KR20120138678A - Curable resin compositions containing alicyclic epoxy group, preparation process thereof, and cured article therefrom - Google Patents

Abstract

PURPOSE: An alicyclic epoxy based - containing curable resin composition, a manufacturing method thereof and the cured product are provided to enhance resin solubility and aging stability. CONSTITUTION: An alicyclic epoxy based - containing curable resin composition comprises a copolymer including monomer units correspond with acrylic epoxy containing polymerizable unsaturated compound and monomer units including alkali soluble group, and solvent containing 30-100 wt% of dipropyl glycol dimethyl ether based on the total solvent. A manufacturing method of the curable resin composition comprises the following steps: manufacturing a copolymer by using solvent including dipropyl glycol dimethyl ether; or solvent exchanging the copolymer solvent into a solvent containing dipropyleneglycol dimethyl ether.

Description

Alicyclic epoxy group-containing curable resin composition, its manufacturing method, and its hardened | cured material {CURABLE RESIN COMPOSITIONS CONTAINING ALICYCLIC EPOXY GROUP, PREPARATION PROCESS THEREOF, AND CURED ARTICLE THEREFROM}

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to lithography using actinic rays such as far ultraviolet rays, electron beams, ion beams, X-rays, semiconductors, liquid crystal display devices, integrated circuit devices, and insulating films provided in electronic components such as solid-state imaging devices. Material for liquid crystal resist for forming radiation-sensitive resin, liquid crystal display material (liquid crystal display photospacer, liquid crystal display rib forming material, overcoating, color filter forming color resist, TFT insulating film, etc.) used for the material for The alicyclic epoxy group containing curable resin composition used for coating, a coating agent, an adhesive agent, etc., its manufacturing method, and its hardened | cured material are related.

As a solvent used for a liquid photoresist (hereinafter also referred to as a "resist"), various kinds of solvents are conventionally known, and an appropriate solvent (solvent) in consideration of the solubility, coating property, sensitivity, developability, pattern characteristics formed, and the like of the resist resin composition. ) Is selected and used. As a solvent having excellent properties such as solubility, coating property, and resist formation property, for example, ethylene glycol monoethyl ether acetate has been known, but it is not used at all as a solvent of a resist after a problem of safety to the human body has been pointed out. Instead, propylene glycol monomethyl ether acetate and the like have been mainly used as solvents having high safety (Patent Documents 1 to 3 and the like). In addition to propylene glycol monomethyl ether acetate, ethyl lactate, methyl-n-amyl ketone and the like are known as solvents having high safety.

However, when looking at these solvents which are higher in safety than ethylene glycol monoethyl ether acetate, there exists a problem that characteristics, such as a resist formation characteristic and resin solubility, are not enough. For example, in the case of propylene glycol monomethyl ether acetate, when the resist is applied onto a substrate and formed into a film, the residual film ratio of the solvent (representing the solvent residual ratio in the film after film formation) is high, and the line width uniformity and the adhesion of the resist film during development There was a problem of degradation. As a cause, propylene glycol monomethyl ether acetate itself is a solvent having a high evaporation rate, but when used as a solvent of the resist resin, only the coating surface evaporates and a so-called film is formed on the surface. Therefore, the solvent contained in the coating surface evaporates. It becomes difficult to do that. Moreover, it is known that propylene glycol monomethyl ether acetate is inferior to resin solubility, initiator solubility, etc. compared with ethylene glycol monoethyl ether acetate. Moreover, especially when curable resin composition containing the copolymer resin which has an alicyclic epoxy group in a side chain is stored for a long time, there also exists a problem that stability of a composition with time is low. For this reason, the solvent which is high in safety and excellent in resin solubility, initiator solubility, and time-lapse stability of a resin composition is calculated | required.

Japanese Patent Publication No. 3-1659 Japanese Patent Publication (Pyeong) 4-56973 Japanese Patent Application Laid-Open No. 4-49938

Accordingly, an object of the present invention is a curable resin composition containing a copolymerized resin containing an alicyclic epoxy group in a side chain, and has high safety, excellent resin solubility, and the like, and excellent curability resin composition with time stability. It is providing the hardened | cured material obtained by hardening a manufacturing method and the said curable resin composition.

Another object of the present invention is to provide a curable resin composition capable of forming a coating film (resist film, etc.) having a uniform film thickness and excellent adhesion to a substrate and solvent resistance, a method for producing the curable resin composition, and the curable resin composition. It is providing the hardened | cured material obtained by hardening.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the present inventors found that copolymer resin which has a structural unit containing an alicyclic epoxy group, and a structural unit containing an alkali-soluble group, and curable resin containing dipropylene glycol dimethyl ether as a solvent. It has been found that the composition can solve the above-mentioned problems, and have completed the present invention.

That is, the present invention provides a copolymer comprising a monomer unit corresponding to (A) an alicyclic epoxy group-containing polymerizable unsaturated compound and (B) a monomer unit containing an alkali-soluble group, and dipropylene glycol dimethyl ether in a total of 30 to 100 solvents. It provides the curable resin composition characterized by including the solvent containing mass%.

(A) The alicyclic epoxy group-containing polymerizable unsaturated compound is 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 or 9-yl (meth It may be at least one compound selected from acrylate.

The said copolymer may further contain the monomeric unit corresponding to (C) epoxy group-containing alicyclic polymerizable unsaturated compound.

Moreover, this invention is the process of manufacturing a copolymer using (1) solvent containing dipropylene glycol dimethyl ether as a polymerization solvent, or (2) the solvent of a copolymer containing dipropylene glycol dimethyl ether. It provides the manufacturing method of said curable resin composition characterized by including the process of solvent-exchange.

Moreover, this invention provides the hardened | cured material obtained by hardening | curing the said curable resin composition.

Curable resin composition of this invention is high in safety, excellent in resin solubility, and excellent in aging stability of a composition. According to the curable resin composition of this invention, the coating film (resist film etc.) which is uniform in film thickness and excellent in adhesiveness with respect to a board | substrate and solvent resistance can be formed. In addition, a resist film with a uniform line width and high hardness can be formed.

Curable Resin Composition

The curable resin composition of this invention is a copolymer containing the monomer unit corresponding to the (A) alicyclic epoxy group containing polymerizable unsaturated compound, and the monomer unit containing (B) alkali-soluble group, and dipropylene glycol dimethyl ether as a whole solvent. It is characterized by including a solvent containing 30 to 100 mass% in.

<Copolymer>

The copolymer contained in curable resin composition of this invention contains the monomer unit (structural unit) corresponding to the (A) alicyclic epoxy group containing polymerizable unsaturated compound, and the monomer unit (structural unit) containing (B) alkali-soluble group. Doing.

<(A) Monomer unit corresponding to alicyclic epoxy group containing polymerizable unsaturated compound>

The monomer unit corresponding to an alicyclic epoxy group containing polymeric unsaturated compound can be introduce | transduced in a polymer by adding a corresponding alicyclic epoxy group containing polymeric unsaturated compound to copolymerization.

Examples of the alicyclic epoxy group-containing polymerizable unsaturated compound include 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 2- (3,4-epoxycyclo). Hexyl) ethyl (meth) acrylate, 2- (3, 4- epoxycyclohexyl methyloxy) ethyl (meth) acrylate, 3- (3, 4- epoxycyclohexyl methyloxy) propyl (meth) acrylate, etc. Polymerizable unsaturated compounds ((meth) acrylic acid ester derivative etc.) containing an epoxy-group containing alicyclic carbocyclic ring, such as a 3, 4- epoxycyclohexane ring; A polymerizable unsaturated compound containing a 5,6-epoxy-2-bicyclo [2.2.1] heptane ring such as 5,6-epoxy-2-bicyclo [2.2.1] heptyl (meth) acrylate ((meth ) Acrylic acid ester derivatives); Epoxidized Dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^{2 , 6} ] decane-8-yl (meth) acrylate, or mixtures thereof], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2- (3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] decane-9-yloxy) ethyl (meth) acrylate, 2- (3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl (meth) acrylate, or these Mixture], 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane ring such as epoxidized dicyclopentenyloxybutyl (meth) acrylate and epoxidized dicyclopentenyloxyhexyl (meth) acrylate A polymerizable unsaturated compound ((meth) acrylic acid ester derivative etc.) containing these etc. are mentioned. These may be used alone or in combination of two or more.

As the alicyclic epoxy group-containing polymerizable unsaturated compound, a polymerizable unsaturated compound (such as (meth) acrylic acid ester derivative) containing an epoxy group-containing alicyclic carbocyclic ring such as a 3,4-epoxycyclohexane ring is preferable. , 4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, epoxidized dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo [5.2.1.0 ^{2 , 6} ] decane-9-yl (meth) acrylate, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, or mixtures thereof] is more preferred.

The proportion of monomer units corresponding to the alicyclic epoxy group-containing polymerizable unsaturated compound in the copolymer also varies depending on the type of monomers used and the type of resist (negative or positive type), but usually all monomer units constituting the copolymer. It is 30-95 mass% with respect to, Preferably it is 50-90 mass%, More preferably, it is 60-85 mass%. By making content of the monomeric unit corresponding to an alicyclic epoxy group containing polymeric unsaturated compound into such a range, chemical-resistance (solvent resistance, alkali resistance, etc.) can be improved more mainly.

<(B) Monomer unit containing alkali-soluble group>

The monomer unit containing an alkali soluble group has a function which gives alkali solubility to a polymer. Thereby, a polymer is melt | dissolved in aqueous alkali solution (developer) at the time of image development.

Monomer units containing alkali-soluble groups can be introduced into the polymer by adding a polymerizable unsaturated compound having an alkali-soluble group to the copolymerization. As said alkali-soluble group, the group normally used in the resist field can be used, For example, a carboxyl group, a phenolic hydroxyl group, etc. are mentioned. Typical examples of the polymerizable unsaturated compound having an alkali-soluble group include, but are not limited to, unsaturated carboxylic acids or acid anhydrides thereof, hydroxystyrenes or derivatives thereof. Among these, especially unsaturated carboxylic acid or its acid anhydride is preferable.

As unsaturated carboxylic acid or its acid anhydride, for example, α, β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and acid anhydride thereof (maleic anhydride, itha anhydride) Conic acid, etc.) is illustrated. Among these, acrylic acid and methacrylic acid are particularly preferable. The polymerizable unsaturated compound which has alkali-soluble group can be used individually or in combination of 2 or more.

Although the ratio of the monomer unit containing an alkali-soluble group to a copolymer also changes according to the kind of monomer to be used and the type of resist (negative type or positive type), it is 5-50 mass with respect to the total monomer unit which comprises a copolymer normally. %, Preferably it is 5-40 mass%, More preferably, it is 5-30 mass%. When this ratio is too small, it will be difficult to melt | dissolve with respect to alkaline developing solution, and developability may worsen. On the contrary, when too large, etching resistance after image development may worsen.

<(C) Monomer unit corresponding to epoxy group-containing alicyclic polymerizable unsaturated compound>

The copolymer contained in curable resin composition of this invention may contain the monomer unit (structural unit) corresponding to the (C) epoxy-group-containing alicyclic polymerizable unsaturated compound other than the said monomer unit (A) and (B). .

The monomer unit corresponding to the epoxy group-free alicyclic polymerizable unsaturated compound can be introduced into the polymer by adding the corresponding epoxy group-free alicyclic polymerizable unsaturated compound to the copolymerization. Examples of the alicyclic ring contained in the epoxy group-containing alicyclic polymerizable unsaturated compound include alicyclic hydrocarbon rings having 5 to 20 carbon atoms, may be monocyclic, or may be polycyclic such as condensed ring or temporary exchange. As typical alicyclic hydrocarbon rings, for example, cyclohexane ring, cyclooctane ring, cyclodecane ring, adamantane ring, norbornane ring, norbornene ring, bornan ring, isobornane ring, perhydroindene ring, decalin ring, per Hydrofluorene ring (tricyclo [7.4.0.0 ^3,8 ] tridecane ring), perhydroanthracene ring, tricyclo [5.2.1.0 ^2,6 ] decane ring, tricyclo [4.2.2.1 ^2,5 ] undecane ring And tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodecane ring. Alicyclic hydrocarbon ring is an alkyl group of a methyl group, etc. (for example, C _{1 - 4} alkyl group and the like), which may be protected, a halogen atom, a protecting group such as a chlorine atom, a fluorine atom, a hydroxyl group, an optionally protected oxo group, the protecting group You may have substituents, such as a carboxyl group. As an alicyclic ring, it is preferable that they are polycyclic alicyclic hydrocarbon rings (crosslinkable hydrocarbon rings), such as a tricyclo [5.2.1.0 ^2,6 ] decane ring and an adamantane ring, for example.

As an epoxy-group-containing alicyclic polymerizable unsaturated compound, cyclohexyl (meth) acrylate, cyclohexyl methyl (meth) acrylate, 2- (cyclohexyl) ethyl (meth) acrylate, 2- (cyclohexyl) is mentioned, for example. Polymerizable unsaturated compounds ((meth) acrylic acid ester derivative etc.) containing cyclohexane rings, such as methyloxy) ethyl (meth) acrylate and 3- (cyclohexyl methyloxy) propyl (meth) acrylate; Polymerizable unsaturated compounds (such as (meth) acrylic acid ester derivatives) containing a 2-bicyclo [2.2.1] heptane ring such as 2-bicyclo [2.2.1] heptyl (meth) acrylate; Polymerizable unsaturated compounds (such as (meth) acrylic acid ester derivatives) containing adamantane rings such as 1-adamantyl (meth) acrylate; Dicyclopentanyl (meth) acrylate {tricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate Or mixtures thereof}, dicyclopentenyl (meth) acrylate {tricyclo [5.2.1.0 ^2,6 ] dec-3-en-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] dec-3-en-8-yl (meth) acrylate, or mixtures thereof}, dicyclopentenyloxyethyl (meth) acrylate {2- (tricyclo [5.2.1.0 ^2,6 ] decane- 9-yloxy) ethyl (meth) acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl (meth) acrylate, or mixtures thereof}, dicyclopentenyloxy Polymerizable unsaturated compounds (such as (meth) acrylic acid ester derivatives) containing tricyclo [5.2.1.0 ^2,6 ] decane rings such as butyl (meth) acrylate and dicyclopentenyloxyhexyl (meth) acrylate; Can be mentioned. An epoxy-group-containing alicyclic polymerizable unsaturated compound can be used individually or in combination of 2 or more types.

As an epoxy-group-containing alicyclic polymerizable unsaturated compound, the polymerizable unsaturated compound containing a tricyclo [5.2.1.0 ^2,6 ] decane ring or an adamantane ring is preferable, and dicyclopentenyl (meth) acrylate among these is preferable. And 1-adamantyl (meth) acrylate are preferred.

The ratio which the monomeric unit corresponding to an epoxy-group-containing alicyclic polymerizable unsaturated compound occupies in a copolymer can be suitably selected according to desired performance requirements.

<Other monomer unit>

The copolymer contained in the alicyclic epoxy group-containing curable resin composition of the present invention may contain monomer units other than the above (A), (B) and (C). Such monomeric units can be introduced into the polymer by adding the corresponding polymerizable unsaturated compounds to the copolymerization.

As a polymerizable unsaturated compound corresponding to another monomeric unit, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acryl, for example. acrylate, hexyl (meth) (meth) acrylic acid alkyl esters such as acrylates [for example, (meth) acrylic acid C _{1 - 10} alkyl ester, etc.]; (Meth) acrylic acid ester which has an aromatic cyclic structure in molecules, such as benzyl (meth) acrylate; Styrene compounds such as styrene, vinyltoluene, and α-methylstyrene vinylnaphthalene; Vinyl ether compounds, such as methyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether, are mentioned.

In addition, the radically polymerizable monomer which has a hydrophilic group is contained in the polymerizable unsaturated compound corresponding to another monomeric unit. As a hydrophilic group, a hydroxyl group (except a phenolic thing), a quaternary ammonium group, an amino group, a heterocyclic group, etc. are mentioned, for example. As a specific example of the radically polymerizable monomer which has a hydrophilic group, it has hydroxyl groups, such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, for example. Meth) acrylic acid esters; Methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylic Alkoxy polyalkylene glycol (meth) acrylates, such as the rate; (Meth) acrylic acid ester which has amino groups, such as 2-aminoethyl (meth) acrylate; Heterocyclic compounds (such as nitrogen-containing heterocyclic compounds) which have vinyl groups, such as 2-vinylpyrrolidone, etc. are mentioned.

<Solvent>

Curable resin composition of this invention contains 30-100 mass% of dipropylene glycol dimethyl ether in all the solvent as a solvent. It is preferable that 50-100 mass% of dipropylene glycol dimethyl ether is contained in all the solvent, It is more preferable that 70-100 mass% is contained, It is further more preferable that 80-100 mass% is contained. By making content of dipropylene glycol dimethyl ether into 30-100 mass% in all the solvent, it becomes excellent in the solubility, time-lapse stability, applicability | paintability, sensitivity, developability, the pattern characteristic formed, etc. of curable resin composition, and safety improves.

Dipropylene glycol dimethyl ether has a higher safety for human body than ethylene glycol solvent. For example, the ethylene glycol solvent is subject to a special medical examination, but the propylene glycol solvent is not. In addition, ethylene glycol, which is a decomposition product of ethylene glycol solvents, has high toxicity, but propylene glycol, which is a decomposition product of propylene glycol solvents, is also used in food additives and the like and has high safety.

Content of the dipropylene glycol dimethyl ether with respect to the whole curable resin composition can be 30-80 mass%, for example, Preferably it is 40-80 mass%, More preferably, it can be 50-80 mass%. . By making content of dipropylene glycol dimethyl ether into such a range, the solubility, temporal stability, applicability | paintability, sensitivity, developability, the pattern characteristic formed, etc. of curable resin composition can be made more excellent, and safety can be improved more. .

Curable resin composition of this invention may contain solvent other than dipropylene glycol dimethyl ether as a solvent. As another solvent, For example, ether [diethyl ether; Ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether (such as diethylene glycol dialkyl ether such as diethylene glycol methyl ethyl ether), propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, Dipropylene glycol mono or dialkyl ether (such as dipropylene glycol diC _2-4 alkyl ether such as dipropylene glycol diethyl ether), tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether Chain ethers such as glycol ethers such as 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono, di or trialkyl ether; Tetrahydrofuran, dioxane and like cyclic ethers, etc.], ester (methyl acetate, ethyl acetate, butyl acetate, isoamyl, ethyl lactate, methyl 3-methoxy propionate, ethyl ethoxy propionate, a 3, C _{5 - 6} cycloalkane diol mono- or di-acetates, C _{5 - 6} cycloalkanediyl methanol mono- or di-acetate, and the like of the carboxylic acid esters; glycol monoalkyl ether acetate, ethylene glycol mono- or di-acetate, diethylene glycol monoalkyl ether acetate, Diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1 , 3-propanediol mono or diacetate, 1,3-butanedi Monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, 1,6-hexanediol mono or diacetate, glycerin mono, di or triacetate, glycerin mono- or di-C _{1 - 4} alkyl ether di- or mono-acetates, tripropylene glycol monoalkyl ether acetates, tripropylene glycol mono- or di-glycol acetates or glycol ether acetates, etc.), ketones such as acetate (acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amide (N, N-dimethylacetamide, N, N-dimethylformamide and the like), sulfoxides (dimethyl sulfoxide, etc.), alcohols (methanol, ethanol, propanol, C _{5 - 6} cycloalkane diols, C _{5 - 6} cycloalkanediyl methanol, etc.), hydrocarbons (benzene, toluene, Aliphatic hydrocarbons such as aromatic hydrocarbons, hexane, such as xylene, may be mentioned aliphatic hydrocarbons, etc.), and the like, such as cyclohexane. These may be used alone or in combination of two or more. Among these, mono or dipropylene glycol monoalkyl ether acetates such as mono or dipropylene glycol dialkyl ethers (except dipropylene glycol dimethyl ether) such as dipropylene glycol methyl n-propyl ether, propylene glycol monomethyl ether acetate, and the like This is preferred.

The solvent content with respect to the whole curable resin composition can be 10-80 mass%, for example, Preferably it is 15-80 mass%, More preferably, it can be 20-80 mass%. By setting it as such a range, the solubility, time-lapse stability, applicability | paintability, sensitivity, developability, the pattern characteristic formed, etc. of curable resin composition can be made more excellent, and safety can be improved more.

In the solvent, the weight ratio of the dipropylene glycol dimethyl ether to other solvents (the former: the latter) is 100: 0 to 30:70, preferably 100: 0 to 50:50, more preferably 100: 0 to 70: 30, More preferably, it may be 100: 0 to 80:20. By setting it as such a ratio, it becomes the thing excellent in the solubility, time-lapse stability, applicability | paintability, sensitivity, developability, the pattern characteristic formed, etc. of curable resin composition, and safety improves.

<Method for Producing Copolymer>

The copolymer contained in curable resin composition of this invention is a polymerizable unsaturated compound corresponding to monomeric units (A) and (B), and a polymerizable unsaturated compound corresponding to monomeric unit (C) and other monomers as needed. It can manufacture by adding the monomer mixture containing to copolymerization (vinyl polymerization).

A normal radical initiator can be used as a polymerization initiator used for superposition | polymerization. For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis (2,4-dimethylvaleronitrile), 2,2'- azobis (4-methoxy-2,4 Dimethylvaleronitrile), dimethyl-2,2'-azobis (2-methylpropionate), 2,2'-azobis (isobutyric acid) dimethyl, diethyl-2,2'-azobis (2 -Methyl propionate), azo compounds such as dibutyl-2,2'-azobis (2-methylpropionate), benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate, 1, Organic peroxides, such as 1-bis (t-butylperoxy) cyclohexane, hydrogen peroxide, etc. are mentioned. When using a peroxide as a radical polymerization initiator, it can also be set as a redox initiator by combining a reducing agent. Among the above, azo compounds are preferable, and in particular, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (iso Butyric acid) dimethyl is preferred.

Although the usage-amount of a polymerization initiator can be suitably selected in the range which does not impair smooth copolymerization, Usually, it is about 1-30 mass% with respect to the total amount of all the monomer components and a polymerization initiator, Preferably it is about 5-25 mass%.

In this invention, the chain transfer agent generally used in radical polymerization can also be used together. Specific examples include thiols (n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene Glycol dimercaptan, etc.), thiol acids (mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, thiomalic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphite (sodium hypophosphite) And the like), α-methylstyrene dimer, terpinolene, myrcene, limonene, α-pinene, β-pinene and the like, and the amount of the chain transfer agent is preferably from 0.001 to the total amount of the radical polymerizable monomer. 3 mass%. When using a chain transfer agent, it is preferable to mix with a polymerizable vinyl monomer beforehand.

Polymerization can be performed by the conventional method used when manufacturing a styrene polymer or an acrylic polymer, such as solution polymerization, block polymerization, suspension polymerization, block-suspension polymerization, and emulsion polymerization. Among these, solution polymerization is preferable. The monomer and the polymerization initiator may be collectively supplied to the reaction system, respectively, or a part or all of them may be added dropwise to the reaction system. For example, a method in which a solution obtained by dissolving a polymerization initiator in a polymerization solvent is added dropwise into a mixed solution of a monomer and a polymerization solvent maintained at a constant temperature and polymerized, or a solution in which the monomer and the polymerization initiator are dissolved in a polymerization solvent in advance at a constant temperature. The method of dripping and superposing | polymerizing in the superposition | polymerization solvent hold | maintained by (dripping polymerization method) etc. can be employ | adopted. Polymerization temperature can be suitably selected, for example in the range of about 30-150 degreeC.

The polymerization solvent can be appropriately selected depending on the monomer composition and the like. As the polymerization solvent, the solvents exemplified above can be used. As a polymerization solvent, the solvent containing 30 mass% or more (further 50 mass% or more, especially 80 mass% or more) of dipropylene glycol dimethyl ether is preferable. By using such a polymerization solvent, the process of solvent substitution etc. at the time of manufacture of curable resin composition can be skipped, and a manufacturing process can be simplified more.

The above method produces the copolymer of the present invention. The weight average molecular weight of the copolymer is, for example, 500 to 100000, preferably 1000 to 40000, and more preferably about 2000 to 30000. Dispersion degree (weight average molecular weight Mw / number average molecular weight Mn) of a copolymer is about 1-3.

[Production Method of Curable Resin Composition]

The manufacturing method of curable resin composition of this invention is a process of manufacturing a copolymer using the solvent containing (1) dipropylene glycol dimethyl ether as a polymerization solvent, or (2) the solvent of a copolymer for dipropylene glycol It is characterized by including the process of solvent exchange with the solvent containing dimethyl ether.

In the manufacturing method of curable resin composition of this invention, solid content concentration can be adjusted, a solvent exchange | exchange, or a filtration process can be performed with respect to the polymerization liquid of the copolymer obtained by the said method as needed. It is preferable that content of dipropylene glycol dimethyl ether in the solvent containing dipropylene glycol dimethyl ether is 30 mass% or more (50 mass% or more, especially 80 mass% or more).

In the manufacturing method of curable resin composition of this invention, further, if necessary, a curing catalyst (a thermal acid generator (thermal curing catalyst, a thermal cationic polymerization initiator), a photoacid generator (photocuring catalyst, a photocationic polymerization initiator)], an optical radical initiator , Curing agent, curing accelerator, radiation sensitive component, reactive diluent, additive (crosslinking agent, filler, pigment for coloring, polymerization inhibitor, adhesion imparting agent, antifoaming agent, flame retardant, antioxidant, ultraviolet absorber, low stress agent, flexibility imparting agent , Waxes, resins, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers and the like). Moreover, curable resin composition can also be obtained by refine | purifying the polymer produced | generated by superposition | polymerization by precipitation, reprecipitation, etc., and dissolving this refined polymer with the said suitable additive in a solvent according to a use. As a solvent which comprises curable resin composition, 30-100 mass% dipropylene glycol dimethyl ether with respect to a total solvent, and the solvent illustrated above can be used as another solvent as needed.

As a thermal acid generator among the said hardening catalysts, for example, San Ade SI-45, left-hand SI-47, left-hand SI-60, left-hand SI-60L, left-hand SI-80, left-hand SI-80L, left-hand SI-100, left-hand SI -100L, left-hand SI-145, left-hand SI-150, left-hand SI-160, left-hand SI-110L, left-hand SI-180L (above, Sanshin Kagaku Kogyo Co., Ltd., brand name), CI-2921, CI-2920, CI- 2946, CI-3128, CI-2624, CI-2639, CI-2064 (above, Nihon Soda Co., Ltd. product, brand name), CP-66, CP-77 (Asahi Denka Kogyo Co., Ltd., brand name), FC- Diazonium salt, iodonium salt, sulfonium salt, phosphonium salt, selenium salt, oxonium salt, ammonium salt, etc. represented by 520 (made by 3M, a brand name) etc. can be used.

As a photo-acid generator, for example, Syracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, American Union Carbide company make, brand name), Irgacure 261 (Shiba specialty chemicals company make, brand name), SP-150, SP-151, SP-170, Optome SP-171 (above, Asahi Denka Kogyo Co., Ltd. make, brand name), CG-24-61 (Shiba specialty Chemicals company make, brand name), DAICATII (the Daicel Chemical Industries, Ltd. make, brand name), UVAC1591 [the Daicel Cytec Co., Ltd. make, brand name], CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI-2823, CI-2758 (above, Nippon Soda company make, brand name), PI-2074 (Long Pulsar make, brand name, pentafluorophenyl borate toluyl cumyl iodonium salt), FFC509 (product of 3M company, brand name), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (manufactured by Midori Kagaku Co., Ltd.) , CD-1012 (Sartomer, USA) May be used, product name) diazo typified by such salts, iodonium salts, sulfonium salts, phosphonium salt, selenium salt, oxo salt, ammonium salt and the like.

As an optical radical initiator, For example, benzophenones, such as benzophenone; Acetophenonebenzyl, benzyl dimethyl ketone; Benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; Acetophenones such as dimethoxyacetophenone, dimethoxyphenylacetophenone and diethoxyacetophenone; Diphenyl disulfite, methyl ortho benzoyl benzoate, ethyl 4-dimethylaminobenzoate (Kayakyu EPA manufactured by Nippon Kayaku Co., Ltd.), 2,4-diethyl thioxanthone (Kayakyu DETX manufactured by Nippon Kayaku Co., Ltd.) Etc.], 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropaneone-1 [Ilgacure 907, such as manufactured by Ciba-Geigi Co., Ltd.], tetra (t-butylperoxycar Bonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, 4,4-bisdiethylaminobenzophenone, 2,2'-bis (2-chlorophenyl)- 4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole (B-CIM by Hodogaya Chemical Co., Ltd.) can be used individually or in mixture, A photosensitizer is needed. Can be added. It is preferable to mix | blend a polymerization initiator by 1-10 mass% in curable resin composition.

The addition amount of a curing catalyst is 0.05-10 mass% with respect to the said copolymer (resin powder) in curable resin composition, for example, Preferably it is 0.5-5 mass%. A curing catalyst can be used individually or in combination of 2 or more types.

As said crosslinking agent, a polyfunctional alcohol compound, a polyfunctional thiol compound, etc. can be used.

The polyfunctional alcohol compound may be a compound having two or more hydroxyl groups. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4 Butylene glycol, glycerin, diglycerin, D-glucose, D-glucitol, isoprene glycol, butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, etc. Polyalkylene glycols such as polyhydric alcohols, polyethylene glycols, polypropylene glycols, polybutylene glycols, polytetramethylene glycols, polycaprolactone diols, polycaprolactone triols, polycarbonate diols, and the like. Can be mentioned.

The polyfunctional thiol compound may be a compound having two or more thiol groups. For example, hexanedithiol, decandithiol, 1,4-butanediolbisthiopropionate, 1,4-butanediolbisthioglycolate, ethylene glycol Bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristyopiothionate, trimethylol propane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate , Pentaerythritol tetrakistiopionopionate, trimercaptopropionate tris (2-hydroxyethyl) isocyanurate, 1,4-dimethyl mercaptobenzene, 2,4,6-trimercapto-s-tri Azine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, tetraethylene glycol bis 3-mercaptopropionate, trimethylolpropane tris 3-mercap Propionate, tris (3-mercaptopropynyloxyethyl) isocyanurate, pentaerythritol tetrakis 3-mercaptopropionate, dipentaerythritol tetrakis 3-mercaptopropionate, 1,4 -Bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H ) -Trione, pentaerythritol tetrakis (3-mercaptobutyrate), etc. are mentioned. The polyfunctional alcohol compound and the polyfunctional thiol compounds may be used alone or in combination of two or more.

Examples of the radiation-sensitive component include polyfunctional (meth) acrylates, polyfunctional epoxy compounds, polyfunctional urethane (meth) acrylates, and polyfunctional epoxy (meth) acrylates (a type in which acrylic acid is added to an epoxy group). Can be. You may mix | blend a polyfunctional (meth) acrylate, a thermal or radiation polymerization initiator, a polyfunctional epoxy compound, and a thermal or radiation acid generator in combination. These radiation sensitive components, heat or radiation polymerization initiators, and heat or radiation acid generators may be used alone or in combination of two or more.

As a specific example of polyfunctional (meth) acrylate, di (meth) acryl of dialkyl (meth) acrylates, such as ethylene glycol and propylene glycol, polyalkylene glycol, such as polyethyleneglycol and polypropylene glycol Di (meth) acrylates of both terminal hydroxylated polymers, such as lates, both terminal hydroxypolybutadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone, glycerin, 1,2,4-butane Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as triol, trimethylol alkanes, tetramethylol alkanes, pentaerythritol, dipentaerythritol, polyalkylene glycol adducts of trihydric or higher polyhydric alcohols ( Poly (meth) acrylates of cyclic polyols such as meth) acrylates, 1,4-cyclohexanediol and 1,4-benzenediols, polyester (meth) acrylates and epoxides Oligo (meth) acrylates such as (meth) acrylate, urethane (meth) acrylate, alkyd resin (meth) acrylate, silicone resin (meth) acrylate, spiran resin (meth) acrylate, and the like. . These may be single 1 type or 2 or more types may exist.

As a polyfunctional epoxy compound, for example, a brand name "Celoxide 2021", a brand name "Celoxide 2081", a brand name "Celoxide 3000", a brand name "EHPE3150", a brand name "Epolyd GT401" (above, Daicel Chemical Industries Kogyo Co., Ltd.), a brand name "Epolite 4000" (made by Kyoeisha Chemical Co., Ltd.), etc. can be used. These may exist individually by 1 type and may exist 2 or more types.

The reactive diluent is not particularly limited as long as the copolymer can be dissolved, and for example, a polymerizable vinyl monomer having one or more (meth) acryl groups can be used. The reactive diluent may also function as the radiation sensitive component.

As a reactive diluent, For example, Alkyl or cycloalkyl (meth) acrylate, such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, and octyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; Mono or di (meth) acrylate of ethylene glycol, (meth) acrylate of methoxyethylene glycol, mono or di (meth) acrylate of tetraethylene glycol, mono or di (meth) acrylate of tripropylene glycol, etc. Mono or di (meth) acrylates of glycols; Epoxy group-containing (meth) acrylates such as 3,4-epoxycyclohexylmethyl (meth) acrylate and glycidyl (meth) acrylate; Polyols such as glycerin di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri or tetra (meth) acrylate of pentaerythritol, dipentaerythritol hexaacrylate, or alkylene oxide adducts thereof (meth ) Acrylates and the like.

Among them, as the reactive diluent, a flash point of 100 ° C or higher is preferable from the viewpoint of ensuring safety in the manufacturing process. As the reactive diluent, polyfunctional (meth) acrylates such as polyols such as trimethylolpropane tri (meth) acrylate or (meth) acrylates of alkylene oxide adducts thereof are particularly preferable.

The reactive diluent may be blended in an amount of, for example, 1 to 1000 parts by mass, preferably 50 to 700 parts by mass, and more preferably 100 to 500 parts by mass based on 100 parts by mass of the copolymer.

As a filler added to the curable resin composition of this invention as needed, reactive resins, such as an epoxy resin, barium sulfate, silicon oxide, talc, clay, calcium carbonate, etc. are mentioned. Phthalocyanine green, crystal violet, titanium oxide, carbon black, etc. are mentioned as a coloring pigment. Hydroquinone, hydroquinone monomethyl ether, phenothiazine, etc. are mentioned as a polymerization inhibitor.

Curable resin composition obtained in this way can not only have high adhesiveness with respect to a base material and a board | substrate by hardening, but can also obtain hardened | cured material (hardened film etc.) excellent in chemical-resistance, such as solvent resistance and alkali resistance. For this reason, it is useful also as structural components, such as a coating material, an ink, a coating agent, and an adhesive agent, in addition to the liquid crystal resist material, and can use it especially suitably in the field of electronic materials.

[Cured goods]

The hardened | cured material of this invention can be obtained by hardening the said coating film, for example, after apply | coating the said curable resin composition to various base materials or boards by methods, such as a spin coater and a slit coater, and forming a coating film. Examples of the substrate or substrate include glass, ceramics, silicon wafers, metals, plastics, and the like. Coating by a spin coater, a slit coater, etc. can be performed by a well-known method. The cured product of the present invention is excellent in various physical properties such as substrate adhesion, solvent resistance, hardness, film thickness uniformity, line width uniformity, sensitivity, developability, and formed pattern characteristics.

Curing of a coating film is performed by heating, irradiating and exposing an active energy ray, or heating after exposure. When hardening the said curable resin composition with heat, heating temperature is the range of 50 degreeC-260 degreeC, Preferably it is the range of 80 degreeC-240 degreeC. In addition, when hardening the said curable resin composition with light, the light ray of various wavelengths, for example, ultraviolet-ray, X-ray, g-ray, i-ray, an excimer laser etc. are used for exposure. Although the thickness of the coating film after hardening can be suitably selected according to a use, it is generally 0.1-40 micrometers, Preferably it is 0.3-20 micrometers, More preferably, it is about 0.5-10 micrometers.

[Example]

Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by these Examples.

Synthesis Example 1

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 250 parts by mass of dipropylene glycol dimethyl ether was added and heated to 65 ° C while stirring. Subsequently, 30 parts by mass of methacrylic acid, 60 parts by mass of tricyclo [5.2.1.0 ^2.6 ] decane-8-ylmethacrylate, and 200 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were 70 parts by mass of dipropylene glycol dimethyl ether. It melt | dissolved in the part, the solution was prepared, and the said solution was dripped in the flask heated to 65 degreeC over 4 hours using the dropping funnel. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 220 mass parts of dipropylene glycol dimethyl ethers, the flask over 3 hours using the other dropping funnel. It dripped in the inside. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 65 ° C for 3 hours, and then diluted with 140 parts by mass of dipropylene glycol dimethyl ether, and then cooled to room temperature to obtain a solution of copolymer A. Solid content of the obtained copolymer A solution was 30.8 mass%, the acid value was 75 mg-KOH / g (solid content conversion), the weight average molecular weight Mw was 11,400, and dispersion degree was 2.23.

Synthesis Example 2

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 250 parts by mass of dipropylene glycol dimethyl ether was added and heated to 65 ° C while stirring. Subsequently, 30 parts by mass of methacrylic acid, 60 parts by mass of tricyclo [5.2.1.0 ^2.6 ] decane-8-ylmethacrylate, and 200 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were 70 parts by mass of dipropylene glycol dimethyl ether. It melt | dissolved in the part, the solution was prepared, and the said solution was dripped in the flask heated to 65 degreeC over 4 hours using the dropping funnel. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 220 mass parts of dipropylene glycol dimethyl ethers, the flask over 3 hours using the other dropping funnel. It dripped in the inside. After the dropwise addition of the solution of the polymerization initiator was completed, the mixture was maintained at 65 ° C. for 3 hours, and then diluted with 70 parts by mass of dipropylene glycol dimethyl ether and 70 parts by mass of dipropylene glycol methyl n-propyl ether, and then cooled to room temperature. A solution of copolymer A was obtained. Solid content of the obtained copolymer A solution was 31.1 mass%, the acid value was 71 mg-KOH / g (solid content conversion), the weight average molecular weight Mw was 11,800, and dispersion degree was 2.22.

Synthesis Example 3

Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 110 parts by mass of dipropylene glycol dimethyl ether and 140 parts by mass of propylene glycol monomethyl ether acetate were added and stirred. Heated to 65 ° C. Subsequently, 30 parts by mass of methacrylic acid, 60 parts by mass of tricyclo [5.2.1.0 ^2.6 ] decane-8-ylmethacrylate, and 200 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were produced from propylene glycol monomethyl ether acetate 70 It melt | dissolved in the mass part, the solution was prepared, and the said solution was dripped in the flask kept warm at 65 degreeC over 4 hours using the dropping funnel. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 230 mass parts of dipropylene glycol dimethyl ethers, the flask over 3 hours using the other dropping funnel. It dripped in the inside. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 65 ° C. for 3 hours, and then diluted with 130 parts by mass of propylene glycol monomethyl ether acetate, and then cooled to room temperature to obtain a solution of copolymer A. Solid content of the obtained copolymer A solution was 31.2 mass%, the acid value was 73 mg-KOH / g (solid content conversion), the weight average molecular weight Mw was 10,800, and dispersion degree was 2.16.

Synthesis Example 4

In a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 250 parts by mass of dipropylene glycol dimethyl ether was added and heated to 65 ° C while stirring. Subsequently, 30 parts by mass of methacrylic acid and 260 parts by mass of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8 or 9-ylacrylate were dissolved in 70 parts by mass of dipropylene glycol dimethyl ether to prepare a solution. And the said solution was dripped in the flask heated at 65 degreeC over 4 hours using the dropping funnel. On the other hand, the flask which melt | dissolved 30 mass parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 220 mass parts of dipropylene glycol dimethyl ethers, the flask over 3 hours using the other dropping funnel. It dripped in the inside. After the dropping of the solution of the polymerization initiator was completed, the solution was maintained at 65 ° C. for 3 hours, and then diluted with 140 parts by mass of dipropylene glycol dimethyl ether, and then cooled to room temperature to obtain a solution of copolymer B. Solid content of the obtained copolymer B solution was 29.8 mass%, the acid value was 68 mg-KOH / g (solid content conversion), the weight average molecular weight Mw was 11,100, and dispersion degree was 2.21.

Comparative Synthesis Example 1

In Synthesis Example 1, Copolymer A was synthesized in the same manner as in Synthesis Example 1 except that dipropylene glycol dimethyl ether was changed to propylene glycol monomethyl ether acetate. Solid content of the obtained copolymer A solution was 31.1 mass%, the acid value was 70 mg-KOH / g (solid content conversion), the weight average molecular weight Mw was 11,600, and dispersion degree was 2.33.

Comparative Synthesis Example 2

In Synthesis Example 1, Copolymer A was synthesized in the same manner as in Synthesis Example 1 except that dipropylene glycol dimethyl ether was changed to ethylene glycol monoethyl ether acetate. Solid content of the obtained copolymer A solution was 31.2 mass%, the acid value was 75 mg-KOH / g (solid content conversion), the weight average molecular weight Mw was 11,600, and dispersion degree was 2.26.

Example 1

50 mass parts of trimethylol propane triacrylate and 2 mass parts of "Irgacure 907" by a Shiva-Geigi product were mix | blended with 50 mass parts of copolymer solutions manufactured by the synthesis example 1, and the curable resin composition 1 was manufactured.

Example 2

Curable resin composition 2 was manufactured like Example 1 except having changed the copolymer solution into what was produced by the synthesis example 2.

Example 3

Curable resin composition 3 was manufactured like Example 1 except having changed the copolymer solution into what was produced by the synthesis example 3.

Example 4

Curable resin composition 4 was manufactured like Example 1 except having changed the copolymer solution into what was produced by the synthesis example 4.

Comparative Example 1

Curable resin composition 5 was manufactured like Example 1 except having changed the copolymer solution into what was produced by comparative synthesis example 1.

Comparative Example 2

Curable resin composition 6 was manufactured like Example 1 except having changed the copolymer solution into what was produced by comparative synthesis example 2.

Evaluation test

(1) Preparation of test specimen for evaluation

After apply | coating the copolymer solution (curable resin composition) obtained by each Example and the comparative example to a base material with a spin coater, it heats for 10 minutes with an 80 degreeC hotplate, and heats for 30 minutes in 230 degreeC oven, respectively. An evaluation test piece was produced. A glass plate and a stainless plate were used as a base material.

(2) stability

In each Example and the comparative example, the test piece (base material: glass plate, stainless steel plate) for evaluation was produced similarly to said (1) using the copolymer solution stored for 2 weeks at room temperature.

Compared to the test specimen for evaluation produced using the copolymer solution before storage [above (1)], if the uniform coating film is the same film thickness, the film thickness changes slightly, but if the coating film is almost the same, the film thickness greatly changes. (Triangle | delta) and when it was not able to form a uniform coating film were made into x. Even when the evaluation test piece made of the glass plate was used, the same result was obtained even when the test piece for evaluation made of the stainless plate was used.

(3) adhesion

The adhesiveness was measured by peeling from a base material based on JISK-5600-5-6 using the test piece for evaluation (substrate: glass plate, stainless steel plate) produced in said (1). Moreover, it evaluated based on the following criteria according to the classification prescribed | regulated in "the classification of the Table 1 test result" described in 8.3 of JISK5600-5-6.

(Double-circle): It was "0" of classification of the test result.

(Circle): It was "1" of classification of the test result.

(Triangle | delta): It was "2" of the classification of the test result.

X: It was "3" and "4" of classification of the test result.

(4) solvent resistance

Isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methylpyrrolidone (NMP) were respectively dripped at the test piece for evaluation produced by the glass plate in the Example and the comparative example, and it was left to stand for 10 minutes. After that, it was washed with water, and the place where the solvent was dripped did not change at all. ◎, traces of the solvent remained, but wiped off. ○, traces of the solvent remained. . The same result was obtained also when the test piece for evaluation made from the stainless plate was used.

The results of the evaluation test are shown in Table 1 below. In addition, the unit of a numerical value in Table 1 represents a weight part.

The abbreviation of a solvent in Table 1 shows the following.

DMM: dipropylene glycol dimethyl ether

DPMNP: dipropylene glycol methyl n-propyl ether

MMPGAC: Propylene Glycol Monomethyl Ether Acetate

EGA: ethylene glycol monoethyl ether acetate

As is clear from the table, the curable resin composition of the Example and the cured coating film obtained from this resin composition were excellent also in any of stability, board | substrate adhesiveness, and solvent resistance. On the other hand, the curable resin composition of the comparative example and the cured coating film obtained from this resin composition were inferior in the aspect of stability and adhesiveness.

According to the present invention, while solving the problem of safety of the solvent used, not only the resin solubility, the stability of the composition and the coating property are excellent, but also various physical properties such as sensitivity, developability, and pattern characteristics to be formed when used as a resist material. Excellent curable resin composition is obtained. Since the coating film obtained by hardening this curable resin composition is excellent in various physical properties, such as film thickness uniformity, adhesiveness with respect to a board | substrate, and solvent resistance, it can be used as a coating material, a coating agent, an adhesive agent, etc. other than a resist material, Especially an electronic material It can be used preferably in the field.

Claims (5)

A copolymer comprising a monomer unit corresponding to (A) an alicyclic epoxy group-containing polymerizable unsaturated compound and (B) a monomer unit containing an alkali-soluble group, and dipropylene glycol dimethyl ether containing 30 to 100% by mass in all solvents. Curable resin composition characterized by including a solvent. The polymerizable unsaturated compound containing (A) an alicyclic epoxy group is selected from the group consisting of 3,4-epoxycyclohexylmethyl (meth) acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8. Or at least one compound selected from 9-yl (meth) acrylates. The curable resin composition of Claim 1 or 2 in which the said copolymer further contains the monomeric unit corresponding to the (C) epoxy group-containing alicyclic polymerizable unsaturated compound. (1) Process of manufacturing a copolymer using the solvent containing dipropylene glycol dimethyl ether as a polymerization solvent, or (2) Solvent-exchanging the solvent of a copolymer with the solvent containing dipropylene glycol dimethyl ether. The manufacturing method of curable resin composition of any one of Claims 1-3 characterized by including. Hardened | cured material obtained by hardening | curing curable resin composition of any one of Claims 1-3.