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WO2025066478A1 - 无三聚氰胺碱性显影型树脂组合物、干膜、固化物和具有该固化物的电子部件 - Google Patents

无三聚氰胺碱性显影型树脂组合物、干膜、固化物和具有该固化物的电子部件 Download PDF

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Publication number
WO2025066478A1
WO2025066478A1 PCT/CN2024/106744 CN2024106744W WO2025066478A1 WO 2025066478 A1 WO2025066478 A1 WO 2025066478A1 CN 2024106744 W CN2024106744 W CN 2024106744W WO 2025066478 A1 WO2025066478 A1 WO 2025066478A1
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WIPO (PCT)
Prior art keywords
hydroxyl
resin
resin composition
melamine
cured product
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PCT/CN2024/106744
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English (en)
French (fr)
Inventor
姚国荣
顾庆华
张鑫
加藤贤治
刘洪兵
王玉彬
王平清
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Taiyo Ink Suzhou Co Ltd
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Taiyo Ink Suzhou Co Ltd
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Publication of WO2025066478A1 publication Critical patent/WO2025066478A1/zh
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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

Definitions

  • the present invention relates to a melamine-free alkaline developing resin composition, a dry film, a cured product, and an electronic component having the cured product.
  • the present invention relates to a melamine-free alkaline developing resin composition, a cured product thereof suitable for a printed circuit board, such as a solder resist, and an electronic component having the cured product.
  • curable resin compositions are usually used.
  • curable resin compositions dry film type compositions, liquid compositions, etc. have been developed.
  • the curable resin composition can be patterned by applying the principle of photography (photolithography), so that fine processing can be performed.
  • photolithography the principle of photography
  • Solder resist also called solder resist ink
  • solder resist ink Alkaline-developable photosensitive compositions are now widely used as solder resists in the manufacture of actual printed circuit boards.
  • a solder resist composition is applied to a substrate with a circuit formed thereon and dried, and then a photomask is vacuum-sealed for exposure, which has become the mainstream.
  • melamine acts as a thermosetting agent and antioxidant to improve the ink's acid and alkali resistance, metal plating resistance, adhesion and hardness.
  • melamine acts as a thermosetting agent and antioxidant to improve the ink's acid and alkali resistance, metal plating resistance, adhesion and hardness.
  • EU REACH regulation Registration, Evaluation, Authorisation and Restriction of Chemicals
  • melamine belongs to the SVHC (Substances of Very High Concern) environmental control substances.
  • Patent Document 1 produces a highly sensitive epoxy solder resist acrylic oligomer containing a hydroxyl group, a carboxyl group and a double bond and having an acid value and epoxy equivalent in a specific range, thereby improving the sensitivity of solder resist ink.
  • a conventional curing agent is still used.
  • Patent document 1 CN114262424A
  • solder resist inks usually contained melamine as a thermosetting agent and antioxidant.
  • melamine as a thermosetting agent and antioxidant.
  • an alkaline-developable resin composition with excellent drying control range, sensitivity, and resolution can be prepared without using melamine, and its cured product has excellent pencil hardness, acid resistance, metal plating resistance, alkali resistance, and solvent resistance.
  • an object of the present invention is to provide an alkali-developable resin composition whose cured product has excellent pencil hardness, acid resistance, metal plating resistance, alkali resistance and solvent resistance and is excellent in drying control range, sensitivity and resolution.
  • Another object of the present invention is to provide a dry film and a cured product having excellent properties as described above, obtained by using such an alkaline developing type solder resist composition, and a printed wiring board having a cured film of a solder resist or the like formed thereon as the cured product.
  • the alkaline-developable resin composition is composed of at least a two-component system resin composition, characterized in that the alkaline-developable resin composition contains: an epoxy resin, a carboxyl group-containing vinyl ester resin, a photopolymerization initiator, a photosensitive monomer, an inorganic filler and a hydroxyl-containing compound component.
  • the carboxyl vinyl ester resin and the inorganic filler are contained in different resin compositions from the epoxy resin and the photosensitive monomer.
  • the pH value of the hydroxyl-containing compound component is greater than or equal to 4.0 and less than or equal to 5.5.
  • the hydroxyl-containing compound component comprises a hydroxyl-containing compound having at least one hydroxyl group in the molecule.
  • the content of the hydroxyl-containing compound component is 1.2 to 7.8 parts by mass relative to 100 parts by mass of the carboxyl-containing vinyl ester resin calculated as a solid content.
  • a preferred embodiment of the present invention relates to an alkaline-developable resin composition, characterized in that the hydroxyl-containing compound having at least one hydroxyl group in the molecule is selected from alcohols, phenols, ethers, esters or polymers. At least one or more of the group consisting of.
  • a preferred embodiment of the present invention relates to an alkaline-developable resin composition, characterized in that the hydroxyl-containing compound having at least one hydroxyl group in the molecule is a polymer having hydroxyl groups in the side chain and/or at the terminal, such as a propylene glycol compound and/or a propylene glycol ether compound.
  • a more preferred embodiment of the present invention relates to an alkali-developable resin composition, wherein the hydroxyl group-containing compound component having at least one hydroxyl group in a molecule has an acid value of 10 to 100 mgKOH/g.
  • a more preferred embodiment of the present invention relates to an alkali-developable resin composition, wherein the number average molecular weight of the hydroxyl group-containing compound having at least one hydroxyl group in the molecule is within a range of 500 to 5,000.
  • a further preferred embodiment of the present invention relates to an alkaline-developable resin composition, characterized in that the carboxyl vinyl ester resin, the photopolymerization initiator, the inorganic filler and the hydroxyl-containing compound component are contained in different resin compositions from the epoxy resin and the photosensitive monomer.
  • another aspect of the present invention relates to a dry film having a resin layer obtained by applying the above-mentioned alkali-developable resin composition on a carrier film and drying the resultant.
  • Still another aspect of the present invention relates to the above-mentioned alkali-developable resin composition, characterized in that the composition is used as a material for a solder resist.
  • Still another aspect of the present invention relates to: a cured product characterized in that it is obtained by curing an alkaline-developable resin composition; a cured product characterized in that it is obtained by curing a resin layer of a dry film; and an electronic component characterized in that it has these cured products.
  • an alkali-developable resin composition whose cured product has excellent pencil hardness, acid resistance, metal plating resistance, alkali resistance and solvent resistance and which is excellent in drying control range, sensitivity and resolution.
  • the present invention can provide a dry film and a cured product having excellent properties as described above obtained by using such an alkali-developable resin composition, and an electronic component such as a printed wiring board having a cured film of a solder resist or the like formed thereon as the cured product.
  • the alkaline developing resin composition of the present invention is preferably composed of at least a two-component system resin composition.
  • a two-component system can be cited in which one resin composition is used as a main agent composition and the other resin composition is used as a curing agent composition.
  • the carboxyl vinyl ester resin and the inorganic filler are contained in different resin compositions from the epoxy resin and the photosensitive monomer.
  • the main agent composition is composed of at least a carboxyl vinyl ester resin, a photopolymerization initiator, an inorganic filler and a hydroxyl-containing compound component
  • the curing agent composition is composed of at least an epoxy resin and a photosensitive monomer.
  • the epoxy resin and the carboxyl group-containing vinyl ester resin are directly contained in different compositions, and the photosensitive monomer and the photopolymerization initiator are directly contained in different compositions.
  • the epoxy resin functions as a thermosetting component in the alkaline-developable resin composition to form a cured product.
  • an epoxy resin a known and commonly used multifunctional epoxy resin having at least two epoxy groups in one molecule can be used.
  • Epoxy resin can be liquid at room temperature, or solid or even semi-solid.
  • the multifunctional epoxy resin preferably bisphenol A type epoxy resin; brominated epoxy resin; novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin; tetrahydroxyphenylethane type epoxy resin; Resin; heterocyclic epoxy resin; diglycidyl phthalate resin; tetraglycidyl ditoluoyl ethane resin; naphthyl-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton; glycidyl methacrylate copolymer epoxy resin; copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; epoxy-modified polybuta
  • epoxy resins can be used alone or in combination of two or more.
  • the epoxy resin that is solid or semi-solid at room temperature can also be a known epoxy resin.
  • bisphenol A epoxy resin jER1001 manufactured by Mitsubishi Chemical Corporation
  • bisphenol F epoxy resin jER1001 manufactured by Mitsubishi Chemical Corporation
  • bisphenol F epoxy resin jER1001 manufactured by Mitsubishi Chemical Corporation
  • epoxy resins that are semi-solid at room temperature bisphenol A type epoxy resin (jER834 manufactured by Mitsubishi Chemical Corporation), naphthalene type epoxy resin (HP-4032 manufactured by DIC Corporation) and the like can be cited.
  • being solid or semisolid at room temperature means being solid or semisolid at 15° C.
  • Determination of solid or semisolid can be made according to Annex 2 “Method for Confirming Liquid State” of the Ministerial Ordinance on Tests and Properties of Dangerous Substances (Ministerial Ordinance No. 1, 1991).
  • biphenyl type epoxy resin a known and commonly used multifunctional epoxy resin having a biphenyl skeleton can be used, for example, a multifunctional solid epoxy resin containing a biphenyl skeleton (NC-3000H and NC-3000 manufactured by Nippon Kayaku Co., Ltd.), a biphenyl type epoxy resin (YX-4000 and YL-6121HA manufactured by Mitsubishi Chemical Corporation), etc. can be mentioned.
  • novolac-type epoxy resins examples include cresol novolac-type epoxy resins (Epiclon N-690 manufactured by DIC Corporation), phenol novolac-type epoxy resins (Epiclon N-770 manufactured by DIC Corporation, jER152 manufactured by Mitsubishi Chemical Corporation), and the like.
  • the content of the epoxy resin described above is preferably in the range of about 30 to 100 parts by mass, more preferably 40 to 90 parts by mass, and even more preferably 50 to 85 parts by mass, relative to 100 parts by mass of the carboxyl group-containing vinyl ester resin in terms of solid content.
  • a carboxyl group-containing vinyl ester resin having an ethylenically unsaturated double bond in the molecule is particularly preferred from the viewpoint of being able to impart alkali developability, photocurability, and development resistance.
  • a resin using an epoxy resin as a starting material a polyurethane resin having a carbamate skeleton, a copolymer resin having a copolymer structure of an unsaturated carboxylic acid, and a resin using a phenol compound as a starting material.
  • Specific examples of the carboxyl group-containing vinyl ester resin are shown below.
  • a carboxyl-containing vinyl ester resin obtained by reacting an unsaturated monocarboxylic acid with a polyfunctional epoxy resin and then reacting the unsaturated monocarboxylic acid with a polyacid anhydride to obtain a carboxyl-containing resin, and then reacting the unsaturated monocarboxylic acid with a polyfunctional epoxy resin to obtain a carboxyl-containing vinyl ester resin;
  • a carboxyl group-containing vinyl ester resin obtained by reacting a polyfunctional epoxy resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A cresol novolac epoxy resin, or a dicyclopentadiene cresol novolac epoxy resin with (meth)acrylic acid, and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to a hydroxyl group present in a side chain;
  • a polyfunctional epoxy resin such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol A cresol novolac epoxy resin, or a dicyclopentadiene cresol novolac epoxy resin with (meth)acrylic acid
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride
  • Carboxyl-containing vinyl ester resins obtained by adding cyclic ethers such as ethylene oxide or cyclic carbonates such as propylene carbonate to polyfunctional phenol compounds such as novolac resins, partially esterifying the resulting hydroxyl groups with (meth)acrylic acid, and reacting the remaining hydroxyl groups with polyacid anhydrides;
  • Carboxyl group-containing vinyl ester resins obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule such as glycidyl (meth)acrylate or a-methylglycidyl (meth)acrylate to any of the resins described in (3) to (5).
  • cresol novolac type and phenol novolac type carboxyl group-containing vinyl ester resins particularly preferred are cresol novolac type and phenol novolac type carboxyl group-containing vinyl ester resins, namely, the carboxyl group-containing vinyl ester resins of (3), (4), (5) and (6) above.
  • (meth)acrylate is a term collectively referring to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
  • the carboxyl group-containing vinyl ester resin described above has a plurality of free carboxyl groups on the side chains of the main chain polymer, it can be developed with a dilute alkaline aqueous solution.
  • the acid value of the carboxyl group-containing vinyl ester resin is preferably in the range of 40 to 200 mgKOH/g, and more preferably in the range of 45 to 120 mgKOH/g.
  • the acid value is less than 40 mgKOH/g, alkali development is difficult, while when it exceeds 200 mgKOH/g, dissolution of the exposed portion by the developer is promoted, so that the line becomes thinner than necessary, and sometimes the exposed portion and the unexposed portion are dissolved and peeled by the developer indiscriminately, making it difficult to draw a normal resist pattern, which is not preferred.
  • the weight average molecular weight of the above-mentioned carboxyl group-containing vinyl ester resin varies depending on the resin skeleton, and is generally preferably in the range of 2000 to 150000, and more preferably in the range of 5000 to 100000.
  • the weight average molecular weight is less than 2000, the coating on the substrate and the non-tackiness (dry to touch) after drying may be deteriorated, and the moisture resistance of the coating film after exposure may deteriorate, the film may be reduced during development, and the resolution may be greatly deteriorated.
  • the weight average molecular weight exceeds 150000, the developability may be significantly deteriorated and the storage stability may be deteriorated.
  • photopolymerization initiator examples include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, and bisacylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphos
  • Monoacylphosphine oxides such as chlorobenzoyldiphenylphosphine oxide, methyl 2,4,6-trimethylbenzoylphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, isopropyl pivaloylphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; hydroxyacetophenones such as 1-hydroxy-cyclohexylphenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- ⁇ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl ⁇ -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one; benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propy
  • the content of the photopolymerization initiator is preferably 5 to 25 parts by mass, more preferably 8 to 20 parts by mass, relative to 100 parts by mass of the carboxyl group-containing vinyl ester resin in terms of solid content.
  • the content is 5 parts by mass or more, the surface curability becomes good, and when the content is 25 parts by mass or less, halation is less likely to occur, resulting in good resolution.
  • the alkaline developing resin composition capable of forming the cured product of the present invention may contain a known and commonly used photosensitive monomer.
  • the photosensitive monomer may be, for example, a compound having one or more ethylenically unsaturated groups in the molecule.
  • Such a photosensitive monomer contributes to the photocuring of the carboxyl vinyl ester resin based on active energy ray irradiation (when containing an ethylenically unsaturated group), thereby curing the alkaline developing resin composition.
  • the photosensitive monomer preferably used in the present invention includes, for example, methyl ⁇ -(allyloxymethyl)acrylate, or diol diacrylates such as 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and 1,10-decanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, diol diacrylates obtained by adding at least one of ethylene oxide and propylene oxide to neopentyl glycol, diol diacrylates such as caprolactone-modified hydroxypivalic acid neopentyl glycol diacrylate, EO
  • the content of the photosensitive monomer is preferably in the range of 5 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 15 to 40 parts by mass, based on 100 parts by mass of the carboxyl group-containing vinyl ester resin in terms of solid content.
  • the alkali-developable resin composition has sufficient photocurability, patterning is further improved during development, and dryness to touch is also improved.
  • the inorganic filler may be used alone or in combination of two or more.
  • the amount of the inorganic filler is preferably in the range of 10 to 100 parts by mass, more preferably in the range of 15 to 80 parts by mass, and further preferably in the range of 20 to 60 parts by mass, relative to 100 parts by mass of the carboxyl group-containing vinyl ester resin in terms of solid content.
  • the amount of the inorganic filler is 10 parts by mass or more, there is a tendency to obtain a cured film having better resistance to soldering heat, insulation reliability, reflectivity, and heat discoloration resistance.
  • the amount of the inorganic filler is 80 parts by mass or less, there is a tendency to obtain an alkaline developing resin composition having better degassing properties, resolution, and deep curing properties.
  • the inorganic filler examples include titanium oxide, silicon dioxide, barium sulfate, barium titanate, Neuburg silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc.
  • an inorganic filler is preferably contained in the main agent.
  • the inorganic filler at least one of silicon dioxide and barium sulfate is preferred.
  • the inorganic filler may be surface-treated and used. More preferably, the surface of the inorganic filler is surface-treated to introduce a curable reactive group.
  • the curing reactive group refers to a group that undergoes a curing reaction with an epoxy resin or a carboxyl group-containing vinyl ester resin, and may be a photocuring reactive group or a thermosetting reactive group.
  • the photocuring reactive group include methacryloyl, acryloyl, vinyl, and styryl groups
  • thermosetting reactive group include epoxy, amino, hydroxyl, carboxyl, isocyanate, imino, oxetanyl, mercapto, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, and oxazoline groups.
  • the method for introducing curable reactive groups into the surface of the inorganic filler is not particularly limited, and the introduction can be carried out using a known and commonly used method, and the surface of the inorganic filler can be treated with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group.
  • a surface treatment agent having a curable reactive group for example, a coupling agent having a curable reactive group as an organic group.
  • silane coupling agents, titanium coupling agents, zirconium coupling agents, aluminum coupling agents, etc. can be used.
  • inorganic fillers treated with surfaces without curable reactive groups for example, silica-alumina surface treatment, titanate coupling agent treatment, aluminate coupling agent treatment, organically treated inorganic fillers, etc. can be cited.
  • the average particle size (D50) of the inorganic filler is 2000 nm or less, more preferably 1200 nm or less.
  • the lower limit thereof is preferably 0.1 nm or more in terms of the average particle size (D50).
  • the average particle size (D50) can be obtained using a laser diffraction particle size distribution measuring device and a measuring device based on a dynamic light scattering method.
  • a measuring device based on the laser diffraction method Microtrac MT3300EXII manufactured by Microtrac BEL Inc. can be cited, and as a measuring device based on the dynamic light scattering method, Nanotrac Wave II UT151 manufactured by Microtrac BEL Inc. can be cited.
  • the alkaline-developable resin composition of the present invention achieves the above-mentioned object of the present invention by using a hydroxyl-containing compound component having a specific pH value range in the main agent component.
  • melamine has the ability to donate electrons, absorb free radicals, and play a certain role in inhibiting polymerization in the process of photoinitiated polymerization, thereby reducing the sensitivity.
  • melamine By replacing melamine with a hydroxyl-containing compound component with a pH value in a specific range, it is possible to slightly reduce its acid resistance and metal plating resistance while ensuring that the drying management range, resolution, alkali resistance, solvent resistance, etc. remain unchanged, but at the same time improve the sensitivity.
  • adding a hydroxyl-containing compound component in a specific pH range at a specific content can further improve acid resistance and metal plating resistance.
  • the pH range of the hydroxyl compound component is above 4.0 and below 5.5, preferably above 4.0 and below 5.2, and more preferably above 4.0 and below 5.0.
  • the pH value is measured according to DIN 19268 standard.
  • the acid value of the hydroxyl-containing compound is 10 to 100 mgKOH/g, preferably 20 to 80 mgKOH/g, and more preferably 25 to 60 mgKOH/g.
  • the hydroxyl compound having at least one hydroxyl group in the molecule As long as the pH value of the hydroxyl compound component is within the above range, the hydroxyl compound having at least one hydroxyl group in the molecule
  • the hydroxyl-containing compound hereinafter sometimes referred to as "hydroxyl-containing compound"
  • any substance can be used.
  • it can be selected from alcohols (including monohydric alcohols and/or polyhydric alcohols), phenols (including monohydric phenols and/or polyhydric phenols), ethers (including ethers formed by monohydric alcohols and/or polyhydric alcohols, ethers formed by monohydric phenols or polyhydric phenols), esters (including esters formed by monohydric alcohols and/or polyhydric alcohols, esters formed by monohydric phenols or polyhydric phenols), polymers having hydroxyl groups on the side chains and/or at the ends, etc.
  • These hydroxyl-containing compounds can be used alone or in combination of two or more.
  • the hydroxyl-containing compound is preferably a polymer having hydroxyl groups on the side chains and/or at the ends, and more preferably a polymer having hydroxyl groups and carboxyl groups on the side chains and/or at the ends.
  • the main chain and/or side chain of the hydroxyl-containing compound may optionally contain other substituents, for example, alkyl (preferably carbon number 1-8, more preferably carbon number 1-4), alkoxy (preferably carbon number 1-8, more preferably carbon number 1-4), alkenyl (preferably carbon number 1-8, more preferably carbon number 1-4), alkynyl (preferably carbon number 1-8, more preferably carbon number 1-4), amino, halogen atom, amine (N atom is preferably substituted by alkyl group with carbon number 1-8, more preferably substituted by alkyl group with carbon number 1-4), carboxyl, etc.
  • substituents for example, alkyl (preferably carbon number 1-8, more preferably carbon number 1-4), alkoxy (preferably carbon number 1-8, more preferably carbon number 1-4), alkenyl (preferably carbon number 1-8, more preferably carbon number 1-4), alkynyl (preferably carbon number 1-8, more preferably carbon number 1-4), amino, halogen atom, amine (N atom is
  • the hydroxyl compound component may also contain other ingredients, such as solvents, without affecting the purpose of the present invention.
  • the content of the hydroxyl compound component in the specific pH range is 1.2 to 7.8 parts by mass, and more preferably 1.5 to 6 parts by mass, relative to 100 parts by mass of the carboxyl vinyl ester resin in terms of solid content. If the content is too low, there is still room for improvement in acid resistance and metal plating resistance. If the content is too high, there is a tendency for acid resistance and pencil hardness to become poor.
  • the alkaline developing resin composition has excellent drying management range, sensitivity, and resolution, and the cured product has excellent pencil hardness, acid resistance, metal plating resistance, alkali resistance, and solvent resistance.
  • acid resistance and metal plating resistance are further improved compared to when melamine is used.
  • the molecular weight of the hydroxyl-containing compound is preferably 500 to 5000, more preferably 1000 to 4000, and further preferably 1500 to 3000 in terms of number average molecular weight. It is preferably 1000 to 6000, more preferably 2000 to 5000, and further preferably 3000 to 4000 in terms of weight average molecular weight.
  • Examples of commercially available products of the hydroxyl compound component within the specific pH range include TECH-7200 (Shanghai Tiger Polymer Technology Co., Ltd.).
  • a solvent may be used in at least one component system.
  • conventional organic solvents may be used, and examples thereof include: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate (CA), butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate
  • solvents can be used alone or in combination of two or more.
  • the content of the solvent in the main agent composition of the alkali-developable resin composition of the present invention is preferably in the range of 25 to 110 parts by mass relative to 100 parts by mass of the carboxyl group-containing vinyl ester resin in terms of solid content.
  • Such components include colorants such as pigments and dyes, thermal inhibitors, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial/antifungal agents, defoaming agents, leveling agents, anti-sag agents, thickeners, adhesion-imparting agents, thixotropy-imparting agents, photoinitiator aids, sensitizers, photobase generators, thermoplastic resins, elastomers, organic fillers, release agents, surface treatment agents, dispersants, dispersing aids, surface modifiers, stabilizers, phosphors, cellulose resins, and the like.
  • colorants such as pigments and dyes, thermal inhibitors, ultraviolet absorbers, plasticizers, flame retardants, antistatic agents, antioxidants, antibacterial/antifungal agents, defoaming agents, leveling agents, anti-sag agents, thickeners, adhesion-imparting agents, thixotropy-imparting agents, photoinitiator aids, sens
  • the base composition and the curing agent composition of the alkali-developable resin composition of the present invention can be prepared by mixing and dispersing the respective components in predetermined amounts, for example, using a three-roll mill or the like.
  • a dry film can be prepared from the alkali-developable resin composition of the present invention.
  • the dry film of the present invention has a resin layer, and the resin layer is obtained by coating the alkaline developing type resin composition of the present invention on a carrier film and drying it.
  • the main agent composition and the curing agent composition are fully mixed with each other to obtain the alkaline developing type resin composition of the present invention, and then directly or indirectly After diluting with a high boiling point solvent to adjust to an appropriate viscosity as needed, the composition is applied to a carrier film to a uniform thickness using a comma coater, a knife coater, a lip coater, a rod coater, an extrusion coater, a reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc.
  • the applied composition is dried at a temperature of 50 to 130° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness There are no particular restrictions on the coating film thickness, and it is usually appropriately selected in the range of 10 to 150 ⁇ m, preferably 20 to 60 ⁇ m, based on the film thickness after drying.
  • a plastic film is used, for example, polyester film such as polyethylene terephthalate (PET), polyimide film, polyamide-imide film, polypropylene film, polystyrene film, etc.
  • PET polyethylene terephthalate
  • the thickness of the carrier film is not particularly limited, and is usually appropriately selected within the range of 10 to 150 ⁇ m.
  • the peelable cover film for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, etc. can be used.
  • the cover film any film can be used as long as it is smaller than the adhesion between the resin layer and the carrier film when the cover film is peeled off.
  • the alkaline developing resin composition of the present invention may be applied to the above-mentioned cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, in the present invention, when a dry film is produced, as a thin film to which the curable composition of the present invention is applied, either a carrier film or a cover film may be used.
  • the alkaline developing resin composition of the present invention is adjusted to a viscosity suitable for the coating method using a high boiling point solvent, for example, and applied to a substrate by a dip coating method, flow coating method, roll coating method, rod coating method, screen printing method, curtain coating method, etc., and then the high boiling point solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of about 60 to 100° C., thereby forming a non-sticky resin layer.
  • a high boiling point solvent for example
  • the resin layer of the present invention is bonded to the substrate by a laminator or the like so that the resin layer is in contact with the substrate, and then the carrier film is peeled off, thereby forming a resin layer on the surface of the substrate.
  • copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates, etc.
  • the copper-clad laminates use materials such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven fabric epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, and copper-clad laminates for high-frequency circuits using fluorine, polyethylene, polyphenylene ether (polyphenylene oxide), cyanate, etc.
  • the alkaline developing resin composition of the present invention When the alkaline developing resin composition of the present invention is used to form a cured product, the composition is applied to a substrate, the solvent is evaporated and dried, and a resin layer is obtained. The obtained resin layer is exposed (light irradiated), so that the exposed part (the part irradiated with light) is cured.
  • active energy rays are selectively used for exposure through a photomask with a pattern, or a laser direct exposure machine is used for direct pattern exposure, and an alkaline aqueous solution (for example, a 0.3-3 mass % sodium carbonate aqueous solution) is used to develop the unexposed part, thereby forming an anti-etching pattern.
  • the volatilization drying or thermal curing when forming the above-mentioned cured product can be carried out, for example, using a hot air circulation drying furnace, IR furnace, hot plate, convection oven, etc. (using a device with a heat source that uses steam to heat the air, a method of making the hot air in the dryer contact by convection, and a method of blowing it onto the support using a nozzle).
  • any device equipped with a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., which irradiates ultraviolet rays in the range of 350 to 450 nm can be used, and a direct drawing device (for example, a laser direct imaging device that directly draws an image with a laser using CAD data from a computer) can also be used.
  • the maximum wavelength of the lamp light source or laser light source of the direct drawing machine can be in the range of 350 to 410 nm.
  • the exposure amount used for image formation varies depending on the film thickness, etc., and can usually be set in the range of 20 to 1000 mJ/ cm2 , preferably 20 to 800 mJ/ cm2 .
  • the resin layer after the exposure step is treated with a developer, thereby removing the unexposed portion of the coating film and forming a pattern film of the alkali-developable resin composition of the present invention.
  • an immersion method, a shower method, a spray method, a brushing method, etc. can be used.
  • a sodium carbonate aqueous solution with a mass concentration of 0.5 to 5% can be used, and other alkaline aqueous solutions can also be used, for example: alkaline aqueous solutions of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, etc.
  • the temperature of the developer is 20 to 40° C. and the development time is within 180 seconds.
  • the obtained pattern film is washed with a rinse liquid as required.
  • a rinse liquid distilled water, methanol, ethanol, isopropyl alcohol, etc. can be used alone or in combination.
  • the present invention can also provide an electronic component comprising the above-mentioned cured product.
  • the alkaline-developable resin composition or dry film of the present invention can be used for protective films of printed circuit boards, semiconductor elements, etc., electrical insulating layers, sealing materials for sealing or embedding electronic components, component embedding layers, adhesive layers for fixing electronic components, etc., and is particularly suitable for high-density wiring requiring low dielectric constant and low dielectric loss tangent, electronic components for processing high-frequency signals, and electronic components for vehicles and robots requiring high temperature and long-term reliability.
  • the electronic components in the present invention refer to components used in electronic circuits, including active components such as printed circuit boards, transistors, light-emitting diodes, laser diodes, etc., as well as passive components such as resistors, capacitors, inductors, connectors, etc.
  • reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added and mixed to the reaction solution to neutralize the potassium hydroxide, thereby obtaining a propylene oxide reaction solution of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 mgKOH/g (307.9 g/eq.).
  • An average of 1.08 mol of propylene oxide was added per 1 equivalent of phenolic hydroxyl groups.
  • reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, and then washed with water. After that, toluene was replaced with 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator, and distilled off to obtain a novolac type acrylate resin solution.
  • novolac type acrylic acid was introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube.
  • 332.5 parts of ester resin solution and 1.22 parts of triphenylphosphine were blown into air at a rate of 10 ml/min, and 60.8 parts of tetrahydrophthalic anhydride were slowly added while stirring, and reacted at 95-101°C for 6 hours, and then cooled and taken out.
  • a carboxyl vinyl ester resin with a solid content of 65% and an acid value of 87.7 mgKOH/g was obtained.
  • Black toner MA100 (carbon black) Mitsubishi Chemical Corporation, JY-140P (carbon black) Hangzhou Junyi New Material Technology Co., Ltd.
  • Defoaming agent KS-66, manufactured by Shin-Etsu Chemical Co., Ltd.
  • Leveling agent BYK-1790, manufactured by BYK Additives (Shanghai) Co., Ltd.
  • Epoxy resin N-770-75EA, manufactured by DIC Corporation, novolac type multifunctional epoxy resin, solid content 75%
  • Photosensitive monomer DPHA, dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
  • the alkaline developing resin composition described in Table 1 was applied to the entire surface of the copper foil substrate with the pattern formed thereon by screen printing, and dried in a hot air circulation drying oven at 80°C. After the start of drying, the substrate was taken out every 10 minutes from 20 minutes to 70 minutes, and slowly cooled to room temperature. The substrate was developed for 60 seconds using a 1wt% sodium carbonate aqueous solution at 30°C at a spray pressure of 0.2MPa, and the maximum allowable drying time without leaving residue was used as the drying management range.
  • the copper-free substrate was polished with a jet scrubber, washed with water, dried, and coated with the alkaline developing resin composition described in Table 1 by screen printing, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After drying, it was exposed with an exposure amount of 300mJ/ cm2 using a step tablet (Kodak No2), and the number of steps of the step tablet remaining when developing for 60 seconds at a spray pressure of 0.2MPa using a 1wt% sodium carbonate aqueous solution at 30°C was evaluated as the sensitivity.
  • a step tablet Kodak No2
  • the alkaline developing resin composition described in Table 1 was applied on a copper-free substrate (FR4) by screen printing or spraying so that the film thickness after drying was 42 ⁇ 2 ⁇ m. After drying (80°C, 30 minutes), a predetermined photomask was brought into close contact with the coating film and exposed (exposure amount on the masking material was 300 mJ/cm 2 ). Subsequently, development was performed (1 wt % Na 2 CO 3 , 30°C, 0.2 MPa, 60 seconds) to prepare a test piece. The thinnest residual line in the test piece was visually confirmed.
  • the substrate production process is as follows:
  • the alkaline developing resin compositions of the examples and comparative examples were respectively coated on the entire surface of the copper foil laminate by screen printing to a thickness of 20 ⁇ m, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After cooling to room temperature, full exposure was performed at 300 mJ/ cm2 using an exposure device equipped with a high-pressure mercury lamp. Next, after developing for 60 seconds in a 1 wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C, it was cured in a hot air circulation drying oven at 150°C for 60 minutes to produce an evaluation substrate A having a cured film.
  • the pencil hardness of the resin surface of substrate A was measured and evaluated according to JIS K 5600-5-4.
  • the evaluation criteria are as follows.
  • the substrate production process is as follows:
  • the alkaline developing resin compositions of the examples and comparative examples were respectively coated on the entire surface of the copper foil laminate by screen printing to a thickness of 20 ⁇ m, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After cooling to room temperature, an exposure device equipped with a high-pressure mercury lamp was used to transfer the image at 300 mJ/ cm2 (a circular window pattern appeared). Next, after developing for 60 seconds in a 1 wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C, the image was transferred to the copper foil laminate. The film was cured in a hot air circulation drying oven at 150° C. for 60 minutes to produce an evaluation substrate B having a cured film.
  • the evaluation substrate B was immersed in a 10 vol% H2SO4 aqueous solution at room temperature for 20 minutes. This was repeated 5 times in total, and the penetration and dissolution of the coating film were visually confirmed, and further, the peeling due to tape peeling was confirmed.
  • the coating film is bulging or swelling and falling off
  • the substrate production process is as follows:
  • the alkaline developing resin composition of the embodiment and the comparative example was respectively coated on the entire surface of the copper foil laminate by screen printing to a thickness of 20 ⁇ m, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After cooling to room temperature, an exposure device equipped with a high-pressure mercury lamp was used to transfer the image at 300 mJ/ cm2 (a circular window pattern appeared). Next, after developing for 60 seconds in a 1wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C, it was cured in a hot air circulation drying oven at 150°C for 60 minutes to produce an evaluation substrate B having a cured film.
  • Plating was performed using commercially available chemical nickel plating baths and chemical gold plating baths at 0.5 ⁇ m for nickel and 0.03 ⁇ m for gold, and the presence or absence of plated penetration was evaluated. The presence or absence of peeling of the cured film on the substrate B was then evaluated by tape peeling.
  • the criteria for evaluation were as follows.
  • the substrate production process is as follows:
  • the alkaline developing resin composition of the embodiment and the comparative example was respectively coated on the entire surface of the copper foil laminate by screen printing to a thickness of 20 ⁇ m, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After cooling to room temperature, an exposure device equipped with a high-pressure mercury lamp was used to transfer the image at 300 mJ/ cm2 (a circular window pattern appeared). Next, after developing for 60 seconds in a 1wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C, it was cured in a hot air circulation drying oven at 150°C for 60 minutes to produce an evaluation substrate B having a cured film.
  • the evaluation substrate B was immersed in a 10 vol% NaOH aqueous solution at room temperature for 20 minutes, and the penetration and dissolution of the coating film were visually confirmed, and further, the peeling due to tape peeling was confirmed.
  • the coating film is bulging or swelling and falling off
  • the substrate production process is as follows:
  • the alkaline developing resin composition of the embodiment and the comparative example was respectively coated on the entire surface of the copper foil laminate by screen printing to a thickness of 20 ⁇ m, and dried in a hot air circulation drying oven at 80°C for 30 minutes. After cooling to room temperature, an exposure device equipped with a high-pressure mercury lamp was used to transfer the image at 300 mJ/ cm2 (opening patterns such as round and square appeared). Next, after developing for 60 seconds in a 1wt% sodium carbonate aqueous solution at a pressure of 0.2 MPa and a liquid temperature of 30°C, it was cured in a hot air circulation drying oven at 150°C for 60 minutes to produce an evaluation substrate B with a cured film.
  • the evaluation substrate B was immersed in propylene glycol monomethyl ether at room temperature for 30 minutes, and the penetration and dissolution of the coating film were visually confirmed, and further, the peeling due to the tape peeling was confirmed.
  • the coating film is bulging or swelling and falling off
  • the curing agent components of Comparative Examples 1 and 2 contain melamine but do not contain hydroxyl-containing compound components, and the sensitivity decreases by 1-2 levels, and as the amount of melamine used decreases, the acid resistance and metal plating resistance tend to decrease.
  • the curing agent component of Comparative Example 3 does not contain both melamine and hydroxyl-containing compound components, and has poor acid resistance and metal plating resistance.
  • the curing agent components of Comparative Examples 4 to 6 do not contain melamine, and contain hydroxyl-containing compound components whose pH is outside a specific range, and have poor acid resistance and metal plating resistance.
  • Comparative Examples 7 and 8 contain hydroxyl-containing compound components whose pH values are within a specific range, their content is insufficient or excessive, and there is still room for improvement in acid resistance and metal plating resistance (compared with Comparative Examples 1 and 2).
  • the pencil hardness of Comparative Example 8 tends to decrease.
  • the alkaline-developable resin composition of each example has excellent drying control range, sensitivity, and resolution by containing a hydroxyl compound component having a pH value within a specific range in a specific content in the main agent, and the cured product has excellent pencil hardness, acid resistance, metal plating resistance, alkali resistance, and solvent resistance.
  • the acid resistance and metal plating resistance are further improved compared to the case of using melamine. Therefore, the melamine-free alkaline-developable resin composition of the present invention is particularly suitable for a cured product of a printed circuit board using a photolithography method, such as a solder resist, and an electronic component having the cured product.

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Abstract

提供：其固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性，且干燥管理幅度、感光度、分辨率优异的无三聚氰胺碱性显影型树脂组合物、干膜、固化物和具有该固化物的电子部件。该组合物含有：环氧树脂、含羧基乙烯基酯树脂、光聚合引发剂、感光性单体、无机填料和含羟基化合物组分，所述含羧基乙烯基酯树脂和所述无机填料，与所述环氧树脂和所述感光性单体分别包含于不同的树脂组合物中，所述含羟基化合物组分的pH值为4.0以上且5.5以下，所述含羟基化合物组分包含分子中至少具有一个羟基的含羟基化合物，所述含羟基化合物组分的含量为，相对于以固体成分计的100质量份含羧基乙烯基酯树脂，为1.2～7.8质量份。

Description

无三聚氰胺碱性显影型树脂组合物、干膜、固化物和具有该固化物的电子部件 技术领域
本发明涉及无三聚氰胺碱性显影型树脂组合物、干膜、固化物和具有该固化物的电子部件。特别是本发明涉及：无三聚氰胺碱性显影型树脂组合物、和适于印刷电路板的其固化物、例如阻焊剂、以及具有该固化物的电子部件。
背景技术
印刷电路板的制造中的阻焊层等永久覆膜的形成中，通常采用固化性树脂组合物。作为这样的固化性树脂组合物，开发了干膜型的组合物、液态的组合物等。进而，为了用于电子部件的小型化、高精细的设计结构、复杂的制造方法，还期望固化性树脂组合物能够通过应用照相法(光刻法)的原理进行图案形成，从而能进行微细加工。近年来，从环境对策的方面出发，能在稀的弱碱水溶液中进行显影的碱性显影型成为主流。
一直以来，印刷电路板上，作为电路板电路的保护材料使用有阻焊剂(也称为阻焊油墨)。碱性显影型的感光性组合物现在在实际的印刷电路板的制造中大量作为阻焊剂使用。作为使用其的阻焊层的形成方法，在形成有电路的基板涂布阻焊剂组合物并干燥，接着将光掩模真空密合以曝光的接触曝光成为主流。
目前市售的阻焊油墨通常含有三聚氰胺，其作为热固化剂、抗氧化剂同时，来提高油墨的耐酸碱性、金属镀覆耐性、附着力和硬度等特性。但油墨中的三聚氰胺也存在诸多问题，其会在焊接过程(260℃)中挥发，并且，基于欧盟REACH法规(Registration，Evaluation，Authorisation and Restriction of Chemicals，《关于化学品注册、评估、授权和限制的法规》)，三聚氰胺属于SVHC(Substances of Very High Concern，高关注度物质)类环境管控物质。
专利文献1中制造了一种含有羟基、羧基和双键且具有特定范围的酸值和环氧当量的高感光度的环氧阻焊丙烯酸寡聚体，改善了阻焊油墨的感光度。然而，其在使用所述环氧阻焊丙烯酸寡聚体制造油墨时，仍使用常规的固化剂。
现有技术文献
专利文献
专利文献1：CN114262424A
发明内容
本发明要解决的技术问题
以往，阻焊油墨通常含有三聚氰胺作为热固化剂、抗氧化剂，随着对环保要求的日趋严格，希望能够在不使用三聚氰胺的前提下，制作具有优异的干燥管理幅度、感光度、分辨率的碱性显影型树脂组合物，进而其固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性。
因此，本发明的目的在于，提供：其固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性，且干燥管理幅度、感光度、分辨率优异的碱性显影型树脂组合物。
进一步本发明的目的在于，提供：使用这种碱性显影型阻焊剂组合物从而得到的上述那样的各特性优异的干膜和固化物、以及形成作为该固化物的阻焊剂等的固化覆膜而成的印刷电路板。
用于解决问题的方案
本发明人进行了深入研究，结果发现，上述课题通过如下碱性显影型树脂组合物可以解决。该碱性显影型树脂组合物由至少双组分体系的树脂组合物构成，其特征在于，该碱性显影型树脂组合物含有：环氧树脂、含羧基乙烯基酯树脂、光聚合引发剂、感光性单体、无机填料和含羟基化合物组分。
所述含羧基乙烯基酯树脂和所述无机填料，与所述环氧树脂和所述感光性单体分别包含于不同的树脂组合物中，
所述含羟基化合物组分的pH值为4.0以上且5.5以下，所述含羟基化合物组分包含分子中至少具有一个羟基的含羟基化合物，所述含羟基化合物组分的含量为，相对于以固体成分计的100质量份所述含羧基乙烯基酯树脂，为1.2～7.8质量份。
其中，本发明的优选方式涉及一种碱性显影型树脂组合物，其特征在于，所述分子中至少具有一个羟基的含羟基化合物为选自由醇类、酚类、醚类、酯类或聚合物类所组 成的组中的至少1种或两种以上。
进而，优选的本发明的方式涉及一种碱性显影型树脂组合物，其特征在于，所述分子中至少具有一个羟基的含羟基化合物为侧链和/或末端具有羟基的聚合物类，例如为丙二醇类化合物和/或丙二醇醚类化合物。
进而，更优选的本发明的方式涉及一种碱性显影型树脂组合物，其特征在于，其特征在于，所述分子中至少具有一个羟基的含羟基化合物组分的酸值为10～100mgKOH/g。
进而，进一步优选的本发明的方式涉及一种碱性显影型树脂组合物，其特征在于，其特征在于，所述分子中至少具有一个羟基的含羟基化合物的数均分子量为500～5000的范围内。
进而，进一步优选的本发明的方式涉及一种碱性显影型树脂组合物，其特征在于，所述含羧基乙烯基酯树脂、所述光聚合引发剂、所述无机填料和所述含羟基化合物组分，与所述环氧树脂和所述感光性单体分别包含于不同的树脂组合物中。
另外，本发明的另一方式涉及一种干膜，其具有通过将上述碱性显影型树脂组合物涂布于载体膜并干燥而得到的树脂层。
本发明的进一步另外方式还涉及上述碱性显影型树脂组合物，其特征在于，其用于阻焊剂的材料。
本发明的进一步另外方式涉及：一种固化物，其特征在于，其是将碱性显影型树脂组合物固化而得到的；一种固化物，其特征在于，其是将干膜的树脂层固化而得到的；一种电子部件，其特征在于，具有这些固化物。
发明的效果
根据本发明，可以提供：其固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性，且干燥管理幅度、感光度、分辨率均优异的碱性显影型树脂组合物。
进一步根据本发明，可以提供：通过使用这种碱性显影型树脂组合物而得到的上述那样的各特性优异的干膜和固化物、以及形成作为该固化物的阻焊剂等的固化覆膜而成的印刷电路板等电子部件。
具体实施方式
本发明的碱性显影型树脂组合物优选由至少双组分体系的树脂组合物构成。例如可以举出：将一个树脂组合物作为主剂组合物、另一个树脂组合物作为固化剂组合物的双组分体系。该情况下，例如，含羧基乙烯基酯树脂和无机填料，与环氧树脂和感光性单体分别包含于不同的树脂组合物中。优选的是，作为主剂组合物，至少由含羧基乙烯基酯树脂、光聚合引发剂、无机填料和含羟基化合物组分构成，作为固化剂组合物，至少由环氧树脂和感光性单体构成。
此处，从防止保存期间中的化学反应的观点出发，优选环氧树脂和含羧基乙烯基酯树脂分别直接包含于彼此不同的组合物，以及感光性单体和光聚合引发剂分别直接包含于彼此不同的组合物。
以下，对构成本发明的碱性显影型树脂组合物的各成分进行说明。
环氧树脂
环氧树脂在碱性显影型树脂组合物作为热固化成分发挥功能，形成固化物。
作为这种环氧树脂，可以使用在1分子中具有至少2个环氧基的公知常用的多官能环氧树脂。
环氧树脂可以是常温下为液态，也可以为固体乃至半固体。
作为多官能环氧树脂，优选可以举出双酚A型环氧树脂；溴化环氧树脂；酚醛清漆型环氧树脂；双酚F型环氧树脂；氢化双酚A型环氧树脂；缩水甘油胺型环氧树脂；乙内酰脲型环氧树脂；脂环式环氧树脂；三羟基苯基甲烷型环氧树脂；联二甲苯酚型或联苯酚型环氧树脂或它们的混合物；双酚S型环氧树脂；双酚A酚醛清漆型环氧树脂；四羟苯基乙烷型环氧树脂；杂环式环氧树脂；邻苯二甲酸二缩水甘油酯树脂；四缩水甘油二甲苯酰基乙烷树脂；含萘基的环氧树脂；具有二环戊二烯骨架的环氧树脂；甲基丙烯酸缩水甘油酯共聚系环氧树脂；环己基马来酰亚胺与甲基丙烯酸缩水甘油酯的共聚环氧树脂；环氧改性的聚丁二烯橡胶衍生物；CTBN改性环氧树脂、具有异氰脲环的环氧树脂等，但当然不限定于这些。
这些环氧树脂可以使用1种或组合2种以上而使用。
“在常温下为固体或半固体的环氧树脂”也可以使用公知常用者。例如，作为在常温下为固体的环氧树脂，双酚A型环氧树脂(三菱化学株式会社制jER1001)、双酚F型 环氧树脂(三菱化学株式会社制jER4004P)、萘型环氧树脂(DIC株式会社制HP-4700)、含萘骨架的多官能固体环氧树脂(日本化药株式会社制NC-7000)、三酚环氧树脂(日本化药株式会社制EPPN-502H)、含二环戊二烯骨架的多官能固体环氧树脂(DIC株式会社制Epiclon HP-7200)、含磷环氧树脂(新日铁住金化学株式会社制TX0712)、三(2,3-环氧丙基)异氰脲酸酯(日产化学工业株式会社制TEPIC)，作为在常温下为半固体的环氧树脂，可以举出双酚A型环氧树脂(三菱化学株式会社制jER834)、萘型环氧树脂(DIC株式会社制HP-4032)等。
此处，本发明中在常温下为固体或半固体是指，在15℃下呈固体或半固体。固体或半固体的判定可以依据涉及危险物的试验和性状的省令(平成元年自治省令第1号)的附件第2“液态的确认方法”进行。
作为联苯型环氧树脂，可以使用具有联苯骨架的公知常用的多官能环氧树脂。例如可以举出含联苯骨架的多官能固体环氧树脂(日本化药株式会社制NC-3000H、NC-3000)、联苯型环氧树脂(三菱化学株式会社制YX-4000、YL-6121HA)等。
作为酚醛清漆型环氧树脂，可以举出甲酚酚醛清漆型环氧树脂(DIC株式会社制Epiclon N-690)、苯酚酚醛清漆型环氧树脂(DIC株式会社制Epiclon N-770、三菱化学株式会社制的jER152)等。
以上说明的环氧树脂的含量相对于以固体成分计的含羧基乙烯基酯树脂的100质量份，优选大致30～100质量份的范围，更优选40～90质量份的范围，进一步优选50～85质量份的范围。
含羧基乙烯基酯树脂
作为本发明中使用的含羧基乙烯基酯树脂，从可以用于赋予碱显影性、光固化性、耐显影性的方面出发，特别优选分子中具有烯属不饱和双键的含羧基乙烯基酯树脂。例如以环氧树脂为起始原料的树脂、具有氨基甲酸酯骨架的聚氨酯树脂、具有不饱和羧酸的共聚结构的共聚树脂、以酚化合物为起始原料的树脂。以下示出含羧基乙烯基酯树脂的具体例子。
(1)使多官能环氧化合物和不饱和单羧酸与1分子中具有至少1个醇性羟基和与环氧基反应的除醇性羟基以外的1个反应性基团的化合物的反应产物、与饱和或不饱和多元酸 酐反应而获得的含羧基乙烯基酯树脂；
(2)对于使不饱和单羧酸与多官能环氧树脂反应之后与多元酸酐反应所得到的含羧基树脂，进一步使分子中具有1个氧杂环丙烷环和1个以上烯属不饱和基团的化合物与其反应而获得的含羧基乙烯基酯树脂；
(3)使苯酚酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A甲酚酚醛清漆型环氧树脂、双环戊二烯甲酚酚醛清漆型环氧树脂等多官能环氧树脂与(甲基)丙烯酸进行反应，对存在于侧链的羟基加成邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐等二元酸酐而得到的含羧基乙烯基酯树脂；
(4)使将前述(3)中多官能环氧树脂的羟基进一步用表氯醇环氧化而成的多官能环氧树脂与(甲基)丙烯酸进行反应,对生成的羟基加成多元酸酐而得到的含羧基乙烯基酯树脂；
(5)对酚醛清漆树脂等多官能酚化合物加成环氧乙烷等环状醚、或碳酸亚丙酯等环状碳酸酯,将得到的羟基用(甲基)丙烯酸偏酯化，使剩余的羟基与多元酸酐进行反应而得到的含羧基乙烯基酯树脂；
(6)对前述(3)～(5)中任意种树脂进一步加成(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸a一甲基缩水甘油酯等分子中具有1个环氧基和1个以上(甲基)丙烯酰基的化合物而得到的含羧基乙烯基酯树脂等。
作为这些例示中特别优选的物质，为甲酚酚醛清漆型和苯酚酚醛清漆型的含羧基乙烯基酯树脂，即所述(3)、(4)、(5)、(6)的含羧基乙烯基酯树脂。
需要说明的是，在本说明书中，(甲基)丙烯酸酯是统称丙烯酸酯、甲基丙烯酸酯及其混合物的术语，对其他类似的表达也同样。
上述那样的含羧基乙烯基酯树脂由于在主链聚合物的侧链上具有多个游离的羧基，因此可以利用稀碱水溶液进行显影。
另外，上述含羧基乙烯基酯树脂的酸值优选为40～200mgKOH/g的范围，更优选为45～120mgKOH/g的范围。酸值不足40mgKOH/g时，难以碱显影，另一方面，超过200mgKOH/g时，会促进显影液对曝光部的溶解，因此，线变得比所需要的更细，有时曝光部和未曝光部无区别地被显影液溶解剥离，难以描绘正常的抗蚀图案，故不优选。
此外，上述含羧基乙烯基酯树脂的重均分子量根据树脂骨架而不同，通常优选为2000～150000、进一步优选为5000～100000的范围。重均分子量不足2000时，有时向基板的涂布、干燥后的不粘手性(指触干燥性)能变差，此外，有时曝光后的涂膜的耐湿性恶化、显影时产生膜减少、分辨率大幅变差。另一方面，重均分子量超过150000时，有时显影性会显著劣化、保存稳定性会变差。
光聚合引发剂
作为光聚合引发剂，例如可以举出双(2,6-二氯苯甲酰基)苯基氧化膦、双(2,6-二氯苯甲酰基)-2,5-二甲基苯基氧化膦、双(2,6-二氯苯甲酰基)-4-丙基苯基氧化膦、双(2,6-二氯苯甲酰基)-1-萘基氧化膦、双(2,6-二甲氧基苯甲酰基)苯基氧化膦、双(2,6-二甲氧基苯甲酰基)-2,4,4-三甲基戊基氧化膦、双(2,6-二甲氧基苯甲酰基)-2,5-二甲基苯基氧化膦、双(2,4,6-三甲基苯甲酰基)-苯基氧化膦等双酰基氧化膦类；2,6-二甲氧基苯甲酰基二苯基氧化膦、2,6-二氯苯甲酰基二苯基氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸甲酯、2-甲基苯甲酰基二苯基氧化膦、新戊酰基苯基膦酸异丙酯、2,4,6-三甲基苯甲酰基二苯基氧化膦等单酰基氧化膦类；1-羟基-环己基苯基酮、1-[4-(2-羟基乙氧基)-苯基]-2-羟基-2-甲基-1-丙烷-1-酮、2-羟基-1-{4-[4-(2-羟基-2-甲基-丙酰基)-苄基]苯基}-2-甲基-丙烷-1-酮、2-羟基-2-甲基-1-苯基丙烷-1-酮等羟基苯乙酮类；苯偶姻、苯偶酰、苯偶姻甲醚、苯偶姻乙醚、苯偶姻正丙醚、苯偶姻异丙醚、苯偶姻正丁醚等苯偶姻类；苯偶姻烷基醚类；二苯甲酮、对甲基二苯甲酮、米氏酮、甲基二苯甲酮、4,4’-二氯二苯甲酮、4,4’-双二乙基氨基二苯甲酮等二苯甲酮类；苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基-2-苯基苯乙酮、1,1-二氯苯乙酮、1-羟基环己基苯基酮、2-甲基-1-[4-(甲硫基)苯基]-2-吗啉基-1-丙酮、2-苄基-2-二甲基氨基-1-(4-吗啉基苯基)-丁酮-1、2-(二甲基氨基)-2-[(4-甲基苯基)甲基)-1-[4-(4-吗啉基)苯基]-1-丁酮、N,N-二甲基氨基苯乙酮等苯乙酮类；噻吨酮、2-乙基噻吨酮、2-异丙基噻吨酮、2,4-二甲基噻吨酮、2,4-二乙基噻吨酮、2-氯噻吨酮、2,4-二异丙基噻吨酮等噻吨酮类；蒽醌、氯蒽醌、2-甲基蒽醌、2-乙基蒽醌、2-叔丁基蒽醌、1-氯蒽醌、2-戊基蒽醌、2-氨基蒽醌等蒽醌类；苯乙酮二甲基缩酮、苯偶酰二甲基缩酮等缩酮类；苯甲酸乙基-4-二甲基氨酯、苯甲酸2-(二甲基氨基)乙酯、对-二甲基苯甲酸乙酯等苯甲酸酯类；1-[4-(苯硫基)苯基]-1,2-辛烷二酮2-(O-苯甲酰肟)、 1-[9-乙基-6-(2-甲基苯甲酰基)-9H-咔唑-3-基]-乙酮1-(O-乙酰肟)等肟酯类；双(η5-2,4-环戊二烯-1-基)-双(2,6-二氟-3-(1H-吡咯-1-基)苯基)钛、双(环戊二烯基)-双[2,6-二氟-3-(2-(1-吡咯-1-基)乙基)苯基]钛等二茂钛类；苯基二硫化2-硝基芴、丁偶姻、茴香偶姻乙醚、偶氮二异丁腈、二硫化四甲基秋兰姆等。光聚合引发剂可以单独使用1种，也可以组合2种以上而使用。
光聚合引发剂的含量相对于以固体成分计的含羧基乙烯基酯树脂100质量份，优选5～25质量份，更优选8～20质量份。5质量份以上的情况下，表面固化性变得良好，25质量份以下的情况下，不易产生晕影，得到良好的分辨率。
感光性单体
能形成本发明的固化物的碱性显影型树脂组合物可以含有公知常用的感光性单体。感光性单体例如可以为在分子中具有1个以上烯属不饱和基团的化合物。这种感光性单体有助于(包含烯属不饱和基团的情况下)基于活性能量射线照射的含羧基乙烯基酯树脂的光固化，使碱性显影型树脂组合物固化。
本发明中优选使用的感光性单体例如可以举出α-(烯丙氧基甲基)丙烯酸甲酯、或1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、1,9-壬二醇二丙烯酸酯、1,10-癸二醇二丙烯酸酯等二醇的二丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二丙烯酸酯、四乙二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、聚丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、在新戊二醇上加成了环氧乙烷和环氧丙烷中的至少任1种而得到的二醇的二丙烯酸酯、己内酯改性羟基特戊酸新戊二醇二丙烯酸酯等二醇的二丙烯酸酯、双酚A的EO加成物二丙烯酸酯、双酚A的PO加成物二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、氢化二环戊二烯基二丙烯酸酯、环己基二丙烯酸酯等具有环状结构的二丙烯酸酯、或者对应于它们的甲基丙烯酸酯单体等2官能(甲基)丙烯酸酯、季戊四醇三丙烯酸酯、三羟甲基丙烷三丙烯酸酯、三羟甲基甲烷三丙烯酸酯、环氧乙烷改性三羟甲基丙烷三丙烯酸酯、环氧丙烷改性三羟甲基丙烷三丙烯酸酯、环氧氯丙烷改性三羟甲基丙烷三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、四羟甲基甲烷四丙烯酸酯、环氧乙烷改性磷酸三丙烯酸酯、环氧氯丙烷改性甘油三丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇单羟基五丙烯酸酯、或者以它 们的倍半硅氧烷改性物等为代表的多官能丙烯酸酯、或者对应于它们的甲基丙烯酸酯单体、3官能甲基丙烯酸酯、ε-己内酯改性三(丙烯酰氧基乙基)异氰脲酸酯等多官能(甲基)丙烯酸酯、或它们的2种以上的组合等。
这种感光性单体的含量相对于以固体成分计的含羧基乙烯基酯树脂100质量份，优选5～50质量份的范围，更优选10～45质量份的范围，进一步优选15～40质量份的范围。
感光性单体的含量如果为这种范围内，则碱性显影型树脂组合物具有充分的光固化性，显影时图案化变得更良好，指触干燥性也变得良好。
无机填料
本发明中，无机填料可以单独使用1种，也可以组合使用2种以上。
无机填料的配混量相对于以固体成分计的含羧基乙烯基酯树脂100质量份，优选为10～100质量份的范围，更优选为15～80质量份的范围，进一步优选为20～60质量份的范围。无机填料的配混量为10质量份以上时，有获得耐焊接热性能、绝缘可靠性、反射率、耐热变色性更加优异的固化膜的倾向。无机填料的配混量为80质量份以下时，有获得脱泡性、分辨率、深部固化性更加优异的碱性显影型树脂组合物的倾向。
作为无机填料，例如有可列举出氧化钛、二氧化硅、硫酸钡、钛酸钡、诺伊堡硅土、滑石、粘土、碳酸镁、碳酸钙、氧化铝、氢氧化铝、氮化硅、氮化铝等。其中，优选包含滑石、二氧化硅、硫酸钡之中的至少任一种，能够抑制碱性显影型树脂组合物的固化物的固化收缩，改善密合性、硬度、反射率等特性。
从改善固化物的机械性能、耐热性、加工性和耐化学性的角度出发，无机填料优选包含于主剂中。作为该无机填料，优选二氧化硅、硫酸钡之中的至少任一种。
无机填料可以使用经表面处理而成者，更优选对它们的表面实施能导入固化性反应基团的表面处理。
此处，固化性反应基团是指：与环氧树脂等、含羧基乙烯基酯树脂发生固化反应的基团，可以为光固化性反应基团，也可以为热固化性反应基团。作为光固化性反应基团，可以举出甲基丙烯酰基、丙烯酰基、乙烯基、苯乙烯基等，作为热固化性反应基团，可以举出环氧基、氨基、羟基、羧基、异氰酸酯基、亚氨基、氧杂环丁烷基、巯基、甲氧基甲基、甲氧基乙基、乙氧基甲基、乙氧基乙基、噁唑啉基等。
对无机填料表面导入固化性反应基团的方法没有特别限定，可以使用公知常用的方法进行导入即可，可以用具有固化性反应基团的表面处理剂、例如具有固化性反应基团作为有机基团的偶联剂等对无机填料的表面进行处理。作为偶联剂，可以使用硅烷偶联剂、钛偶联剂、锆偶联剂、铝偶联剂等。需要说明的是，作为经不具有固化性反应基团的表面处理的无机填料，例如可以举出二氧化硅-氧化铝表面处理、钛酸酯系偶联剂处理、铝酸盐系偶联剂处理、经有机处理的无机填料等。
作为无机填料的平均粒径(D50)，为2000nm以下、更优选1200nm以下。另外，其下限值以平均粒径(D50)计、优选0.1nm以上。
无机填料的平均粒径越小，越抑制光照射时的漫反射，可以使固化物图案的微细加工容易。平均粒径(D50)可以利用激光衍射式粒径分布测定装置和基于动态光散射法的测定装置而求出。作为基于激光衍射法的测定装置，可以举出MicrotracBEL Inc.制的MicrotracMT3300EXII，作为基于动态光散射法的测定装置，可以举出MicrotracBEL Inc.制的Nanotrac Wave II UT151。
含羟基化合物组分
本发明的碱性显影型树脂组合物通过在主剂成分中使用特定pH值范围的含羟基化合物组分，从而实现了上述本发明的目的。
详细地说，发明人通过积极研究发现，三聚氰胺具有供电子的能力，会吸收自由基，在光引发聚合的过程中起到一定的阻聚作用，由此会使感光度降低。通过用pH值位于特定范围的含羟基化合物组分替换三聚氰胺，可以在保证干燥管理幅度、解像性、耐碱性、耐溶剂性能等不变的情况下，可能略微降低其耐酸性和金属镀覆耐性，但同时提高感光度。在此基础上，出乎意料的是，以特定的含量添加特定pH值范围的含羟基化合物组分还能够进一步改善耐酸性、金属镀覆耐性。
从实现以上本发明目的的角度出发，所述含羟基化合物组分的pH范围为4.0以上且5.5以下，优选为4.0以上且5.2以下，更优选为4.0以上且5.0以下。所述pH值按照DIN 19268标准进行测定。另外，所述含羟基化合物的酸值为10～100mgKOH/g，优选20～80mgKOH/g，更优选25～60mgKOH/g。
只要含羟基化合物组分的pH值为以上范围内，所述分子中至少具有一个羟基的含羟 基化合物(下文有时简称为“含羟基化合物”)，可以使用任意的物质。例如分子中具有一个或多个醇性羟基和/或酚性羟基的物质。更具体地，可以举出例如，选自醇类(包括一元醇和/或多元醇类)、酚类(包括一元酚和/或多元酚类)、醚类(包括一元醇和/或多元醇形成的醚、一元酚或多元酚形成的醚)、酯类(包括一元醇和/或多元醇形成的酯、一元酚或多元酚形成的酯)、侧链和/或末端具有羟基的聚合物类等。这些含羟基化合物可以单独使用、或组合2种以上而使用。所述含羟基化合物优选侧链和/或末端具有羟基的聚合物类，更优选侧链和/或末端具有羟基和羧基的聚合物类。
在不影响本发明目的的情况下，含羟基化合物的主链和/或侧链中也可以任选地含有其它取代基。例如，烷基(优选碳原子数1～8，更优选碳原子数1～4)、烷氧基(优选碳原子数1～8，更优选碳原子数1～4)、烯基(优选碳原子数1～8，更优选碳原子数1～4)、炔基(优选碳原子数1～8，更优选碳原子数1～4)、氨基、卤原子、胺基(N原子优选被碳原子数1～8的烷基取代，更优选被碳原子数1～4的烷基取代)、羧基等。
在不影响本发明目的的情况下，含羟基化合物组分也可以包含其它成分，例如溶剂等。
所述特定pH值范围的含羟基化合物组分的含量为，相对于以固体成分计的100质量份含羧基乙烯基酯树脂，为1.2～7.8质量份，进一步优选1.5～6质量份。若含量过低，则耐酸性和耐金属镀覆耐性仍有改善余地。若含量过高，则有耐酸性和铅笔硬度变得不佳的倾向。通过在上述含量范围内添加特定pH值范围的含羟基化合物组分，碱性显影型树脂组合物具有优异的干燥管理幅度、感光度、分辨率，固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性，特别出乎意料的是，耐酸性和金属镀覆耐性相比使用三聚氰胺时进一步改善。
从进一步有利于实现本发明目的的角度出发，所述含羟基化合物的分子量以数均分子量计，优选为500～5000，更优选1000～4000，进一步优选1500～3000。以重均分子量计，优选为1000～6000，更优选2000～5000，进一步优选3000～4000。
作为所述特定pH值范围的含羟基化合物组分的市售产品，可以举出TECH-7200(上海泰格聚合物技术有限公司)等。
溶剂
本发明中，出于一般性的目的，例如为了制备碱性显影型树脂组合物的各个组分体系以及调节其粘度，可以在至少一个组分体系中使用溶剂。
作为所述，可以为常规的有机溶剂，作为其例子，可以列举：甲乙酮、环己酮等酮类；甲苯、二甲苯、四甲基苯等芳香族烃类；溶纤剂、甲基溶纤剂、丁基溶纤剂、卡必醇、甲基卡必醇、丁基卡必醇、丙二醇单甲醚、二丙二醇单甲醚(DPM)、二丙二醇二乙醚、三丙二醇单甲醚等二醇醚类；乙酸乙酯、乙酸丁酯、乳酸丁酯、溶纤剂乙酸酯、丁基溶纤剂乙酸酯、卡必醇乙酸酯(CA)、丁基卡必醇乙酸酯、丙二醇单甲醚乙酸酯、二丙二醇单甲醚乙酸酯、碳酸亚丙酯等酯类；辛烷、癸烷等脂肪族烃类；石油醚、石油石脑油、溶剂石脑油、重芳烃溶剂石脑油等石油系溶剂等。
这些溶剂可以单独使用、或组合2种以上而使用。
相对于以固体成分计的100质量份含羧基乙烯基酯树脂，本发明的碱性显影型树脂组合物的主剂组合物中溶剂的含量，优选为25～110质量份的范围。
其他成分
本发明的碱性显影型树脂组合物中，在不脱离本发明的目的的范围内，当然也可以根据需要配混进一步的添加剂作为其他成分。
作为这种成分，例如可以举出颜料和染料等着色料、热阻聚剂、紫外线吸收剂、增塑剂、阻燃剂、抗静电剂、防老剂、抗菌/防霉剂、消泡剂、流平剂、防垂流剂、增稠剂、密合性赋予剂、触变性赋予剂、光引发助剂、敏化剂、光产碱剂、热塑性树脂、弹性体、有机填料、脱模剂、表面处理剂、分散剂、分散助剂、表面改性剂、稳定剂、荧光体、纤维素树脂等。
本发明的碱性显影型树脂组合物的主剂组合物和固化剂组合物可以如下制备：将这些各成分以规定的量、例如用三辊磨等进行混合分散，从而可以制备。
干膜
从本发明的碱性显影型树脂组合物可以制作干膜。
本发明的干膜具有树脂层，所述树脂层是通过在载体膜上涂布本发明的碱性显影型树脂组合物并干燥而得到的。形成干膜时，首先，双组分体系的情况下，将该主剂组合物和固化剂组合物彼此充分混合，得到本发明的碱性显影型树脂组合物后，直接或者根 据需要用高沸点溶剂进行稀释调整至适当的粘度后，利用逗点涂布机、刮刀涂布机、唇口涂布机、棒涂机、挤压涂布机、逆式涂布机、传递辊涂布机、凹版涂布机、喷涂机等，在载体膜上涂布为均匀的厚度。之后，使涂布后的组合物通常以50～130℃的温度干燥1～30分钟，从而可以形成树脂层。对于涂布膜厚，没有特别限制，通常以干燥后的膜厚计、在10～150μm、优选20～60μm的范围内适宜选择。
作为载体膜，使用塑料薄膜，例如可以使用聚对苯二甲酸乙二醇酯(PET)等聚酯薄膜、聚酰亚胺薄膜、聚酰胺酰亚胺薄膜、聚丙烯薄膜、聚苯乙烯薄膜等。对于载体膜的厚度没有特别限制，通常在10～150μm的范围内适宜选择。
在载体膜上形成由本发明的碱性显影型树脂组合物形成的树脂层后，为了防止在树脂层的表面附着尘埃等，优选进一步在树脂层的表面层叠能剥离的覆盖膜。作为能剥离的覆盖膜，例如可以使用聚乙烯薄膜、聚四氟乙烯薄膜、聚丙烯薄膜、表面处理过的纸等。作为覆盖膜，只要在剥离覆盖膜时小于树脂层与载体膜的粘接即可。
需要说明的是，本发明中，也可以在上述覆盖膜上涂布本发明的碱性显影型树脂组合物并干燥，从而形成树脂层，在其表面层叠载体膜。即，本发明中制造干膜时作为涂布本发明的固化性组合物的薄膜，可以使用载体膜和覆盖膜均可。
此处，将本发明的碱性显影型树脂组合物例如使用高沸点溶剂调整至适于涂布方法的粘度，通过浸涂法、流涂法、辊涂法、棒涂法、丝网印刷法、帘涂法等方法涂布在基材上后，在约60～100℃的温度下使组合物中所含的高沸点溶剂挥发干燥(临时干燥)，从而也可以形成无粘性的树脂层。另外，将上述组合物涂布于载体膜上并干燥而以薄膜的形式卷取成的干膜的情况下，利用层压机等以本发明的树脂层与基材接触的方式贴合在基材上后，剥离载体膜，从而可以在基材的表面形成树脂层。
作为上述基材，除了预先由铜等形成有电路的印刷电路板、柔性印刷电路板之外，还可以举出：全部等级(FR-4等)的覆铜层叠板、以及金属基板、聚酰亚胺薄膜、PET薄膜、聚萘二甲酸乙二醇酯(PEN)薄膜、玻璃基板、陶瓷基板、晶圆板等，所述覆铜层叠板使用了纸苯酚、纸环氧、玻璃布环氧、玻璃聚酰亚胺、玻璃布/无纺布环氧、玻璃布/纸环氧、合成纤维环氧、使用了氟·聚乙烯·聚苯醚(聚亚苯基氧化物)·氰酸酯等的高频电路用覆铜层叠板等的材质。
固化物
使用本发明的碱性显影型树脂组合物形成固化物时，将该组合物涂布于基板上，使溶剂挥发干燥后，得到树脂层，对于得到的树脂层进行曝光(光照射)，从而曝光部(经光照射的部分)固化。具体而言，利用接触式或非接触方式，通过形成有图案的光掩模选择性地利用活性能量射线进行曝光、或利用激光直接曝光机直接进行图案曝光，利用碱水溶液(例如0.3～3质量％碳酸钠水溶液)使未曝光部显影，从而形成抗蚀图案。进一步加热至约100～180℃的温度，进行热固化(后固化)，从而可以形成耐热性、耐化学药品性、耐吸湿性、密合性、电特性等各特性优异的固化膜(固化物)。
形成上述固化物时的挥发干燥或热固化例如可以利用热风循环式干燥炉、IR炉、热板、对流烘箱等(使用具备利用蒸汽的空气加热方式的热源的装置，使干燥机内的热风对流接触的方法和利用喷嘴吹送到支撑体上的方式)来进行。
另外，作为上述活性能量射线照射中使用的曝光机，只要为搭载高压汞灯、超高压汞灯、金属卤化物灯、水银短弧灯等而在350～450nm的范围内照射紫外线的装置即可，进而也可以使用直接描绘装置(例如利用来自计算机的CAD数据直接用激光描绘图像的激光直接成像装置)。作为直描机的灯光源或激光光源，最大波长可以处于350～410nm的范围。用于图像形成的曝光量根据膜厚等而不同，通常可以设为20～1000mJ/cm2、优选可以设为20～800mJ/cm2的范围内。
接着，作为显影工序，对曝光工序后的树脂层用显影液进行处理。由此，将涂膜中的未曝光部分去除，可以形成本发明的碱性显影型树脂组合物的图案膜。
此处，作为该显影工序中使用的方法，可以使用浸渍法、冲淋法、喷雾法、刷涂法等。作为显影液，通常可以使用质量浓度为0.5～5％的碳酸钠水溶液，也可以使用其他碱性水溶液，例如：氢氧化钾、氢氧化钠、碳酸钾、磷酸钠、硅酸钠、氨、胺类等的碱性水溶液。
该显影工序中，在显影液的温度为20～40℃、显影时间为180秒以内进行。
需要说明的是，该显影工序中，根据需要，将得到的图案膜利用冲洗液进行清洗。作为冲洗液，可以单独或组合使用蒸馏水、甲醇、乙醇、异丙醇等。
电子部件
另外，本发明还可以提供具有上述固化物的电子部件。
本发明的碱性显影型树脂组合物或干膜可以用于印刷电路板、半导体元件等的保护膜、电绝缘层、封固或内置电子部件等的封固材料、部件内置层、固定电子部件的粘接层等，特别适合于要求低介电常数、低介质损耗角正切的高密度布线、处理高频信号的电子部件、要求高温且长期的可靠性的车载、机器人用的电子部件。
需要说明的是，本发明中电子部件是指，用于电子电路的部件，除印刷电路板、晶体管、发光二极管、激光二极管等有源部件之外，还包括电阻、电容器、电感、连接器等无源部件。
以下，根据实施例具体示出本发明的一个方式，但当然不意图限定本发明权利要求所涉及的发明的范围。
另外，此外只要没有特别记载，所示的“份”和“％”就基于质量。
实施例
[合成例：含羧基乙烯基酯树脂的合成]
在具备温度计、氮气导入装置兼环氧烷导入装置和搅拌装置的高压釜中，导入甲酚酚醛清漆树脂(Aica Kogyo Co..Ltd.制Shonol CRG-951、OH当量:119.4)119.4份、氢氧化钾1.19份和甲苯119.4份，进行搅拌的同时将体系内进行氮气置换，进行加热升温。接着，缓慢地滴加环氧丙烷63.8份，以125～132℃、0～4.8kg/cm2反应16小时。之后，冷却至室温，在该反应溶液中添加混合89％磷酸1.56份，中和氢氧化钾，得到不挥发成分为62.1％、羟值为182.2mgKOH/g(307.9g/eq.)的酚醛清漆型甲酚树脂的环氧丙烷反应溶液。其相对于每1当量酚性羟基、平均加成了1.08摩尔环氧丙烷。
在具备搅拌机、温度计和空气吹入管的反应器中导入得到的酚醛清漆型甲酚树脂的环氧丙烷反应溶液293.0份、丙烯酸43.2份、甲磺酸11.53份、甲基氢醌0.18份和甲苯252.9份，以10ml/分钟的速度吹入空气，边搅拌边以110℃反应12小时。由反应生成的水作为与甲苯的共沸混合物馏出12.6份的水。之后，冷却至室温，将得到的反应溶液用15％氢氧化钠水溶液35.35份中和，然后进行水洗。之后，在蒸发仪中将甲苯用二乙二醇单乙醚乙酸酯118.1份置换，且进行蒸馏去除，得到酚醛清漆型丙烯酸酯树脂溶液。
接着，在具备搅拌器、温度计和空气吹入管的反应器中导入得到的酚醛清漆型丙烯 酸酯树脂溶液332.5份和三苯基膦1.22份，以10ml/分钟的速度吹入空气，边搅拌边缓慢地加入四氢邻苯二甲酸酐60.8份，以95～101℃反应6小时，冷却后取出。如此得到固体成分65％、固体成分的酸值87.7mgKOH/g的含羧基乙烯基酯树脂。
[实施例1～3和比较例1～8]
将表1所示的各成分以各配混量、在搅拌机中预先混合后，用三辊磨进行混炼，分别制备实施例1～3和比较例1～8的碱性显影型树脂组合物(由主剂组合物和固化剂组合物形成的双组分体系)。
[表1]
表1中记载的各成分如下所述。
*1：通过合成例得到的相同的含羧基乙烯基酯树脂，固体成分65％，溶剂35％
*2：黑色色粉:MA100(炭黑)三菱化学株式会社，JY-140P(炭黑)杭州君一新材料科技有限公司制
*3：消泡剂：KS-66，信越化学工业公司制
*4：流平剂：BYK-1790，毕克助剂(上海)有限公司制
*5：光聚合引发剂：ITX，#369E天津久日新材料股份有限公司制
*6：二氧化硅，A-8，矽比科Sibelco公司制
*7：硫酸钡：B-30，Sakai Chemical Industry Co.,Ltd.制
*8：溶剂：DPM：台湾利安德股份有限公司制
*9：环氧树脂：N-770-75EA，DIC公司制，酚醛清漆型的多官能环氧树脂，固体成分75％
*10：感光性单体：DPHA，二季戊四醇六丙烯酸酯，日本化药公司制
*11：三聚氰胺：MELAMINE-JC,江苏金象赛瑞化工科技有限公司制
*12：含羟基化合物组分：TECH-7200，上海泰格聚合物技术有限公司制，pH：4.0～5.0、含羟基聚酯化合物、酸值：30mgKOH/g、数均分子量：2037、重量平均分子量：3115
*13：含羟基化合物组分：BYK-102，pH：2.8，BYK Japan株式会社制
*14：含羟基化合物组分：BYK-220SN，pH：3.5，BYK Japan株式会社制
*15：含羟基化合物组分：BYK-174，pH：6.0，BYK Japan株式会社制
对于得到的实施例和比较例的主剂组合物、固化剂组合物和混合它们得到的碱性显影型树脂组合物，进行了如下述的试验。
＜干燥管理幅度(干燥后直至可曝光并显影时间)＞
用丝网印刷分别将表1记载的碱性显影型树脂组合物整面涂布在形成有图案的铜箔基板上，在80℃的热风循环式干燥炉中干燥。干燥开始后，从20分钟～70分钟期间，每隔10分钟取出基板，缓慢冷却至室温。使用30℃的1wt％碳酸钠水溶液、对该基板在喷压0.2MPa下显影60秒钟，将不留残渣的最大允许干燥时间作为干燥管理幅度。
○：不留残渣的最大允许干燥时间为50分钟以上
×：不留残渣的最大允许干燥时间小于50分钟
＜感光度＞
对无铜基板使用喷砂磨刷(Jet Scrubber)研磨后，水洗、干燥，通过丝网印刷法分别涂布表1记载的碱性显影型树脂组合物，在80℃的热风循环式干燥炉中干燥30分钟。干燥后，通过阶段式曝光表(step tablet)(Kodak No2)以300mJ/cm2的曝光量曝光，使用30℃的1wt％碳酸钠水溶液，在喷压0.2MPa下进行60秒显影时残留的阶段式曝光表的段数作为感光度进行评价。
＜分辨率＞
利用丝网印刷或喷涂，将表1记载的碱性显影型树脂组合物涂布在无铜基板(FR4)上，使得干燥后的膜厚成为42±2μm，干燥(80℃，30分钟)后，使规定的光掩模密合于涂膜，进行曝光(遮蔽材料上的曝光量为300mJ/cm2)，接着，进行显影(1wt％Na2CO3，30℃，0.2MPa，60秒)，制作试验片。以目视确认该试验片中最细的残留线。
＜铅笔硬度＞
基板制作流程如下：
将实施例和比较例的碱性显影型树脂组合物通过丝网印刷分别涂覆在铜箔层压板的整个表面，使其厚度为20μm，并在80℃下在热风循环干燥箱中干燥30分钟。冷却至室温后，使用配备高压汞灯的曝光装置在300mJ/cm2下进行完全曝光。接下来，在1wt％碳酸钠水溶液中，在0.2MPa的压力和30℃的液体温度下显影60秒后，在150℃的热风循环干燥箱中固化60分钟，以产生具有固化膜的评价基板A。
根据JIS K 5600-5-4测定评价基板A的树脂表面的铅笔硬度。评价基准如下。
◎：铅笔硬度6H以上
〇：铅笔硬度4H以上且低于6H
△：铅笔硬度低于4H
＜耐酸性＞
基板制作流程如下：
将实施例和比较例的碱性显影型树脂组合物通过丝网印刷分别涂覆在铜箔层压板的整个表面，使其厚度为20μm，并在80℃下在热风循环干燥箱中干燥30分钟。冷却至室温后，使用配备高压汞灯的曝光装置在300mJ/cm2下进行图像转移(出现圆形等开窗图形)。接下来，在1wt％碳酸钠水溶液中，在0.2MPa的压力和30℃的液体温度下显影60秒后，在 150℃的热风循环干燥箱中固化60分钟，以产生具有固化膜的评价基板B。
将评价基板B在10vol％H2SO4水溶液中在室温下浸渍20分钟，重复进行总计5次，通过目视确认浸渗、涂膜的溶出，进而确认由带剥离造成的剥脱。
○：未观察到变化
△：仅稍稍变化
×：涂膜存在鼓起或溶胀脱落
<金属镀覆耐性>
基板制作流程如下：
将实施例和比较例的碱性显影型树脂组合物通过丝网印刷分别涂覆在铜箔层压板的整个表面，使其厚度为20μm，并在80℃下在热风循环干燥箱中干燥30分钟。冷却至室温后，使用配备高压汞灯的曝光装置在300mJ/cm2下进行图像转移(出现圆形等开窗图形)。接下来，在1wt％碳酸钠水溶液中，在0.2MPa的压力和30℃的液体温度下显影60秒后，在150℃的热风循环干燥箱中固化60分钟，以产生具有固化膜的评价基板B。
使用市售品的化学镀镍浴和化学镀金浴，在镍0.5μm、金0.03μm的条件下进行镀敷，评价有无镀敷的渗入，然后通过带剥离来评价评价基板B的固化膜有无剥离。判断基准如下。
○：看不到渗入、剥离
△：镀敷后可看到轻微渗入，带剥离后还可看到剥离
×：镀敷后有剥离
＜耐碱性＞
基板制作流程如下：
将实施例和比较例的碱性显影型树脂组合物通过丝网印刷分别涂覆在铜箔层压板的整个表面，使其厚度为20μm，并在80℃下在热风循环干燥箱中干燥30分钟。冷却至室温后，使用配备高压汞灯的曝光装置在300mJ/cm2下进行图像转移(出现圆形等开窗图形)。接下来，在1wt％碳酸钠水溶液中，在0.2MPa的压力和30℃的液体温度下显影60秒后，在150℃的热风循环干燥箱中固化60分钟，以产生具有固化膜的评价基板B。
将评价基板B在10vol％NaOH水溶液中在室温下浸渍20分钟，通过目视确认浸渗、涂膜的溶出，进而确认由带剥离造成的剥脱。
○：未观察到变化
△：仅稍稍变化
×：涂膜存在鼓起或溶胀脱落
＜耐溶剂性＞
基板制作流程如下：
将实施例和比较例的碱性显影型树脂组合物通过丝网印刷分别涂覆在铜箔层压板的整个表面，使其厚度为20μm，并在80℃下在热风循环干燥箱中干燥30分钟。冷却至室温后，使用配备高压汞灯的曝光装置在300mJ/cm2下进行图像转移(出现圆形、方形等开窗图形)。接下来，在1wt％碳酸钠水溶液中，在0.2MPa的压力和30℃的液体温度下显影60秒后，在150℃的热风循环干燥箱中固化60分钟，以产生具有固化膜的评价基板B。
将评价基板B在丙二醇单甲醚中在室温下浸渍30分钟，通过目视确认浸渗、涂膜的溶出，进而确认由带剥离造成的剥脱。
○：未观察到变化
△：仅稍稍变化
×：涂膜存在鼓起或溶胀脱落
由表1中所示的结果可知，本发明的碱性显影型树脂组合物具有优异的干燥管理幅度、感光度、分辨率，其形成的固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性。
另一方面，比较例1、2的固化剂组分含有三聚氰胺且不含含羟基化合物组分，感光度下降1-2阶，且随着三聚氰胺用量减少，耐酸性和金属镀覆耐性有降低的倾向。比较例3的固化剂组分不含三聚氰胺和含羟基化合物组分这两者，耐酸性和金属镀覆耐性较差。比较例4～6的固化剂组分不含三聚氰胺，包含pH位于特定范围外的含羟基化合物组分，耐酸性和金属镀覆耐性较差。比较例7、8虽然包含pH值位于特定范围内的含羟基化合物组分，但其含量不足或过多，耐酸性和金属镀覆耐性仍有改进的余地(与比较例1、2基 本相同的水准)，以及比较例8有铅笔硬度降低的倾向。
与此相对，各实施例的碱性显影型树脂组合物通过在主剂中以特定含量包含pH值位于特定范围内含羟基化合物组分，其组合物具有优异的干燥管理幅度、感光度、分辨率，固化物具有优异的铅笔硬度、耐酸性、金属镀覆耐性、耐碱性和耐溶剂性，特别出乎意料的是，耐酸性和金属镀覆耐性相比使用三聚氰胺的情况进一步得到改善。因此，本发明的无三聚氰胺碱性显影型树脂组合物特别适用于应用光刻法的印刷电路板的固化物、例如阻焊剂、以及具有该固化物的电子部件。

Claims (10)

  1. 一种无三聚氰胺碱性显影型树脂组合物，其由至少双组分体系的树脂组合物构成，其特征在于，该碱性显影型树脂组合物含有：环氧树脂、含羧基乙烯基酯树脂、光聚合引发剂、感光性单体、无机填料和含羟基化合物组分，
    所述含羧基乙烯基酯树脂和所述无机填料，与所述环氧树脂和所述感光性单体分别包含于不同的树脂组合物中，
    所述含羟基化合物组分的pH值为4.0以上且5.5以下，所述含羟基化合物组分包含分子中至少具有一个羟基的含羟基化合物，
    所述含羟基化合物组分的含量为，相对于以固体成分计的100质量份所述含羧基乙烯基酯树脂，为1.2～7.8质量份。
  2. 根据权利要求1所述的无三聚氰胺碱性显影型树脂组合物，其特征在于，所述分子中至少具有一个羟基的含羟基化合物为选自由醇类、酚类、醚类、酯类和聚合物类所组成的组中的至少1种或两种以上。
  3. 根据权利要求1或2所述的无三聚氰胺碱性显影型树脂组合物，其特征在于，所述分子中至少具有一个羟基的含羟基化合物为侧链和/或末端具有羟基的聚合物类。
  4. 根据权利要求1或2所述的无三聚氰胺碱性显影型树脂组合物，其特征在于，所述分子中至少具有一个羟基的含羟基化合物组分的酸值为10～100mgKOH/g。
  5. 根据权利要求1或2所述的无三聚氰胺碱性显影型树脂组合物，其特征在于，所述分子中至少具有一个羟基的含羟基化合物的分子量以数均分子量计，为500～5000的范围内。
  6. 根据权利要求1或2所述的无三聚氰胺碱性显影型树脂组合物，其特征在于，所述含羧基乙烯基酯树脂、所述光聚合引发剂、所述无机填料和所述含羟基化合物组分，与所述环氧树脂和所述感光性单体分别包含于不同的树脂组合物中。
  7. 一种干膜，其具有通过将权利要求1～6中任一项所述的无三聚氰胺碱性显影型树脂组合物涂布于载体膜并干燥而得到的树脂层。
  8. 一种固化物，其特征在于，其是将权利要求1～6中任一项所述的无三聚氰胺碱性显影型树脂组合物固化而得到的。
  9. 一种固化物，其特征在于，其是将权利要求7所述的干膜的树脂层固化而得到的。
  10. 一种电子部件，其特征在于，具有权利要求8或9所述的固化物。
PCT/CN2024/106744 2023-09-28 2024-07-22 无三聚氰胺碱性显影型树脂组合物、干膜、固化物和具有该固化物的电子部件 Pending WO2025066478A1 (zh)

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