CN112105991A - Pattern forming material, cured film, and method for producing cured pattern - Google Patents

Pattern forming material, cured film, and method for producing cured pattern Download PDF

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CN112105991A
CN112105991A CN201980032106.0A CN201980032106A CN112105991A CN 112105991 A CN112105991 A CN 112105991A CN 201980032106 A CN201980032106 A CN 201980032106A CN 112105991 A CN112105991 A CN 112105991A
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acrylate
forming material
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CN112105991B (en
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山田骏介
狩野佑介
樱井宏子
中岛道也
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DIC Corp
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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

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  • Manufacturing & Machinery (AREA)
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  • Materials For Photolithography (AREA)
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Abstract

A pattern forming material, comprising: an acid group-containing resin having a polymerizable double bond, and a lithium-moiety-immobilized smectite.

Description

Pattern forming material, cured film, and method for producing cured pattern
Technical Field
The present invention relates to a pattern forming material, a cured film, and a method for producing a cured pattern.
Background
Pattern forming materials such as resin materials used for solder resists for printed circuit boards are required to be cured with a small amount of exposure light, to have excellent alkali developability, and the like.
As a pattern forming material, for example, an acid group-containing resin (acid-containing epoxy acrylate resin) obtained by further reacting tetrahydrophthalic anhydride with an intermediate obtained by reacting a novolak-type epoxy resin, acrylic acid and phthalic anhydride is known (for example, see patent document 1), but the sensitivity and alkali developability are insufficient, and the required performance, which is currently increasing, cannot be satisfied.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 8-259663
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a pattern-forming material having excellent sensitivity 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.
Means for solving the problems
In one aspect, the present invention provides a pattern forming material comprising: an acid group-containing resin having a polymerizable double bond, and a lithium-moiety-immobilized smectite.
The pattern forming material is excellent in sensitivity and alkali developability because it combines an acid group-containing resin having a polymerizable double bond and a lithium-part-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 acid group-containing resin may have a weight average molecular weight of 1000 to 20000.
The positive ion exchange capacity of the partially lithium immobilized smectite may be 1 to 70meq/100 g.
The content of the lithium-part-fixed smectite may be 3 to 70% by mass based on the total amount of nonvolatile components in the pattern forming material.
An aspect of the present invention provides a cured film comprising 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 method for producing a cured pattern, including a step of curing a part of a film formed of the pattern forming material, and a step of obtaining a cured pattern by removing an uncured part of the film.
By the above manufacturing method, a cured pattern with high resolution can be manufactured.
The step of curing a part of the film may include a step of irradiating the film with an active energy ray in a pattern.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention can provide a pattern forming material having excellent sensitivity 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.
Detailed Description
Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
< Pattern Forming Material >
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-moiety-immobilized smectite.
The pattern forming material of the embodiment is excellent in sensitivity, and thus a high-resolution cured pattern can be produced by the pattern forming material. Further, since the pattern forming material of the embodiment is also excellent in alkali developability, when a cured pattern is formed by alkali developability using the pattern forming material of the embodiment, a cured pattern with high resolution can be easily produced.
Further, a cured film (for example, a cured pattern) having excellent gas barrier properties such as a water vapor barrier property and an oxygen barrier property (for example, an oxygen barrier property under high humidity) can be easily obtained from the pattern forming material of the embodiment because the lithium partially fixed type smectite exhibits high dispersibility in the acid group-containing resin. That is, the pattern forming material of the embodiment makes it easy to produce a cured pattern having excellent gas barrier properties with high resolution.
In addition, a cured film (for example, a cured pattern) having a small average linear expansion coefficient can be easily obtained by the pattern forming material of the embodiment. Therefore, the occurrence of warpage in the substrate provided with the cured film (e.g., cured pattern) formed of the pattern forming material is easily reduced. When a conventional pattern forming material is used, a substrate having a cured pattern is likely to warp, and it is difficult to achieve both reduction of warp and improvement of resolution, but reduction of warp and improvement of resolution are likely to be achieved by the pattern forming material of the embodiment.
In addition, a cured film (for example, a cured pattern) formed on a substrate using the pattern forming material of the embodiment tends to have high adhesion to the substrate. In the conventional pattern forming material, when the filler content is increased from the viewpoint of reducing warpage, the adhesion of the cured film (for example, cured pattern) to the substrate tends to be reduced, but the pattern forming material of the embodiment is easy to achieve both high adhesion to the substrate and reduction of warpage.
[ partial lithium fixation type smectite ]
Smectite (smectite) is one of phyllosilicate minerals (layered clay minerals) having a layer structure. Specific examples of the smectite structure include montmorillonite (montmorillonite), beidellite, saponite, hectorite, stevensite, and sauconite. Among these, the structure of the clay material is preferably at least one structure selected from the group consisting of montmorillonite and stevensite. These structures have isomorphic substitution, defects, and the like with low-valence metal elements in a part of metal elements of an octahedral sheet. Thus, the octahedral sheets are negatively charged. As a result, these structures have vacant sites on the octahedral sheet, and the smectite having these structures can exist stably after lithium ions migrate as described later.
A smectite having a lithium ion as a cation is called a lithium type smectite (however, in the present specification, a lithium partially fixed type smectite described later is not included). Examples of a method for converting cations contained in the smectite into lithium ions include a method in which a lithium salt such as lithium hydroxide or lithium chloride is added to a dispersion (dispersion slurry) of a natural sodium-type smectite to exchange cations. By adjusting the amount of lithium added to the dispersion, the amount of lithium ions in the amount of extracted cations of the obtained lithium type smectite can be appropriately adjusted. The lithium-type smectite can also be obtained by a column method or a batch method using a resin in which a cation exchange resin is ion-exchanged with lithium ions.
In the embodiment, the lithium partially fixed type smectite refers to a smectite in which a part of lithium ions in the lithium type smectite is fixed at a vacancy point of an octahedral sheet. The lithium-partially fixed smectite is obtained by fixing lithium ions between layers at vacancy points of an octahedral sheet by heat treatment of the lithium-partially fixed smectite, for example. The smectite is made resistant to hydration by being immobilized by lithium ions.
The temperature condition of the heat treatment for partially fixing lithium is not particularly limited as long as lithium ions can be fixed. As described later, when 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 type smectite are further improved. Therefore, from the viewpoint of efficiently immobilizing lithium ions and greatly reducing the cation exchange capacity, it is preferable to heat at 150 ℃ or higher. The temperature of the heat treatment is more preferably 150 to 600 ℃, still more preferably 180 to 600 ℃, particularly preferably 200 to 500 ℃, and most preferably 250 to 500 ℃. By heating at the above temperature, the cation exchange capacity can be more efficiently reduced, and dehydration reaction of hydroxyl groups in the smectite can be suppressed. The heat treatment is preferably carried out in an open electric furnace. In this case, the relative humidity during heating is 5% or less, and the pressure is normal pressure. The time of the heat treatment is not particularly limited as long as the lithium part can be fixed, but is preferably 0.5 to 48 hours, more preferably 1 to 24 hours, from the viewpoint of production efficiency.
Whether or not it is a partially lithium-immobilized smectite can be judged by X-ray Photoelectron Spectroscopy (XPS: X-ray photon Spectroscopy) analysis. Specifically, the peak position derived from the binding energy of Li ions in the XPS spectrum measured by XPS analysis was confirmed. For example, when the smectite is montmorillonite, lithium type smectite is made into lithium partially fixed type smectite by heat treatment or the like, whereby the peak position derived from the binding energy of Li ion in XPS spectrum shifts from 57.0ev to 55.4 ev. Therefore, when the smectite is montmorillonite, whether it is a partially fixed type can be judged by whether it has a binding energy peak of 55.4 eV.
The cation exchange capacity of the lithium-part-fixed type smectite is preferably 70meq/100g or less, more preferably 60meq/100g or less, from the viewpoint of further excellent water vapor barrier property and oxygen barrier property (for example, oxygen barrier property under high humidity). The cation exchange capacity of the lithium partially immobilized smectite is 1meq/100g or more, more preferably 5meq/100g or more, and still more preferably 10meq/100g or more, from the viewpoint of further excellent water vapor barrier property and oxygen barrier property (for example, oxygen barrier property under high humidity). From these viewpoints, the cation exchange capacity of the lithium partially immobilized smectite is 1 to 70meq/100g, more preferably 5 to 70meq/100g, and still more preferably 10 to 60meq/100 g. For example, when the smectite is montmorillonite, the ion exchange capacity is usually about 80 to 150meq/100g, but it can be 5 to 70meq/100g by partial immobilization. The cation exchange capacity of the partially lithium immobilized smectite may be less than 60meq/100g, or may be 50meq/100g or less. For example, the cation exchange capacity of the lithium-part immobilized smectite may be 1meq/100g or more and less than 60meq/100g, 5meq/100g or more and less than 60meq/100g, or 10meq/100g or more and less than 60meq/100 g.
The cation exchange capacity of smectite can be determined by a method according to Schollenberger's method (third edition of the Clay handbook, edited by the society of Japan Clay, 5 months 2009, p.453-454). More specifically, the measurement can be carried out by the method described in the Japanese Bentonite society for testing Standard test method JBAS-106-77.
The amount of cations leached for smectite can be calculated as follows: the interlayer cations of the smectite were leached out for 4 hours or more using 100mL of a 1M ammonium acetate aqueous solution for 0.5g of the smectite, and the concentrations of the various cations in the obtained solution were measured by ICP emission analysis, atomic absorption spectrometry, or the like, to calculate the amount of leached cations of the smectite.
The content of the lithium-part-fixed smectite is preferably 3% by mass or more based on the total amount of nonvolatile components in the pattern forming material. When the content of the lithium-part-fixed smectite is 3% by mass or more based on the total amount of the nonvolatile components, the water vapor barrier property and the oxygen barrier property (for example, the oxygen barrier property under high humidity) are more excellent. From the same viewpoint, the content of the lithium-part-fixed smectite may be 5% by mass or more, 7% by mass or more, 9% by mass or more, 10% by mass or more, 15% by mass or more, 18% by mass or more, 20% by mass or more, 25% by mass or more, or 30% by mass or more with respect to the total amount of nonvolatile components in the pattern forming material. The content of the lithium-part-fixed smectite is preferably 70% by mass or less with respect to the total amount of nonvolatile components in the pattern forming material. When the content of the lithium-part-fixed type smectite is 70% by mass or less, the formability (for example, coatability) of the pattern forming material is more excellent, and the adhesion to the base material is improved. In addition, higher oxygen barrier properties can be obtained at high humidity. From the same viewpoint, the content of the lithium-part-fixed type smectite may be 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less with respect to the total amount of nonvolatile components in the pattern forming material. The upper limit value and the lower limit value may be arbitrarily combined. That is, the content of the lithium-part-fixed smectite may be, for example, 3 to 70 mass%, 3 to 50 mass%, 3 to 35 mass%, 5 to 30 mass%, 7 to 30 mass%, 9 to 30 mass%, or 10 to 30 mass% with respect to the total amount of nonvolatile components in the pattern forming material. In the same description in the present specification, the upper limit and the lower limit described individually may be arbitrarily combined. The nonvolatile component means a mass obtained by removing a mass of the diluting solvent and a mass of the volatile component contained in the acid-group-containing resin, the modifier, and various additives from the total mass of the pattern forming material.
[ acid group-containing resin ]
The acid-group-containing resin is a compound having a weight average molecular weight of 1000 or more, and has a polymerizable double bond in its molecular structure. The polymerizable double bond may be referred to as an ethylenically unsaturated bond or a polymerizable unsaturated double bond.
(polymerizable 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 a group having an acid group and a polymerizable double bond, or may contain a group having a polymerizable double bond separately from the acid group. The term "meth (acryloyl group" means an acryloyl group or a methacryloyl group, and similar expressions apply.
From the viewpoint of increasing the hydrophilicity of the acid-group-containing resin and further improving the affinity of the acid-group-containing resin with the lithium-type partially immobilized smectite, the group having a polymerizable double bond is preferably a (meth) acryloyl group, and more preferably a group represented by the following formula (1-1) or formula (1-2).
Figure BDA0002775481470000071
In the formulae (1-1) to (1-2), R represents a hydrogen atom or a methyl group, and represents an atomic bond.
The acid group-containing resin may contain one or more groups having a polymerizable double bond, and preferably contains 2 or more, more preferably 3 or more groups having a polymerizable double bond, from the viewpoint of improving sensitivity. The number of groups having a polymerizable double bond in the acid-group-containing resin may be 30 or less, or 15 or less. In the acid group-containing resin, the number of (meth) acryloyl groups is preferably within the above range, and more preferably the number of groups represented by the above formula (1-1) or formula (1-2).
(acid group)
Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group is preferable from the viewpoint of exerting 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 a (meth) acrylic resin skeleton, a urethane resin skeleton, an epoxy resin skeleton, a phenol resin skeleton, and a polyester resin skeleton.
The weight average molecular weight of the acid group-containing resin of the embodiment is 1000 or more, and may be 2000 or more from the viewpoint of obtaining a pattern-forming material excellent in sensitivity. The weight average molecular weight of the acid group-containing resin of the embodiment may be 20000 or less, or 15000 or less, from the viewpoint of obtaining a pattern-forming material excellent in alkali developability. From these viewpoints, the weight average molecular weight of the acid group-containing resin may be, for example, 1000 to 20000 or 2000 to 15000. In the present specification, the weight average molecular weight represents a value measured by Gel Permeation Chromatography (GPC) and is a molecular weight in terms of polystyrene. The number average molecular weight of the acid group-containing resin in terms of polystyrene, measured by Gel Permeation Chromatography (GPC), may be in the same range as described above.
Hereinafter, more preferable acid group-containing resins of the embodiments will be specifically described.
More preferred acid group-containing resins are resins 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) is not particularly limited as long as it has an acid group and a (meth) acryloyl group, and various resins can be used without particular limitation to other specific structures, molecular weights, and the like. Hereinafter, 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, carboxyl groups are preferable from the viewpoint of exhibiting excellent alkali developability.
Examples of the acid group-containing (meth) acrylate resin (A) include [ 1 ] an epoxy resin (A-1) having an acid group and a (meth) acryloyl group, [ 2 ] an acrylamide resin (A-2) having an acid group and a (meth) acryloyl group, [ 3 ] an amide imide resin (A-3) having an acid group and a (meth) acryloyl group, [ 4 ] an acrylic resin (A-4) having an acid group and a (meth) acryloyl group, and [ 5 ] a urethane resin (A-5) having an acid group and a (meth) acryloyl group.
The epoxy resin (A-1) having an acid group and a (meth) acryloyl group will be described.
Examples of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group include epoxy resins obtained by using an epoxy resin (a1-1), an unsaturated monocarboxylic acid (a1-2), and a polycarboxylic acid anhydride (a1-3) as essential reaction raw materials.
The specific structure of the epoxy resin (a1-1) is not particularly limited as long as the resin has a plurality of epoxy groups.
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, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol novolak type epoxy resin, naphthol-cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenyl aralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, and the like.
The unsaturated monocarboxylic acid (a1-2) is a compound having a (meth) acryloyl group and a carboxyl group in one molecule, and examples thereof include acrylic acid and methacrylic acid. Further, an esterified product, an acid halide, an acid anhydride or the like of the above-mentioned unsaturated monocarboxylic acid (a1-2) may also be used. These unsaturated monocarboxylic acids (a1-2) may be used alone or in combination of two or more.
Examples of the esterified compound of the unsaturated monocarboxylic acid (a1-2) include alkyl (meth) acrylate compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; hydroxyl group-containing (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; nitrogen-containing (meth) acrylate compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; other (meth) acrylate compounds such as glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, isobornyl (meth) acrylate, and cyclohexyl (meth) acrylate.
Examples of the acid halide of the unsaturated monocarboxylic acid (a1-2) include (meth) acryloyl chloride.
Examples of the acid anhydride of the unsaturated monocarboxylic acid (a1-2) include (meth) acrylic acid anhydride and the like.
Any acid anhydride may be used as the polyvalent carboxylic acid anhydride (a1-3) as long as it is an acid anhydride of a compound having 2 or more carboxyl groups in one molecule. Examples of the polyvalent carboxylic 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, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, and the like, Acid anhydrides of dicarboxylic acid compounds such as biphenyltricarboxylic acid, biphenyltetracarboxylic acid and benzophenonetetracarboxylic acid.
The method for producing the epoxy resin (A-1) having an acid group and a (meth) acryloyl group is not particularly limited as long as the epoxy resin (a1-1), the unsaturated monocarboxylic acid (a1-2), and the polycarboxylic acid anhydride (a1-3) are required as reaction raw materials, and any method can be used. For example, the compound can be produced by a method in which all the reaction materials are reacted at once, or by a method in which the reaction materials are reacted sequentially. Among them, a method of reacting the epoxy resin (a1-1) with the unsaturated monocarboxylic acid (a1-2) and then with the polycarboxylic anhydride (a1-3) is preferable from the viewpoint of easiness of control of the reaction. This reaction can be carried out, for example, by the following method: a method comprising reacting an epoxy resin (a1-1) and an unsaturated monocarboxylic acid (a1-2) at a temperature of 100 to 150 ℃ in the presence of an esterification catalyst, adding a polycarboxylic acid anhydride (a1-3) to the reaction system, and reacting the mixture at a temperature of 80 to 120 ℃.
The reaction ratio of the epoxy resin (a1-1) and the unsaturated monocarboxylic acid (a1-2) is preferably 0.9 to 1.1 mol of the unsaturated monocarboxylic acid (a1-2) relative to 1 mol of the epoxy group in the epoxy resin (a 1-1). The reaction ratio of the polycarboxylic acid anhydride (a1-3) is preferably 0.2 to 1.0 mol based on 1 mol of epoxy groups in the epoxy resin (a 1-1).
Examples of the esterification catalyst include phosphorus compounds such as trimethylphosphine, tributylphosphine, and triphenylphosphine, amine compounds such as triethylamine, tributylamine, and dimethylbenzylamine, and imidazole compounds such as 2-methylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 1-isobutyl-2-methylimidazole. These reaction catalysts may 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 relative to 100 parts by mass of the 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) may be carried out in an organic solvent, if necessary.
Examples of the organic solvent 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; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is preferably in the range of about 0.1 to 5 times the total mass of the reaction raw materials, from the viewpoint of satisfactory reaction efficiency.
The acid value of the epoxy resin (A-1) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition that can form a cured product having excellent sensitivity, alkali developability, and adhesion, and having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability can be obtained. In the present specification, 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 according to JIS K0070 (1992).
Next, the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group will be described.
Examples of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group include an acrylamide resin obtained by using a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), an unsaturated monocarboxylic acid (a2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and a polycarboxylic anhydride (a2-4) as essential reaction raw materials.
The phenolic hydroxyl group-containing resin (a2-1) is a resin having 2 or more phenolic hydroxyl groups in the molecule, and examples thereof include a novolak-type phenol resin using 1 or 2 or more of an aromatic polyhydroxy compound and a compound having at least 1 phenolic hydroxyl group in the molecule as reaction raw materials, and a reaction product using the compound having at least 1 phenolic hydroxyl group and a compound (x) represented by any one of the following structural formulae (x-1) to (x-5) as essential reaction raw materials.
Figure BDA0002775481470000121
(wherein h is 0 or 1. R)1Each independently represents 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 any of vinyl, halomethyl, hydroxymethyl, and alkoxymethyl. 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. )
Examples of the aromatic polyhydroxy compound include dihydroxybenzene, trihydroxybenzene, tetrahydroxybenzene, dihydroxynaphthalene, trihydroxynaphthalene, tetrahydroxynaphthalene, dihydroxyanthracene, trihydroxyanthracene, tetrahydroxyanthracene, biphenol, tetrahydroxybiphenyl, bisphenol, and the like, and compounds having 1 or more substituents on the aromatic nucleus thereof. Examples of the substituent on the aromatic nucleus include aliphatic hydrocarbon groups such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups; alkoxy groups such as methoxy, ethoxy, propoxy and butoxy; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, etc.; phenyl, naphthyl, anthryl, and aryl groups having the aromatic nucleus thereof substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, or the like; phenoxy group, naphthoxy group, and aryloxy group having the aromatic nucleus thereof substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, or the like; benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and aralkyl groups in which the aromatic nucleus thereof is substituted with the aliphatic hydrocarbon group, the alkoxy group, the halogen atom, and the like. These aromatic polyhydroxy compounds may be used alone, or two or more thereof may be used in combination. Among these, halogen-free compounds are preferable from the viewpoint that an acid group-containing (meth) acrylate resin having high insulation reliability can be obtained.
Examples of the novolak phenol resin include novolak phenol resins obtained by reacting 1, 2 or more compounds having at least 1 phenolic hydroxyl group in the molecule with an aldehyde compound in the presence of an acidic catalyst.
The compound having at least 1 phenolic hydroxyl group in the molecule may be any compound as long as it is an aromatic compound having at least 1 hydroxyl group on the aromatic nucleus, and examples thereof include phenol, dihydric phenol, trihydric phenol, a phenol compound having 1 or more substituents on the aromatic nucleus of phenol, naphthol, a naphthol compound having 1 or more substituents on the aromatic nucleus of naphthol, anthraphenol, an anthraphenol compound having 1 or more substituents on the aromatic nucleus of anthraphenol, and the like. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, an aryloxy group, and an aralkyl group, and specific examples thereof are as described above. These compounds having at least 1 phenolic hydroxyl group may be used alone or in combination of two or more.
Examples of the aldehyde compound include formaldehyde; alkyl aldehydes such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, and caproaldehyde; hydroxybenzaldehydes such as salicylaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 2-hydroxy-4-methylbenzaldehyde, 2, 4-dihydroxybenzaldehyde, and 3, 4-dihydroxybenzaldehyde; benzaldehydes having both a hydroxyl group and an alkoxy group, such as 2-hydroxy-3-methoxybenzaldehyde, 3-hydroxy-4-methoxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and 4-hydroxy-3, 5-dimethoxybenzaldehyde; alkoxybenzaldehydes such as methoxybenzaldehyde and ethoxybenzaldehyde; hydroxy naphthaldehyde such as 1-hydroxy-2-naphthaldehyde, 2-hydroxy-1-naphthaldehyde, 6-hydroxy-2-naphthaldehyde and the like; halogenated benzaldehydes such as bromobenzaldehyde.
Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, and lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These acidic catalysts may be used alone or in combination of two or more.
The reaction product of the compound having at least 1 phenolic hydroxyl group and the compound (x) as essential reaction raw materials can be obtained, for example, by the following method: and (b) heating and stirring the compound having at least 1 phenolic hydroxyl group in the molecule and the compound (x) in the presence of an acid catalyst at a temperature of about 80 to 200 ℃. The reaction ratio of the compound having at least 1 phenolic hydroxyl group in the molecule to the compound (x) is preferably 0.5 to 5 mol based on 1 mol of the compound (x).
The acidic catalyst is the same as the acidic catalyst.
Examples of the cyclic carbonate compound (a2-2a) include ethylene carbonate, propylene carbonate, butylene carbonate, and pentylene carbonate. These cyclic carbonate compounds may be used alone or in combination of two or more. Among these, ethylene carbonate and propylene carbonate are preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition which can form a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability can be obtained.
Examples of the cyclic ether compound (a2-2b) include ethylene oxide, propylene oxide, and tetrahydrofuran. These cyclic ether compounds may be used alone or in combination of two or more. Among these, ethylene oxide and propylene oxide are preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition which can form a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability can be obtained.
As the unsaturated monocarboxylic acid (a2-3a), those similar to the unsaturated monocarboxylic acid (a1-2) described above can be used.
Examples of the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) include N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-methoxyethyl (meth) acrylamide, N-ethoxyethyl (meth) acrylamide, and N-butoxyethyl (meth) acrylamide. Among these, N-methoxymethyl (meth) acrylamide is preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition which can form a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability can be obtained. These N-alkoxyalkyl (meth) acrylamide compounds may be used alone or in combination of two or more.
As the polycarboxylic anhydride (a2-4), the same one as the polycarboxylic anhydride (a1-3) can be used.
The equivalent ratio [ (b2-3b)/(b2-4) ] of the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) to the polyvalent carboxylic acid anhydride (a2-4) when used is preferably in the range of 0.2 to 7, more preferably in the range of 0.25 to 6.7, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition which can form a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, an oxygen permeability and a low vapor permeability.
The method for producing the acrylamide resin (a-2) having an acid group and a (meth) acryloyl group is not particularly limited, and any method can be used. For example, the compound can be produced by a method in which all the reaction materials are reacted at once, or by a method in which the reaction materials are reacted sequentially. Among them, the following method is preferable in terms of easy control of the reaction: the phenolic hydroxyl group-containing resin (a2-1) is reacted with a cyclic carbonate compound (a2-2a) or a cyclic ether compound (a2-2b), and then, an unsaturated monocarboxylic acid (a2-3a) and/or an N-alkoxyalkyl (meth) acrylamide compound (a2-3b) are reacted, and then, a polycarboxylic anhydride (a2-4) is reacted. This reaction can be carried out, for example, by the following method: a method comprising reacting the phenolic hydroxyl group-containing resin (a2-1) with the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b) in the presence of a basic catalyst at a temperature of 100 to 200 ℃, then reacting the unsaturated monocarboxylic acid (a2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b) in the presence of an acidic catalyst at a temperature of 80 to 140 ℃, then adding the polycarboxylic anhydride (a2-4), and reacting the resulting mixture at a temperature of 80 to 140 ℃.
Examples of the basic catalyst include N-methylmorpholine, pyridine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (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) aminopropylmethyldimethoxysilane, Amine compounds such as tetramethylammonium hydroxide; quaternary ammonium salts such as trioctylmethylammonium chloride and trioctylmethylammonium acetate; phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; phosphonium salts such as tetramethylphosphonium chloride, tetraethylphosphonium chloride, tetrapropylphosphonium chloride, tetrabutylphosphonium bromide, trimethyl (2-hydroxypropyl) phosphonium chloride, triphenylphosphonium chloride and benzylphosphonium chloride; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dioctyltin dineodecanoate, dibutyltin diacetate, tin octylate, 1,3, 3-tetrabutyl-1, 3-dodecanoyldistannoxane (distannoxane); organic metal compounds such as zinc octylate and bismuth octylate; inorganic tin compounds such as tin octylate; inorganic metal compounds, and the like. These basic catalysts may be used alone or in combination of two or more.
Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, lewis acids such as boron trifluoride, anhydrous aluminum chloride and zinc chloride. These acidic catalysts may be used alone or in combination of two or more.
The reaction of the phenolic hydroxyl group-containing resin (a2-1), the cyclic carbonate compound (a2-2a) or the cyclic ether compound (a2-2b), the unsaturated monocarboxylic acid (a2-3a) and/or the N-alkoxyalkyl (meth) acrylamide compound (a2-3b), and the polycarboxylic acid anhydride (a2-4) may be carried out in an organic solvent, if necessary.
The organic solvent may be the same as the above-mentioned organic solvent, and the organic solvents may be used alone or in combination of two or more.
The amount of the organic solvent is preferably in the range of 10 to 500 parts by mass relative to 100 parts by mass of the total of the reaction raw materials, from the viewpoint of satisfactory reaction efficiency.
The specific structure of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group is not particularly limited as long as it is obtained by using a phenolic hydroxyl group-containing resin (a2-1), a cyclic carbonate compound (a2-2a) or a cyclic 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) as essential reaction raw materials and having an acid group and a (meth) acryloyl group in the resin, and examples of the resulting acrylamide resin (A-2) having an acid group and a (meth) acryloyl group include resin structures having a repeating structural unit of a structural site (I) represented by the following structural formula (a-1) and a structural site (II) represented by the following structural formula (a-2), A resin structure having a repeating structural unit comprising a structural moiety (III) represented by the following structural formula (a-3) and a structural moiety (IV) represented by the following structural formula (a-4).
Figure BDA0002775481470000171
[ in the formula, R2Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R3Each independently represents 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 1 or 2. R4Each independently represents a methylene group or a structural portion represented by any one of the following structural formulae (x '-1) to (x' -5). R5、R6Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R may be5And R6Linked to form a saturated or unsaturated ring. R7Is a hydrocarbon group having 1 to 12 carbon atoms. R8Is a hydrogen atom or a methyl group. x is the aforementioned R3Structural sites as shown, or by R marked with a symbol4A bonding site that is linked to the structural moiety (I) represented by the structural formula (a-1) or the structural moiety (II) represented by the structural formula (a-2).]
Figure BDA0002775481470000172
[ in the formula, R2Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R3Each independently represents 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 1 or 2. R4Each independently represents a methylene group or a structural portion represented by any one of the following structural formulae (x '-1) to (x' -5). R5、R6Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition In addition, R may be substituted5And R6Linked to form a saturated or unsaturated ring. R7Is a hydrocarbon group having 1 to 12 carbon atoms. R8Is a hydrogen atom or a methyl group. x is the aforementioned R3Structural sites as shown, or R marked by a mark4A bonding site that is linked to the structural moiety (III) represented by the structural formula (a-3) or the structural moiety (IV) represented by the structural formula (a-4).]
Figure BDA0002775481470000181
[ wherein h is 0 or 1. R9Each independently represents 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. R10Is 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.]
Figure BDA0002775481470000191
(R in the formula11Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. R12、R13Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. In addition, R may be12And R13Linked to form a saturated or unsaturated ring. R14Is a hydrocarbon group having 1 to 12 carbon atoms. R15Is a hydrogen atom or a methyl group. )
The acid value of the acrylamide resin (A-2) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition that can form a cured product having excellent sensitivity, alkali developability, and adhesion, and having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability can be obtained. In the present specification, the acid value of the acid group-containing (meth) acrylate resin is a value measured by a neutralization titration method according to JIS K0070 (1992).
Next, the amide imide resin [ 3 ] having an acid group and a (meth) acryloyl group (A-3) will be described.
The amide imide resin (A-3) having an acid group and a (meth) acryloyl group includes, for example, an amide imide resin obtained by using an amide imide resin (a3-1) having an acid group or an acid anhydride group and a hydroxyl group-containing (meth) acrylate compound (a3-2) as essential reaction raw materials.
The amide imide resin (a3-1) may have either only an acid group or an acid anhydride group, or both. From the viewpoint of reactivity with the hydroxyl group-containing (meth) acrylate compound (a3-2) and reaction control, the compound preferably has an acid anhydride group, and more preferably has both an acid group and an acid anhydride group. The acid value of the amide imide resin (a3-1) is preferably in the range of 60 to 350mgKOH/g as measured under neutral conditions, that is, under conditions in which the acid anhydride group is not ring-opened. On the other hand, the measured value under the conditions for ring-opening the acid anhydride group in the presence of water or the like is preferably in the range of 61 to 360 mgKOH/g.
The specific structure and production method of the amide imide resin (a3-1) are not particularly limited, and a general amide imide resin and the like can be widely used. For example, an amide imide resin obtained by reacting a polyisocyanate compound with a polycarboxylic acid or an anhydride thereof as a reaction raw material can be mentioned.
Examples of the polyisocyanate compound include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, and 2,4, 4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1, 5-naphthalene diisocyanate, 4 '-diisocyanato-3, 3' -dimethylbiphenyl, o-tolidine diisocyanate and the like; a polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (i-1); these isocyanurate-modified products, biuret-modified products, allophanate-modified products, and the like. These polyisocyanate compounds may be used alone or in combination of two or more.
Figure BDA0002775481470000201
[ in the formula, R21Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R 22Each independently is any one of an alkyl group having 1 to 4 carbon atoms or a bonding site connected to the structural site represented by the structural formula (i-1) via a methylene group labeled with a symbol. l is 0 or an integer of 1 to 3, and m is an integer of 1 or more.]
In addition, as the polyisocyanate compound, from the viewpoint of obtaining an acid group-containing (meth) acrylate resin composition having high solvent solubility, an alicyclic diisocyanate compound or a modified product thereof, an aliphatic diisocyanate compound or a modified product thereof are preferable, and an alicyclic diisocyanate or an isocyanurate modified product thereof, and an aliphatic diisocyanate or an isocyanurate modified product thereof are more preferable.
In addition, the ratio of the total mass of the alicyclic diisocyanate compound or its modified product to the total mass of the aliphatic diisocyanate compound or its modified product is preferably 70 mass% or more, and preferably 90 mass% or more, of the total mass of the polyisocyanate compounds.
When the alicyclic diisocyanate compound or a modified product thereof and the aliphatic diisocyanate compound or a modified product thereof are used in combination, the mass ratio of the two is preferably in the range of 30/70 to 70/30.
The polycarboxylic acid or anhydride thereof is not particularly limited in specific structure as long as it is a compound having a plurality of carboxyl groups in the molecular structure or anhydride thereof, and various compounds can be used. In order to make the amide imide resin (a3-1) have both an amide group and an imide group, both a carboxyl group and an acid anhydride group need to be present in the system, and in the present embodiment, a compound having both a carboxyl group and an acid anhydride group in the molecule may be used, or a compound having a carboxyl group and a compound having an acid anhydride group may be used in combination.
Examples of the polycarboxylic acid or anhydride thereof include aliphatic polycarboxylic acid compounds or anhydrides thereof, alicyclic polycarboxylic acid compounds or anhydrides thereof, and aromatic polycarboxylic acid compounds or anhydrides thereof.
The aliphatic polycarboxylic acid compound or its anhydride may have an aliphatic hydrocarbon group of a straight chain type or a branched chain type, and may have an unsaturated bond in its structure.
Examples of the aliphatic polycarboxylic acid compound or an 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, citraconic acid, itaconic acid, glutaconic acid, 1,2,3, 4-butanetetracarboxylic acid, and acid anhydrides thereof.
In the present embodiment, the alicyclic polycarboxylic acid compound or its anhydride is one in which a carboxyl group or an anhydride group is bonded to an alicyclic structure, and the presence or absence of an aromatic ring in other structural parts is not limited. Examples of the alicyclic polycarboxylic acid compound or its anhydride include 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, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid, and anhydrides thereof.
Examples of the aromatic polycarboxylic acid compound or an acid anhydride thereof include phthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, biphenyldicarboxylic acid, biphenyltricarboxylic acid, biphenyltetracarboxylic acid, and benzophenonetetracarboxylic acid.
Among these, the alicyclic polycarboxylic acid compound or anhydride thereof, or the aromatic polycarboxylic acid compound or anhydride thereof is preferable in that an acid group-containing (meth) acrylate resin composition which can form a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability can be obtained. In addition, from the viewpoint of efficiently producing the amide imide resin (a3-1), it is preferable to use a tricarboxylic acid anhydride having both a carboxyl group and an acid anhydride group in the molecular structure, and it is particularly preferable to use cyclohexanetricarboxylic acid anhydride or trimellitic anhydride. Further, the ratio of the total amount of the alicyclic tricarboxylic acid anhydride and the aromatic tricarboxylic acid anhydride is preferably 70% by mass or more, and more preferably 90% by mass or more, relative to the total mass of the polycarboxylic acid or anhydride thereof.
When the amide imide resin (a3-1) is obtained by using the polyisocyanate compound and the polycarboxylic acid or anhydride thereof as reaction raw materials, other reaction raw materials may be used in combination depending on the desired resin performance and the like. In this case, the ratio of the total mass of the polyisocyanate compound and the polycarboxylic acid or anhydride thereof to the total mass of the reaction raw materials of the amide imide resin (a3-1) is preferably 90 mass% or more, and more preferably 95 mass% or more, from the viewpoint that the effects exerted by the present invention can be more sufficiently exerted.
The amide imide resin (a3-1) is not particularly limited when a polyisocyanate compound and a polycarboxylic acid or an anhydride thereof are used as reaction raw materials, and can be produced by any method. For example, the resin can be produced by the same method as that for a general amide imide resin. Specific examples thereof include the following methods: and a method of reacting the polyisocyanate compound with a polycarboxylic acid or an anhydride thereof in an amount of 0.5 to 2.0 mol per 1 mol of isocyanate group in the polyisocyanate compound under stirring and mixing at a temperature of about 120 to 180 ℃.
The reaction of the polyisocyanate compound with the polycarboxylic acid or anhydride thereof may be carried out in the presence of a basic catalyst, if necessary. The reaction may be carried out in an organic solvent as needed.
The basic catalyst may be the same as the basic catalyst, and the basic catalysts may be used alone or in combination of two or more.
The organic solvent may be the same as the above-mentioned organic solvent, and the organic solvents may be used alone or in combination of two or more.
The amount of the organic solvent is preferably in the range of 10 to 500 parts by mass relative to 100 parts by mass of the total of the reaction raw materials, from the viewpoint of satisfactory reaction efficiency.
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 its molecular structure, and various compounds can be used. Examples thereof include hydroxy (meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like; (poly) oxyalkylene modified products in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above various hydroxy (meth) acrylate compounds; lactone modifications having a (poly) lactone structure are introduced into the molecular structures of the above-mentioned various hydroxy (meth) acrylate compounds. Among these, the acid group-containing (meth) acrylate resin composition having a molecular weight of 1000 or less is preferable in that it can form a cured product excellent in sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability. When the hydroxyl group-containing (meth) acrylate compound (a3-2) is the oxyalkylene-modified product or the lactone-modified product, the weight-average molecular weight is preferably 1000 or less. These hydroxyl group-containing (meth) acrylate compounds may be used alone or in combination of two or more.
Further, as the amide imide resin (A-3) having an acid group and a (meth) acryloyl group, a (meth) acryloyl group-containing epoxy compound (a3-3) may be used in combination as a reaction raw material, in addition to the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), as required. Further, as the amide imide resin (A-3) having an acid group and a (meth) acryloyl group, a (meth) acryloyl group-containing epoxy compound (a3-3) and a polyvalent carboxylic acid anhydride (a3-4) may be used in combination as reaction raw materials in addition to the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), as required.
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 its molecular structure, and various compounds can be used. Examples thereof include glycidyl group-containing (meth) acrylate monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and epoxycyclohexylmethyl (meth) acrylate; and mono (meth) acrylate compounds of diglycidyl ether compounds such as dihydroxybenzene diglycidyl ether, dihydroxynaphthalene diglycidyl ether, biphenol diglycidyl ether, and bisphenol diglycidyl ether. Among these, a glycidyl group-containing (meth) acrylate monomer is preferable from the viewpoint that an acid group-containing (meth) acrylate resin composition which can form a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability can be obtained. Further, the molecular weight thereof is preferably 500 or less. Further, 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 mass% or more, and more preferably 90 mass% or more.
As the polycarboxylic acid anhydride (a3-4), those exemplified for the polycarboxylic acid anhydride (a1-3) can be used, and the polycarboxylic acid (b3-4) can be used alone or in combination of two or more.
The amide imide resin (A-3) having an acid group and a (meth) acryloyl group may be used in combination with other reaction raw materials, in addition to the amide imide resin (a3-1) having an acid group or an acid anhydride group, the hydroxyl group-containing (meth) acrylate compound (a3-2), the (meth) acryloyl group-containing epoxy compound (a3-3), and the polycarboxylic acid anhydride (a3-4), depending on the desired resin performance and the like. In this case, the proportion of the total mass of the components (B3-1) to (B3-4) in the total mass of the reaction raw materials for the acid group-containing (meth) acrylate resin (B-3) is preferably 80 mass% or more, and more preferably 90 mass% or more.
The method for producing the amide imide resin (a-3) having an acid group and a (meth) acryloyl group is not particularly limited, and any method can be used. For example, the resin composition can be produced by a method in which all the reaction raw materials comprising the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) are reacted at once, or by a method in which the reaction raw materials are reacted sequentially.
The reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is mainly a reaction between an acid group and/or an acid anhydride group in the amide imide resin (a3-1) and a hydroxyl group in the hydroxyl group-containing (meth) acrylate compound (a 3-2). Since the hydroxyl group-containing (meth) acrylate compound (a3-2) is particularly excellent in reactivity with an acid anhydride group, the amide imide resin (a3-1) preferably has an acid anhydride group as described above. The content of the acid anhydride group in the amide imide resin (a3-1) can be calculated from the difference between the measured values of the two acid values, that is, the difference between the acid value under the condition of ring-opening the acid anhydride group and the acid value under the condition of not ring-opening the acid anhydride group.
The reaction ratio between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is preferably such that the number of moles of hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (a3-2) is 0.9 to 1.1 based on 1 mole of the acid anhydride groups of the amide imide resin (a3-1) when the amide imide resin (a3-1) has an acid group and an acid anhydride group, or when the amide imide resin (a3-1) has an acid anhydride group. When the amide imide resin (a3-1) has an acid group, the reaction ratio between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is preferably such that the molar number of hydroxyl groups of the hydroxyl group-containing (meth) acrylate compound (a3-2) is 0.01 to 1.0 relative to 1 mole of the acid groups of the amide imide resin (a 3-1).
The reaction of the amide imide resin (a3-1) with the hydroxyl group-containing (meth) acrylate compound (a3-2) may also use a basic catalyst or an acidic catalyst, as required. Among them, it is preferable to use a basic catalyst when the amide imide resin (a3-1) has an acid group and an acid anhydride group, and to use an acid catalyst when the amide imide resin (a3-1) has an acid anhydride group, and to use an acid catalyst when the amide imide resin (a3-1) has an acid group.
The basic catalyst may be any one of the basic catalysts mentioned above, and the basic catalysts may be used alone or in combination of two or more.
The acidic catalyst may be one exemplified as the acidic catalyst, and the acidic catalyst may be used alone or in combination of two or more.
The amount of the basic catalyst or the acidic catalyst to be added is preferably in the range of 0.001 to 5 parts by mass relative to 100 parts by mass of the total mass of the reaction raw materials.
The reaction between the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) can be carried out by heating and stirring in the presence of an appropriate catalyst at a temperature of about 80 to 140 ℃.
The reaction may be carried out in an organic solvent as required, and the same organic solvent as the above-mentioned organic solvent may be used as the organic solvent, and the organic solvents may be used alone or in combination of two or more. When the reaction is continuously carried out with the production of the amide imide resin (a3-1), the reaction may be continuously carried out in the organic solvent used for the production of the amide imide resin (a 3-1).
When the (meth) acryloyl group-containing epoxy compound (a3-3) is used as a reaction raw material in addition to the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), the amide imide resin (a-3) having an acid group and a (meth) acryloyl group can be produced by a method in which all of the reaction raw materials including the amide imide resin (a3-1), the hydroxyl group-containing (meth) acrylate compound (a3-2), and the (meth) acryloyl group-containing epoxy compound (a3-3) are reacted at once, or can be produced by a method in which the reaction raw materials are reacted sequentially. Among them, from the viewpoint of easy control of the reaction, it is preferably produced by the following method: the amide imide resin (a3-1) is reacted with the hydroxyl group-containing (meth) acrylate compound (a3-2) to obtain a product (hereinafter, may be referred to as "product (1)"), and the product is reacted with the (meth) acryloyl group-containing epoxy compound (a 3-3).
The reaction of the product (1) with the (meth) acryloyl group-containing epoxy compound (a3-3) is mainly a reaction of the acid group in the product (1) with the (meth) acryloyl group-containing epoxy compound (a 3-3). The reaction ratio is preferably: the ratio of the number of moles of epoxy groups contained in the (meth) acryloyl group-containing epoxy compound (a3-3) to 1 mole of acid groups contained in the product (1) is 0.05 to 1.1. The reaction can be carried out, for example, by heating and stirring at a temperature of about 90 to 140 ℃ in the presence of an appropriate basic catalyst. When the reaction with the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2) is continuously carried out, the addition of a basic catalyst may be omitted or may be carried out as appropriate. The reaction may be carried out in an organic solvent, if necessary. The basic catalyst and the organic solvent may be the same as those described above, and these may be used alone or in combination of two or more.
The amide imide resin (A-3) having an acid group and a (meth) acryloyl group can be produced by a method in which, when a (meth) acryloyl epoxy compound (a3-3) and a polyvalent carboxylic acid anhydride (a3-4) are used as reaction raw materials in addition to the amide imide resin (a3-1) and the hydroxyl group-containing (meth) acrylate compound (a3-2), all of the reaction raw materials including the amide imide resin (a3-1), the hydroxyl group-containing (meth) acrylate compound (a3-2), the (meth) acryloyl epoxy compound (a3-3), and the polyvalent carboxylic acid anhydride (a3-4) are reacted at once, or by a method in which the reaction raw materials are reacted sequentially. Among them, from the viewpoint of easy control of the reaction, it is preferably produced by the following method: the amide imide resin (a3-1) is reacted with the hydroxyl group-containing (meth) acrylate compound (a3-2) to obtain a product (1), and the product is reacted with the (meth) acryloyl group-containing epoxy compound (a3-3) to obtain a product (hereinafter, sometimes referred to as "product (2)") which is reacted with the polycarboxylic anhydride (a 3-4).
The reaction of the product (2) with the polyvalent carboxylic acid anhydride (a3-4) is mainly a reaction of the hydroxyl group in the product (2) with the polyvalent carboxylic acid anhydride. In this case, the reaction ratio of the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) with respect to the product (2) is preferably 0.1 to 1.2, more preferably 0.2 to 1.1, in terms of the number of moles of epoxy groups contained in the (meth) acryloyl group-containing epoxy compound (a3-3) with respect to 1 mole of acid groups contained in the product (1). In the product (2), for example, a hydroxyl group formed by ring opening of an epoxy group in the (meth) acryloyl group-containing epoxy compound (a3-3) is present. The reaction ratio of the polycarboxylic acid anhydride (a3-4) is preferably adjusted so that the acid value of the produced amide imide resin (A-3) having an acid group and a (meth) acryloyl group is about 50 to 120 mgKOH/g. The reaction can be carried out, for example, by heating and stirring at a temperature of about 80 to 140 ℃ in the presence of an appropriate basic catalyst. When the reaction with the product (1) and the (meth) acryloyl group-containing epoxy compound (a3-3) is continuously carried out, the addition of a basic catalyst may be omitted or may be carried out as appropriate. The reaction may be carried out in an organic solvent as required. The basic catalyst and the organic solvent may be the same as those described above, and these may be used alone or in combination of two or more.
The acid value of the acid group-containing (meth) acrylate resin (a-3) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that a cured product having excellent sensitivity, alkali developability, and adhesion, and having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability can be obtained. In the present specification, the acid value of the amide imide resin (a-3) having an acid group and a (meth) acryloyl group is a value measured by a neutralization titration method according to JIS K0070 (1992).
Next, the acrylic resin [ 4 ] having an acid group and a (meth) acryloyl group (A-4) will be described.
Examples of the acrylic resin (a-4) having an acid group and a (meth) acryloyl group include a reaction product obtained by polymerizing, as an essential component, a (meth) acrylate compound (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group to obtain an acrylic resin intermediate, and further reacting the obtained acrylic resin intermediate with a (meth) acrylate compound (β) having a reactive functional group reactive with these functional groups to introduce a (meth) acryloyl group; and a reaction product obtained by reacting a polybasic acid anhydride with a hydroxyl group in the reaction product.
The acrylic resin intermediate may be copolymerized with other polymerizable unsaturated group-containing compounds as necessary in addition to the (meth) acrylate compound (α). Examples of the other polymerizable unsaturated group-containing compound include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; alicyclic structure-containing (meth) acrylates such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like; aromatic ring-containing (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl acrylate, and the like; silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; styrene derivatives such as styrene, α -methylstyrene and chlorostyrene. These may be used alone or in combination of two or more.
The (meth) acrylate compound (β) is not particularly limited as long as it can react with the reactive functional group of the (meth) acrylate compound (α), and the following combinations are preferred from the viewpoint of reactivity. That is, when a hydroxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (α), an isocyanate group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (β). When a carboxyl group-containing (meth) acrylate is used as the (meth) acrylate compound (. alpha.), a glycidyl group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (. beta.). When an isocyanate group-containing (meth) acrylate is used as the (meth) acrylate compound (. alpha.), a hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (. beta.). When a glycidyl group-containing (meth) acrylate is used as the (meth) acrylate compound (. alpha.), a carboxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate compound (. beta.). The (meth) acrylate compound (β) may be used alone or in combination of two or more.
Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, octenylsuccinic anhydride, tetrapropenylsuccinic anhydride, and the like. These polybasic acid anhydrides may be used alone or in combination of two or more.
The method for producing the acrylic resin (A-4) having an acid group and a (meth) acryloyl group is not particularly limited, and any method may be used. The acrylic resin (A-4) having an acid group and a (meth) acryloyl group may be produced in an organic solvent if necessary, or a basic catalyst may be used if necessary.
The organic solvent may be the same as the above-mentioned organic solvent, and the organic solvents may be used alone or in combination of two or more.
The basic catalyst may be the same as the basic catalyst, and the basic catalysts may be used alone or in combination of two or more.
The acid value of the acrylic resin (A-4) having an acid group and a (meth) acryloyl group is preferably in the range of 30 to 150mgKOH/g, and more preferably in the range of 40 to 120mgKOH/g, from the viewpoint that an acid group-containing (meth) acrylate resin composition that can form a cured product having excellent sensitivity, alkali developability, and adhesion, and having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability can be obtained. In the present specification, 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 according to JIS K0070 (1992).
Next, the urethane resin having an acid group and a (meth) acryloyl group (A-5) will be described.
Examples of the urethane resin (a-5) having an acid group and a (meth) acryloyl group include urethane resins obtained by reacting a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a carboxyl group-containing polyol compound, and if necessary, a polybasic acid anhydride, and a polyol compound other than the carboxyl group-containing polyol compound; a urethane resin obtained by reacting with a polyisocyanate compound, a hydroxyl group-containing (meth) acrylate compound, a polybasic acid anhydride, and a polyol compound other than a carboxyl group-containing polyol compound; urethane resin obtained by reacting with epoxy resin, unsaturated monobasic acid, polybasic acid anhydride and polyisocyanate compound; urethane resins obtained by reacting with epoxy resins, unsaturated monobasic acids, polybasic acid anhydrides, polyisocyanate compounds, and hydroxyl group-containing (meth) acrylate compounds, and the like.
The polyisocyanate compound may be the same as the polyisocyanate compound, and the polyisocyanate compounds may be used alone or in combination of two or more.
The hydroxyl group-containing (meth) acrylate compound may be the same as the hydroxyl group-containing (meth) acrylate compound (a3-2), and the hydroxyl group-containing (meth) acrylate compound may be used alone or in combination of two or more.
Examples of the carboxyl group-containing polyol compound include 2, 2-dimethylolpropionic acid, 2-dimethylolbutyric acid, 2-dimethylolpentanoic acid and the like. The carboxyl group-containing polyol compounds may be used alone or in combination of two or more.
The polybasic acid anhydrides exemplified above may be used, and the polybasic acid anhydrides may be used alone or in combination of two or more.
Examples of the polyol compound other than the carboxyl group-containing polyol compound include aliphatic polyol compounds such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol and the like; aromatic polyhydric alcohol compounds such as biphenol and bisphenol; (poly) oxyalkylene modifications in which (poly) oxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above-mentioned various polyol compounds; lactone modifications having a (poly) lactone structure introduced into the molecular structure of the above-mentioned various polyol compounds, and the like. The polyol compounds other than the above-mentioned carboxyl group-containing polyol compound may be used alone, or two or more kinds may be used in combination.
The epoxy resins exemplified as the epoxy resin (a1-1) can be used, and the epoxy resins can be used alone or in combination of two or more.
Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α -cyanocinnamic acid, β -styrylacrylic acid, β -furfurylacrylic acid, and the like. Further, the above-mentioned esters, acid halides, acid anhydrides of the unsaturated monobasic acids, and the like can also be used. These unsaturated monobasic acids may 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 any method may be used. The production of the urethane resin having an acid group and a polymerizable unsaturated bond may be carried out in an organic solvent as required, and a basic catalyst may be used as required.
The organic solvent may be the same as the above-mentioned organic solvent, and the organic solvents may be used alone or in combination of two or more.
The basic catalyst may be the same as the basic catalyst, and the basic catalysts may be used alone or in combination of two or more.
The content of the acid-group-containing resin is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total amount of nonvolatile components in the pattern-forming material, from the viewpoint of obtaining a pattern-forming material capable of forming a cured product having excellent sensitivity, alkali developability, and adhesion, and having a low linear expansion coefficient, a low oxygen permeability, and a low water vapor permeability. That is, the content of the acid group-containing resin may be 10 mass% or more or 20 mass% or more, and may be 90 mass% or 80 mass% or less, with respect to the total amount of nonvolatile components in the pattern forming material.
[ other ingredients ]
The pattern forming material of the embodiment has a polymerizable double bond in its molecular structure, and thus can be cured by adding a polymerization initiator, for example. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among these, a photopolymerization initiator is preferable from the viewpoint of easy formation of a pattern.
Examples of the photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl propane-1-one, 1- [ 4- (2-hydroxyethoxy) phenyl ] -2-hydroxy-2-methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2' -dimethoxy-1, 2-diphenylethane-1-one, diphenyl (2,4, 6-trimethoxybenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bis (2,4, 6-trimethylbenzoyl) phenyl phosphine oxide, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, and the like, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.
Examples of commercially available photopolymerization initiators include "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-754", "nonirad-784", "Omnirad-500", "Omnirad-81" (manufactured by IGM), "Kayakure-DETX", "Kayakure-MBP", "Kayakure-DMBI", "Kacure-EPA", "Kacure-OA" (manufactured by Japan Chemical Co., Ltd), "Vicure-10", "Vicure-55" (manufactured by Akkara-55) "," Sanyakure-CmP "," Kayakure-DMBI "," Kayakure-EPA "," Kayakure-OA "(manufactured by Japan Chemical Co., Ltd.," Sanyaku Chemical Co., Ltd., "Sanyakure-35Z", and "D., "DEAP" (manufactured by Upjohn company), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinson company), "Runtercure-1104" (manufactured by Runtec company), and the like.
The amount (content) of the photopolymerization initiator is preferably 1 to 20 parts by mass based on the polymerizable compound (for example, acid group-containing resin) of the pattern forming material.
The pattern forming material of the embodiment may contain other polymerizable compounds than the acid group-containing resin having a polymerizable double bond. Examples of the other polymerizable compound include resins having a (meth) acryloyl group obtained by reacting an epoxy compound such as a bisphenol-type epoxy compound or a novolak-type epoxy compound with (meth) acrylic acid, (meth) acrylic anhydride, and the like; various (meth) acrylate monomers, and the like.
Examples of the (meth) acrylate ester monomer include aliphatic mono (meth) acrylate ester compounds such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (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; mono (meth) acrylate compounds such as aromatic mono (meth) acrylate compounds including benzyl (meth) acrylate, phenyl (meth) acrylate, phenylbenzyl (meth) acrylate, phenoxy ester (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, phenoxybenzyl (meth) acrylate, benzylbenzyl (meth) acrylate, and phenylphenoxyethyl (meth) acrylate: (poly) oxyalkylene-modified mono (meth) acrylate compounds in which polyoxyalkylene chains such as (poly) oxyethylene chains, (poly) oxypropylene chains, and (poly) oxytetramethylene chains are introduced into the molecular structures of the above-mentioned various mono (meth) acrylate monomers; lactone-modified mono (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of each of the above mono (meth) acrylate compounds; aliphatic di (meth) acrylate compounds such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate; alicyclic di (meth) acrylate compounds such as 1, 4-cyclohexanedimethanol di (meth) acrylate, norbornyl dimethanol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate; aromatic di (meth) acrylate compounds such as biphenol di (meth) acrylate and bisphenol di (meth) acrylate; polyoxyalkylene-modified di (meth) acrylate compounds in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of each of the above di (meth) acrylate compounds; lactone-modified di (meth) acrylate compounds having a (poly) lactone structure introduced into the molecular structure of each of the above di (meth) acrylate compounds; aliphatic tri (meth) acrylate compounds such as trimethylolpropane tri (meth) acrylate and glycerol tri (meth) acrylate; a (poly) oxyalkylene-modified tri (meth) acrylate compound in which a (poly) oxyalkylene chain such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, or a (poly) oxytetramethylene chain is introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; a lactone-modified tri (meth) acrylate compound having a (poly) lactone structure introduced into the molecular structure of the aliphatic tri (meth) acrylate compound; aliphatic poly (meth) acrylate compounds having 4 or more functions such as pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate; a (poly) oxyalkylene-modified poly (meth) acrylate compound having 4 or more functional (poly) oxyalkylene groups, such as a (poly) oxyethylene chain, a (poly) oxypropylene chain, and a (poly) oxytetramethylene chain, introduced into the molecular structure of the aliphatic poly (meth) acrylate compound; a lactone-modified poly (meth) acrylate compound having 4 or more functions, in which a (poly) lactone structure is introduced into the molecular structure of the aliphatic poly (meth) acrylate compound. The various (meth) acrylate monomers mentioned above may be used alone or in combination of two or more.
The pattern forming material of the embodiment may further contain a modifier. Examples of the modifier include a coupling agent, a silane compound, and an acid anhydride. When the pattern forming material contains these modifiers, the wettability of the lithium-part-fixed smectite is improved, and the dispersibility of the smectite in the pattern forming material is improved. The modifier may be used alone or in combination of two or more.
Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent.
Examples of the silane coupling agent include epoxy group-containing silane coupling agents, amino group-containing silane coupling agents, (meth) acryl group-containing silane coupling agents, isocyanate group-containing silane coupling agents, and the like. Examples of the epoxy group-containing silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane. Examples of the aminosilane-containing coupling agent include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethylbutylidene) propylamine, N-phenyl-gamma-aminopropyltrimethoxysilane and the like. Examples of the (meth) acryloyl silane-containing coupling agent include 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-methacryloyloxypropyltriethoxysilane. Examples of the isocyanate-containing silane coupling agent include 3-isocyanatopropyltriethoxysilane, and the like.
Examples of the titanium coupling agent include isopropyltriisostearoyltitanate, isopropyltrioctyl titanate, isopropyldimethacryloylstearoyltitanate, isopropylisostearoldiacryloyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraoctylbis (ditridecylphosphonoxy) titanate, tetrakis (2, 2-diallyloxymethyl-1-butyl) bis (ditridecylphosphoryloxy) titanate, oxoacetic acid bis (dioctylpyrophosphate) titanate, and bis (dioctylpyrophosphate) ethylene titanate.
Examples of the zirconium coupling agent include zirconium acetate, ammonium zirconium carbonate, and zirconium fluoride.
Examples of the aluminum coupling agent include aluminum isopropoxide, aluminum diisopropoxide monoethylacetoacetate, aluminum triethylacetoacetate, and aluminum triacetylacetonate.
Examples of the silane compound include alkoxysilane, silazane, and siloxane. Examples of the alkoxysilane include methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1, 6-bis (trimethoxysilyl) hexane, trifluoropropyltrimethoxysilane and the like. Examples of the silazane include hexamethyldisilazane. Examples of the siloxane include a hydrolyzable group-containing siloxane.
Examples of the acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride alkenylsuccinic anhydride.
The amount (content) of the modifier is preferably 0.1 to 50% by mass based on the total amount of the lithium-part-immobilized smectite. When the amount of the modifier is 0.1% by mass or more, the dispersibility of the lithium partially fixed smectite in the pattern forming material is further improved. When the amount of the modifier is 50% by mass or less, the influence of the modifier on the mechanical properties of the pattern forming material can be further suppressed. The 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 also contain an organic solvent for the purpose of coating viscosity adjustment or the like. The kind and amount (content) of the organic solvent may be appropriately selected and adjusted depending on the desired performance.
Examples of the organic solvent 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; aromatic solvents such as toluene, xylene, solvent naphtha and the like; alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether, and the like; glycol ether solvents such as alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, and dialkylene glycol monoalkyl ether acetate; methoxypropanol, cyclohexanone, methyl cellosolve, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and the like. These organic solvents may be used alone or in combination of two or more.
The pattern forming material of the embodiment may contain various additives such as a curing agent, a curing accelerator, inorganic fine particles other than the lithium-part-fixed smectite, polymer fine particles, a pigment, an antifoaming agent, a viscosity adjuster, a leveling agent, a flame retardant, and a storage stabilizer, if necessary.
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 carboxyl group) in the acid group-containing (meth) acrylate resin, and examples thereof include epoxy resins. Examples of the epoxy resin include bisphenol type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol-phenol condensed novolac type epoxy resins, naphthol-cresol condensed novolac type epoxy resins, phenol aralkyl type epoxy resins, naphthol aralkyl type epoxy resins, dicyclopentadiene-phenol addition reaction type epoxy resins, biphenyl aralkyl type epoxy resins, fluorene type epoxy resins, xanthene type epoxy resins, dihydroxybenzene type epoxy resins, trihydroxybenzene type epoxy resins, and the like. These epoxy resins may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining a curable resin composition (pattern forming material) capable of forming a cured product having excellent sensitivity, alkali developability and adhesion, and having a low linear expansion coefficient, a low oxygen permeability and a low water vapor permeability, a novolac-type epoxy resin such as a phenol novolac-type epoxy resin, a cresol novolac-type epoxy resin, a bisphenol novolac-type epoxy resin, a naphthol-phenol co-condensed novolac-type epoxy resin, or a naphthol-cresol co-condensed novolac-type epoxy resin is preferable, and an epoxy resin having a softening point in the range of 20 to 120 ℃ is particularly preferable.
Examples of the curing accelerator that accelerates the curing reaction of the curing agent, and when an epoxy resin is used as the curing agent, include a phosphorus compound, an amine compound, imidazole, an organic acid metal salt, a lewis acid, and an amine complex salt. These curing accelerators may be used alone or in combination of two or more. The amount of the curing accelerator added is preferably in the range of, for example, 1 to 10 parts by mass per 100 parts by mass of the curing agent.
< cured film and cured Pattern >
By curing the film formed of the pattern forming material of the above embodiment, a cured film (a cured film including a cured product of the pattern forming material) can be obtained. In addition, a cured pattern can be obtained by curing a part of the film formed of the pattern forming material of the embodiment and then removing an uncured part of the film (for example, a dried product of the pattern forming material).
The method for producing a cured pattern includes, for example, a step (curing step) of curing a part of a film formed of a pattern forming material, and a step of obtaining a cured pattern by removing an uncured part of the film after the curing step. The method for producing a cured pattern may further include a step (coating step) of coating the pattern-forming material on the base material to obtain a film (film formed of the pattern-forming material) before the curing step. That is, a film formed of a pattern forming material may be formed on the base material.
The method of applying the pattern forming material to the substrate in the coating step is not particularly limited. When the pattern forming material contains an organic solvent, the coating step may include a step of removing the organic solvent by drying the resulting coating film after the pattern forming material is coated to obtain the coating film. That is, the film formed of the pattern forming material may be a film containing a dried product of the pattern forming material.
In the curing step, an uncured portion (for example, a portion formed of a dried product of the pattern forming material) and a cured portion (a portion formed of a cured product of the pattern forming material) of the film are selectively formed, whereby a cured pattern can be obtained.
The curing method in the curing step may be appropriately changed depending on the polymerization initiator used. For example, when a photopolymerization initiator is used, the curing step may include a step of irradiating the film with active energy rays, and when a thermal polymerization initiator is used, the curing step may include a step of applying heat to the film. The curing step preferably includes a step of curing the resin with an active energy ray.
The step of curing the film with an active energy ray may be a step of irradiating the film with an active energy ray in a pattern. Specifically, for example, the step of irradiating the film with an active energy ray through a photomask may be included, or the step of selectively irradiating the film with an active energy ray without using a photomask (for example, the step of irradiating the film with an active energy ray in a pattern by using a point light source such as a laser light source) may be included.
Examples of the active energy ray include ionizing radiation rays such as ultraviolet rays, electron beams, α rays, β rays, and γ rays. In the case where ultraviolet rays are used as the active energy rays, irradiation may be performed in an inert gas atmosphere such as nitrogen gas or in an air atmosphere in order to more efficiently perform the curing reaction by ultraviolet rays.
As the ultraviolet light source, an ultraviolet lamp can 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 cumulative amount of the active energy rays is not particularly limited, but is preferably 10 to 5000mJ/cm2More preferably 50 to 1000mJ/cm2. When the cumulative light amount is in the above range, generation of uncured portions can be prevented or suppressed, and therefore, it is preferable.
A laser may also be used as the active energy ray. Examples of the exposure light source include carbon arc lamps, mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps, and halogen lamps; laser sources such as HeNe laser, argon ion laser, YAG laser, HeCd laser, semiconductor laser, and ruby laser. Among these, a light source that generates a laser beam having a wavelength in the blue-violet region of 350 to 430nm is preferable, and a light source that generates a laser beam having a center wavelength of about 405nm is more preferable. Specifically, an indium gallium nitride semiconductor laser having an oscillation wavelength of 405nm is mentioned. The scanning exposure method by the laser light source is not particularly limited, and examples thereof include a plane scanning exposure method, an outer surface roller scanning exposure method, an inner surface roller scanning exposure method, and the like, and scanning exposure is performed under scanning exposure conditions in which the output light intensity of the laser light is preferably 1 to 100mW, more preferably 3 to 70mW, the oscillation wavelength is preferably 390 to 430nm, more preferably 400 to 420nm, the beam spot diameter is preferably 2 to 30 μm, more preferably 4 to 20 μm, the scanning speed is preferably 50 to 500 m/sec, more preferably 100 to 400 m/sec, the scanning density is preferably 2000dpi or more, and more preferably 4000dpi or more. By the laser, a pattern can be formed on the cured film without using a photomask.
In the step of irradiating the active energy ray through the photomask, it is preferable to use ultraviolet rays, and in the step of selectively irradiating the active energy ray, it is preferable to use a laser. From the viewpoint of productivity, the curing step preferably includes a step of irradiating the active energy ray through a photomask.
The step of removing the uncured portion of the film to obtain a cured pattern includes, for example, a step of removing the uncured portion by development using an alkaline aqueous solution, an organic solvent, or the like.
As the aqueous alkali solution, an aqueous solution of sodium carbonate, potassium carbonate, or the like can be used. As the aqueous alkali solution, a 0.5 to 3 mass% aqueous sodium carbonate solution is generally used.
Examples of the organic solvent include the organic solvents used for adjusting the viscosity of the pattern forming material.
The cured pattern of the embodiment is excellent in sensitivity and alkali developability, and thus can be used as a resist film. Examples of the resist film include a solder resist layer.
When the pattern forming material of the embodiment is formed into a resist film, for example, the following method can be mentioned as one specific method: a method of applying a pattern-forming material on a substrate, volatilizing and drying an organic solvent at a temperature of about 60 to 100 ℃, exposing the material to an active energy ray through a photomask having a desired pattern formed thereon, developing the unexposed portion with an aqueous alkali solution, and further heating and curing the material at a temperature of about 140 to 180 ℃, and the method of forming a resist film is not limited to the above-mentioned method.
The cured pattern according to the embodiment can also be suitably used as an interlayer insulating material, an encapsulating material, an underfill material, an encapsulating adhesive layer for a circuit element or the like, an adhesive layer for an integrated circuit element and a circuit board, or the like. In addition, the present invention can be suitably used for a thin display represented by an LCD and an OELD, for example, a protective film for a thin film transistor, a protective film for a liquid crystal color filter, a pigment resist for a color filter, a resist for a black matrix, a spacer, and the like.
Examples
Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
(preparation of lithium partial fixation type smectite)
As the filler contained in the resin composition (pattern forming material), a lithium partially fixed type smectite was used. For the lithium partial immobilization type smectite, montmorillonite dispersed slurry (trade name: RCEC-W, cation exchange capacity 39.0meq/100g) made by KUNMINE INDUSTRIES CO. The content (w/w%) of the lithium-partially fixed type smectite in the dispersion slurry was 20 w/w%.
(preparation of modifier liquid)
As the modifier, 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, product of shin-Etsu chemical Co., Ltd.) was used as a silane coupling agent. 0.24 part by mass of 3-methacryloxypropyltrimethoxysilane (trade name: KBM503, manufactured by shin-Etsu chemical Co., Ltd.), 0.06 part by mass of ion-exchanged water, and 0.012 part by mass of 0.1% hydrochloric acid were added to 12.0 parts by mass of isopropyl alcohol, and the mixture was stirred at 25 ℃ for 4 hours to obtain a modifier liquid.
(Synthesis example 1)
143 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a thermometer, a stirrer and a reflux condenser, 428 parts by mass of an o-cresol novolak type epoxy compound EPICLON N-680 (available from DIC corporation, epoxy equivalent: 214, and EPICLON "are registered trademarks) was dissolved, 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 part by mass of p-hydroxyanisole as a thermal polymerization inhibitor were added, 144 parts by mass of acrylic acid and 1.7 parts by mass of triphenylphosphine were added, and esterification reaction was carried out at 120 ℃ for 10 hours while blowing air. Then, 201 parts by mass of propylene glycol monomethyl ether acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ℃ for 3 hours to obtain the target acid group-containing acrylate resin (acid-side-type epoxy acrylate) as a resin solution containing 68% by mass of solid content. The acid value of the system at this time was 56.4KOH-mg/g (calculated as solid content: 83KOH-mg/g), and the weight average molecular weight of the acid group-containing acrylate resin was 2900.
< method for measuring weight average molecular weight of resin >
A sample for measurement was prepared by filtering a diluted solution obtained by diluting an acid group-containing acrylate resin with Tetrahydrofuran (THF) by a factor of 50 with a filter (material: polytetrafluoroethylene, pore diameter: 0.2 μm). Then, the measurement sample was subjected to gel permeation chromatography (product name: HLC-8220GPC, manufactured by Tosoh corporation of GPC) and measured under conditions of a sample flow rate of 1 ml/min and a column temperature of 40 ℃. The value obtained by measuring the molecular weight of the acid group-containing acrylate resin in terms of polystyrene was defined as the weight average molecular weight of the acid group-containing acrylate resin. In the GPC measurement, HXL-X, G5000HXL, G3000HXL, G2000HXL, and G2000HXL (all available from Tosoh Corp.) were used as columns, and a differential refractometer was used as a detector.
(example 1)
To 100 parts by mass (solid content: 68 parts by mass) of the acid group-containing acrylate resin obtained in synthesis example 1 were added 68 parts by mass of the lithium-part-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 liquid, and the mixture was stirred and held for 8 hours. The obtained dispersion was desolventized under reduced pressure while being heated at 50 ℃ using a planetary mixer manufactured by PRIMIX Corporation, to obtain a filler resin dispersion having a solid content of 68 mass%. 25.8 parts by mass of an o-cresol novolak type epoxy compound ("EPICLON N-680", manufactured by DIC corporation) as a curing agent, 3.4 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Omnirad-907, manufactured by IGM) as a photopolymerization initiator, 0.52 part by mass of 2-ethyl-4-methylimidazole as a curing accelerator, 13.9 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent, and 0.65 part by mass of phthalocyanine green as a pigment were compounded and kneaded by a roll mill to obtain the pattern-forming material of example 1. In the pattern forming material, the content (filler amount) of the lithium partial immobilization type smectite was 12% by mass with respect to the total nonvolatile matter.
Comparative example 1
To 100 parts by mass (solid content: 68 parts by mass) of the acid group-containing acrylate resin obtained in Synthesis example 1 were added 13.6 parts by mass of fused silica ("Denka fused silica (DF) FB-5604", manufactured by electrochemical Co., Ltd.), and to this, 25.8 parts by mass of an o-cresol novolak-type epoxy compound ("EPICLON-680", manufactured by DIC Co., Ltd.) as a curing agent, 3.4 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Omnirad-907", manufactured by IGM) as a photopolymerization initiator, 0.52 part by mass of 2-ethyl-4-methylimidazole as a curing accelerator, 13.9 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent, and 0.65 part by mass of phthalocyanine green as a pigment were blended, the resultant mixture was kneaded by a roll mill to obtain a pattern forming material of comparative example 1. In the pattern-forming material, the content of fused silica (filler amount) was 12% by mass with respect to the total nonvolatile content.
[ method for evaluating sensitivity ]
The pattern-forming materials obtained in example 1 and comparative example 1 were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and dried at 80 ℃ for 30 minutes. Then, the dried coating film was irradiated with 500mJ/cm of radiation using a metal halide lamp, Step tablet No.2 manufactured by Kodak corporation 2Ultraviolet rays of (1). This was developed with a 1% aqueous solution of sodium carbonate at 30 ℃ for 180 seconds, and the sensitivity of the pattern forming material was evaluated by the residual order of Step tablet based on the Step tablet method. Note that a larger number of residual orders indicates a higher sensitivity. The results are shown in Table 1.
[ method for evaluating alkali developability ]
The pattern-forming materials obtained in example 1 and comparative example 1 were applied to a glass substrate with an applicator so that the film thickness became 50 μm, and then dried at 80 ℃ for 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, and 100 minutes, respectively, to prepare samples having different drying times. These were developed with a 1% aqueous solution of sodium carbonate at 30 ℃ for 180 seconds, and the drying time of a sample having no residue left on the substrate at 80 ℃ was evaluated as the drying control width. The longer the drying control width is, the more excellent the alkali developability is. The results are shown in Table 1.
[ Table 1]
Resin composition Example 1 Comparative example 2
Sensitivity (order) 7 4
Breadth of drying management (minutes) 60 40
(example 2)
To 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 (solid content: 13.6 parts by mass) of the lithium-part fixed type smectite dispersion slurry, 433 parts by mass of acetonitrile, and 52 parts by mass of the modifier liquid were added, and the mixture was stirred for 8 hours. The obtained dispersion was desolventized under reduced pressure while being heated at 50 ℃ using a planetary mixer manufactured by PRIMIX Corporation, to obtain a filler resin dispersion having a solid content of 68 mass%. 25.8 parts by mass of an o-cresol novolak type epoxy compound ("EPICLON N-680", manufactured by DIC corporation) as a curing agent, 3.4 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (Omnirad-907, manufactured by IGM) as a photopolymerization initiator, and 13.9 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent were compounded and kneaded by a roll mill to obtain the pattern-forming material of example 2. In the pattern forming material, the content (filler amount) of the lithium partial immobilization type smectite was 12% by mass with respect to the total nonvolatile matter.
Comparative example 2
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 electrochemical Co., Ltd.) was added, and 25.8 parts by mass of an o-cresol novolac-type epoxy compound ("EPICLON-680", manufactured by DIC Co., Ltd.) as a curing agent, 3.4 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one ("Omnirad-907", manufactured by IGM) as a photopolymerization initiator, and 13.9 parts by mass of propylene glycol monomethyl ether acetate as an organic solvent were blended by a roll mill to obtain a pattern-forming material of comparative example 2. In the pattern-forming material, the content of fused silica (filler amount) was 12% by mass with respect to the total nonvolatile content.
[ method for evaluating average Linear expansion Rate ]
The pattern-forming materials obtained in example 2 and comparative example 2 were applied to electrolytic copper foil "F2-WS" manufactured by Kogawa industries, Ltd., using an applicator so that the film thickness became 50 μm, and dried at 80 ℃ for 30 minutes. Then, the dried coating film was irradiated with 1000mJ/cm using a metal halide lamp 2The coating film was cured at 160 ℃ for 1 hour after the ultraviolet ray of (2). The obtained laminate was cut into a size of 20mm × 5mm, and the cut product was used as a test piece. Using a thermomechanical analyzer (TMA, manufactured by Shimadzu corporation)"TMA-60") manufactured by the same manner as above, the test piece was subjected to thermomechanical analysis in a tensile mode under the following measurement conditions in a nitrogen atmosphere.
Measurement conditions
Measuring the frame weight: 6mN
Temperature rise rate: 10 deg.C/min 2 times
Measurement temperature range: 1, time: 0 ℃ to 220 ℃, 2 nd time: -60 ℃ to 240 DEG C
The same sample was subjected to 2 measurements under the above conditions, and the average linear expansion coefficient in the temperature range of 40 to 60 ℃ in the 2 nd measurement was evaluated as the linear expansion coefficient. The results are shown in Table 2.
[ method for evaluating peeling Strength ]
The pattern-forming materials obtained in example 2 and comparative example 2 were applied to electrolytic copper foil "F2-WS" manufactured by Kogaku industries Co., Ltd, using an applicator so that the film thickness became 50 μm, and dried at 80 ℃ for 30 minutes. Then, the dried coating film was irradiated with 1000mJ/cm using a metal halide lamp2The coating film was cured at 160 ℃ for 1 hour after the ultraviolet ray of (2). The obtained laminate was cut into 1cm × 12cm to obtain a test piece. The 90 DEG peel strength of the cured coating film of the test piece was measured using "AG-IS-1 kN" manufactured by Shimadzu corporation under conditions of a test speed of 50 mm/min, a humidity of 50% and a temperature of 23 ℃. The results are shown in Table 2.
[ Table 2]
Resin composition Example 2 Comparative example 2
Average linear expansion coefficient/40-60 DEG C 41 57
Peel strength (N/cm) 2.28 0.63
(example 3)
To 146 parts by mass of the acid group-containing acrylate resin obtained in synthesis example 1 (solid content: 100 parts by mass), 5 parts by mass of a UV radical initiator 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide (trade name: Omnirad (registered trademark) -TPO, manufactured by IGM corporation), 86 parts by mass of the above-mentioned lithium partially fixed type smectite dispersion slurry (solid content: 17.2 parts by mass), 636 parts by mass of acetonitrile, and 66 parts by mass of the above-mentioned modifier liquid were added, and the mixture was stirred and held for 8 hours. Thus, a pattern-forming material of example 3 was obtained. In the pattern forming material, the content (filler amount) of the lithium partial immobilization type smectite was 14 mass% with respect to the total nonvolatile matter.
The pattern-forming material of example 3 thus obtained was coated on a corona-treated surface of a 12 μm PET film (trade name: E-5100, manufactured by Toyo Co., Ltd.) by using a bar coater so that the coating thickness became 2 μm after drying. Immediately after coating, the coated PET film was heated in a dryer at 150 ℃ for 5 minutes to be solvent-dried. After cooling at room temperature, the mixture was irradiated with a metal halide lamp at 2000mJ/cm 2And UV-cured to form a cured film on the PET film.
Comparative example 3
A cured film was produced in the same manner as in example 3 except that 17.2 parts by mass of fused silica ("Denka fused silica (DF) FB-5604", manufactured by Kogyo Co., Ltd.) was added in place of 86 parts by mass of the lithium partially fixed smectite dispersion slurry (solid content: 17.2 parts by mass), and a modifier solution was not used.
[ evaluation method of oxygen permeability ]
The oxygen permeability was measured according to JIS-K7126 (isobaric method) using an oxygen permeability measuring apparatus OX-TRAN1/50 manufactured by Mocon Inc., under an atmosphere of 23 ℃ and 0% RH and an atmosphere of 23 ℃ and 90% RH. RH represents relative humidity. The results are shown in Table 3.
[ method for evaluating Water vapor Transmission Rate ]
The water vapor transmission rate was measured in accordance with JIS-K7129 using a water vapor transmission rate measuring apparatus 7001 manufactured by Illinois Inc. under an atmosphere of 40 ℃ and 90% RH of humidity. The results are shown in Table 3.
[ Table 3]
Figure BDA0002775481470000451

Claims (11)

1. A pattern forming material, comprising: an acid group-containing resin having a polymerizable double bond, and a lithium-moiety-immobilized smectite.
2. The pattern forming material according to claim 1, wherein the acid group-containing resin contains a (meth) acryloyl group.
3. The pattern forming material according to claim 1 or 2, wherein the acid group is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
4. The pattern forming material according to any one of claims 1 to 3, wherein the acid group-containing resin has a weight average molecular weight of 1000 to 20000.
5. The pattern forming material according to any one of claims 1 to 4, wherein the lithium-part-fixed type smectite has a cation exchange capacity of 1 to 70meq/100 g.
6. The pattern forming material according to any one of claims 1 to 5, wherein the content of the lithium-part fixing type smectite is 3 to 70% by mass with respect to the total amount of nonvolatile components in the pattern forming material.
7. A cured film comprising a cured product of the pattern forming material according to any one of claims 1 to 6.
8. The cured film according to claim 7, which is formed in a pattern.
9. The cured film according to claim 7 or 8, which is a resist film.
10. A method for manufacturing a cured pattern, comprising:
Curing a part of a film formed of the pattern forming material according to any one of claims 1 to 6; and
and a step of removing the uncured portion of the film after the step to obtain a cured pattern.
11. The method of manufacturing a cured pattern according to claim 10, wherein the step of curing a part of the film includes a step of irradiating the film with an active energy ray in a pattern.
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