JP4752650B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition.

  The black photosensitive resin is used for forming a black matrix. The black matrix is a light shielding layer used for a color filter of a liquid crystal display in order to improve the contrast of three colors of red, green, and blue. The thickness of the black matrix is generally 1 μm or less.

JP 11-327137 A JP-A-11-52564

  However, the conventional black photosensitive resin composition has a problem that it is relatively difficult to obtain sufficient adhesion to the substrate after photocuring. In particular, this problem tends to become apparent when a thick resin layer is formed. This is considered to be due to the fact that when the thick photosensitive resin composition is irradiated with light, photocuring at the bottom does not sufficiently proceed due to the light shielding property.

  Accordingly, an object of the present invention is to provide a photosensitive resin composition having a light shielding property that can be used as a black photosensitive resin, and capable of obtaining sufficient adhesion even when the film is thickened. is there.

  In order to achieve the above object, the present invention provides a photosensitive resin composition in which a resin layer having a film thickness of 250 μm having a light transmittance of 5% or less at a wavelength of 450 nm to 650 nm is formed by photocuring, and (A) A photosensitive resin composition containing a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a red pigment, (E) a yellow pigment, and (F) a leuco dye. Offer things.

  The above-mentioned photosensitive resin composition can provide sufficient adhesion of the resin layer to the substrate even when the light-cured resin layer having a film thickness of 250 μm has a light transmittance of 5% or less at a wavelength of 450 nm to 650 nm.

  Further, (D) is preferably Pigment Red 254, (E) is Pigment Yellow 150, and (F) is preferably Leuco Crystal Violet.

  Further, the photosensitive resin composition may contain a black pigment or carbon black. Even if the photosensitive resin composition further contains a black pigment or the like, a further excellent light-shielding property can be obtained while maintaining high adhesion to the substrate after photocuring.

  In the above photosensitive resin composition, the ratio of the total amount of (D), (E), and (F) to the total amount of (A) and (B) is preferably 3 to 10% by weight. .

  If the above ratio is less than 3% by weight, the light transmittance at a wavelength of 450 nm to 650 nm tends to exceed 5%, and if it exceeds 10% by weight, the photocuring does not proceed sufficiently and the pattern formation tends to be difficult. is there.

  The above (C) is preferably an α-aminoketone or an acridine derivative.

  When α-aminoketone or an acridine derivative is used as a photopolymerization initiator, adhesion to the substrate is further improved after photocuring. The effect is more remarkable as compared with the case where other photopolymerization initiators such as imidazole photopolymerization initiators are used.

Moreover, it is preferable that said photosensitive resin composition is a film form.

  In the case of a liquid photosensitive resin composition (liquid resist), it is difficult to increase the thickness of the resin layer. However, if a film-like photosensitive resin composition is used, it is easy to increase the thickness of the resin layer.

  If the photosensitive resin composition of the present invention is used, even if the light transmittance at a wavelength of 450 nm to 650 nm of the photocured resin layer having a thickness of 250 μm is 5% or less, the adhesion of the resin layer to the substrate is sufficient. The thick black photosensitive resin obtained and excellent in light shielding properties can be suitably produced. Further, even if the photosensitive resin composition further contains a black pigment or carbon black, it is possible to obtain further excellent light-shielding properties while maintaining high adhesion to the substrate after photocuring.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylic acid” means acrylic acid and methacrylic acid corresponding thereto, “(meth) acrylate” means acrylate and methacrylate corresponding thereto, and “(meth) acrylic acid”. ") Acryloyl" means acryloyl and the corresponding methacryloyl.

  The photosensitive resin composition of the present invention comprises (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a red pigment, (E) a yellow pigment, and (F) a leuco dye. It is characterized by containing. This photosensitive resin composition is black-like and can form a resin layer having a film thickness of 250 μm having a light transmittance of 5% or less at a wavelength of 450 nm to 650 nm by photocuring.

  Examples of “(A) binder polymer” include acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, and the like. An acrylic resin is preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more binder polymers. Examples of the combination of two or more binder polymers include two or more binder polymers composed of different copolymerization components, two or more binder polymers having different weight average molecular weights, and two or more binder polymers having different dispersities. . In addition, a polymer having a multimode molecular weight distribution described in JP-A No. 11-327137 can also be used. In addition, the binder polymer may have a photosensitive group as necessary.

  The “(A) binder polymer” can be produced, for example, by radical polymerization of a polymerizable monomer. Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinylton, α-methylstyrene, p-methylstyrene, and p-ethylstyrene, and vinyl alcohols such as acrylamide, acrylonitrile, and vinyl-n-butyl ether. Esters, (meth) acrylic acid alkyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2, 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α-chloro (meth) acrylic Acid, β-furyl (meth) ac Maleic acid monoesters such as phosphoric acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic Acid, itaconic acid, crotonic acid, propiolic acid and the like can be mentioned. These may be used alone to form a homopolymer, or two or more types may be combined to form a copolymer.

  Examples of the (meth) acrylic acid alkyl ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and structural isomers thereof. These can be used alone or in combination of two or more.

  The binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. The binder polymer containing a carboxyl group can be produced, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. The polymerizable monomer having a carboxyl group is preferably methacrylic acid from the viewpoint of stability. The acid value of the binder polymer is preferably 30 mgKOH / g or more from the viewpoint of development time, preferably 250 mgKOH / g or less from the viewpoint of developer resistance of the photocured resist, and is 45 to 200 mgKOH / g. More preferably. When performing solvent development as a development step, it is preferable to prepare a small amount of a polymerizable monomer having a carboxyl group.

  The weight average molecular weight of the binder polymer is preferably 20,000 or more from the viewpoint of developer resistance, preferably 300,000 or less from the viewpoint of shortening the development time, and 25,000 to 150,000. More preferably, it is more preferably 30,000 to 100,000. This weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted by a calibration curve using standard polystyrene.

The “(B) photopolymerizable compound” is preferably a photopolymerizable compound having at least one ethylenically unsaturated group in the molecule, and is a bisphenol A-based (meth) acrylate compound (for example, EO-modified bisphenol A). And dimethacrylate (trade name: FA-321M, Hitachi Chemical Co., Ltd.). Although there is no restriction | limiting in particular in a bisphenol A type (meth) acrylate compound, For example, it is preferable that it is a compound represented by the following general formula (I). The "EO" above refers to the "ethylene oxide", an "EO-modified" means having a block structure of ethylene oxide units (-CH ₂ CH 2 _O-).

In general formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. In general formula (I), X and Y each independently represent an alkylene group having 2 to 6 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group. In general formula (I), p and q are positive integers selected so that p + q = 4 to 40, preferably 6 to 34, more preferably 8 to 30, and more preferably 8 to 28. Is particularly preferable, 8 to 20 is very preferable, 8 to 16 is very particularly preferable, and 8 to 12 is very preferable. When p + q is less than 4, the compatibility with the binder polymer tends to decrease, and when p + q exceeds 40, the hydrophilicity increases and the water absorption rate of the cured film tends to increase.

  Examples of the alkylene group having 2 to 6 carbon atoms include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group, and a hexylene group.

  In addition, the aromatic ring in the general formula (I) may have a substituent. Examples of the substituent include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a cycloalkyl having 3 to 10 carbon atoms. Group, aryl group having 6 to 18 carbon atoms, phenacyl group, amino group, alkylamino group having 1 to 10 carbon atoms, dialkylamino group having 2 to 20 carbon atoms, nitro group, cyano group, carbonyl group, mercapto group, carbon A C1-C10 alkyl mercapto group, an allyl group, a hydroxyl group, a C1-C20 hydroxyalkyl group, a carboxyl group, a carboxyalkyl group having a C1-C10 alkyl group, and a C1-C10 alkyl group. An acyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, and an alkeni having 2 to 10 carbon atoms. Group, N- alkylcarbamoyl group or a group containing a heterocyclic ring having 2 to 10 carbon atoms, an aryl group substituted by these substituents. The above substituents may form a condensed ring. Moreover, the hydrogen atom in these substituents may be substituted with the above substituents such as halogen atoms. When the number of substituents is 2 or more, each of the two or more substituents may be the same or different.

  Examples of the compound represented by the general formula (I) include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane and 2,2-bis (4-((meth) acryloxy). Polypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane And bisphenol A-based (meth) acrylate compounds.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptaethoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonane) Xyl) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl), 2,2 -Bis (4-((meth) acryloxydodecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecaethoxy) phenyl), 2,2-bis (4-((meth)) (Acryloxytetradecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is commercially available as BPE-500 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Are possible, 2,2-bis (4- (methacryloxy pentadecanoyl) phenyl) is, BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) is commercially available as. These can be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydipropoxy) phenyl) propane, 2,2 -Bis (4-((meth) acryloxytripropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyheptapropoxy) phenyl) Propane, 2,2-bis (4-((meth) acryloxyoctapropoxy) phenyl) propane, 2,2-bis (4-((meth) a) Liloxynonapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyundecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxydodecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxytridecapropoxy) phenyl), 2,2-bis (4- ( (Meth) acryloxytetradecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxypentadecapropoxy) phenyl), 2,2-bis (4-((meth) acryloxyhexadecapropoxy) ) Phenyl) and the like. These can be used alone or in combination of two or more.

  Examples of the 2,2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane include 2,2-bis (4-((meth) acryloxydiethoxyoctapropoxy) phenyl) propane. 2,2-bis (4-((meth) acryloxytetraethoxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxyhexapropoxy) phenyl) propane and the like. . These can be used alone or in combination of two or more.

  Examples of the compound similar to the bisphenol A-based (meth) acrylate compound include a compound obtained by adding acrylic acid to bisphenol A-diepoxy. Viscort # 540 (Osaka Organic Chemical Industry Co., Ltd.) is commercially available. These can be used alone or in combination of two or more.

  Examples of photopolymerizable compounds other than the bisphenol A-based (meth) acrylate compounds include tricyclodecane dimethanol, neopentyl glycol-modified trimethylolpropane diacrylate, and, for example, α, β-unsaturated carboxylic acid in polyhydric alcohol. Compounds obtained by reaction, compounds obtained by reacting glycidyl group-containing compounds with α, β-unsaturated carboxylic acids, urethane monomers such as (meth) acrylate compounds having a urethane bond, nonylphenyldioxylene (meth) acrylate , Γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate (for example, trade name: FA-MECH, Osaka Organic Chemical Industry Co., Ltd.), β-hydroxyethyl-β ′ -(Meth) acryloyloxyethyl-o-phthalate, - hydroxypropyl-beta '- (meth) acryloyloxyethyl -o- phthalate, (meth) acrylic acid alkyl esters, EO-modified nonylphenyl (meth) acrylate. These can be used alone or in combination of two or more.

  Examples of the compound obtained by reacting the polyhydric alcohol with an α, β-unsaturated carboxylic acid include, for example, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups and 2 to 2 propylene groups. 14 polypropylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, trimethylolpropane diethoxytri (meth) acrylate, Trimethylolpropane triethoxytri (meth) acrylate, trimethylolpropanetetraethoxytri (meth) acrylate, trimethylolpropane pentaethoxytri (meth) acrylate, tetramethylolmethanetri (meta) Examples include acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 14 propylene groups, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. .

  As the “photopolymerization initiator”, α-aminoketone or acridine derivative is preferable. Examples of the α-aminoketone include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (for example, Irg-369, Ciba Specialty Chemicals Co., Ltd.) and the like. Examples of the derivative include 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane (for example, N-1717, Asahi Denka Kogyo Co., Ltd.), and the like. In addition to the above, as a photopolymerization initiator, hexaarylbiimidazole benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′- Diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] Aromatic ketones such as 2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenyl Anthraquinone, 2,3-diphenyla Quinones such as traquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, benzoin methyl ether Benzoin ether compounds such as benzoin ethyl ether and benzoin phenyl ether, benzoin compounds such as benzoin, methyl benzoin and ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, N-phenyl glycine, N-phenyl glycine derivatives, coumarin compounds, etc. It can also be used. Moreover, a combination of a thioxanthone compound and a tertiary amine compound may be used, such as a combination of diethylthioxanthone and dimethylaminobenzoic acid. Other photopolymerization initiators include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer. , 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4 , 5-diphenylimidazole dimer and the like. Further, the aryl group substituents of the two 2,4,5-triarylimidazoles may be the same to give the target compound, or differently give an asymmetric compound. These can be used alone or in combination of two or more.

  Examples of “(D) red pigment” include naphthol type pigment 112 and the like, and a diketopyrrolopyrrole type organic pigment such as pigment red 254 is preferable. Examples of “(E) yellow pigment” include benzoimidazolone-type pigment yellow 120, but a metal complex-type organic pigment such as pigment yellow 150 is preferable. These pigments may be used alone or, if necessary, in the form of a solution dispersed in a solvent or a dispersant. The “(F) leuco dye” is preferably leuco crystal violet, and a photochromic agent such as tribromophenylsulfone can be used in combination as required.

  The content of the binder polymer is preferably in the range of 40 to 80 parts by weight and more preferably 45 to 70 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. If this content is less than 40 parts by weight, the photocured product tends to be brittle and tends to be inferior in coating properties, and if it exceeds 80 parts by weight, the sensitivity tends to be insufficient. The content of the photopolymerizable compound is preferably in the range of 20 to 60 parts by weight and more preferably 30 to 50 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. If this content is less than 20 parts by weight, the resolution tends to decrease, and if it exceeds 60 parts by weight, edge fusion tends to occur.

  The blending amount of the photopolymerization initiator is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. preferable. If the blending amount is less than 0.1 parts by weight, the photosensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the composition increases during exposure and the internal photocuring is insufficient. Tend to be.

  The blending amount of the red pigment, the yellow pigment and the leuco dye is preferably 3 to 10 parts by weight as the total amount of the red pigment, the yellow pigment and the leuco dye with respect to 100 parts by weight of the total amount of the binder polymer and the photopolymerizable compound. Yes. When this blending amount is less than 3 parts by weight, the light transmittance is deteriorated, and when it exceeds 10 parts by weight, the photocuring of the film bottom tends to be insufficient.

  The resin composition containing the components as described above may further include a dye such as malachite green, a thermochromic inhibitor, a plasticizer such as p-toluenesulfonamide, a pigment, a filler, an antifoaming agent, and a flame retardant. , Stabilizer, adhesion-imparting agent, leveling agent, peeling accelerator, antioxidant, perfume, imaging agent, thermal crosslinking agent, etc., each 0.01 parts per 100 parts by weight of the total amount of binder polymer and photopolymerizable compound. It is preferable to contain about -20 weight part. These can be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention containing the above components can be obtained, for example, by uniformly kneading and mixing the blended components with a roll mill, a bead mill or the like. If necessary, dissolve in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof to obtain a solid content. It can apply | coat as a 30-60 weight% solution.

  The said photosensitive resin composition can be apply | coated as a liquid resist on substrate surfaces, such as glass, a silicon wafer, copper, a copper-type alloy, iron, and an iron-type alloy, and can be used after drying. The thickness of the resin composition layer to be applied varies depending on the use, but is preferably about 1 to 300 μm after drying.

  Moreover, it is preferable that the photosensitive resin composition is a film form. A photosensitive film can be mentioned as a film-form photosensitive resin composition. As the photosensitive film, for example, a polymer film such as polyethylene terephthalate, polypropylene, polyethylene, or polyester is used as a support, and a film formed by forming a film-like photosensitive resin composition layer is preferably used. be able to. The thickness of the polymer film is preferably about 1 to 300 μm. Although the formation method of the photosensitive resin composition layer on a support body is not specifically limited, It can implement preferably by apply | coating and drying the solution of the photosensitive resin composition. Although the thickness of the photosensitive resin composition layer to be applied varies depending on the application, it is preferably about 1 to 300 μm after drying. The coating can be performed by a known method such as a roll coater, a comma coater, a gravure coater, an air knife coater, a die coater, or a bar coater. Drying can be performed, for example, at 70 to 150 ° C. for about 5 to 30 minutes. Further, the amount of the remaining organic solvent in the photosensitive resin composition layer is preferably 2% by weight or less from the viewpoint of preventing the organic solvent from diffusing in the subsequent step. You may coat | cover the photosensitive resin composition layer surface using the said polymer film used as a support body as a protective film. The photosensitive film is used by coating a protective film as necessary. As the protective film, the adhesive strength between the photosensitive resin composition layer and the protective film is higher than the adhesive strength between the photosensitive resin composition layer and the support. A smaller one is preferred, and a low fisheye film is preferred. Moreover, the photosensitive film may have intermediate | middle layers and protective layers, such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer other than the photosensitive resin composition layer, a support body, and a protective film.

  The produced photosensitive film is stored, for example, as it is or further by laminating a protective film on the surface of the photosensitive resin composition layer and winding it around a cylindrical core. In this case, it is preferable to wind the support so that the support is on the outside. An end face separator is preferably installed on the end face of the roll-shaped photosensitive film from the viewpoint of end face protection, and a moisture-proof end face separator is preferably installed from the viewpoint of edge fusion resistance. Moreover, as a packing method, it is preferable to wrap and package in a black sheet with low moisture permeability. Examples of the core include plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and ABS resin (acrylonitrile-butadiene-styrene copolymer).

In producing a resist pattern using the photosensitive film, if the protective film is present, after removing the protective film, while heating the photosensitive resin composition to 70 ° C to 130 ° C, Examples include a method of laminating by pressure bonding to various substrates at a pressure of about 0.1 to 1 MPa (about 1 to 10 kgf / cm ² ), and it is possible to laminate under reduced pressure, and if necessary, It is also possible to increase the thickness of the photosensitive resin composition layer by performing the above operation a plurality of times. There is no restriction | limiting in particular about the surface to laminate | stack.

  The photosensitive resin composition layer thus laminated is irradiated with an active light source in an image form through a negative or positive mask pattern. As the light source of the actinic light, a known light source, for example, a light source that effectively irradiates ultraviolet rays, visible light, or the like of a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, or a xenon lamp lamp is used. It is also used for laser direct drawing exposure.

  Next, after exposure, when a support is present on the photosensitive resin composition layer, the support is removed, and then wet development or dry development with a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent. The resist pattern can be manufactured by removing the unexposed portion with development or the like and developing. Examples of the alkaline aqueous solution include a dilute solution of 0.1 to 5 wt% sodium carbonate, a dilute solution of 0.1 to 5 wt% potassium carbonate, a dilute solution of 0.1 to 5 wt% sodium hydroxide, and the like. It is done. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent, or the like may be mixed in the alkaline aqueous solution. Examples of the development method include a dip method, a spray method, brushing, and slapping.

As processing after development, heating at about 60 to 250 ° C. or 0.2 to 10 J / c as necessary
The resist pattern may be further cured by performing exposure of about m ² .

  The photosensitive resin composition layer forms a light-shielding resin layer. More specifically, when the thickness of the photocured photosensitive resin composition layer is 250 μm, the light transmittance in the wavelength range of 450 nm to 650 nm after photocuring is 5% or less (preferably 3% or less). A layer is formed. When the light transmittance exceeds 5%, light interference between pixels not covered with the photosensitive resin composition layer is likely to occur, or when used as a solder resist or a cover lay for covering a circuit, There is a tendency that the hiding power of the underlying circuit is insufficient.

  When the metal surface is etched after development, for example, a cupric chloride solution, a ferric chloride solution, an alkaline etching solution, or the like can be used.

  When a printed wiring board is manufactured using a photosensitive film, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask. Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating. Next, the resist pattern can be peeled with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development, for example. As said strong alkaline aqueous solution, 1-10 weight% sodium hydroxide aqueous solution, 1-10 weight% potassium hydroxide aqueous solution, etc. are used, for example. Examples of the peeling method include an immersion method and a spray method. The printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples without departing from the technical idea of the present invention. In the examples, “%” means% by weight.

(Examples 1-4, Comparative Examples 1-4)
In order to form the photosensitive resin layers of Examples 1 to 4 and Comparative Examples 1 to 4, first, the materials shown in Table 1 were blended to prepare the solution 1 necessary for forming the photosensitive resin composition layer. did.

  The binder polymer solution in Table 1 is a copolymer obtained by copolymerizing methacrylic acid, methyl methacrylate and ethyl acrylate in a weight ratio of 17.5: 52.8: 29.7 (weight average molecular weight: 80000, dispersity). : 2.0) was dissolved in acetone so as to have a nonvolatile content of 44%. At this time, in order to obtain 150 g of the binder polymer solution, 65 g of solid content was required.

  Next, the pigments (MHI Red # 4828M, MHI Yellow # 4943M, Leuco Crystal Violet, MHI Cyan A133, F456 Blue, MHI Black # 220) shown in Table 2 and a photopolymerization initiator (N-1717) were added to Solution 1 described above. , Irg-369, B-CIM) were added in predetermined amounts, and the photosensitive resin layers of Examples 1 to 4 and Comparative Examples 1 to 4 were formed by the following procedure. MHI Red # 4828M is Pigment Red 254, MHI Yellow # 4943M is Pigment Yellow 150, N-1717 is an acridine derivative, Irg-369 is an α-aminoketone, and B-CIM is 2 , 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (Hampford).

  First, a solution obtained by adding a predetermined amount of each pigment and photopolymerization initiator shown in Table 2 to Solution 1 was uniformly applied on a polyethylene terephthalate film having a thickness of 16 μm. Then, it dried for 10 minutes with a 100 degreeC hot-air convection dryer, and obtained the photosensitive film by protecting with the protective film made from polyethylene (NF-15; Tamapoly Co., Ltd.). The film thickness of the resin composition layer after drying was 50 μm, and the tensile strength of the polyethylene protective film was 16 Mpa (film longitudinal direction) and 12 Mpa (film width direction), respectively.

  On the other hand, the glass substrate was washed with isopropyl alcohol and then air-dried. Thereafter, the glass substrate was heated to 80 ° C., and the photosensitive resin composition layer of the photosensitive film was laminated on the surface of the glass substrate while peeling the polyethylene protective film. This laminating operation was performed by passing a laminating roll heated to 110 ° C. Then, the photosensitive resin composition layer of the said photosensitive film was laminated on the laminated photosensitive resin composition layer again, peeling the polyethylene protective film, and the photosensitive resin composition was piled up. This operation was repeated 5 times, the thickness of the photosensitive resin composition layer was 250 μm, and in the fifth operation, the photosensitive resin composition layer was laminated without peeling off the polyethylene protective film. The structure of the laminate thus obtained was a glass substrate, a photosensitive resin composition layer, and a polyethylene terephthalate film from the bottom.

  Next, as a negative for resolution evaluation, a photo tool having a wiring pattern with a line width / space width of 30/30 to 200/200 (unit: μm) is brought into close contact with this laminate, and the scattered light exposure having a high-pressure mercury lamp lamp It exposed with the machine (HMW-201GX; Oak Manufacturing Co., Ltd. product). After the exposure, the polyethylene terephthalate film was peeled off, and a 1% by weight aqueous sodium carbonate solution was sprayed at 30 ° C. for 255 seconds to remove the unexposed portion, and the adhesion was evaluated. The adhesion is represented by the minimum value (μm) of the line width remaining without being peeled off by the developer, and the smaller this value, the higher the adhesion.

  For the measurement of light transmittance, as described above, a sample laminated on a glass substrate was prepared so that the thickness of the photosensitive resin composition layer was 250 μm, and the sample after exposure without using a negative was prepared. It cut | disconnected to 2 cm x 3 cm, and measured the light transmittance in wavelength 450nm -650nm with the spectrophotometer (U-3310; product made from Hitachi High-Technologies Corporation).

  “100” described in the column of adhesion in Table 2 indicates that a line having a line width of 100 μm or more remained without being peeled by the developer, and “200” represents a line having a line width of 200 μm or more. Indicates that it remains without being peeled off. In addition, “≦ 5%” described in the column of light transmittance in Table 2 indicates that the light transmittance value is 5% or less in the entire wavelength range of 450 nm to 650 nm, and “> 5%” This indicates that there is a portion where the light transmittance exceeds 5% in the wavelength range of 450 nm to 650 nm.

  As a result, when the light transmittance is 5% or less, the photosensitive resin composition contains at least three kinds of pigments of a red pigment, a yellow pigment and leuco crystal violet, and a photopolymerization initiator. When N-1717 or Irg-369 is used, it has been found that the adhesion is remarkably increased.

Claims (6)

A photosensitive resin composition for forming a resin layer having a film thickness of 250 μm having a light transmittance of 5% or less at a wavelength of 450 nm to 650 nm by photocuring,
(A) a binder polymer;
(B) a photopolymerizable compound;
(C) a photopolymerization initiator;
(D) a red pigment;
(E) a yellow pigment;
(F) a leuco dye,
The photosensitive resin composition containing this. (D) is Pigment Red 254,
(E) is Pigment Yellow 150,
(F) is leuco crystal violet.
The photosensitive resin composition of Claim 1. The ratio of the total amount of (D), (E) and (F) to the total amount of (A) and (B) is 3 to 10% by weight.
The photosensitive resin composition according to claim 1 or 2.   The photosensitive resin composition according to claim 1, wherein (C) is an α-aminoketone or an acridine derivative.   Furthermore, the photosensitive resin composition as described in any one of Claims 1-4 containing a black pigment or carbon black. The photosensitive resin composition as described in any one of Claims 1-5 which is a film form.