Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate

Definitions

• the present invention relates to a photosensitive resin composition, and more particularly, a photosensitive resin composition that can be suitably used for forming an insulating layer such as a solder resist, a dry film using the photosensitive resin composition, and a photosensitive resin composition. Or it relates to a cured product of a dry film and a printed wiring board using the cured product.
• solder resist layer is formed on the patterned substrate except for the connection holes.
• the solder resist layer is formed by a so-called photosolder resist, in which a photosensitive resin composition is applied to a substrate, dried, patterned by exposure and development, and then the patterned resin is fully cured by heating or light irradiation. is the mainstream. It has also been proposed to form a solder resist layer using a photosensitive dry film without using the liquid photosensitive resin composition as described above.
• photosensitive resin compositions and photosensitive dry films each contain a photocurable component in addition to an alkali-soluble photosensitive resin component such as an acid-modified (meth)acrylate resin so that they can be exposed and developed.
• alkali-soluble photosensitive resin component such as an acid-modified (meth)acrylate resin
• thermosetting components such as epoxy are included in consideration of heat resistance and substrate adhesion.
• Patent Document 1 discloses that, as an alkali-soluble resin component, polybasic It has been proposed to use a carboxyl group-containing resin having an acid-added structure.
• Patent Document 2 in order to improve the insulation reliability of the solder resist material, it is proposed to use a biphenyl type epoxy resin and a bisphenol A type epoxy resin together as a thermosetting component in the photosensitive resin composition. (Patent Document 2).
• the insulation reliability is improved by blending the biphenyl-type epoxy resin in the photosensitive resin composition as described above, development residues tend to re-adhere during exposure and development, and re-adhesion of development residues is suppressed. Therefore, it is necessary to increase the water solubility of the resin composition. Therefore, by using an ethylene oxide-modified (meth)acrylate as a photopolymerizable monomer, reattachment of development residue can be suppressed while maintaining insulation reliability.
• an object of the present invention is to provide a photosensitive resin composition that can suppress re-adhesion of development residues while maintaining insulation reliability, and that can provide a cured film that is less prone to roller marks.
• the gist of the present invention is as follows.
• a photosensitive resin composition comprising a carboxyl group-containing resin, a photopolymerizable monomer, and a thermosetting component
• the photopolymerizable monomer contains a (meth)acrylate having an isocyanuric ring
• the thermosetting component contains a biphenyl-type epoxy resin
• a photosensitive resin composition characterized by: [2] The photosensitive resin composition according to [1], wherein the biphenyl-type epoxy resin is at least one selected from the group consisting of tetramethylbiphenyl-type epoxy resins and biphenylaralkyl-type epoxy resins.
• thermosetting component further contains a bisphenol A type epoxy resin having a weight average molecular weight of 500 or less.
• thermosetting component further contains a bisphenol A type epoxy resin having a weight average molecular weight of 500 or less.
• the photosensitive resin composition according to the present invention contains a carboxyl group-containing resin, a photopolymerizable monomer, and a thermosetting component as essential components. Each component constituting the photosensitive resin composition according to the present invention will be described below.
• carboxyl group-containing resin conventionally known various resins having a carboxyl group in the molecule can be used. By including a carboxyl group-containing resin in the photosensitive resin composition, alkali developability can be imparted to the photosensitive resin composition.
• a carboxyl group-containing resin having an ethylenically unsaturated double bond in the molecule is particularly preferable as the carboxyl group-containing resin from the viewpoint of photocurability and development resistance.
• the ethylenically unsaturated double bonds are preferably derived from acrylic acid or methacrylic acid or derivatives thereof.
• a (meth)acrylate such as a bifunctional or higher (meth)acrylate having an isocyanuric ring, which will be described later, may be used in combination. can impart photosensitivity to the composition.
• carboxyl group-containing resins include the following compounds (both oligomers and polymers).
• Carboxyl group-containing resins obtained by copolymerizing unsaturated carboxylic acids such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, ⁇ -methylstyrene, lower alkyl (meth)acrylates, and isobutylene.
• Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates; Polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, carboxyl group-containing urethane resins obtained by polyaddition reaction of diol compounds such as compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
• a diisocyanate such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, or a biphenol type epoxy resin ( Carboxyl group-containing photosensitivity obtained by polyaddition reaction of partial acid anhydride-modified reaction product with monocarboxylic acid compound having ethylenically unsaturated double bond such as meth)acrylic acid, carboxyl group-containing dialcohol compound and diol compound Urethane resin.
• a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a bixylenol type epoxy resin, or a biphenol type epoxy resin ( Carboxyl group-containing photosensitivity obtained by polyaddition reaction of partial acid anhydride-modified reaction product with monocarboxylic acid compound having
• one isocyanate group and one or more (meth)acryloyl groups are added in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
• a carboxyl group-containing photosensitive resin obtained by reacting (meth)acrylic acid with a polyfunctional (solid) epoxy resin having two or more functionalities and adding a dibasic acid anhydride to the hydroxyl groups present in the side chains.
• Group-containing photosensitive resin A carboxyl obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the resulting hydroxyl group.
• a bifunctional oxetane resin is reacted with a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid, and the resulting primary hydroxyl group is treated with a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
• a dicarboxylic acid such as adipic acid, phthalic acid, and hexahydrophthalic acid
• a dibasic such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride.
• Carboxyl group-containing polyester resin to which acid anhydride is added.
• an epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol;
• a carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
• (11) Obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with a monocarboxylic acid containing an unsaturated group.
• a carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.
• a carboxyl group-containing photosensitive resin obtained by adding a compound having one epoxy group and one or more (meth)acryloyl groups in one molecule to the resins (1) to (11).
• (meth)acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
• cresol novolak type epoxy resin as the epoxy resin in the photosensitive resin of (6) and the photosensitive resin of (12) can be preferably used.
• a cresol novolak type epoxy resin can be used more preferably as the epoxy resin.
• carboxyl group-containing resins can be used without being limited to those listed above, and one type may be used alone or a plurality of types may be mixed and used.
• the acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g.
• the acid value of the carboxyl group-containing resin is preferably 40-150 mgKOH/g.
• the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, it is generally preferable to be 2,000 to 150,000. By setting the weight average molecular weight to 2,000 or more, tack-free performance and resolution can be improved. Further, by setting the weight average molecular weight to 150,000 or less, the developability and storage stability can be improved. More preferably, it is 5,000 to 15,000.
• the weight average molecular weight can be measured by gel permeation chromatography (GPC).
• the blending amount of the carboxyl group-containing resin is preferably 20 to 60% by mass in terms of solid content in the photosensitive resin composition. By making it 20% by mass or more, the strength of the coating film can be improved. Moreover, by making it 60% by mass or less, the viscosity becomes appropriate and the printability improves. More preferably, it is 30 to 50% by mass.
• the photosensitive resin composition according to the present invention contains a (meth)acrylate having an isocyanuric ring as a photopolymerizable monomer.
• the photosensitive resin composition according to the present invention contains a biphenyl-type epoxy resin as a thermosetting component as described later. While maintaining the properties, it is possible to suppress the problem of redeposition of development residues caused by blending the biphenyl type epoxy resin as described above, and also suppress the problem of roller marks adhering to the cured film.
• the (meth)acrylate having an isocyanuric ring has the function of improving the water solubility of the photosensitive resin composition in the same manner as the ethylene oxide-modified (meth)acrylate, and suppresses development residue.
• this is because the hardness of the cured product when the photosensitive resin composition is cured can be maintained at a relatively high level, and the adhesion of roller marks can be suppressed.
• the amount of (meth)acrylate having an isocyanuric ring in the photosensitive resin composition is preferably 1 to 50 parts by mass, preferably 5 to 40 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. Part is more preferred.
• the photosensitive resin composition according to the present invention may contain, as a photopolymerizable monomer, a monomer having a photopolymerizable group consisting of a (meth)acryloyl group in addition to the (meth)acrylate having an isocyanuric ring described above. good.
• photopolymerizable monomers include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, and epoxy (meth)acrylates.
• hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate
• glycol diacrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol
• N,N-dimethylacrylamide N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide
• aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate
• hexanediol trimethylolpropane
• Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate, or polyhydric acrylates such as their ethyloxide adducts, propylene oxide adducts, or ⁇ -caprolactone adducts
• the amount of the compound is 0.1 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is preferably from 1 to 10 parts by mass.
• the photosensitive resin composition according to the present invention contains a biphenyl-type epoxy resin as a thermosetting component.
• a biphenyl-type epoxy resin as a thermosetting component By adding a biphenyl-type epoxy resin as a thermosetting component to the photosensitive resin composition, the heat resistance of the cured film can be improved, and the insulation reliability can be improved.
• biphenyl-type epoxy resins include tetramethylbiphenyl-type epoxy resins and biphenylaralkyl-type epoxy resins.
• the weight average molecular weight of the biphenyl type epoxy resin is not particularly limited, but is preferably 300 to 10,000, more preferably 300 to 3,000.
• the weight average molecular weight can be measured by gel permeation chromatography (GPC).
• the amount of the biphenyl type epoxy resin compounded in the photosensitive resin composition is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. more preferred.
• the photosensitive resin composition according to the present invention includes, as thermosetting components, in addition to the biphenyl-type epoxy resins described above, amino resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, and cyclocarbonates.
• thermosetting components such as compounds, epoxy compounds other than biphenyl-type epoxy resins, oxetane compounds, episulfide resins, bismaleimide, and carbodiimide resins may be contained.
• bisphenol A type epoxy resin bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type Polyfunctional epoxy compounds such as epoxy resins, bisphenol A novolac type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, and triphenylmethane type epoxy resins can be preferably used.
• a bisphenol A type epoxy resin As the epoxy resin, it is preferable to use a bisphenol A type epoxy resin as the epoxy resin.
• a bisphenol A type epoxy resin together as a thermosetting component, redeposition of development residues can be more effectively suppressed.
• the glass transition temperature of the cured product after curing the photosensitive resin composition is increased, the heat resistance of the cured product is further improved.
• the bisphenol A type epoxy resin used in combination with the biphenyl type epoxy resin preferably has a weight average molecular weight of 500 or less.
• the mixing ratio of the biphenyl-type epoxy resin and the bisphenol-A-type epoxy resin is 2:8 to 8:2 on a mass basis. 2 is preferred, and 3:7 to 5:5 is more preferred.
• the blending ratio of the biphenyl-type epoxy resin and the bisphenol A-type epoxy resin is within the above range, re-adhesion of development residues can be further suppressed, and roller marks are less likely to occur.
• the blending amount of the thermosetting component is preferably 1 to 100 parts by mass, more preferably 5 to 55 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content.
• the photosensitive resin composition according to the present invention preferably contains a photopolymerization initiator for photopolymerization.
• a photopolymerization initiator for photopolymerization.
• known ones can be used, for example, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino- 1-(4-morpholinophenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- ⁇ -Aminoacetophenone-based photopolymerization initiators such as butanone and N,N-dimethylaminoacetophenone: 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4-[4-
• ⁇ -aminoacetophenone photopolymerization initiators include Omnirad 907, 369, 369E and 379 manufactured by IGM Resins.
• Commercially available acylphosphine oxide photopolymerization initiators include Omnirad 819 manufactured by IGM Resins.
• Commercially available titanocene-based photopolymerization initiators are available from Yueyang Kimoutain Sci-tech Co., Ltd.; , Ltd. JMT-784 manufactured by Hubei Gurun Technology Co., Ltd. and GR-FMT manufactured by Hubei Gurun Technology Co., Ltd.
• a photopolymerization initiator having two oxime ester groups in the molecule can also be suitably used, and specific examples thereof include oxime ester compounds having a carbazole structure represented by the following general formula (I). .
• X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, group, amino group, alkylamino group having an alkyl group having 1 to 8 carbon atoms or dialkylamino group), naphthyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, substituted by an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms, or a dialkylamino group), Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and 1 ⁇ 8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atom
• oxime wherein X 1 , Y 1 are each a methyl or ethyl group, Z is methyl or phenyl, n is 0, and Ar is phenylene, naphthylene, thiophene or thienylene Ester-based photopolymerization initiators are preferred.
• benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, xanthone compounds, and the like can be used as photopolymerization initiators.
• thioxanthone compounds and tertiary amine compounds are preferable, and thioxanthone compounds are more preferable, from the viewpoint of deep-part curability.
• the amount of the photopolymerization initiator in the photosensitive resin composition is preferably 1 to 50 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin in terms of solid content. is more preferred. Thereby, the curability of the deep part can be improved.
• the photosensitive resin composition contains the benzoin compound or the like as a photopolymerization initiation aid or the like, the blending amount is 0.01 to 10 parts per 100 parts by mass of the carboxyl group-containing resin in terms of solid content. It is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 5 parts by mass. Thereby, the curability of the deep part can be improved.
• thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzyl amines, amine compounds such as 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and
• commercially available products include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Kasei Co., Ltd. (all are trade names of imidazole compounds), and U-CAT manufactured by San-Apro Co., Ltd. 3513N (trade name of dimethylamine compounds), DBU, DBN, U-CAT SA 102 (all of which are bicyclic amidine compounds and salts thereof), and the like.
• the compounds are not limited to the above-mentioned compounds, and may be thermosetting catalysts for epoxy resins or oxetane compounds, or those that promote the reaction between at least one of epoxy groups and oxetanyl groups and carboxyl groups. You may use it individually or in mixture of 2 or more types.
• thermosetting catalyst a compound selected from the group consisting of melamine and its derivatives (hereinafter also referred to as "melamine compound”) as a thermosetting catalyst.
• the melamine compound acts as a curing accelerator for the thermosetting reaction, and can further improve properties such as heat resistance in addition to the adhesion of the cured product to the conductor circuit.
• Melamine compounds include guanamines such as acetoguanamine and benzoguanamine; melamine; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xylyl-S-triazine Triazine derivatives can be mentioned, and these can be used singly or in combination of two or more. Among these, melamine can be preferably used.
• the melamine compound is preferably contained in a proportion of 0.01 to 10 parts by mass, more preferably in a proportion of 0.1 to 5 parts by mass, relative to the entire photosensitive resin composition. Also, the melamine compound is preferably contained in a proportion of 1 to 20 parts by mass, more preferably in a proportion of 5 to 15 parts by mass, based on the entire thermosetting component. Adhesion and heat resistance can be further improved by containing the melamine compound in the above range.
• the melamine compound when included as the thermosetting component, is preferably included in a proportion of 5 to 40 parts by mass, more preferably 5 to 30 parts by mass, relative to the biphenyl type epoxy resin. more preferably.
• the melamine compound is contained in the above range with respect to the biphenyl-type epoxy resin, it is possible to further improve electrical properties in addition to adhesion and heat resistance.
• the photosensitive resin composition according to the present invention may optionally contain a filler in order to increase the physical strength of the cured film.
• a filler known inorganic or organic fillers can be used, in particular silica, talc, mica, aluminum oxide, calcium oxide, magnesium oxide, zinc oxide, calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, kaolin, clay, calcium hydroxide, aluminum hydroxide, magnesium hydroxide, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, xonolite, boron nitride, Aluminum borate, silica balloons, glass flakes, glass balloons, steelmaking slag, copper, iron, iron oxide, sendust, alnico magnets, magnetic powders such as various ferrites, cement, glass powders, Neuburg silica, diatomaceous earth, antimony trioxide
• Silica includes amorphous silica, crystalline silica, fused silica and spherical silica.
• silica and talc are used in combination because the heat resistance and cold/heat cycle resistance of the photosensitive resin composition are significantly improved.
• silica and talc are used together, it is preferable that they are blended in the photosensitive resin composition at a ratio of 1:1 to 3:1 on a mass basis.
• the filler to be used preferably has an average particle size (D50) of 0.1 to 100 ⁇ m, more preferably 0.1 to 50 ⁇ m, from the viewpoint of dispersibility.
• the average particle size means the particle size at 50% volume accumulation obtained by using a laser diffraction/scattering particle size distribution measurement method.
• the average particle diameter of the filler is the value measured as described above for the filler before preparation (preliminary stirring and kneading) of the photosensitive resin composition.
• the amount of the filler compounded in the photosensitive resin composition is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin, in terms of solid content. . As a result, it is possible to further improve the adhesion force reduction prevention property and the thermal cycle resistance of the photosensitive resin composition.
• the above filler may be surface-treated in order to improve dispersibility in the photosensitive resin composition. Aggregation can be suppressed by using a surface-treated filler.
• the surface treatment method is not particularly limited, and a known and commonly used method may be used.
• the surface of the inorganic filler is treated with a surface treatment agent having a curable reactive group, such as a coupling agent having a curable reactive group as an organic group. treatment is preferred.
• silane-based, titanate-based, aluminate-based, and zirco-aluminate-based coupling agents can be used.
• silane coupling agents are preferred.
• examples of such silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminomethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-amino propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-anilinopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxy Cyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysi
• silane-based coupling agents are preferably immobilized in advance on the surface of the filler by adsorption or reaction.
• the amount of the coupling agent treated with respect to 100 parts by mass of spherical silica is preferably 0.5 to 10 parts by mass.
• the photosensitive resin composition according to the present invention may optionally contain a colorant, an elastomer, a mercapto compound, a urethanization catalyst, a thixotropic agent, an adhesion promoter, a block copolymer, a chain transfer agent, At least one of polymerization inhibitors, copper damage inhibitors, antioxidants, rust inhibitors, thickeners such as organic bentonite and montmorillonite, silicone-based, fluorine-based, polymer-based defoaming agents, and leveling agents , phosphinates, phosphate ester derivatives, and phosphorus compounds such as phosphazene compounds. As these, those known in the field of electronic materials can be used.
• the photosensitive resin composition of the present invention may contain an organic solvent from the viewpoint of ease of preparation and coating properties.
• organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether; , dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate
• the blending amount of the organic solvent in the photosensitive resin composition can be appropriately changed according to the materials constituting the photosensitive resin composition. 30 to 300 parts by mass.
• the photosensitive resin composition of the present invention may be used as a dry film or as a liquid. Moreover, when it is used as a liquid, it may be one-liquid or two-liquid or more.
• the photosensitive resin composition of the present invention can also be in the form of a dry film comprising a first film and a resin layer made of the above photosensitive resin composition formed on the first film.
• the first film in the dry film according to the present invention is integrally formed by laminating a base material such as a substrate by heating or the like so that the resin layer side made of a photosensitive resin composition formed on the dry film is in contact with the base material. In some cases, it means that it is adhered to at least the resin layer.
• the first film may be peeled off from the resin layer in a step after lamination. In particular, in the present invention, it is preferable to separate from the resin layer in a step after exposure.
• the photosensitive resin composition of the present invention is diluted with an organic solvent to adjust the viscosity to an appropriate value, and is coated with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll.
• a film can be obtained by coating the first film with a uniform thickness using a coater, gravure coater, spray coater, or the like, and drying at a temperature of 50 to 130° C. for 1 to 30 minutes.
• the coating thickness is not particularly limited, but is generally selected appropriately within the range of 1 to 150 ⁇ m, preferably 10 to 60 ⁇ m, in terms of film thickness after drying.
• any known film can be used without any particular limitation.
• a film made of a plastic resin can be preferably used.
• a polyester film is preferable from the viewpoint of heat resistance, mechanical strength, handleability, and the like.
• a laminate of these films can also be used as the first film.
• thermoplastic resin film as described above is preferably a uniaxially or biaxially stretched film from the viewpoint of improving mechanical strength.
• the thickness of the first film is not particularly limited, it can be, for example, 10 ⁇ m to 150 ⁇ m.
• a peelable second film is attached to the surface of the resin layer.
• the second film in the dry film according to the present invention refers to a film that is peeled off from the resin layer before lamination when the resin layer side of the dry film is laminated on a base material such as a substrate by heating or the like so as to be in contact with the resin layer. say.
• the second film that can be peeled off from the resin layer for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. It is sufficient that the adhesive force between the resin layer and the second film is smaller than the adhesive force between the resin layer and the first film.
• the thickness of the second film is not particularly limited, it can be, for example, 10 ⁇ m to 150 ⁇ m.
• the cured product of the present invention is obtained by curing the photosensitive resin composition described above or the resin layer of the dry film described above.
• the printed wiring board of the present invention has a cured product obtained from the resin layer of the photosensitive resin composition or dry film of the present invention.
• the photosensitive resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above organic solvent, and is coated on the substrate by a dip coating method, After applying by a method such as flow coating method, roll coating method, bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C. Thus, a tack-free resin layer is formed.
• the resin layer is formed on the substrate by laminating it on the substrate with a laminator or the like so that the resin layer is in contact with the substrate, and then peeling off the carrier film.
• the substrate examples include printed wiring boards and flexible printed wiring boards on which circuits are formed in advance using copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy. , Synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, and other materials such as copper-clad laminates for high-frequency circuits, all grades (FR-4, etc.) of copper-clad laminates Plates, metal substrates, polyimide films, polyethylene terephthalate films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can also be used.
• Synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, and other materials such as copper-clad laminates for high-frequency circuits, all grades (FR-4, etc.) of copper-clad laminates Plates, metal substrates, polyimide films,
• the base material When it is in the form of a dry film, it is preferable that lamination on the base material is performed under pressure and heat using a vacuum laminator or the like.
• a vacuum laminator By using such a vacuum laminator, when using a circuit-formed substrate, even if the surface of the circuit substrate has unevenness, the dry film adheres to the circuit substrate, so there is no entrapment of air bubbles. It also improves the ability to fill recesses on the substrate surface.
• the pressure condition is preferably about 0.1 to 2.0 MPa, and the heating condition is preferably 40 to 120°C.
• the photosensitive resin composition of the present invention contains an organic solvent
• Volatilization drying is performed by using a hot air circulating drying oven, IR oven, hot plate, convection oven, etc. (equipped with a heat source that heats the air using steam) and bringing the hot air in the dryer into countercurrent contact with the substrate through the nozzle. method) can be used.
• a resin layer on the substrate After forming a resin layer on the substrate, it is selectively exposed to active energy rays through a photomask having a predetermined pattern, and the unexposed area is treated with a dilute alkaline aqueous solution (eg, 0.3 to 3% by mass aqueous solution of sodium carbonate). to form a pattern of the cured product.
• a dilute alkaline aqueous solution eg, 0.3 to 3% by mass aqueous solution of sodium carbonate.
• the first film is peeled off from the dry film and developed to form a patterned cured product on the substrate.
• the first film may be peeled off from the dry film before exposure, and the exposed resin layer may be exposed and developed as long as the characteristics are not impaired.
• heat curing for example, 100 to 220 ° C
• final finish curing main curing
• the exposure machine used for the active energy ray irradiation may be any device equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury short arc lamp, etc., and irradiating ultraviolet rays in the range of 350 to 450 nm.
• a direct writing device eg, a laser direct imaging device that draws an image with a laser directly from CAD data from a computer
• the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm.
• the amount of exposure for image formation varies depending on the film thickness and the like, but can generally be in the range of 10-1000 mJ/cm 2 , preferably in the range of 20-800 mJ/cm 2 .
• Examples of the developing method include a dipping method, a shower method, a spray method, a brush method, and the like.
• Alkaline aqueous solutions such as ammonia and amines can be used.
• solder reflow treatment can be performed by a conventionally known method. Also, solder reflow is generally performed under processing conditions of, for example, 245 to 260° C. for 5 to 10 seconds.
• the photosensitive resin composition or dry film of the present invention is preferably used for manufacturing electronic parts such as printed wiring boards, and more preferably for forming permanent coatings. At that time, using the photosensitive resin composition or dry film of the present invention, a cured product is formed by the above-described method or the like.
• the resin layer of the photosensitive resin composition or dry film of the present invention is insulating, it is preferably used to form a solder resist, coverlay, or interlayer insulating layer.
• the photosensitive resin composition according to the present invention may also be used for forming solder dams.
• ⁇ Synthesis Example 1 (synthesis of carboxyl group-containing resin varnish A)> 220 parts by mass of a cresol novolak type epoxy resin (manufactured by DIC Corporation, EPICLON N-695, epoxy equivalent: 220) is placed in a four-necked flask equipped with a stirrer and a reflux condenser, 214 parts by mass of carbitol acetate is added, Dissolved by heating. Next, 0.1 parts by mass of hydroquinone as a polymerization inhibitor and 2.0 parts by mass of dimethylbenzylamine as a reaction catalyst were added. This mixture was heated to 95 to 105° C., 72 parts by mass of acrylic acid was gradually added dropwise, and reacted for 16 hours.
• a cresol novolak type epoxy resin manufactured by DIC Corporation, EPICLON N-695, epoxy equivalent: 220
• This reaction product was cooled to 80 to 90° C., 106 parts by mass of tetrahydrophthalic anhydride was added, reacted for 8 hours, cooled, and taken out.
• the thus obtained photosensitive resin having both ethylenically unsaturated bonds and carboxyl groups had a non-volatile content of 65%, a solid matter acid value of 100 mgKOH/g, and a weight average molecular weight Mw of about 3,500.
• This resin solution is hereinafter referred to as Varnish A.
• the measurement of the weight average molecular weight of the obtained resin was measured by GPC.
• varnish B a resin solution having a solid content acid value of 67 mgKOH/g and a solid content concentration of 65%.
• varnish B a resin solution having a solid content acid value of 67 mgKOH/g and a solid content concentration of 65%.
• ⁇ Evaluation of photosensitive resin composition (1) Reattachment of development residue Each photosensitive resin composition obtained as described above is applied to a copper-clad laminate of 0.5 m ⁇ 0.5 m ⁇ 1.6 mm that has been polished with a buff. A coating film was formed by double-sided screen printing so as to have a thickness of 20 ⁇ m. After holding the printed substrate for 10 minutes, it was dried at 80° C. for 40 minutes in a hot air circulating drying oven. After leaving the dried substrate at room temperature for 30 minutes, a developing machine (manufactured by Tokyo Kakoki Co., Ltd., solder resist developing device (150 L tank)) containing 1% Na 2 CO 3 aqueous solution (liquid temperature 30 ° C.). , and the presence or absence of redeposition of development residue was confirmed. The evaluation criteria were as follows. ⁇ : No redeposition observed ⁇ : Slight redeposition observed ⁇ : Redeposition clearly observed The evaluation results were as shown in Tables 1 and 2 below.
• the insulation reliability of the resulting substrate was evaluated using an insulation deterioration evaluation tester (MIG-8600B manufactured by IMV Co., Ltd.) under the conditions of an applied voltage of 100 V, a temperature of 85 ° C., and a humidity of 85% for 1000 hours. After that, the insulation resistance value outside the tank was measured.
• the evaluation criteria were as follows. ⁇ : 10 12 ⁇ or more ⁇ : 10 10 to 10 11 ⁇ ⁇ : 10 8 to 10 9 ⁇ ⁇ : less than 10 8 ⁇
• the evaluation results are shown in Tables 1 and 2 below. rice field.
• Each photosensitive resin composition is applied to a glossy surface of a copper foil (F2-WS manufactured by Furukawa Electric Co., Ltd., 18 ⁇ m thick) using a film applicator to a thickness of 30 ⁇ m after curing. After drying at 80° C. for 40 minutes in a hot air circulating drying oven, the dried copper foil was allowed to stand at room temperature for 30 minutes, then exposed at an exposure dose of 400 mJ/cm 2 . After post curing at 150° C. for 60 minutes, the copper foil was peeled off to prepare a cured film having a thickness of 30 ⁇ m.
• thermomechanical analyzer Q400EM manufactured by TA Instruments Co., Ltd.
• Tg glass transition point
• thermomechanical analysis the sample was heated from room temperature to 200°C at a heating rate of 10°C/min under a test load of 5g, then air-cooled to room temperature. °C.
• the inflection point in the process of raising the temperature for the second time was taken as the glass transition temperature (Tg).
• the photosensitive resin composition (Examples 1 to 11) containing a biphenyl-type epoxy resin as a thermosetting component and a (meth)acrylate having an isocyanuric ring as a photopolymerizable monomer, It can be seen that the problem of redeposition of development residues and roller marks is improved while maintaining insulation reliability.
• a photosensitive resin composition containing a biphenyl-type epoxy resin as a thermosetting component and a (meth)acrylate having no isocyanuric ring as a photopolymerizable monomer (Comparative Examples 1 and 2) and isocyanurate as a photopolymerizable monomer
• the problem of redeposition of development residues and roller marks cannot be improved while maintaining insulation reliability. Recognize.

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• 2022
  • 2022-09-28 JP JP2023551806A patent/JP7445095B2/ja active Active
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