WO2019221194A1 - Matériau de formation de motif, film durci, et procédé de production pour motif durci - Google Patents

Matériau de formation de motif, film durci, et procédé de production pour motif durci Download PDF

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Publication number
WO2019221194A1
WO2019221194A1 PCT/JP2019/019364 JP2019019364W WO2019221194A1 WO 2019221194 A1 WO2019221194 A1 WO 2019221194A1 JP 2019019364 W JP2019019364 W JP 2019019364W WO 2019221194 A1 WO2019221194 A1 WO 2019221194A1
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group
meth
acid
acrylate
resin
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PCT/JP2019/019364
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English (en)
Japanese (ja)
Inventor
駿介 山田
佑介 狩野
宏子 桜井
中嶋　道也
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Dic株式会社
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Priority to JP2019549595A priority Critical patent/JP6638871B1/ja
Priority to CN201980032106.0A priority patent/CN112105991A/zh
Publication of WO2019221194A1 publication Critical patent/WO2019221194A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a pattern forming material, a cured film, and a method for producing a cured pattern.
  • a pattern forming material such as a resin material used for a solder resist for a printed wiring board is required to be cured with a small exposure amount and to be excellent in alkali developability.
  • an acid group-containing resin obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a resole novolak-type epoxy resin, acrylic acid and phthalic anhydride.
  • epoxy acrylate resin epoxy acrylate resin
  • photosensitivity and alkali developability are not sufficient, and it has not satisfied the increasingly required performance.
  • An object of the present invention is to provide a pattern forming material excellent in photosensitivity and alkali developability, a cured film formed using the pattern forming material, and a method for producing a cured pattern using the pattern forming material. is there.
  • the present invention provides a pattern forming material containing an acid group-containing resin having a polymerizable double bond and lithium partially fixed smectite.
  • the above-mentioned pattern forming material is excellent in photosensitivity and alkali developability because it combines an acid group-containing resin having a polymerizable double bond and lithium partially fixed smectite.
  • the acid group-containing resin may contain a (meth) acryloyl group.
  • the acid group may be at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • the weight average molecular weight of the acid group-containing resin may be 1,000 to 20,000.
  • the cation exchange capacity of the lithium partially fixed smectite may be 1 to 70 meq / 100 g.
  • the content of the lithium partially fixed smectite may be 3 to 70% by mass with respect to the total amount of nonvolatile components in the pattern forming material.
  • the present invention provides a cured film containing a cured product of the above-described pattern forming material.
  • the cured film may be formed in a pattern. That is, the cured film may be a cured pattern.
  • the cured film may be a resist film.
  • the present invention provides a cured pattern comprising: a step of curing a part of a film formed of the pattern forming material described above; and a step of removing an uncured portion of the film to obtain a cured pattern.
  • a cured pattern comprising: a step of curing a part of a film formed of the pattern forming material described above; and a step of removing an uncured portion of the film to obtain a cured pattern.
  • a high-resolution cured pattern can be produced.
  • the step of curing a part of the film may include a step of irradiating the film with active energy rays in a pattern.
  • the present invention it is possible to provide a pattern forming material excellent in photosensitivity and alkali developability, a cured film formed using the pattern forming material, and a method for producing a cured pattern using the pattern forming material. it can.
  • the pattern forming material of the embodiment is a material (curable resin composition) used for forming a cured pattern.
  • the pattern forming material contains an acid group-containing resin having a polymerizable double bond (hereinafter also simply referred to as “acid group-containing resin”) and a lithium partially fixed smectite.
  • the pattern forming material of the embodiment is excellent in light sensitivity, a high-resolution cured pattern can be produced according to the pattern forming material.
  • the pattern forming material of the embodiment is excellent in alkali developability, according to the pattern forming material of the embodiment, when a cured pattern is formed by alkali development, a high-resolution cured pattern can be easily manufactured. Can do.
  • the lithium partially fixed smectite exhibits high dispersibility with respect to the acid group-containing resin.
  • a cured film (for example, a cured pattern) excellent in gas barrier properties such as (oxygen barrier properties) is easily obtained. That is, according to the pattern forming material of the embodiment, a cured pattern having excellent gas barrier properties can be easily produced with high resolution.
  • a cured film for example, a cured pattern
  • a cured film having a small average linear expansion coefficient is easily obtained. Therefore, it is easy to reduce the occurrence of warping of a substrate provided with a cured film (for example, a cured pattern) formed of a pattern forming material.
  • a conventional pattern forming material it is easy to generate a warp of a substrate provided with a cured pattern, and it is difficult to achieve both a reduction in warpage and an improvement in resolution, but according to the pattern forming material of the embodiment, It is easy to achieve both reduction of warpage and improvement of resolution.
  • a cured film (for example, a cured pattern) formed on the substrate using the pattern forming material of the embodiment tends to have high adhesion to the substrate.
  • the adhesiveness of the cured film (for example, the cured pattern) to the substrate tends to be reduced. Therefore, it is easy to achieve both high adhesion to the substrate and reduction of warpage.
  • Smectite is a kind of phyllosilicate mineral (layered clay mineral) having a layer structure.
  • smectite structures such as montmorillonite, beidellite, saponite, hectorite, stevensite, and soconite are known.
  • the structure of the clay material is preferably at least one structure selected from the group consisting of montmorillonite and stevensite.
  • These structures have isomorphous substitution with a low-valent metal element, defects, and the like in part of the metal element of the octahedral sheet. Therefore, the octahedral sheet is negatively charged.
  • these structures have vacant sites in the octahedron sheet, and in the smectite having these structures, lithium ions can exist stably after movement as described later.
  • lithium type smectite Smectite whose cation is lithium ion is referred to as lithium type smectite (however, in this specification, excluding lithium partially fixed type smectite described later).
  • a method for exchanging cations of smectite with lithium ions for example, there is a method in which a lithium salt such as lithium hydroxide or lithium chloride is added to a natural sodium type smectite dispersion (dispersion slurry) to exchange cations. Can be mentioned. By adjusting the amount of lithium added to the dispersion, the amount of lithium ions in the amount of leaching cations of the obtained lithium smectite can be appropriately adjusted.
  • Lithium smectite can also be obtained by a column method or a batch method using a resin obtained by ion exchange of a cation exchange resin with lithium ions.
  • the lithium partially fixed smectite refers to a smectite in which a part of lithium ions in the lithium smectite is fixed to an empty site of the octahedral sheet.
  • Lithium partially fixed smectite can be obtained, for example, by fixing lithium ions between layers at an empty site of an octahedral sheet by heat treatment of lithium smectite. By fixing lithium ions, smectite is water-resistant.
  • the temperature condition of the heat treatment for partially fixing lithium is not particularly limited as long as lithium ions can be fixed.
  • the cation exchange capacity (CEC) is small, the water vapor barrier property and the oxygen barrier property of the pattern forming material (curable resin composition) containing the lithium partially fixed smectite are further improved. . Therefore, it is preferable to heat at 150 ° C. or higher from the viewpoint of efficiently fixing lithium ions and greatly reducing the cation exchange capacity.
  • the temperature of the heat treatment is more preferably 150 to 600 ° C., further preferably 180 to 600 ° C., particularly preferably 200 to 500 ° C., and most preferably 250 to 500 ° C.
  • the heat treatment is preferably performed in an open electric furnace.
  • the relative humidity during heating is 5% or less
  • the pressure is normal pressure.
  • the time for the heat treatment is not particularly limited as long as lithium can be partially fixed. However, from the viewpoint of production efficiency, it is preferably 0.5 to 48 hours, and more preferably 1 to 24 hours. .
  • XPS X-ray photoelectron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • the cation exchange capacity of the lithium partially fixed smectite is preferably 70 meq / 100 g or less, more preferably 60 meq / from the viewpoint of further excellent water vapor barrier properties and oxygen barrier properties (for example, oxygen barrier properties under high humidity). 100 g or less.
  • the cation exchange capacity of the lithium partially fixed smectite is 1 meq / 100 g or more, more preferably 5 meq / 100 g or more from the viewpoint of further excellent water vapor barrier properties and oxygen barrier properties (for example, oxygen barrier properties under high humidity). More preferably, it is 10 meq / 100 g or more.
  • the cation exchange capacity of the lithium partially fixed smectite is 1 to 70 meq / 100 g, more preferably 5 to 70 meq / 100 g, and still more preferably 10 to 60 meq / 100 g.
  • the ion exchange capacity is usually about 80 to 150 meq / 100 g, but it can be 5 to 70 meq / 100 g by performing partial immobilization treatment.
  • the cation exchange capacity of the lithium partially fixed smectite may be less than 60 meq / 100 g or 50 meq / 100 g or less.
  • the cation exchange capacity of the lithium partially fixed smectite may be 1 meq / 100 g or more and less than 60 meq / 100 g, may be 5 meq / 100 g or more and less than 60 meq / 100 g, and may be 10 meq / 100 g or more and less than 60 meq / 100 g. It's okay.
  • the cation exchange capacity of smectite can be measured by a method according to the Schollenberger method (Clay Handbook 3rd edition, edited by the Japan Clay Society, May 2009, p. 453-454). More specifically, it can be measured by the method described in Japan Bentonite Industry Association Standard Test Method JBAS-106-77.
  • the amount of smectite leaching cation was determined by leaching the smectite interlayer cation with 0.5 mL of smectite using 100 mL of 1 M ammonium acetate aqueous solution over 4 hours, and the concentration of various cations in the resulting solution. It can be measured and calculated by ICP emission analysis, atomic absorption analysis or the like.
  • the content of the lithium partially fixed smectite is preferably 3% by mass or more with respect to the total nonvolatile content in the pattern forming material.
  • the content of the lithium partially fixed smectite is 3% by mass or more with respect to the total nonvolatile content, the water vapor barrier property and the oxygen barrier property (for example, the oxygen barrier property under high humidity) are further improved.
  • the content of the lithium partially fixed smectite is 5% by mass, 7% by mass, 9% by mass, 10% by mass, 15% by mass or more with respect to the total amount of nonvolatile components in the pattern forming material. 18 mass% or more, 20 mass% or more, 25 mass% or more, or 30 mass% or more.
  • the content of the lithium partially fixed smectite is preferably 70% by mass or less based on the total nonvolatile content in the pattern forming material.
  • the content of the lithium partially fixed smectite is 70% by mass or less, the moldability (for example, coating property) of the pattern forming material is further improved, and the adhesion to the substrate is improved. Moreover, higher oxygen barrier properties can be obtained under high humidity.
  • the content of the lithium partially fixed smectite is 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less with respect to the total nonvolatile content in the pattern forming material. It may be.
  • the content of the lithium partially fixed smectite is, for example, 3 to 70% by mass, 3 to 50% by mass, 3 to 35% by mass, 5 to 35% by mass, 5% to 5% by mass with respect to the total nonvolatile content in the pattern forming material. It may be ⁇ 30 mass%, 7 ⁇ 30 mass%, 9 ⁇ 30 mass% or 10 ⁇ 30 mass%. Also in the same description in this specification, the individually described upper limit value and lower limit value can be arbitrarily combined.
  • the non-volatile content is the mass excluding the mass of the diluting solvent and the mass of volatile components contained in the acid group-containing resin, modifier and various additives from the total mass of the pattern forming material.
  • the acid group-containing resin is a compound having a weight average molecular weight of 1,000 or more, and has a polymerizable double bond in its molecular structure.
  • the polymerizable double bond can also be referred to as an ethylenically unsaturated bond or a polymerizable unsaturated double bond.
  • the polymerizable double bond may be contained in a group contained in the acid group-containing resin. That is, the acid group-containing resin may contain a group having a polymerizable double bond. Examples of the group having a polymerizable double bond include a vinyl group, an allyl group, and a (meth) acryloyl group.
  • the group having a polymerizable double bond may be a group having an acid group. That is, the acid group-containing resin may contain an acid group and a group having a polymerizable double bond, and may contain a group having a polymerizable double bond separately from the acid group. Good.
  • the (meth) acryloyl group means an acryloyl group or a methacryloyl group, and similar expressions are also the same.
  • the group having a polymerizable double bond is preferably a (meth) acryloyl group from the viewpoint of improving the hydrophilicity of the acid group-containing resin and further increasing the affinity between the acid group-containing resin and the lithium-type partially fixed smectite. And more preferably a group represented by the following formula (1-1) or formula (1-2).
  • R represents a hydrogen atom or a methyl group
  • * represents a bond
  • the acid group-containing resin only needs to have one or more groups having a polymerizable double bond, and from the viewpoint of improving photosensitivity, preferably two or more groups having a polymerizable double bond, Preferably three or more.
  • the number of groups having a polymerizable double bond in the acid group-containing resin may be 30 or less, or 15 or less.
  • the number of (meth) acryloyl groups is preferably within the above range, more preferably the number of groups represented by the above formula (1-1) or formula (1-2).
  • the acid group examples include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
  • a carboxyl group is preferable because it exhibits excellent alkali developability.
  • the basic skeleton of the acid group-containing resin is not particularly limited.
  • Examples of the basic skeleton of the resin include (meth) acrylic resin skeleton, urethane resin skeleton, epoxy resin skeleton, phenol resin skeleton, and polyester resin skeleton.
  • the weight average molecular weight of the acid group-containing resin of the embodiment is 1,000 or more, and may be 2,000 or more because a pattern forming material having excellent photosensitivity can be obtained.
  • the weight average molecular weight of the acid group-containing resin of the embodiment is 20,000 or less and may be 15,000 or less because a pattern forming material excellent in alkali developability is obtained. From these viewpoints, the weight average molecular weight of the acid group-containing resin may be, for example, 1,000 to 20,000 or 2,000 to 15,000.
  • a weight average molecular weight shows the value measured using gel permeation chromatography (GPC), and is a polystyrene conversion molecular weight.
  • the number average molecular weight of the acid group-containing resin in terms of polystyrene, measured using gel permeation chromatography (GPC), may be in the same range as described above.
  • a more preferred acid group-containing resin is a resin having an acid group and a (meth) acryloyl group (hereinafter also referred to as “acid group-containing (meth) acrylate resin (A)”).
  • the acid group-containing (meth) acrylate resin (A) only needs to have an acid group and a (meth) acryloyl group, and other specific structures and molecular weights are not particularly limited, and a wide variety of resins can be used.
  • the pattern forming material (curable resin composition) containing the acid group-containing (meth) acrylate resin (A) as the acid group-containing resin is also referred to as “acid group-containing (meth) acrylate resin composition”.
  • Examples of the acid group contained in the acid group-containing (meth) acrylate resin (A) include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable because it exhibits excellent alkali developability.
  • Examples of the acid group-containing (meth) acrylate resin (A) include [1] epoxy resin (A-1) having an acid group and (meth) acryloyl group, [2] an acid group and (meth) acryloyl group.
  • Acrylamide resin (A-2) [3] Amidoimide resin (A-3) having acid group and (meth) acryloyl group, [4] Acrylic resin (A-4) having acid group and (meth) acryloyl group, [5] Urethane resin (A-5) having an acid group and a (meth) acryloyl group.
  • Examples of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group include an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2), and a polycarboxylic acid anhydride ( a1-3) and the like obtained as essential reaction raw materials.
  • the specific structure of the epoxy resin (a1-1) is not particularly limited as long as it has a plurality of epoxy groups in the resin.
  • Examples of the epoxy resin (a1-1) include bisphenol type epoxy resins, hydrogenated bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, biphenyl type epoxy resins, hydrogenated biphenyl type epoxy resins, and triphenyl.
  • Methane type epoxy resin phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, phenol Aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene-phenol addition reaction epoxy resin, biphenyl aralkyl epoxy resin Carboxymethyl resins, fluorene type epoxy resin, a xanthene type epoxy resin, dihydroxybenzene type epoxy resin, and trihydroxybenzene type epoxy resin or the like.
  • the unsaturated monocarboxylic acid (a1-2) refers to a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, esterified products, acid halides, acid anhydrides and the like of the unsaturated monocarboxylic acid (a1-2) can also be used. These unsaturated monocarboxylic acids (a1-2) can be used alone or in combination of two or more.
  • esterified product of the unsaturated monocarboxylic acid (a1-2) examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) acrylic acid alkyl esters such as n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Compound; Hydroxyl group-containing (meth) acrylate compound such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, (meth) acrylic Nitrogen-containing (meth) acrylic acid ester such as dieth
  • Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid chloride.
  • Examples of the acid anhydride of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid anhydride.
  • any acid anhydride of a compound having two or more carboxyl groups in one molecule can be used.
  • the polycarboxylic acid anhydride include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, Glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane- 2,3-dicarboxylic acid, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,
  • the method for producing the epoxy resin (A-1) having an acid group and a (meth) acryloyl group includes the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride.
  • the product (a1-3) is not particularly limited as long as it is an essential reaction raw material, and may be produced by any method. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially.
  • the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) are first reacted, and then the polycarboxylic acid anhydride (a1-3)
  • the method of reacting is preferred.
  • the reaction is carried out, for example, by reacting an epoxy resin (a1-1) and an unsaturated monocarboxylic acid (a1-2) in the temperature range of 100 to 150 ° C. in the presence of an esterification reaction catalyst.
  • the polycarboxylic acid anhydride (a1-3) may be added to the reaction mixture and reacted at a temperature in the range of 80 to 120 ° C.
  • the reaction ratio of the epoxy resin (a1-1) to the unsaturated monocarboxylic acid (a1-2) is the amount of the unsaturated monocarboxylic acid (a1-2) relative to 1 mol of the epoxy group in the epoxy resin (a1-1). ) Is preferably in a ratio of 0.9 to 1.1 mol. Further, the reaction ratio of the polycarboxylic acid anhydride (a1-3) is such that the polycarboxylic acid anhydride (a1-3) is 0.2 to 0.2 mol per 1 mol of the epoxy group in the epoxy resin (a1-1). The ratio is preferably 1.0 mol.
  • esterification reaction catalyst examples include phosphorus compounds such as trimethylphosphine, tributylphosphine and triphenylphosphine, amine compounds such as triethylamine, tributylamine and dimethylbenzylamine, 2-methylimidazole, 2-heptadecylimidazole, 2- Examples thereof include imidazole compounds such as ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and 1-isobutyl-2-methylimidazole. These reaction catalysts can be used alone or in combination of two or more.
  • the amount of the reaction catalyst added is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass in total of the reaction raw materials.
  • the reaction of the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride (a1-3) can be performed in an organic solvent as necessary.
  • organic solvent examples include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; toluene, xylene, solvent Aromatic solvents such as naphtha; Alicyclic solvents such as cyclohexane and methylcyclohexane; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; Alkylene glycol monoalkyl ether and dialkylene glycol monoalkyl ether Glycol ether solvents such as dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, Chiruserosor
  • the acid value of the epoxy resin (A-1) having the acid group and the (meth) acryloyl group is excellent in photosensitivity, alkali developability and adhesion, and has low linear expansion coefficient, low oxygen permeability and low water vapor permeability.
  • the acid group-containing (meth) acrylate resin composition capable of forming a cured product having the above content is obtained, so the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 120 mgKOH / g is more preferable.
  • the acid value of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method of JIS K 0070 (1992).
  • Examples of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group include a phenolic hydroxyl group-containing resin (a2-1) and a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2- 2b), unsaturated monocarboxylic acid (a2-3a) and / or N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and polycarboxylic acid anhydride (a2-4) as essential reaction raw materials What is obtained is mentioned.
  • the phenolic hydroxyl group-containing resin (a2-1) refers to a resin having two or more phenolic hydroxyl groups in the molecule, such as an aromatic polyhydroxy compound or a compound having at least one phenolic hydroxyl group in the molecule.
  • a novolak-type phenol resin using one or more of these as a reaction raw material, a compound having at least one phenolic hydroxyl group, and Examples thereof include reaction products using compound (x) as an essential reaction raw material.
  • R 1 is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, or an aralkyl group, and i is 0. Or an integer of 1 to 4.
  • Z is a vinyl group, a halomethyl group, a hydroxymethyl group, or an alkyloxymethyl group, and Y is an alkylene group having 1 to 4 carbon atoms, an oxygen atom, or a sulfur atom.
  • carbonyl group, j is an integer of 1 to 4.
  • aromatic polyhydroxy compound examples include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, In addition to bisphenol and the like, compounds having one or more substituents on these aromatic nuclei may be mentioned.
  • substituent on the aromatic nucleus examples include a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, and a nonyl group.
  • Aliphatic hydrocarbon group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and aromatic nucleus thereof
  • These aromatic polyhydroxy compounds can be used alone or in combination of
  • Examples of the novolak type phenol resin include those obtained by reacting one or more compounds having at least one phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.
  • the compound having at least one phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having at least one hydroxyl group on the aromatic nucleus, such as phenol, dihydroxyphenol, trihydroxyphenol or phenol.
  • substituent on the aromatic nucleus examples include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples of each are as described above. These compounds having at least one phenolic hydroxyl group can be used alone or in combination of two or more.
  • aldehyde compound examples include formaldehyde; alkyl aldehydes such as acetaldehyde, propyl aldehyde, butyraldehyde, isobutyraldehyde, pentyl aldehyde, hexyl aldehyde; salicyl aldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4 -Hydroxybenzaldehydes such as methylbenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde; 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3 -Ethoxy-4-hydroxybenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde Benzaldehydes having both hydroxy groups and alkoxy groups; alky
  • the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. These acidic catalysts can be used alone or in combination of two or more.
  • a compound having at least one phenolic hydroxyl group in the molecule and the compound (x) can be obtained by heating and stirring under a temperature condition of about 80 to 200 ° C. under an acidic catalyst.
  • the reaction ratio between the compound (x) and the compound having at least one phenolic hydroxyl group in the molecule is such that the compound having at least one phenolic hydroxyl group in the molecule is 1 mol of the compound (x).
  • the ratio is preferably 0.5 to 5 mol.
  • the acid catalyst is the same as described above.
  • Examples of the cyclic carbonate compound (a2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, pentylene carbonate, and the like. These cyclic carbonate compounds can be used alone or in combination of two or more. Among these, an acid group-containing (meth) acrylate resin composition that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability. Therefore, ethylene carbonate or propylene carbonate is preferable.
  • Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds can be used alone or in combination of two or more. Among these, an acid group-containing (meth) acrylate resin composition that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability. Therefore, ethylene oxide or propylene oxide is preferable.
  • the same unsaturated monocarboxylic acid (a1-2) as described above can be used as the unsaturated monocarboxylic acid (a1-2) as described above.
  • N-alkoxyalkyl (meth) acrylamide compound (a2-3b) examples include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, and N-methoxy. Examples include ethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, and N-butoxyethyl (meth) acrylamide.
  • an acid group-containing (meth) acrylate resin composition is obtained that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen transmission rate, and a low water vapor transmission rate. Therefore, N-methoxymethyl (meth) acrylamide is preferable. Moreover, these N-alkoxyalkyl (meth) acrylamide compounds can be used alone or in combination of two or more.
  • polycarboxylic acid anhydride (a2-4) the same polycarboxylic acid anhydride (a1-3) described above can be used.
  • the equivalent ratio [(b2-3b) / (b2-4)] to the polycarboxylic acid anhydride (a2-4) is Since an acid group-containing (meth) acrylate resin composition that is excellent in sensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen transmission rate, and a low water vapor transmission rate is obtained.
  • the range of 2 to 7 is preferable, and the range of 0.25 to 6.7 is more preferable.
  • the method for producing the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group is not particularly limited, and may be produced by any method. For example, it may be produced by a method in which all of the reaction raw materials are reacted together, or may be produced by a method in which the reaction raw materials are reacted sequentially.
  • the phenolic hydroxyl group-containing resin (a2-1) is first reacted with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), Next, after reacting the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b), the polycarboxylic acid anhydride (a2-4) is reacted. preferable.
  • the reaction is performed, for example, by combining the phenolic hydroxyl group-containing resin (a2-1) and the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b) in the presence of a basic catalyst at 100 to 200 ° C.
  • a basic catalyst at 100 to 200 ° C.
  • the unsaturated monocarboxylic acid (a2-3a) and / or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) is in the temperature range of 80 to 140 ° C.
  • polycarboxylic acid anhydride (a2-4) is added in a temperature range of 80 to 140 ° C.
  • Examples of the basic catalyst include N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonene. 5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, imidazole, 1 -Methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- ( 2-Aminoethyl) aminopropyltri Amine compounds such as toxisilane, 3- (2-aminoethyl)
  • the acidic catalyst examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Etc. These acidic catalysts can be used alone or in combination of two or more.
  • the reaction of the alkyl (meth) acrylamide compound (a2-3b) and the polycarboxylic acid anhydride (a2-4) can be carried out in an organic solvent as necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvents can be used alone or in combination of two or more.
  • the amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass in total of the reaction raw materials because the reaction efficiency is good.
  • the specific structure of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group is not particularly limited, and the phenolic hydroxyl group-containing resin (a2-1) and the cyclic carbonate compound (a2-2a) or cyclic An ether compound (a2-2b), an unsaturated monocarboxylic acid (a2-3a) and / or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic acid anhydride (a2-4)
  • the essential reaction raw material may be any resin having an acid group and a (meth) acryloyl group in the resin.
  • Examples of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group to be obtained include And a structural unit (I) represented by the following structural formula (a-1) and a structural site (II) represented by the following structural formula (a-2) Or a structural part (III) represented by the following structural formula (a-3) and a structural part (IV) represented by the following structural formula (a-4) as repeating structural units What has a resin structure is mentioned.
  • R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • R 3 is each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is each independently 1 or 2.
  • R 4 is each independently a methylene group or a structural moiety represented by any of the following structural formulas (x′-1) to (x′-5).
  • R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 and R 6 may be linked to form a saturated or unsaturated ring.
  • R 7 is a hydrocarbon group having 1 to 12 carbon atoms.
  • R 8 is a hydrogen atom or a methyl group.
  • x represents the structural site represented by R 3 or the structural site (I) represented by the structural formula (a-1) or the structural site (II) represented by the structural formula (a-2).
  • R 2 is independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • R 3 is each independently a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom, and n is each independently 1 or 2.
  • R 4 is each independently a methylene group or a structural moiety represented by any of the following structural formulas (x′-1) to (x′-5).
  • R 5 and R 6 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 5 and R 6 may be linked to form a saturated or unsaturated ring.
  • R 7 is a hydrocarbon group having 1 to 12 carbon atoms.
  • R 8 is a hydrogen atom or a methyl group.
  • x is the structural site represented by R 3 or the structural site (III) represented by the structural formula (a-3) or the structural site (IV) represented by the structural formula (a-4).
  • h is 0 or 1.
  • R 9 is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and i is 0 or an integer of 1 to 4.
  • R 10 is a hydrogen atom or a methyl group.
  • W is the following structural formula (w-1) or (w-2).
  • Y is any one of an alkylene group having 1 to 4 carbon atoms, an oxygen atom, a sulfur atom, and a carbonyl group.
  • j is an integer of 1 to 4.
  • R 11 is each independently a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
  • R 12 and R 13 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • R 12 and R 13 may be linked to form a saturated or unsaturated ring,
  • R 14 is a hydrocarbon group having 1 to 12 carbon atoms, and
  • R 15 is hydrogen. An atom or a methyl group.
  • the acid value of the acrylamide resin (A-2) having the acid group and (meth) acryloyl group is excellent in photosensitivity, alkali developability and adhesion, and has low linear expansion coefficient, low oxygen permeability and low water vapor permeability.
  • the acid group-containing (meth) acrylate resin composition capable of forming a cured product having the above content is obtained, so the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 120 mgKOH / g is more preferable.
  • the acid value of the acid group-containing (meth) acrylate resin is a value measured based on the neutralization titration method of JIS K 0070 (1992).
  • Examples of the amideimide resin (A-3) having an acid group and a (meth) acryloyl group include an amideimide resin (a3-1) having an acid group or an acid anhydride group, and a hydroxyl group-containing (meth) acrylate compound (a3). -2) and the like obtained as essential reaction raw materials.
  • the amideimide resin (a3-1) may have only one of an acid group or an acid anhydride group, or may have both. From the viewpoint of reactivity with the hydroxyl group-containing (meth) acrylate compound (a3-2) and reaction control, those having an acid anhydride group are preferred, those having both an acid group and an acid anhydride group It is more preferable that
  • the acid value of the amideimide resin (a3-1) is preferably in the range of 60 to 350 mgKOH / g under neutral conditions, that is, under conditions where the acid anhydride group is not ring-opened.
  • the measured value under the condition where the acid anhydride group is opened is preferably in the range of 61 to 360 mgKOH / g.
  • the specific structure and production method of the amideimide resin (a3-1) are not particularly limited, and general amideimide resins and the like can be widely used.
  • amideimide resins and the like can be widely used.
  • what can be obtained by using a polyisocyanate compound and polycarboxylic acid or its acid anhydride as a reaction raw material is mentioned.
  • polyisocyanate compound examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, Cycloaliphatic diisocyanate compounds such as hydrogenated xylylene diisocyanate and hydrogenated diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3 , 3'-dimethylbiphenyl, o-tolidine diisocyanate, etc.
  • aliphatic diisocyanate compounds such as butane diis
  • Cyanate compound polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanurate modified product, a biuret modified product, and the like allophanate modified product. These polyisocyanate compounds can be used alone or in combination of two or more.
  • R 21 is independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • R 22 is each independently an alkyl group having 1 to 4 carbon atoms, or a bonding point that is linked to a structural site represented by the structural formula (i-1) via a methylene group marked with *. is there.
  • l is 0 or an integer of 1 to 3
  • m is an integer of 1 or more.
  • an acid group-containing (meth) acrylate resin composition having high solvent solubility is obtained, and therefore, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof is used.
  • An alicyclic diisocyanate or its isocyanurate-modified product, and an aliphatic diisocyanate or its isocyanurate-modified product are more preferable.
  • the ratio of the total mass of an alicyclic diisocyanate compound or its modified body and an aliphatic diisocyanate compound or its modified body in the total mass of the said polyisocyanate compound is 70 mass% or more, and 90 mass % Or more is preferable.
  • the mass ratio of the two is preferably in the range of 30/70 to 70/30.
  • the polycarboxylic acid or its acid anhydride is not particularly limited as long as it is a compound having a plurality of carboxyl groups in its molecular structure or its acid anhydride, and a wide variety of compounds can be used.
  • the amideimide resin (a3-1) In order for the amideimide resin (a3-1) to have both an amide group and an imide group, it is necessary that both a carboxyl group and an acid anhydride group exist in the system. May use a compound having both a carboxyl group and an acid anhydride group in the molecule, or may use a compound having a carboxyl group and a compound having an acid anhydride group in combination.
  • polycarboxylic acid or acid anhydride thereof examples include aliphatic polycarboxylic acid compounds or acid anhydrides thereof, alicyclic polycarboxylic acid compounds or acid anhydrides thereof, aromatic polycarboxylic acid compounds or acid anhydrides thereof. Etc.
  • the aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure.
  • Examples of the aliphatic polycarboxylic acid compound or acid anhydride thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, Examples include citraconic acid, itaconic acid, glutaconic acid, 1,2,3,4-butanetetracarboxylic acid, and acid anhydrides thereof.
  • the alicyclic polycarboxylic acid compound or acid anhydride thereof is a compound in which a carboxyl group or acid anhydride group is bonded to an alicyclic structure.
  • the presence or absence of an aromatic ring at other structural sites is not questioned.
  • the alicyclic polycarboxylic acid compound or acid anhydride thereof include tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, cyclohexanetricarboxylic acid, cyclohexanetetracarboxylic acid, and bicyclo [2.2.1].
  • Heptane-2,3-dicarboxylic acid methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-dicarboxylic acid, and acid anhydrides thereof.
  • aromatic polycarboxylic acid compound or acid anhydride thereof examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, and biphenyl.
  • aromatic polycarboxylic acid compound or acid anhydride thereof examples include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, and biphenyl.
  • examples thereof include tetracarboxylic acid and benzophenone tetracarboxylic acid.
  • an acid group-containing (meth) acrylate resin composition is obtained that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen transmission rate, and a low water vapor transmission rate. Therefore, the alicyclic polycarboxylic acid compound or acid anhydride thereof, or the aromatic polycarboxylic acid compound or acid anhydride thereof is preferable.
  • the amideimide resin (a3-1) can be efficiently produced, it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and cyclohexanetricarboxylic acid anhydride or It is particularly preferable to use trimellitic anhydride.
  • the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride to the total mass of the polycarboxylic acid or acid anhydride is preferably 70% by mass or more, and 90% by mass or more. It is more preferable that
  • the amide-imide resin (a3-1) is a reaction raw material comprising the polyisocyanate compound and the polycarboxylic acid or acid anhydride thereof
  • other reaction raw materials depending on the desired resin performance and the like May be used in combination.
  • the total mass of the polyisocyanate compound and the polycarboxylic acid or the acid anhydride thereof with respect to the total mass of the reaction raw material of the amideimide resin (a3-1) The ratio is preferably 90% by mass or more, and more preferably 95% by mass or more.
  • the amideimide resin (a3-1) is a polyisocyanate compound and polycarboxylic acid or acid anhydride thereof as reaction raw materials
  • it is not particularly limited and may be produced by any method.
  • it can be produced by the same method as a general amideimide resin.
  • 0.5 to 2.0 moles of polycarboxylic acid or its acid anhydride is used with respect to 1 mole of isocyanate group of the polyisocyanate compound, and the mixture is stirred and mixed at a temperature of about 120 to 180 ° C. The method of making it react is mentioned.
  • the reaction between the polyisocyanate compound and polycarboxylic acid or acid anhydride thereof can be performed in the presence of a basic catalyst, if necessary. Moreover, this reaction can also be performed in an organic solvent as needed.
  • the same basic catalyst as described above can be used, and the basic catalyst can be used alone or in combination of two or more.
  • organic solvent the same organic solvents as described above can be used, and the organic solvents can be used alone or in combination of two or more.
  • the amount of the organic solvent used is preferably in the range of 10 to 500 parts by mass with respect to 100 parts by mass in total of the reaction raw materials because the reaction efficiency is good.
  • the hydroxyl group-containing (meth) acrylate compound (a3-2) is not particularly limited as long as it has a hydroxyl group and a (meth) acryloyl group in the molecular structure, and a wide variety of compounds are used. be able to.
  • an acid group-containing (meth) acrylate resin composition is obtained that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen transmission rate, and a low water vapor transmission rate. Therefore, those having a molecular weight of 1,000 or less are preferable.
  • the weight average molecular weight is preferably 1,000 or less.
  • These hydroxyl group-containing (meth) acrylate compounds can be used alone or in combination of two or more.
  • the amideimide resin (A-3) having an acid group and a (meth) acryloyl group the amideimide resin (a3-1) and a hydroxyl group-containing (meth) acrylate compound (a3-2) are optionally used.
  • a (meth) acryloyl group-containing epoxy compound (a3-3) can also be used as a reaction raw material.
  • the amideimide resin (A-3) having an acid group and a (meth) acryloyl group the amideimide resin (a3-1) and a hydroxyl group-containing (meth) acrylate compound (a3-2) are optionally used.
  • a (meth) acryloyl group-containing epoxy compound (a3-3) and a polycarboxylic acid anhydride (a3-4) can be used together as a reaction raw material.
  • the (meth) acryloyl group-containing epoxy compound (a3-3) is not particularly limited as long as it has a (meth) acryloyl group and an epoxy group in the molecular structure, and a wide variety of compounds can be used. Can be used.
  • glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; dihydroxybenzene diglycidyl ether, dihydroxynaphthalenediglycidyl ether, And mono (meth) acrylates of diglycidyl ether compounds such as biphenol diglycidyl ether and bisphenol diglycidyl ether.
  • an acid group-containing (meth) acrylate resin composition is obtained that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen transmission rate, and a low water vapor transmission rate. Therefore, a glycidyl group-containing (meth) acrylate monomer is preferable. Moreover, it is preferable that the molecular weight is 500 or less. Furthermore, the proportion of the glycidyl group-containing (meth) acrylate monomer in the total mass of the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 70% by mass or more, and 90% by mass or more. Is more preferable.
  • polycarboxylic acid anhydride (a3-4) those exemplified as the above-mentioned polycarboxylic acid anhydride (a1-3) can be used, and the polycarboxylic acid (b3-4) is used alone. Two or more kinds can be used in combination.
  • the amideimide resin (A-3) having an acid group and a (meth) acryloyl group includes the amideimide resin (a3-1) having an acid group or an acid anhydride group depending on the desired resin performance, etc.
  • the (meth) acrylate compound (a3-2) the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic acid anhydride (a3-4)
  • other reaction raw materials can be used in combination.
  • the ratio of the total mass of the components (b3-1) to (b3-4) in the total reaction mass of the acid group-containing (meth) acrylate resin (B-3) is 80% by mass or more. Preferably, it is 90 mass% or more.
  • the method for producing the amideimide resin (A-3) having an acid group and a (meth) acryloyl group is not particularly limited, and may be produced by any method.
  • it may be produced by a method in which all reaction raw materials including the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) are reacted together, or the reaction raw materials are sequentially reacted. You may manufacture by the method to make.
  • the reaction between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) mainly includes an acid group and / or an acid anhydride group in the amideimide resin (a3-1). It reacts with a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a3-2). Since the hydroxyl group-containing (meth) acrylate compound (a3-2) is particularly excellent in reactivity with an acid anhydride group, as described above, the amideimide resin (a3-1) has an acid anhydride group. It is preferable.
  • the content of the acid anhydride group in the amideimide resin (a3-1) is the difference between the above-described two acid value measurement values, that is, the acid value under the condition where the acid anhydride group is ring-opened. And the difference between the acid value under the condition that the acid anhydride group is not ring-opened.
  • the reaction ratio between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is determined when the amideimide resin (a3-1) has an acid group and an acid anhydride group, and When the amideimide resin (a3-1) has an acid anhydride group, the hydroxyl group-containing (meth) acrylate compound (a3-2) has 1 mol of the acid anhydride group of the amideimide resin (a3-1). It is preferable that the number of moles of the hydroxyl group is 0.9 to 1.1.
  • the reaction ratio between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is determined by the amideimide resin (a3 It is preferable that the number of moles of the hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a3-2) is 0.01 to 1.0 with respect to 1 mole of the acid group in -1).
  • a basic catalyst or an acidic catalyst may be used as necessary.
  • a basic catalyst when the amideimide resin (a3-1) has an acid group and an acid anhydride group, and when the amideimide resin (a3-1) has an acid anhydride group, it is preferable to use a basic catalyst.
  • the amideimide resin (a3-1) has an acid group, it is preferable to use an acidic catalyst.
  • the basic catalyst those exemplified above as the basic catalyst can be used, and the basic catalyst can be used alone or in combination of two or more.
  • the acidic catalyst those exemplified as the above-mentioned acidic catalyst can be used, and the acidic catalyst can be used alone or in combination of two or more.
  • the addition amount of the basic catalyst or the acidic catalyst is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the total mass of the reaction raw materials.
  • the reaction between the amideimide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is performed by heating and stirring at a temperature of about 80 to 140 ° C. in the presence of an appropriate catalyst. It can be carried out.
  • the reaction may be carried out in an organic solvent as necessary.
  • the organic solvent the same organic solvent as described above can be used, and the organic solvent can be used alone or in combination of two or more. It can also be used together.
  • the reaction may be continued as it is in the organic solvent used in the production of the amideimide resin (a3-1).
  • the amideimide resin (A-3) having the acid group and (meth) acryloyl group is used as a reaction raw material.
  • the (meth) acryloyl group-containing epoxy compound (a3-3) is used, the amideimide resin (a3-1), the hydroxyl group-containing (meth) acrylate compound (a3-2), and the (meth) acryloyl group-containing epoxy compound All of the reaction raw materials including (a3-3) may be produced by a method of reacting all at once, or may be produced by a method of reacting the reaction raw materials sequentially.
  • production a product obtained by reacting the amideimide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a3-2) (hereinafter referred to as “production”).
  • the product (1) may be referred to as “(1)”) and the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably produced.
  • the reaction between the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) mainly comprises an acid group in the product (1) and the (meth) acryloyl group-containing epoxy compound ( a3-3).
  • the reaction ratio was such that the number of moles of the epoxy group of the (meth) acryloyl group-containing epoxy compound (a3-3) relative to 1 mole of the acid group of the product (1) was 0.05 to 1.1. It is preferable that the ratio is
  • the reaction can be carried out, for example, with heating and stirring under a temperature condition of about 90 to 140 ° C. in the presence of a suitable basic catalyst.
  • a basic catalyst may not be added or may be added as appropriate. . Moreover, you may perform this reaction in an organic solvent as needed.
  • the said basic catalyst and the said organic solvent can use the same thing as the above-mentioned basic catalyst and the organic solvent, and they can be used individually or can use 2 or more types together.
  • the amideimide resin (A-3) having the acid group and (meth) acryloyl group is used as a reaction raw material.
  • the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic acid anhydride (a3-4) are used, the amideimide resin (a3-1), the hydroxyl group-containing (meth) acrylate compound (a3-2)
  • the reaction raw material including the (meth) acryloyl group-containing epoxy compound (a3-3) and the polycarboxylic acid anhydride (a3-4) may be produced by a method of reacting all together.
  • the product obtained by reacting the (meth) acryloyl group-containing epoxy compound (a3-3) (hereinafter sometimes referred to as “product (2)”) to the polycarboxylic acid anhydride (a3 -4) is preferably produced by a reaction method.
  • the reaction between the product (2) and the polycarboxylic acid anhydride (a3-4) is mainly a reaction between the hydroxyl group in the product (2) and the polybasic acid anhydride.
  • the reaction ratio between the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) is 1 mol of acid groups contained in the product (1).
  • the number of moles of the epoxy group of the (meth) acryloyl group-containing epoxy compound (a3-3) is preferably 0.1 to 1.2, preferably 0.2 to 1.1.
  • the ratio is
  • the product (2) for example, a hydroxyl group generated by ring opening of the epoxy group in the (meth) acryloyl group-containing epoxy compound (a3-3) is present.
  • the reaction rate of the polycarboxylic acid anhydride (a3-4) is adjusted so that the acid value of the produced amideimide resin (A-3) having an acid group and a (meth) acryloyl group is about 50 to 120 mgKOH / g. It is preferred that The reaction can be carried out, for example, with heating and stirring under a temperature condition of about 80 to 140 ° C. in the presence of a suitable basic catalyst.
  • a basic catalyst may not be added or may be added as appropriate. Moreover, you may perform this reaction in an organic solvent as needed.
  • the said basic catalyst and the said organic solvent can use the same thing as the above-mentioned basic catalyst and the organic solvent, and they can be used individually or can use 2 or more types together.
  • the acid value of the amideimide resin (A-3) having an acid group and a (meth) acryloyl group is excellent in photosensitivity, alkali developability and adhesion, and has low linear expansion coefficient, low oxygen permeability, and low water vapor permeability.
  • the acid group-containing (meth) acrylate resin composition capable of forming a cured product having the above content is obtained, so the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 120 mgKOH / g is more preferable.
  • the acid value of the amideimide resin (A-3) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method of JIS K 0070 (1992).
  • Acrylic resin (A-4) having an acid group and a (meth) acryloyl group will be described.
  • Examples of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group include a (meth) acrylate compound ( ⁇ ) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group.
  • the (meth) acryloyl group is introduced into the acrylic resin intermediate obtained by polymerization as an essential component by further reacting with a (meth) acrylate compound ( ⁇ ) having a reactive functional group capable of reacting with these functional groups.
  • reaction products obtained by reacting polybasic acid anhydrides with hydroxyl groups in the reaction products are examples of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group.
  • the acrylic resin intermediate may be a copolymer obtained by copolymerizing other polymerizable unsaturated group-containing compound as required, in addition to the (meth) acrylate compound ( ⁇ ).
  • the other polymerizable unsaturated group-containing compound include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
  • Acrylic acid alkyl ester Cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, alicyclic structure-containing (meth) acrylate such as dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxy Aromatic ring-containing (meth) acrylates such as ethyl acrylate; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, ⁇ -methylstyrene, and chlorostyrene That. These can be used alone or in combination of two or more.
  • the said (meth) acrylate compound ((beta)) will not be specifically limited if it can react with the reactive functional group which the said (meth) acrylate compound ((alpha)) has, it is the following combinations from a reactive viewpoint. Is preferred. That is, when a hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate compound ( ⁇ ).
  • the (meth) acrylate compound ( ⁇ ) When a glycidyl group-containing (meth) acrylate is used as the (meth) acrylate compound ( ⁇ ), it is preferable to use a carboxyl group-containing (meth) acrylate as the (meth) acrylate compound ( ⁇ ).
  • the (meth) acrylate compound ( ⁇ ) can be used alone or in combination of two or more.
  • polybasic acid anhydride examples include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydro anhydride
  • polybasic acid anhydrides can be used alone or in combination of two or more.
  • the production method of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group is not particularly limited, and may be produced by any method.
  • the production of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group may be carried out in an organic solvent if necessary, and a basic catalyst may be used if necessary. .
  • organic solvent the same organic solvents as described above can be used, and the organic solvents can be used alone or in combination of two or more.
  • the same basic catalyst as described above can be used, and the basic catalyst can be used alone or in combination of two or more.
  • the acid value of the acrylic resin (A-4) having the acid group and (meth) acryloyl group is excellent in photosensitivity, alkali developability and adhesion, and has a low linear expansion coefficient, low oxygen permeability and low water vapor permeability.
  • the acid group-containing (meth) acrylate resin composition capable of forming a cured product having the above content is obtained, so the range of 30 to 150 mgKOH / g is preferable, and the range of 40 to 120 mgKOH / g is more preferable.
  • the acid value of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method of JIS K 0070 (1992).
  • Examples of the urethane resin (A-5) having an acid group and a (meth) acryloyl group include a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and, if necessary, a polybasic acid anhydride.
  • Products obtained by reacting polyol compounds other than the carboxyl group-containing polyol compound, polyols other than polyisocyanate compounds, hydroxyl group-containing (meth) acrylate compounds, polybasic acid anhydrides, and carboxyl group-containing polyol compounds One obtained by reacting with a compound, one obtained by reacting an epoxy resin, an unsaturated monobasic acid, a polybasic acid anhydride and a polyisocyanate compound, an epoxy resin, an unsaturated monobasic acid, Polybasic acid anhydride, polyisocyanate compound, and hydroxyl group-containing ( Data) what the acrylate compound obtained by reacting the like.
  • polyisocyanate compound the same polyisocyanate compounds can be used, and the polyisocyanate compounds can be used alone or in combination of two or more.
  • the hydroxyl group-containing (meth) acrylate compound As the hydroxyl group-containing (meth) acrylate compound, the same hydroxyl group-containing (meth) acrylate compound (a3-2) as described above can be used, and the hydroxyl group-containing (meth) acrylate compound can be used alone. Two or more kinds can be used in combination.
  • carboxyl group-containing polyol compound examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid, and the like.
  • the carboxyl group-containing polyol compound can be used alone or in combination of two or more.
  • polybasic acid anhydride those exemplified as the above-mentioned polybasic acid anhydride can be used, and the polybasic acid anhydride can be used alone or in combination of two or more.
  • polyol compounds other than the carboxyl group-containing polyol compound examples include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol; Aromatic polyol compounds such as biphenol and bisphenol; (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, (poly) oxytetramethylene chains) in the molecular structures of the various polyol compounds.
  • aliphatic polyol compounds such as ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaery
  • epoxy resin those exemplified as the above-mentioned epoxy resin (a1-1) can be used, and the epoxy resins can be used alone or in combination of two or more.
  • the unsaturated monobasic acid examples include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, ⁇ -cyanocinnamic acid, ⁇ -styrylacrylic acid, ⁇ -furfurylacrylic acid and the like. Further, esterified products, acid halides, acid anhydrides, and the like of the unsaturated monobasic acid can also be used. These unsaturated monobasic acids can be used alone or in combination of two or more.
  • the method for producing the urethane resin (A-5) having an acid group and a (meth) acryloyl group is not particularly limited, and may be produced by any method.
  • the production of the urethane resin having an acid group and a polymerizable unsaturated bond may be performed in an organic solvent as necessary, and a basic catalyst may be used as necessary.
  • organic solvent the same organic solvents as described above can be used, and the organic solvents can be used alone or in combination of two or more.
  • the same basic catalyst as described above can be used, and the basic catalyst can be used alone or in combination of two or more.
  • the content of the acid group-containing resin is excellent in photosensitivity, alkali developability and adhesion, and a pattern forming material capable of forming a cured product having a low linear expansion coefficient, a low oxygen transmission rate and a low water vapor transmission rate is obtained. Therefore, the content is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass with respect to the total amount of nonvolatile components in the pattern forming material. That is, the content of the acid group-containing resin may be 10% by mass or more or 20% by mass or more, and 90% by mass or less or 80% by mass or less with respect to the total nonvolatile content in the pattern forming material. Good.
  • the pattern forming material of the embodiment can be cured, for example, by adding a polymerization initiator.
  • the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among these, a photopolymerization initiator is preferable from the viewpoint of easily forming a pattern.
  • photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethane-1-one, diphenyl (2,4,6-trimethoxybenzoyl) phosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4-morpholinopheny ) - butan-1-one, and the like.
  • photopolymerization initiators include, for example, “Omnirad-1173”, “Omnirad-184”, “Omnirad-127”, “Omnirad-2959”, “Omnirad-369”, “Omnirad-379”, “Omnirad” -907 “,” Omnirad-4265 “,” Omnirad-1000 “,” Omnirad-651 “,” Omnirad-TPO “,” Omnirad-819 “,” Omnirad-2022 “,” Omnirad-2100 “,” Omnirad-2754 “ ”,“ Omnirad-784 ”,“ Omnirad-500 ”,“ Omnirad-81 ”(manufactured by IGM),“ Kayacure-DETX ”,“ Kayacure-MBP ”,“ Kayacure-DMBI ”,“ Kayacure-EPA ” “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Bicure-10”, “Bicure-55” (manufactured by Stow
  • the addition amount (content) of the photopolymerization initiator is preferably 1 to 20 parts by mass with respect to the polymerizable compound (eg, acid group-containing resin) of the pattern forming material, for example.
  • the pattern forming material of the embodiment may contain other polymerizable compound other than the acid group-containing resin having a polymerizable double bond.
  • examples of other polymerizable compounds include (meth) acryloyl obtained by reacting (meth) acrylic acid, (meth) acrylic anhydride, etc. with an epoxy compound such as a bisphenol type epoxy compound or a novolak type epoxy compound. Resin which has group; Various (meth) acrylate monomers etc. are mentioned.
  • Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl ( Aliphatic mono (meth) acrylate compounds such as meth) acrylate and octyl (meth) acrylate; alicyclic mono (meth) acrylate compounds such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and adamantyl mono (meth) acrylate; Heterocyclic mono (meth) acrylate compounds such as glycidyl (meth) acrylate and tetrahydrofurfuryl acrylate; benzyl (meth) acrylate, phenyl (meth) acrylate,
  • the pattern forming material of the embodiment may further contain a modifier.
  • the modifier include a coupling agent, a silane compound, and an acid anhydride.
  • the pattern forming material contains these modifiers, the wettability of the lithium partially fixed smectite is improved and the dispersibility of the smectite in the pattern forming material is improved.
  • a modifier may be used individually by 1 type and may be used in combination of multiple types.
  • the coupling agent examples include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent.
  • silane coupling agent examples include an epoxy group-containing silane coupling agent, an amino group-containing silane coupling agent, a (meth) acryloyl group-containing silane coupling agent, and an isocyanate group-containing silane coupling agent.
  • the epoxy group-containing silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3,4 epoxycyclohexyl). ) Ethyltrimethoxysilane and the like.
  • amino group-containing silane coupling agents examples include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl). Butylidene) propylamine, N-phenyl- ⁇ -aminopropyltrimethoxysilane and the like.
  • Examples of the (meth) acryloyl group-containing silane coupling agent examples include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltriethoxysilane.
  • isocyanate group-containing silane coupling agent examples include 3-isocyanatopropyltriethoxysilane.
  • titanium coupling agent examples include isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraoctyl bis (ditridecyl).
  • Examples thereof include phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, and bis (dioctylpyrophosphate) ethylene titanate.
  • zirconium coupling agent examples include zirconium acetate, zirconium carbonate ammonium, zirconium fluoride and the like.
  • aluminum coupling agent examples include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.
  • silane compound examples include alkoxysilane, silazane, siloxane and the like.
  • Alkoxysilanes include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltri Examples include methoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane, and the like.
  • Examples of silazane include hexamethyldisilazane.
  • siloxane examples include hydrolyzable group-containing
  • Acid anhydrides include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride alkenyl succinic anhydride and the like.
  • the blending amount (content) of the modifying agent is preferably 0.1 to 50% by mass with respect to the total amount of the lithium partially fixed smectite.
  • the blending amount of the modifier is 0.1% by mass or more, the dispersibility of the lithium partially fixed smectite in the pattern forming material becomes better.
  • the compounding quantity of a modifier is 50 mass% or less, the influence on the mechanical physical property of the modifier with respect to pattern formation material can be suppressed more.
  • the blending amount of the modifier is preferably 0.3 to 30% by mass, more preferably 0.5 to 15% by mass.
  • the pattern forming material of the embodiment may contain an organic solvent for the purpose of adjusting the coating viscosity.
  • the kind and addition amount (content) of the organic solvent are appropriately selected and adjusted according to the desired performance.
  • organic solvents examples include ketone solvents such as methyl ethyl ketone, acetone, dimethylformamide, and methyl isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; toluene, xylene, solvent naphtha, and the like Aromatic solvents; cycloaliphatic, methylcyclohexane and other alicyclic solvents; carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene Glycol ether solvents such as glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cell
  • curing agent curing accelerator, inorganic fine particles other than lithium partially fixed smectite, polymer fine particles, pigment, antifoaming agent, viscosity modifier, leveling agent, flame retardant, Various additives such as a storage stabilizer can also be contained.
  • the curing agent is not particularly limited as long as it has a functional group capable of reacting with an acid group (for example, a carboxy group) in the acid group-containing (meth) acrylate resin, and examples thereof include an epoxy resin.
  • the epoxy resin include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition Reactive epoxy resin, biphenyl aralkyl epoxy resin, fluorene epoxy resin, xanthene epoxy resin, dihydride
  • epoxy resins can be used alone or in combination of two or more.
  • a curable resin composition that is excellent in photosensitivity, alkali developability and adhesion, and can form a cured product having a low linear expansion coefficient, a low oxygen transmission rate, and a low water vapor transmission rate.
  • Novolak type epoxy resins are preferred, and those having a softening point in the range of 20 to 120 ° C. are particularly preferred.
  • the curing accelerator which accelerates the curing reaction of the curing agent, and when using an epoxy resin as the curing agent, phosphorus compound, amine compound, imidazole, organic acid metal salt, Lewis acid, Examples include amine complex salts. These curing accelerators can be used alone or in combination of two or more.
  • the addition amount of the curing accelerator is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curing agent, for example.
  • a cured film (cured film including a cured product of the pattern forming material) can be obtained by curing the film formed of the pattern forming material of the embodiment described above. Moreover, after hardening a part of film
  • the method for producing a cured pattern includes, for example, a step of curing a part of a film formed of a pattern forming material (curing step), a step of removing an uncured portion of the film and obtaining a cured pattern after the curing step, Is provided.
  • the method for producing a cured pattern may further include a step (coating step) of applying a pattern forming material to a substrate to obtain a film (a film formed of the pattern forming material) before the curing step. . That is, the film formed of the pattern forming material may be formed on the substrate.
  • the method for coating the pattern forming material on the substrate in the coating process is not particularly limited. Further, when the pattern forming material contains an organic solvent, the coating step includes a step of applying the pattern forming material to obtain a coating film, and then drying the obtained coating film to remove the organic solvent. You may go out. That is, the film formed of the pattern forming material may be a film containing a dried product of the pattern forming material.
  • a cured pattern is obtained by selectively generating an uncured portion of the film (for example, a portion made of a dried pattern forming material) and a cured portion (a portion made of a hardened pattern forming material). be able to.
  • the curing method in the curing step may be appropriately changed according to the polymerization initiator used.
  • the curing step when using a photopolymerization initiator, the curing step may include a step of irradiating the film with active energy rays, and when using a thermal polymerization initiator, the curing step includes a step of applying heat to the film. May be.
  • the curing step preferably includes a step of curing with active energy rays.
  • the step of curing with an active energy ray may be a step of irradiating the film with an active energy ray in a pattern. Specifically, for example, it may be a step of irradiating the film with active energy rays through a photomask, and a step of selectively irradiating the film with active energy rays without using a photomask (for example, a laser light source) A step of irradiating the film with active energy rays in a pattern using a point light source such as
  • active energy rays include ionizing radiation such as ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, and ⁇ rays.
  • ionizing radiation such as ultraviolet rays, electron rays, ⁇ rays, ⁇ rays, and ⁇ rays.
  • irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere in order to efficiently perform a curing reaction with ultraviolet rays.
  • an ultraviolet lamp may be used from the viewpoint of practicality and economy.
  • Specific examples of the ultraviolet lamp include a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED.
  • the integrated light amount of the active energy ray is not particularly limited, but is preferably 10 to 5,000 mJ / cm 2 , and more preferably 50 to 1,000 mJ / cm 2 . It is preferable for the integrated light amount to be in the above-mentioned range because the generation of uncured portions can be prevented or suppressed.
  • Laser light may be used as the active energy ray.
  • the exposure light source carbon arc lamp, mercury lamp, xenon lamp, metal halide lamp, fluorescent lamp, tungsten lamp, halogen lamp; laser light source such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, ruby laser, etc. Is mentioned.
  • a light source that generates laser light in a blue-violet region having a wavelength range of 350 to 430 nm is preferable, and a light source that generates laser light having a central wavelength of about 405 nm is more preferable.
  • Specific examples include an indium gallium nitride semiconductor laser that oscillates at a wavelength of 405 nm.
  • the scanning exposure method using a laser light source is not particularly limited, and examples thereof include a plane scanning exposure method, an outer drum scanning exposure method, an inner drum scanning exposure method, and the like.
  • the output light intensity is preferably 1 to 100 mW, more preferably 3 to 70 mW
  • the oscillation wavelength is preferably 390 to 430 nm, more preferably 400 to 420 nm
  • the beam spot diameter is preferably 2 to 30 ⁇ m
  • more preferably 4 Scan exposure is performed at a scanning speed of ⁇ 20 ⁇ m, a scanning speed of preferably 50 to 500 m / second, more preferably 100 to 400 m / second, and a scanning density of preferably 2,000 dpi or higher, more preferably 4,000 dpi or higher.
  • With laser light it is possible to form a pattern on the cured film without using a photomask.
  • the curing step preferably includes a step of irradiating active energy rays through a photomask.
  • Examples of the step of removing the uncured portion of the film to obtain a cured pattern include a step of developing and removing the uncured portion using an alkaline aqueous solution, an organic solvent, or the like.
  • alkaline aqueous solution an aqueous solution of sodium carbonate, potassium carbonate or the like may be used.
  • a sodium carbonate aqueous solution of 0.5 to 3% by mass is generally used.
  • organic solvent examples include the organic solvents described above for adjusting the viscosity of the pattern forming material.
  • the cured pattern of the embodiment is excellent in photosensitivity and alkali developability, it can be publicly used as a resist film.
  • the resist film include a solder resist.
  • the pattern forming material of the embodiment is used as a resist film, for example, as one of the specific methods, the pattern forming material is applied onto a base material, and the organic solvent is evaporated and dried in a temperature range of about 60 to 100 ° C. Thereafter, there may be mentioned a method of exposing with an active energy ray through a photomask on which a desired pattern is formed, developing an unexposed portion with an alkaline aqueous solution, and further heat-curing in a temperature range of about 140 to 180 ° C.
  • the method for forming the resist film is not limited to the above method.
  • the cured pattern of the embodiment can also be suitably used as an interlayer insulating material, a package material, an underfill material, a package adhesive layer such as a circuit element, an adhesive layer between an integrated circuit element and a circuit board, and the like. Further, it can be suitably used for a thin film transistor protective film, a liquid crystal color filter protective film, a color filter pigment resist, a black matrix resist, a spacer and the like in thin display applications typified by LCD and OELD.
  • Lithium partially fixed smectite was used as a filler to be contained in the resin composition (pattern forming material).
  • the lithium partially fixed smectite montmorillonite dispersed slurry (trade name: RCEC-W, cation exchange capacity 39.0 meq / 100 g) manufactured by Kunimine Kogyo Co., Ltd. was used.
  • the lithium partially fixed smectite content (w / w%) in the dispersion slurry was 20 w / w%.
  • modifier liquid As the modifier, 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silane coupling agent, was used. With respect to 12.0 parts by mass of isopropyl alcohol, 0.24 parts by mass of 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by Shin-Etsu Chemical Co., Ltd.), 0.06 parts by mass of ion-exchanged water, 0.1% 0.012 parts by mass of hydrochloric acid was added and stirred at 25 ° C. for 4 hours to obtain a modifier solution.
  • Mass part was added, and esterification was performed at 120 ° C. for 10 hours while blowing air. Thereafter, 201 parts by mass of propylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 3 hours.
  • the target acid group-containing acrylate resin (acid pendant type epoxy acrylate) had a solid content of 68% by mass. Obtained as a resin solution.
  • the acid value of the system at this time was 56.4 KOH-mg / g (calculated solid content 83 KOH-mg / g), and the weight average molecular weight of the acid group-containing acrylate resin was 2900.
  • a measurement sample was prepared by filtering a diluted solution obtained by diluting an acid group-containing acrylate resin 50 times with tetrahydrofuran (THF) with a filter (material: polytetrafluoroethylene, pore diameter: 0.2 ⁇ m).
  • THF tetrahydrofuran
  • this measurement sample was supplied to a gel permeation chromatograph (trade name “HLC-8220GPC” manufactured by GPC Tosoh Corporation), and measurement was performed under the conditions of a sample flow rate of 1 ml / min and a column temperature of 40 ° C.
  • the value obtained by measuring the molecular weight in terms of polystyrene of the acid group-containing acrylate resin was taken as the weight average molecular weight of the acid group-containing acrylate resin.
  • HXL-X, G5000HXL, G3000HXL, G2000HXL, and G2000HXL (all manufactured by Tosoh Corporation) were used as columns, and a differential refractometer was used as a detector.
  • Example 1 For 100 parts by mass (solid content: 68 parts by mass) of the acid group-containing acrylate resin obtained in Synthesis Example 1, 68 parts by mass of lithium partially fixed smectite dispersion slurry (solid content: 13.6 parts by mass), 433 parts by mass of acetonitrile And 52 parts by mass of the modifier solution were added and stirred for 8 hours. The obtained dispersion was subjected to solvent removal under reduced pressure while heating at 50 ° C. using a planetary mixer manufactured by PRIMIX Co., Ltd. to obtain a filler resin dispersion having a solid content of 68% by mass.
  • Example 2 For 100 parts by mass (solid content: 68 parts by mass) of the acid group-containing acrylate resin obtained in Synthesis Example 1, 68 parts by mass of lithium partially fixed smectite dispersion slurry (solid content: 13.6 parts by mass), 433 parts by mass of acetonitrile And 52 parts by mass of the modifier solution were added and stirred for 8 hours.
  • the obtained dispersion was subjected to solvent removal under reduced pressure while heating at 50 ° C. using a planetary mixer manufactured by PRIMIX Co., Ltd. to obtain a filler resin dispersion having a solid content of 68% by mass.
  • Comparative Example 2 With respect to 100 parts by mass (solid content: 68 parts by mass) of the acid group-containing acrylate resin obtained in Synthesis Example 1, 13.6 parts by mass of fused silica (“DENKA Fused Silica (DF) FB-5604” manufactured by Denka Co., Ltd.) In addition, 25.8 parts by mass of an orthocresol novolak type epoxy compound (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent and 2-methyl-1- (4-methylthiophenyl)-as a photopolymerization initiator Blended is 3.4 parts by mass of 2-morpholinopropan-1-one (“OMNIRAD-907” manufactured by IGM) and 13.9 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent, and kneaded by a roll mill.
  • the pattern forming material of Comparative Example 2 was obtained. In the pattern forming material, the content of fused silica (filler amount) was 12% by mass with respect to the total non
  • Example 2 [Evaluation method of average linear expansion coefficient]
  • the pattern forming materials obtained in Example 2 and Comparative Example 2 were applied on an electrolytic copper foil “F2-WS” manufactured by Furukawa Sangyo Co., Ltd. using an applicator so as to have a film thickness of 50 ⁇ m, and 30 ° C. at 30 ° C. Dried for minutes.
  • the dried coating film was irradiated with 1,000 mJ / cm 2 of ultraviolet rays using a metal halide lamp, and then cured at 160 degrees for 1 hour to cure the coating film.
  • the obtained laminate was cut into a size of 20 mm ⁇ 5 mm and used as a test piece.
  • thermomechanical analyzer (TMA: “TMA-60” manufactured by Shimadzu Corporation)
  • TMA thermomechanical analyzer
  • Measurement weight 6mN
  • Temperature increase rate 2 times at 10 ° C / minute
  • Measurement temperature range 1st time: 0 ° C to 220 ° C, 2nd time: -60 ° C to 240 ° C
  • the measurement under the above conditions was performed twice for the same sample, and the average linear expansion coefficient in the temperature range of 40 ° C. to 60 ° C. in the second measurement was evaluated as the linear expansion coefficient.
  • Table 2 The results are shown in Table 2.
  • Example 2 [Evaluation method of peel strength]
  • the pattern forming materials obtained in Example 2 and Comparative Example 2 were applied on an electrolytic copper foil “F2-WS” manufactured by Furukawa Sangyo Co., Ltd. using an applicator so as to have a film thickness of 50 ⁇ m, and 30 ° C. at 30 ° C. Dried for minutes.
  • the dried coating film was irradiated with 1,000 mJ / cm 2 of ultraviolet rays using a metal halide lamp, and then cured at 160 degrees for 1 hour to cure the coating film.
  • the obtained laminate was cut into 1 cm ⁇ 12 cm and used as a test piece.
  • Example 3 The UV radical initiator 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Omnirad (registered trademark) with respect to 146 parts by mass (solid content: 100 parts by mass) of the acid group-containing acrylate resin obtained in Synthesis Example 1 ) -TPO, manufactured by IGM), 86 parts by mass of the lithium partially fixed smectite dispersion slurry (solid content: 17.2 parts by mass), 636 parts by mass of acetonitrile, and 66 parts by mass of the modifier liquid were added. For 8 hours. Thereby, the pattern forming material of Example 3 was obtained. In the pattern forming material, the content (filler amount) of the lithium partially fixed smectite was 14% by mass with respect to the total nonvolatile content.
  • Omnirad registered trademark
  • Example 3 The obtained pattern forming material of Example 3 was coated on a corona-treated surface of a 12 ⁇ m PET film (trade name: E-5100, manufactured by Toyobo Co., Ltd.) using a bar coater so that the coating thickness was 2 ⁇ m after drying. Worked. The coated PET film was heated in a dryer at 150 ° C. for 5 minutes immediately after coating to dry the solvent. After cooling at room temperature, a cured film was formed on the PET film by irradiating with a metal halide lamp at 2,000 mJ / cm 2 and UV curing.
  • a metal halide lamp at 2,000 mJ / cm 2 and UV curing.
  • the oxygen permeability is measured according to JIS-K7126 (isobaric method) using an oxygen permeability measuring device OX-TRAN1 / 50 manufactured by Mocon, in an atmosphere of a temperature of 23 ° C. and a humidity of 0% RH, and a temperature of 23 It implemented with respect to the said cured film in the atmosphere of 90 degreeC and humidity 90% RH. RH represents relative humidity.
  • Table 3 The results are shown in Table 3.

Abstract

La présente invention concerne un matériau de formation de motif contenant : une résine contenant un groupe acide ayant une double liaison polymérisable ; et une smectite partiellement fixée au lithium.
PCT/JP2019/019364 2018-05-16 2019-05-15 Matériau de formation de motif, film durci, et procédé de production pour motif durci WO2019221194A1 (fr)

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