinitiator is 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N -phenylglycine, and the mass ratio of 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycine is 1.5-1.8:0.4-0.7:0.05-0.1:0.05:0.1.

[0033] In order to further improve the comprehensive performance of the photosensitive resin, in one embodiment of the present application, the photosensitive resin composition preferably further includes 0.05 to 4.0 parts of an additive; the additive is preferably selected from any one or more of a photocolorizer, a dye, a plasticizer, an antioxidant, a deodorant, a coloring heat stabilizer, an adhesion promoter, a leveling agent, a defoamer and an inhibitor.

[0034] The types of the photocolorizer, dye, plasticizer, antioxidant, deodorant, color heat stabilizer, adhesion promoter, leveling agent, defoamer and polymerization inhibitor in the present application can be those commonly used in the art, for example, the photocolorizer is leuco crystal violet, the dye is malachite green, the plasticizer is p-toluenesulfonamide, the antioxidant is antioxidant 1010, the deodorant is activated carbon, the color heat stabilizer is phenolphthalein, the adhesion promoter is formic acid, the leveling agent is polydimethylsiloxane, the defoamer is polymethylsiloxane, and the polymerization inhibitor is hydroquinone.

[0035] In another typical embodiment of the present application, a resist ink is provided, wherein the resist ink contains the aforementioned photosensitive resin composition.

[0036] In another typical embodiment of the present application, a resist laminate is provided, comprising a support layer, a photosensitive resin layer and a protective layer stacked in sequence, wherein the photosensitive resin layer is prepared from the aforementioned photosensitive resin composition or the aforementioned resist ink.

[0037] Since the photosensitive resin layer in the above-mentioned resist laminate is prepared from the photosensitive resin composition of the present application, the resist laminate has excellent comprehensive properties such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability.

[0038] Including but not limited to, the material of the supporting layer is polyethylene terephthalate and / or polypropylene; the material of the protective layer is polyethylene.

[0039] In another typical embodiment of the present application, there is provided application of the aforementioned resist laminate on a circuit board.

[0040] The beneficial effects of the present application will be further illustrated below in conjunction with embodiments.

[0041] Example 1

[0042] Alkali soluble resin A: prepared by solution polymerization, with azobisisobutyronitrile as the initiator and acetone as the solvent, and reacted in a closed reactor at 80°C for a period of time;

[0043] A1: the main components and mass fraction ratio of the polymerized monomers are methacrylic acid / methyl methacrylate / butyl acrylate / butyl methacrylate = 24 / 46 / 20 / 10, the weight average molecular weight Mw of A1 is 55000, and the polydispersity index is 1.78;

[0044] A2: prepared by solution polymerization, with azobisisobutyronitrile as the initiator and acetone as the solvent, and reacted in a closed reactor at 80°C for a period of time. The main components and mass fractions of the polymerized monomers are methacrylic acid / methyl methacrylate / styrene / butyl methacrylate = 27 / 7 / 46 / 10, the weight average molecular weight Mw of A2 = 55,000, and the polydispersity index = 1.78.

[0045] Photopolymerizable monomer B:

[0046] B1: allyl methacrylate;

[0047] B2: (10) ethoxylated bisphenol A dimethacrylate, Shanxi Meiyuan Chemical Co., Ltd.;

[0048] B3: (6) Ethoxylated trimethylolpropane triacrylate, Sartomer Chemical Co., Ltd.

[0049] B4: bis(3-mercaptopropionic acid)ethylene glycol, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0050] B5: 2,4,6-Triallyloxy-1,3,5-triazine, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0051] B6: 12-Hydroxy-9-octadecenoic acid, Hangzhou Jieheng Chemical Co., Ltd.

[0052] Photoinitiator C:

[0053] C1: 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, Changzhou Qiangli Electronic New Materials Co., Ltd.

[0054] C2: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0055] C3: 4,4-bis(N,N'-dimethylamino)benzophenone, Changzhou Qiangli Electronic New Materials Co., Ltd.;

[0056] C4: azobisisobutyronitrile, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0057] C5: N-phenylglycine, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0058] Adding additive D:

[0059] D1: Malachite green, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0060] D2: Leuco crystal violet, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0061] D3: p-Toluenesulfonamide, Shanghai TiXIA Chemical Trading Co., Ltd.;

[0062] According to the weight of each component of the dry film resist in Table 1, mix them in proportion, add a certain amount of acetone, and then stir them thoroughly until they are completely dissolved to prepare a resist solution with a solid content of 42%. Use a coating machine to evenly coat it on the surface of a 15μm thick PET support film, place it in a 95℃ oven for 6 minutes, and form a photosensitive resin layer with a thickness of 25μm, which appears blue-green under a yellow light. Then, a polyethylene film protective layer with a thickness of 18μm is attached to its surface to obtain a 3-layer dry film agent laminate.

[0063] Table 1

[0064]

[0065]

[0066] Example 8

[0067] The difference from Example 3 is that the weight portion of the alkali-soluble resin is 69.85 parts, the weight portion of the photopolymerizable monomer is 30 parts, the weight portion of the photoinitiator is 0.1 parts, and the weight portion of the additive is 0.05 parts, and finally a dry film agent laminate is obtained.

[0068] Example 9

[0069] The difference from Example 3 is that the weight parts of alkali-soluble resin are 42 parts, the weight parts of photopolymerizable monomer are 50 parts, the weight parts of photoinitiator are 4.0 parts, and the weight parts of additives are 4.0 parts, and finally a dry film agent laminate is obtained.

[0070] Example 10

[0071] The difference from Example 3 is that the weight portion of 2,4,6-triallyloxy-1,3,5-triazine is 10.41 parts, the mass proportion of 2,4,6-triallyloxy-1,3,5-triazine in the photopolymerizable monomer is 28wt%, the weight portion of bis(3-mercaptopropionic acid)ethylene glycol is 2.59 parts, the mass proportion of bis(3-mercaptopropionic acid)ethylene glycol in the photopolymerizable monomer is 7wt%, and finally a dry film agent laminate is obtained.

[0072] Embodiment 11

[0073] The difference from Example 3 is that the weight proportion of (10) ethoxylated bisphenol A di(meth)acrylate is 21 parts, and the weight proportion of (6) ethoxylated trimethylolpropane tri(meth)acrylate is 3 parts, and finally a dry film agent laminate is obtained.

[0074]

Film

[0075] The copper clad laminate was polished by a grinder, washed with water, and dried to obtain a bright and fresh copper surface. The laminating machine roller temperature was set to 110°C, the conveying speed was 1.5m / min, and the heat lamination was performed under standard pressure.

[0076]

exposure

[0077] After film application, the sample was left to stand for more than 15 minutes, and then exposed using an Orbotech Nuvogo 80F laser direct imaging (LDI) exposure machine. A stouffer 41-step exposure ruler was used for photosensitivity testing. The number of exposure grids was controlled at 14 to 20 grids, and the exposure energy was 10 to 40 mJ / cm 2 .

[0078]

development

[0079] After exposure, the sample was left to stand for more than 15 minutes, the developing temperature was 30°C, and the pressure was 1.2Kg / cm 2 The developer is a 1 wt % sodium carbonate aqueous solution, the developing time is 1.5 to 2.0 times the minimum developing time, and the film is washed with water and dried after development.

[0080]

Removal of film

[0081] The stripping solution is NaOH, with a concentration of 3.0wt%, a temperature of 50°C, and a developing pressure of 1.2Kg / cm 2 The film stripping time is 1.5 to 2.0 times of the minimum film stripping time. After film stripping, wash and dry.

[0082] [Evaluation of resolution]

[0083] Exposure is performed using a mask having a wiring pattern with an exposed portion and an unexposed portion having a width of n:n (n is 10 to 100 μm). After development for 1.5 times the minimum development time, the minimum mask width at which a cured resist line is normally formed is taken as the resolution value and observation is performed using a two-dimensional imager or a scanning electron microscope (SEM).

[0084]

Evaluation of adhesion

[0085] A photosensitive dry film resist is laminated on a copper plate by hot pressing, and exposure is performed using a mask having a wiring pattern with a width of n:400 (n is 10 to 100 μm) between the exposed and unexposed parts. After development for 1.5 times the minimum development time, the minimum mask width at which a cured resist line is normally formed is taken as the adhesion value, and observation is performed using a two-dimensional imager or a scanning electron microscope (SEM).

[0086] Make an observation.

[0087]

Evaluation of electroplating resistance

[0088] At 40°C, the developed substrate was placed in a 10% acidic degreasing solution and soaked for 10 minutes, then washed with water for 5 minutes, and after micro-etching with sodium persulfate, soaked in a 10% sulfuric acid aqueous solution at room temperature for 2 minutes. The substrate was then immersed in a pre-configured copper plating solution with a current density of 2ASD and electroplated for 70 minutes; then immersed in a 10% sulfuric acid aqueous solution at room temperature for 2 minutes, and immersed in a pre-configured tin plating solution with a current density of 1ASD and electroplated for 10 minutes. After washing with water, the cured dry film was removed, and the appearance of the sample was observed using a 500x high-resolution scanning electron microscope to see if any permeation occurred.

[0089]

Evaluation of film stripping speed

[0090] Take a substrate after filming, exposure and development, cut it into a 4*5cm square, put it into a beaker containing 100mL of film stripping solution (concentration 3wt%, temperature 50℃), stir it with magnetic force for 1min, and record the time when the dry film is completely detached. The film stripping speed is evaluated by testing the film stripping time. The shorter the film stripping time, the faster the film stripping speed.

[0091]

Evaluation of film removal fragment size

[0092] Take a substrate after filming, exposure and development, cut it into a 4*5cm square, put it into a beaker containing 100mL of film stripping solution (concentration 3wt%, temperature 50℃), stir it with magnetic force for 1min, and observe the size of the film stripping fragments. Good: fragment size 5-15mm; average: fragment size 20-30mm; poor: fragment size more than 30mm or less than 5mm.

[0093]

Evaluation of storage stability

[0094] Place the cut photosensitive dry film rolls in a constant temperature and humidity chamber at 23°C and 60% relative humidity for accelerated testing, and regularly observe the glue overflow on the sides of the dry film rolls. ◎: No glue flow after 45 days, which means excellent storage stability; ○: No glue flow after 30 days, which means good storage stability;

[0095] Δ: No gel flow after 21 days, slight gel flow after more than 21 days, i.e., the storage stability is average; ×: Gel flow after more than 14 days, i.e., the storage stability is insufficient.

[0096] The samples prepared by the above-mentioned manufacturing method (including film lamination, exposure, development, electroplating, and film stripping) were evaluated. The evaluation results of Examples 1 to 11 and Comparative Examples 1 and 2 are shown in Table 2.

[0097] Table 2

[0098]

[0099] By comparing Examples 1 to 11 with Comparative Examples 1 to 2, it can be found that Examples 1 to 11 can obtain resist laminates with excellent resolution, adhesion, film stripping speed, film stripping fragment size, electroplating resistance, and storage stability. Although Comparative Example 1 has good film stripping performance, it is lacking in resolution performance and adhesion performance, and its performance in electroplating resistance is average. Comparative Example 2 is a resist laminate without the introduction of a mercapto-ene reaction system. In addition to average resolution adhesion and film stripping performance, it also has poor performance in electroplating resistance.

[0100] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0101] The present application introduces an allyl compound and a mercapto compound into a photosensitive resin composition, and the alkenyl group in the allyl compound can undergo an addition polymerization reaction with the mercapto group in the mercapto compound. Since the polymerization reaction of the mercapto-ene reaction system lasts longer than the free radical double bond copolymerization reaction of other photopolymerizable monomers, it is helpful to make the prepared photosensitive resin have a more uniform cross-linking after exposure, and the shrinkage stress of the polymerization process is alleviated to obtain a photosensitive resin with low polymerization shrinkage stress. The photosensitive resin with low polymerization shrinkage stress shows good adhesion during the bonding process of the copper substrate. Since the introduction of the mercapto-ene reaction system makes the photosensitive resin have a good bonding force with the copper substrate, it is helpful to reduce the risk of abnormalities such as infiltration plating in the graphic electroplating process, thereby helping to improve the yield of the product. The photosensitive resin composition of the present invention adds an initiator that can be decomposed by light or heat to trigger the mercapto-ene reaction system to partially react during the drying process, which helps to make the photosensitive resin have a slightly cross-linked network support, thereby helping to reduce the risk of glue flow and overflow, and then helping to improve the storage stability of the photosensitive resin. Among them, if the mass proportion of the thiol compound in the photopolymerizable monomer is too low, it is not conducive to improving the film stripping performance, electroplating resistance and storage stability of the photosensitive resin; if the mass proportion of the thiol compound in the photopolymerizable monomer is too high, it is not conducive to improving the resolution performance and adhesion performance of the photosensitive resin. It is preferred to control the mass proportion of the thiol compound in the photopolymerizable monomer within the above-mentioned range, which will help improve the comprehensive performance of the photosensitive resin such as resolution performance, adhesion performance, film stripping performance, electroplating resistance and storage stability.

[0102] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that The photosensitive resin composition comprises, by weight: 50-70 parts of alkali-soluble resin; 30 to 50 parts of a photopolymerizable monomer; and 0.1 to 4.0 parts of a photoinitiator; wherein, The photopolymerizable monomer comprises an allyl compound and a mercapto compound, and the mass content of the mercapto compound in the photopolymerizable monomer is 7wt% to 22wt%.

2. The photosensitive resin composition according to claim 1, characterized in that The mass proportion of the allyl compound in the photopolymerizable monomer is 5wt% to 14wt%; and / or the mass proportion of the thiol compound in the photopolymerizable monomer is 8wt% to 22wt%; preferably, the mass ratio of the allyl compound to the thiol compound is 0.625 to 1:

1.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that: The allyl compound is selected from any one or more of allyl (meth)acrylate, diallyl carbonate, allyl benzyl ether, 2,4,6-triallyloxy-1,3,5-triazine, tert-butoxy N-propylene carbamate, allyl diethyl malonate, eugenol and its derivatives, safrole and its derivatives, estragole and its derivatives; And / or, the thiol compound is selected from any one or more of methyl mercaptan, ethyl mercaptan, 1-propanethiol, n-butyl mercaptan, dodecanethiol, ethanedithiol, 1,3-propanedithiol, 2,3-dimercaptopropanol, hexanedithiol, 1,4-dimethylthiophenol, tris(2-hydroxyethyl)isocyanurate tris(mercaptopropionate), diethanolamine tris(mercaptopropionate), bis(3-mercaptopropionic acid)ethylene glycol, hydroxymethylpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), benzylmercaptopropionate, cysteine, and bis(3-mercaptopropionic acid)ethylene glycol.

4. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that: The photopolymerizable monomer includes an acrylate compound; preferably, the mass proportion of the acrylate compound in the photopolymerizable monomer is 65wt% to 86wt%; and / or, the photopolymerizable monomer includes an unsaturated fatty acid; preferably, the mass proportion of the unsaturated fatty acid in the photopolymerizable monomer is 1wt% to 5wt%; further preferably, the photopolymerizable monomer includes the acrylate compound and the unsaturated fatty acid, and the mass ratio of the acrylate compound to the unsaturated fatty acid is 12.5 to 26:

1.

5. The photosensitive resin composition according to claim 4, characterized in that: The acrylate compound is selected from any one or more of lauryl (meth)acrylate, octadecyl (meth)acrylate, nonylphenol acrylate, ethoxylated (propoxylated) nonylphenol acrylate, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, ethoxylated (propoxylated) bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate; Preferably, the acrylate compound is a combination of ethoxylated (propoxylated) bisphenol A di(meth)acrylate and ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, and the mass ratio of the ethoxylated (propoxylated) bisphenol A di(meth)acrylate to the ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate is 12-20:5-16; And / or, the unsaturated fatty acid is selected from any one or more of 9-octadecenoic acid, 9,12-octadecadienoic acid, 9,12,15-octadecatrienoic acid, 9,11,13-octadecatrienoic acid, and 12-hydroxy-9-octadecenoic acid.

6. The photosensitive resin composition according to any one of claims 1 to 5, characterized in that: The acid value of the alkali-soluble resin is 120 to 250 mg KOH / g; and / or, the weight average molecular weight of the alkali-soluble resin is 20,000 to 120,000; and / or, the polydispersity index of the alkali-soluble resin is 1.3 to 2.5; And / or, the alkali-soluble resin is prepared from polymerized monomers, and the polymerized monomers are selected from any one or more of (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, isooctyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl methacrylate, allyl (meth)acrylate, polyethylene (or propylene) glycol (meth)acrylate, styrene and its derivatives, benzyl (meth)acrylate, p-oxyphenyl benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, o-phenylphenoxyethyl (meth)acrylate, adamantyl (meth)acrylate, cyclopentadienyl (meth)acrylate, and isobornene (meth)acrylate; Preferably, the polymerizable monomer is selected from any one or more of methacrylic acid, methyl methacrylate, butyl acrylate, styrene and butyl methacrylate.

7. The photosensitive resin composition according to any one of claims 1 to 6, characterized in that: The photoinitiator is selected from any one or more of azo compounds, peroxide compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, α-oxyacyloxime ester compounds, hexaarylbiimidazole derivatives, acridine derivatives, benzoin ether, benzophenone and its derivatives, thioxanthone derivatives, anthraquinone and its derivatives, aromatic diazonium salts, iodonium salts, sulfonium salts, aromatic ferrocenium salt compounds, titanocene photoinitiators and non-ionic acid generators; Preferably, the photoinitiator is selected from any one or more of 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycine; It is further preferred that the photoinitiator is a combination of 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 4,4-bis(N,N'-dimethylamino)benzophenone, azobisisobutyronitrile and N-phenylglycine, and the mass ratio of the 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, the 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, the 4,4-bis(N,N'-dimethylamino)benzophenone, the azobisisobutyronitrile and the N-phenylglycine is 1.5-1.8:0.4-0.7:0.05-0.1:0.05:0.

1.

8. A resist ink, characterized in that: The resist ink contains the photosensitive resin composition according to any one of claims 1 to 7.

9. A resist laminate, comprising a support layer, a photosensitive resin layer and a protective layer stacked in sequence, characterized in that: The photosensitive resin layer is prepared from the photosensitive resin composition according to any one of claims 1 to 7 or the resist ink according to claim 8.

10. Use of the resist laminate according to claim 9 in a circuit board.

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