TW201307995A - Curable resin composition containing alicyclic epoxy group, method for preparing the same, and cured article thereof - Google Patents

Abstract

The present invention provides a curable resin composition, which can improve solibilty and stability during preparing resist composition, meanwhile, can increase uniformity of membrane thickness during film formation, uniformity of line width, adhesiveness of resist film during developing, and safety. It is provided a curable resin composition comprising a copolymer and a solvent, wherein said copolymer contains (A) a monomer unit corresponding to polymerizable unsaturated compound containing alicyclic epoxy group, and (B) a monomer unit containing alkali soluble group, and said solvent contains 30 to 100 mass% of dipropylene glycol dimethyl ether with respect to the amount of total solvent.

Description

Curing resin composition containing alicyclic epoxy group, preparation method thereof and cured product thereof

The present invention relates to a lithography for forming active light using a far ultraviolet ray, an electron beam, an ion beam, an X ray or the like in a semiconductor process, or an electronic component such as a liquid crystal display element, an integrated circuit element, a solid state photographic element, or the like. a radiation-sensitive resin used for a material such as an insulating film or a protective film, or a liquid crystal display material (photospacer for liquid crystal display, rib forming material for liquid crystal display, overcoat, color filter) a serocyclic epoxy group-containing curable resin composition used for a liquid crystal resist material, a coating material, a coating agent, an adhesive, or the like for forming a color resist or a TFT insulating film. Method and its hardened material.

In the case of a solvent used for a liquid photoresist (hereinafter, abbreviated as "resist"), various types of solvents have been known, and solubility and coating properties of the photoresist resin composition are considered. The sensitivity, developability, pattern characteristics to be formed, and the like, and a suitable solvent (solvent) are selected and used. As a solvent excellent in properties such as solubility, applicability, and photoresist formation characteristics, for example, ethylene glycol monoethyl ether acetate is known, but it cannot be completely used because it is criticized for its safety to human body. As a solvent for the photoresist, propylene glycol monomethyl ether acetate or the like is generally used as a solvent having high safety (Patent Documents 1 to 3, etc.). Further, as a highly safe solvent, in addition to propylene glycol monomethyl ether acetate, ethyl lactate and methyl-n-amyl ketone are also known.

However, when such a solvent having high safety compared with ethylene glycol monoethyl ether acetate is observed, characteristics such as photoresist formation characteristics and resin solubility are insufficient. For example, in the case of propylene glycol monomethyl ether acetate, when a photoresist is applied onto a substrate to form a film, there is a solvent residual film ratio (refer to a solvent residual ratio in a film after film formation), and a line width is uniform. The problem of the decrease in the adhesion of the photoresist film during development and development. For the reason, propylene glycol monomethyl ether acetate itself is a solvent having a high evaporation rate, but when used as a solvent for a photoresist resin, only the surface evaporation of the coating surface proceeds to form a so-called film on the surface, and thus coating The solvent contained inside the surface becomes difficult to evaporate. Further, propylene glycol monomethyl ether acetate is known to have poor solubility in a resin, solubility in an initiator, and the like, as compared with ethylene glycol monoethyl ether acetate. In addition, in particular, when the curable resin composition containing the copolymer resin having an alicyclic epoxy group in the side chain is stored for a long period of time, there is a problem that the composition has a low stability with time. Therefore, a solvent having high safety, resin solubility, solubility of the initiator, and excellent stability with time of the resin composition is being sought.

Prior technical literature Patent literature

Patent Document 1 Special Fair 3-1659

Patent Document 2 Special Fair No. 4-56973

Patent Document 3 Special Fair No. 4-49938

Accordingly, an object of the present invention is to provide a curable resin composition containing a copolymerized resin having an alicyclic epoxy group in a side chain, which is safe A curable resin composition excellent in stability over time and excellent in resin solubility, and a curable resin composition excellent in stability over time, a method for producing the curable resin composition, and a cured product obtained by curing the curable resin composition.

Further, another object of the present invention is to provide a curable resin composition which can form a coating film (such as a photoresist film) which is uniform in film thickness, excellent in adhesion to a substrate, and solvent resistance, and a method for producing the curable resin composition. And a cured product obtained by curing the curable resin composition.

In order to solve the above problems, the inventors of the present invention have found that a copolymerized resin containing a structural unit containing an alicyclic epoxy group and a structural unit containing an alkali-soluble group, and a dipropylene glycol as a solvent are found. The curable resin composition of the ether ether can solve the above problems, and the present invention has been completed.

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

(A) The polymerizable unsaturated compound containing an alicyclic epoxy group may be selected from 3,4-epoxycyclohexylmethyl (meth) acrylate and 3,4-epoxytricyclo[5.2. A compound of at least one of 1.0 ^2,6 ]癸-8 or 9-yl(meth)acrylate.

The above copolymer may further contain (C) a monomer unit corresponding to an alicyclic polymerizable unsaturated compound not containing an epoxy group.

Moreover, the present invention provides a method for producing the curable resin composition, which comprises the steps of (1) producing a copolymer using a solvent containing dipropylene glycol dimethyl ether as a polymerization solvent, or (2) copolymerizing The solvent of the substance and the solvent containing dipropylene glycol dimethyl ether are used as a solvent exchange step.

Moreover, the present invention provides a cured product obtained by curing the above-mentioned curable resin composition.

The curable resin composition of the present invention has high safety and excellent resin solubility, and is excellent in stability over time of the composition. According to the curable resin composition of the present invention, a coating film (such as a photoresist film) having a uniform film thickness and excellent adhesion to a substrate and solvent resistance can be formed. Further, a photoresist film having uniform line width and high hardness can be formed.

[Formation for implementing the invention] [Curable resin composition]

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

<copolymer>

The copolymer contained in the curable resin composition of the present invention contains (A) a monomer unit (structural unit) containing a polymerizable unsaturated compound containing an alicyclic epoxy group, and (B) an alkali-soluble group. Monomer unit (construction unit).

<(A) corresponds to a monomer unit of a polymerizable unsaturated compound containing an alicyclic epoxy group>

The monomer unit corresponding to the polymerizable unsaturated compound containing an alicyclic epoxy group can be introduced into the polymer by delivering a polymerizable unsaturated compound containing a corresponding alicyclic epoxy group to a copolymerization.

As the polymerizable unsaturated compound containing an alicyclic epoxy group, for example, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl group (A) can be exemplified. Acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, 2-(3,4-epoxycyclohexylmethoxy)ethyl(meth)acrylic acid An epoxy group-containing alicyclic ring such as an ester or a 3,4-epoxycyclohexane ring such as 3-(3,4-epoxycyclohexylmethoxy)propyl (meth)acrylate a carbocyclic unsaturated compound ((meth) acrylate derivative, etc.); 5,6-epoxy-2-bicyclo[2.2.1] heptyl (meth) acrylate, etc. - a polymerizable unsaturated compound of a cyclooxy-2-bicyclo[2.2.1]heptane ring ((meth) acrylate derivative, etc.); epoxidized dicyclopentenyl (meth) acrylate [ 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]non-9-yl(meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]癸-8- (meth) acrylate, or a mixture of such], epoxidized dicyclopentenyloxyethyl (meth) acrylate [2-(3,4-epoxytricyclo[5.2.1.0] ^2,6] dec-9-yloxy) ethyl (meth) propionate Ester, 2- (3,4-epoxy-tricyclo [5.2.1.0 ^2,6] dec-8-oxy) ethyl (meth) acrylate, or mixtures of these], epoxidized Tricyclopentenyloxybutyl (meth) acrylate, epoxidized dicyclopentenyloxyhexyl (meth) acrylate, etc. containing 3,4-epoxytricyclo[5.2.1.0 ^{2, 6} ] A polymerizable unsaturated compound (such as a (meth) acrylate derivative) of an anthracene ring. These may be used alone or in combination of two or more.

In the case of a polymerizable unsaturated compound containing an alicyclic epoxy group, a polymerizable unsaturated compound containing an epoxy group-containing alicyclic carbocyclic ring such as a 3,4-epoxycyclohexane ring (( A methyl) acrylate derivative or the like is preferred, and 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, Epoxylated dicyclopentenyl (meth) acrylate [3,4-epoxytricyclo[5.2.1.0 ^2,6 ]non-9-yl (meth) acrylate, 3,4-ring More preferably, oxytricyclo[5.2.1.0 ^2,6 ]non-8-yl (meth) acrylate, or a mixture thereof.

The ratio of the monomer unit corresponding to the polymerizable unsaturated compound containing an alicyclic epoxy group to the copolymer varies depending on the type of the monomer to be used or the form of the photoresist (negative or positive), usually It is 30 to 95% by mass, preferably 50 to 90% by mass, and more preferably 60 to 85% by mass based on the total monomer unit constituting the copolymer. When the content of the monomer unit corresponding to the polymerizable unsaturated compound containing an alicyclic epoxy group is in such a range, chemical resistance (solvent resistance, alkali resistance, etc.) can be further improved.

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

The monomer unit containing an alkali-soluble group has a function of imparting alkali solubility to the polymer. Thereby, the polymer is dissolved in an aqueous alkali solution (developing solution) at the time of development.

The monomer unit containing an alkali-soluble group can be subjected to copolymerization of a polymerizable unsaturated compound having an alkali-soluble group into a polymer. As the aforementioned alkali-soluble group, a group which is generally used in the field of photoresist, for example, a carboxyl group, a phenolic hydroxyl group or the like can be used. Representative examples of the polymerizable unsaturated compound having an alkali-soluble group include unsaturated carboxylic acids or anhydrides thereof, hydroxystyrene or derivatives thereof, and the like, which are not limited. Among these, in particular, an unsaturated carboxylic acid or an anhydride thereof is preferred.

The unsaturated carboxylic acid or an anhydride thereof may, for example, be an α,β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid or fumaric acid. Its anhydride (maleic anhydride, itaconic anhydride, etc.). Among these, acrylic acid and methacrylic acid are particularly preferred. The polymerizable unsaturated compound having an alkali-soluble group may be used singly or in combination of two or more.

The ratio of the monomer unit containing an alkali-soluble group to the copolymer varies depending on the kind of the monomer to be used or the form of the photoresist (negative or positive), and is usually 5 to the total monomer unit constituting the copolymer. 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the ratio is too small, the alkali developer is difficult to dissolve and the developability is deteriorated. On the contrary, when the ratio is too large, the etching property after development may be deteriorated.

<(C) corresponds to a monomer unit of an alicyclic unsaturated unsaturated compound containing an epoxy group>

The copolymer contained in the curable resin composition of the present invention may contain (C) an alicyclic polymerizable unsaturated compound not containing an epoxy group, in addition to the above monomer units (A) and (B). Monomer unit (construction unit).

The monomer unit corresponding to the non-epoxy group-containing alicyclic polymerizable unsaturated compound can be subjected to copolymerization of a corresponding non-epoxy group-containing alicyclic polymerizable unsaturated compound into a polymer. The alicyclic ring contained in the alicyclic unsaturated polymerizable compound containing an epoxy group may, for example, be an alicyclic hydrocarbon ring having 5 to 20 carbon atoms, and may be a single ring or a fused ring. Multiple rings such as rings or bridge rings. As the alicyclic hydrocarbon ring represented, for example, a cyclohexane ring, a cyclooctane ring, a cyclodecane ring, an adamantane ring, and a descending ring are exemplified. Alkane ring Olefin, Alkane ring Alkane ring, perhydroindene ring, decahydronaphthalene ring, perhydroindole ring (tricyclo[7.4.0.0 ^3,8 ] tridecane ring), perhydroindole ring, tricyclic ring [5.2.1.0 ^{2, 6} ] decane ring, tricyclo[4.2.2.1 ^2,5 ] undecane ring, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodecane ring. The alicyclic hydrocarbon ring may have an alkyl group such as a methyl group (for example, a C _1-4 alkyl group or the like), a halogen atom such as a chlorine atom or a fluorine atom, a hydroxyl group which may be protected by a protective group, a pendant oxy group, and may be protected. A substituent such as a carboxyl group protected by a group. As the alicyclic ring, for example, a polycyclic alicyclic hydrocarbon ring (bridged cyclic hydrocarbon ring) such as a tricyclo[5.2.1.0 ^2,6 ]decane ring or an adamantane ring is preferred.

With respect to the alicyclic polymerizable unsaturated compound not containing an epoxy group, for example, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, 2-(cyclohexyl)ethyl group can be exemplified. a cyclohexane ring containing (meth) acrylate, 2-(cyclohexylmethoxy)ethyl (meth) acrylate, 3-(cyclohexyl methoxy) propyl (meth) acrylate, etc. Polymerizable unsaturated compound ((meth) acrylate derivative, etc.); polymerizable property of 2-bicyclo[2.2.1] heptane ring such as 2-bicyclo[2.2.1]heptyl (meth) acrylate Unsaturated compound (such as a (meth) acrylate derivative); a polymerizable unsaturated compound containing adamantane ring such as 1-adamantyl (meth) acrylate (such as a (meth) acrylate derivative) Dicyclopentanyl (meth) acrylate {tricyclo[5.2.1.0 ^2,6 ]癸-9-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]癸-8-yl (Meth) acrylate, or a mixture of such}, dicyclopentenyl (meth) acrylate {tricyclo[5.2.1.0 ^2,6 ]non-3-ene-9-yl (meth)acrylic acid Ester, tricyclo[5.2.1.0 ^2,6 ]non-3-en-8-yl (meth) acrylate, or a mixture of these, Pentenyloxyethyl (meth) acrylate {2-(tricyclo[5.2.1.0 ^2,6 ]non-9-oxy)ethyl (meth) acrylate, 2-(tricyclic [5.2. 1.0 ^2,6 ]癸-8-oxy)ethyl(meth)acrylate, or a mixture of such}, dicyclopentenyloxybutyl (meth) acrylate, dicyclopentenyloxyhexyl A polymerizable unsaturated compound (such as a (meth) acrylate derivative) containing a tricyclo[5.2.1.0 ^2,6 ]nonane ring such as (meth) acrylate. The alicyclic polymerizable unsaturated compound which does not contain an epoxy group can be used individually or in combination of 2 or more types.

In the case of an alicyclic polymerizable unsaturated compound not containing an epoxy group, a polymerizable unsaturated compound containing a tricyclo[5.2.1.0 ^2,6 ]nonane ring or an adamantane ring is preferred, wherein A cyclopentenyl (meth) acrylate or 1-adamantyl (meth) acrylate is preferred.

The ratio of the copolymer of the monomer unit corresponding to the alicyclic polymerizable unsaturated compound containing no epoxy group can be appropriately selected depending on the desired properties.

<Other monomer units>

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

Examples of the polymerizable unsaturated compound corresponding to other monomer units include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylate. (meth)acrylic acid alkyl ester such as ester, amyl (meth)acrylate, hexyl (meth)acrylate [for example, C _1-10 alkyl (meth)acrylate, etc.]; (meth)acrylic acid a (meth) acrylate having an aromatic cyclic structure in a molecule such as a benzyl ester; a styrene compound such as styrene, vinyl toluene or α-methylstyrene vinyl naphthalene; methyl vinyl ether; A vinyl ether compound such as butyl vinyl ether or phenyl vinyl ether.

Further, the polymerizable unsaturated compound corresponding to another monomer unit also contains a radical polymerizable monomer having a hydrophilic group. The hydrophilic group may, for example, be a hydroxyl group (except for a phenolic one), a fourth-order ammonium group, an amine group, a heterocyclic group or the like. Specific examples of the radical polymerizable monomer having a hydrophilic group include, for example, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate. And other (meth) acrylates having a hydroxyl group; methoxydiethylene glycol (meth) acrylate, ethoxy diethylene glycol (meth) acrylate, isooctyloxy diethylene glycol Alkoxy polyalkylene glycol (meth) acrylate such as (meth) acrylate, methoxy triethylene glycol (meth) acrylate or methoxy polyethylene glycol (meth) acrylate a (meth) acrylate having an amine group such as 2-aminoethyl (meth)acrylate; a heterocyclic compound having a vinyl group such as 2-vinylpyrrolidone (nitrogen-containing heterocyclic compound) and many more.

<Solvent>

The curable resin composition of the present invention contains 30 to 100% by mass of dipropylene glycol dimethyl ether as a solvent in the total solvent. The dipropylene glycol dimethyl ether is preferably 50 to 100% by mass in the total solvent, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass. By setting the content of the dipropylene glycol dimethyl ether to 30 to 100% by mass in the total solvent, the solubility, the stability over time, the coatability, the sensitivity, the developability, the formed pattern characteristics, and the like of the curable resin composition are obtained. It is excellent and its safety is high.

Dipropylene glycol dimethyl ether is safer to humans than glycol-based solvents. For example, a glycol-based solvent is a subject for special health diagnosis, but a propylene glycol-based solvent is not a target. Further, ethylene glycol which is a decomposition product of a glycol-based solvent is highly toxic, but propylene glycol which is a decomposition product of a propylene glycol-based solvent can be used for food additives and the like, and is highly safe.

The content of the dipropylene glycol dimethyl ether relative to the entire curable resin composition can be, for example, 30 to 80% by mass, preferably 40 to 80% by mass, and more preferably 50 to 80% by mass. When the content of the dipropylene glycol dimethyl ether is in such a range, the solubility, the stability over time, the coatability, the sensitivity, the developability, and the pattern characteristics to be formed of the curable resin composition are excellent, and Security can be improved.

The curable resin composition of the present invention may contain a solvent other than dipropylene glycol dimethyl ether as a solvent. As the other solvent, for example, ether [diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether (diethylene glycol methyl ethyl ether, etc.) can be exemplified. Diethylene glycol dialkyl ether, etc.), propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether (dipropylene glycol diethyl ether, etc. dipropylene glycol di C _{2- 4} alkyl ether, etc.), tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol single Or a chain ether of a glycol ether such as a dialkyl ether or a glycerol mono-, di- or trialkyl ether; tetrahydrofuran, two a cyclic ether such as an alkane, etc.], an ester (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, 3-ethoxypropionic acid a carboxylate such as an ester, a C _5-6 cycloalkane mono or diacetate, a C _5-6 cycloalkanediethanol mono or diacetate; an ethylene glycol monoalkyl ether acetate, B Diol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, two Propylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol 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, glycerol mono, di or triacetate, glycerol mono or di C _1-4 alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether Acetate, ethylene glycol ester such as tripropylene glycol mono- or diacetate or glycol ether acetate, etc.), ketone (acetone, methyl group) Ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc., decylamine (N,N-dimethylacetamide, N,N-dimethylformamide, etc.), hydrazine (dimethyl hydrazine, etc.), alcohol (methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 naphthenic dimethanol) And the like, a hydrocarbon (an aromatic hydrocarbon such as benzene, toluene or xylene, an aliphatic hydrocarbon such as hexane or the like, or an alicyclic hydrocarbon such as cyclohexane). These may be used alone or in combination of two or more. Among these, mono or dipropylene glycol monoalkane such as dipropylene glycol methyl n-propyl ether or the like, such as mono- or dipropylene glycol dialkyl ether (excluding dipropylene glycol dimethyl ether) or propylene glycol monomethyl ether acetate. Alkyl ether acetate or the like is preferred.

The content of the solvent relative to the entire curable resin composition is, for example, 10 to 80% by mass, preferably 15 to 80% by mass, and more preferably 20 to 80% by mass. By setting it in such a range, the solubility, the stability with time, the coatability, the sensitivity, the developability, the pattern characteristics to be formed, and the like of the curable resin composition can be made more excellent, and the safety can be made higher.

The weight ratio of dipropylene glycol dimethyl ether to other solvent in the solvent (the former: the latter) may be 100:0 to 30:70, preferably 100:0 to 50:50, more preferably 100:0 to 70: 30, and more preferably 100:0~80:20. By making such a ratio, the solubility, the stability over time, the coatability, the sensitivity, the developability, the pattern characteristics to be formed, and the like of the curable resin composition are more excellent, and the safety is improved.

<Method for producing copolymer>

The copolymer contained in the curable resin composition of the present invention can be obtained by including a polymerizable unsaturated compound containing the corresponding monomer units (A) and (B), and a monomer unit (C) necessary for the reaction, and other The monomer mixture of the monomeric polymerizable unsaturated compound is produced by copolymerization (vinyl polymerization).

As the polymerization initiator used in the polymerization, a usual radical initiator can be used. 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(isobutyrate) dimethyl ester, two Azo compound such as ethyl-2,2'-azobis(2-methylpropionate), dibutyl-2,2'-azobis(2-methylpropionate), peroxidation Organic peroxide such as benzamidine, laurate, t-butylperoxypivalate, 1,1-bis(t-butylperoxy)cyclohexane, hydrogen peroxide Wait. In the case where a peroxide is used as the radical polymerization initiator, a reducing agent may be combined to serve as a redox-type initiator. Among the above, an azo compound is preferred, especially 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-even Nitrogen bis(isobutyrate) dimethyl ester is preferred.

The amount of the polymerization initiator to be used can be appropriately selected within the range which does not impair the smooth copolymerization, but it is usually about 1 to 30% by mass, preferably about 1 to 30% by mass based on the total of the total monomer component and the polymerization initiator. It is about 5 to 25 mass%.

In the present invention, it can also be used in combination with a chain transfer agent generally used in radical polymerization. Specific examples thereof include mercaptans (n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol , mercaptopropanol, triethylene glycol dithiol, etc.), thiol acids (mercaptopropionic acid, thiobenzoic acid, thioglycolic acid, sulfur malic acid, etc.), alcohols (isopropyl alcohol, etc.), amines (dibutylamine, etc.), hypophosphites (sodium hypophosphite, etc.), α-methylstyrene dimer, terpinolene, myrcene, limonene, α- The amount of the chain transfer agent, such as terpene or β-pinene, is preferably 0.001 to 3% by mass based on the total amount of the radical polymerizable monomer. In the case of using a chain transfer agent, it is preferred to mix it with a polymerizable vinyl monomer in advance.

The polymerization can be carried out by a conventional method used for producing a styrene polymer or an acrylic polymer such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization or emulsion polymerization. Among these, solution polymerization is preferred. Each of the monomer and the polymerization initiator may be supplied to the reaction system at the same time, or a part or all of it may be added dropwise to the reaction system. For example, a method in which a solution of a polymerization solvent in which a polymerization initiator is dissolved is added dropwise to a mixture of a monomer and a polymerization solvent maintained at a certain temperature may be used; or a monomer or a polymerization initiator may be previously used. The solution dissolved in the polymerization solvent is added dropwise to a polymerization solvent maintained at a constant temperature to be polymerized (drop polymerization method). The polymerization temperature can be suitably selected, for example, in the range of about 30 to 150 °C.

The polymerization solvent can be appropriately selected depending on the monomer composition and the like. As the polymerization solvent, the above-exemplified solvent can be used. The polymerization solvent is preferably a solvent containing 30% by mass or more of dipropylene glycol dimethyl ether (more preferably 50% by mass or more, particularly preferably 80% by mass or more). By using such a polymerization solvent, the treatment such as solvent replacement can be omitted in the production of the curable resin composition, and the production steps can be further simplified.

The copolymer of the present invention is produced according to the above method. The weight average molecular weight of the copolymer is, for example, 500 to 100,000, preferably 1,000 to 40,000, more preferably about 2,000 to 30,000. The degree of dispersion (weight average molecular weight Mw / number average molecular weight Mn) of the copolymer is about 1 to 3.

[Method for Producing Curable Resin Composition]

The method for producing a curable resin composition of the present invention is characterized by comprising (1) a step of producing a copolymer using a solvent containing dipropylene glycol dimethyl ether as a polymerization solvent, or (2) preparing a solvent and a copolymer of the copolymer A solvent exchange step for solvent exchange of propylene glycol dimethyl ether.

According to the method for producing a curable resin composition of the present invention, the polymerization liquid of the copolymer obtained by the above method can be adjusted by adjusting the solid content concentration, performing solvent exchange, and applying a filtration treatment. The content of the dipropylene glycol dimethyl ether in the solvent containing dipropylene glycol dimethyl ether is preferably 30% by mass or more (more preferably 50% by mass or more, particularly preferably 80% by mass or more).

According to the method for producing a curable resin composition of the present invention, a curing catalyst can be further blended as necessary [thermal acid generator (thermosetting catalyst, thermal cationic polymerization initiator), photoacid generator (photohardening contact) Medium, photocationic polymerization initiator), photoradical initiator, hardener, hardening accelerator, radiation sensitive component, reactive diluent, additive (crosslinking) Agent, filler, pigment for coloring, polymerization inhibitor, adhesion imparting agent, antifoaming agent, flame retardant, oxidation inhibitor, ultraviolet absorber, low stress agent, flexibility imparting agent, wax, resin , cross-linking agent, halogen scavenger, leveling agent, wetting improver, etc.). Further, the polymer produced by precipitation or reprecipitation polymerization is purified, and the purified polymer is dissolved in a solvent together with the above-mentioned suitable additive to obtain a curable resin composition. In the solvent constituting the curable resin composition, 30 to 100% by mass of dipropylene glycol dimethyl ether can be used for the total solvent, and the above-exemplified solvent which is another solvent can be used as necessary.

Among the aforementioned hardening catalysts, for the thermal acid generator, for example, San-Aid SI-45, San-Aid SI-47, San-Aid SI-60, San-Aid SI-60L, San-Aid SI can be used. -80, San-Aid SI-80L, San-Aid SI-100, San-Aid SI-100L, San-Aid SI-145, San-Aid SI-150, San-Aid SI-160, San-Aid SI- 110L, San-Aid SI-180L (above, Sanxin Chemical Industry Co., Ltd., trade name), CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 ( The diazonium salt represented by the above-mentioned products of Japan, Co., Ltd., product name, CP-66, CP-77 (product of Asahi Denki Chemical Co., Ltd., product name), FC-520 (product of 3M company, trade name) , barium salts, barium salts, barium salts, selenium salts, oxonium salts, ammonium salts, and the like.

As the photoacid generator, for example, Cyracure UVI-6970, Cyracure UVI-6974, Cyracure UVI-6990, Cyracure UVI-950 (above, trade name, manufactured by Union Carbide, USA), Irgacure 261 (Ciba Speciality Chemicals) can be used. Company system, trade name) , SP-150, SP-151, SP-170, Optomer SP-171 (above, manufactured by Asahi Kasei Kogyo Co., Ltd., trade name), CG-24-61 (manufactured by Ciba Speciality Chemicals, trade name), DAICATII ( Daicel Chemical Industry Co., Ltd., trade name), UVAC1591 [Daicel‧CYTEC Co., Ltd., trade name], CI-2064, CI-2639, CI-2624, CI-2481, CI-2734, CI-2855, CI -2823, CI-2758 (above, product of Japan Soda Corporation, trade name), PI-2074 (manufactured by Rhône-Poulenc, trade name, pentafluorophenyl borate tolyl fenyl sulfonium salt), FFC509 (3M company) Product, trade name), BBI-102, BBI-101, BBI-103, MPI-103, TPS-103, MDS-103, DTS-103, NAT-103, NDS-103 (manufactured by Midori Chemical Co., Ltd., trade name) And diazonium salt, sulfonium salt, sulfonium salt, sulfonium salt, selenium salt, oxonium salt, ammonium salt, etc. represented by CD-1012 (manufactured by Sartomer Co., Ltd., trade name).

As the photoradical initiator, for example, benzophenones such as benzophenone may be used alone; acetophenone, benzyldimethyl ketone; benzoin, benzoin A Benzoin such as benzyl ether, benzoin ethyl ether, benzoin isopropyl ether; dimethoxyacetamidine, dimethoxyphenyl acetophenone, diethoxy acetophenone, etc. Benzene benzene; diphenyl di sulfite, methyl phthalate benzoate, ethyl 4-dimethylamino benzoate [Kayacure EPA, etc. made by Nippon Kayaku Co., Ltd.], 2, 4-Diethylthioxanthone [Kayacure DETX, etc. made by Nippon Kayaku Co., Ltd.], 2-methyl-1-[4-(methyl)phenyl]-2- Phytylacetone-1 [Irgacure 907, etc., manufactured by Ciba-Geigy Co., Ltd.], tetrakis(t-butylperoxycarbonyl)benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl -propan-1-one, 4,4-bisdiethylaminobenzophenone, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl- 1,2'-diimidazolyl [B-CIM, etc. manufactured by Toya Chemical Co., Ltd.] or a mixture may be used, and a photosensitizer may be added as necessary. It is preferred that the polymerization initiator is blended in the curable resin composition at a ratio of from 1 to 10% by mass.

The amount of the curing catalyst added is, for example, 0.05 to 10% by mass, preferably 0.5 to 5% by mass, based on the copolymer (resin fraction) in the curable resin composition. The curing catalyst can be used singly or in combination of two or more.

As the crosslinking agent, a polyfunctional alcohol compound, a polyfunctional thiol compound, or the like can be used.

The polyfunctional alcohol compound may be a compound having two or more hydroxyl groups, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and 1,3-butyl. Alcohol, 1,4-butanediol, glycerin, diglycerin, D-glucose, d-glucitol, isoprene diol, butanediol, 1,5-pentanediol, 1,6 - Polyols such as hexanediol, 1,9-nonanediol, neopentyl glycol, etc.; polyethylene glycols, polypropylene glycols, polytetramethylene glycols, polytetramethylene glycols, etc. Alkanediols; polycaprolactone glycols, polycaprolactone triols, polycarbonate glycols, and the like.

The polyfunctional thiol compound may be a compound having two or more thiol groups, and examples thereof include hexane dithiol, decane dithiol, and 1,4-butanediol disulfide. Propionate, 1,4-butanediol dithioacetate, ethylene glycol dithioacetate, ethylene glycol dithiopropionate, trimethylolpropane trithiol acetate, three Hydroxymethylpropane trithiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol thiol acetate, pentaerythritol thiopropionate, tris-propionic acid tris(2-hydroxyethyl) Trimeric isocyanate, 1,4-dimethylnonylbenzene, 2,4,6-trimethyl-s-three , 2-(N,N-dibutylamino)-4,6-dimercapto-s-three , tetraethylene glycol bis 3-mercaptopropionate, trimethylolpropane tris 3-mercaptopropionate, tris(3-decylpropargyloxyethyl) trimer isocyanate, pentaerythritol 肆 3-mercaptopropionic acid Ester, dipentaerythritol 肆 3-mercaptopropionate, 1,4-bis(3-mercaptobutyloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3, 5-three -2,4,6(1H,3H,5H)-trione, pentaerythritol bismuth (3-mercaptobutyrate), and the like. The polyfunctional alcohol compound or the polyfunctional thiol compound may be present alone or in combination of two or more.

The above-mentioned radiation-sensitive component may, for example, be a polyfunctional (meth) acrylate, a polyfunctional epoxy compound, a polyfunctional urethane (meth) acrylate, or a polyfunctional epoxy group ( Methyl) acrylate (in the form of an epoxy group-added acrylic acid) or the like. It is also possible to combine a polyfunctional (meth) acrylate with a thermal or radiation polymerization initiator, a polyfunctional epoxy compound, and a thermal or radiation acid generator. These radiation-sensitive components, or a heat or radiation polymerization initiator, a heat or a radiation acid generator may be used alone or in combination of two or more.

Specific examples of the polyfunctional (meth) acrylate include poly(ethylene) acrylates such as ethylene glycol and propylene glycol, and polyethylene glycol, polypropylene glycol, and the like. Two (terminal) hydroxylated polymers of alkanediol di(meth)acrylates, two terminal hydroxyl polybutadienes, two terminal hydroxyl polyisoprene, two terminal hydroxyl polycaprolactones, etc. a poly(methyl group) of a trivalent or higher polyvalent alcohol such as acrylate, glycerin, 1,2,4-butanetriol, trimethylolane alkane, tetramethylolalkane, pentaerythritol or dipentaerythritol a poly(meth)acrylate, a 1,4-cyclohexanediol, a 1,4-benzenediol, etc. of an alkylene oxide adduct of an acrylate or a trivalent or higher polyvalent alcohol Poly(meth) acrylates of polycyclic alcohols, poly Ester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, alkyd (meth) acrylate, decyl (meth) acrylate An oligo (meth) acrylate such as a spirane resin (meth) acrylate. These may be used alone or in combination of two or more.

For the polyfunctional epoxy compound, for example, the trade name "CELLOXIDE 2021", trade name "CELLOXIDE 2081", trade name "CELLOXIDE 3000", trade name "EHPE 3150", trade name "EPOLEAD GT401" (above) can be used. , manufactured by Daicel Chemical Industry Co., Ltd., trade name "EPOLIGHT 4000" (manufactured by Kyoeisha Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The reactive diluent is not particularly limited as long as it can dissolve the copolymer. For example, a polymerizable vinyl monomer having one or more (meth)acrylic groups can be used. Further, the reactive diluent may also function as the aforementioned radiation sensitive component.

With regard to the reactive diluent, specifically, for example, an alkyl group or a naphthene such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate or the like can be exemplified. a hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate; or a single or two ethylene glycol (meth) acrylate, (meth) acrylate of methoxy glycol, mono or di (meth) acrylate of tetraethylene glycol, mono or di (meth) acrylate of tripropylene glycol, etc. a mono- or di(meth)acrylate of a diol; an epoxy group-containing (3,4-epoxycyclohexylmethyl (meth) acrylate, a glycidyl (meth) acrylate, etc. Acrylate; glycerol di(meth) acrylate, trimethylol A polyhydric alcohol such as propane tri(meth)acrylate, tris or tetra(meth)acrylate of pentaerythritol, dipentaerythritol hexaacrylate or the like, or a (meth) acrylate of an alkylene oxide adduct thereof.

Among them, in the case of the reactive diluent, it is preferable that the ignition point is 100 ° C or more, and the safety is ensured in the manufacturing step. Further, in the case of the reactive diluent, polyfunctionality such as a polyol such as trimethylolpropane tri(meth)acrylate or a (meth) acrylate of an alkylene oxide adduct thereof ( Methyl) acrylate is particularly preferred.

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

The filler to be added as necessary in the curable resin composition of the present invention may, for example, be a reactive resin such as an epoxy resin, barium sulfate, cerium oxide, talc, clay or calcium carbonate. Examples of the pigment for coloring include phthalocyanine green, crystal violet, titanium oxide, carbon black, and the like. As the polymerization inhibiting agent, hydroquinone, hydroquinone monomethyl ether, and thiophene can be exemplified. Wait.

The curable resin composition thus obtained has high adhesion to the substrate or the substrate via curing, and a cured product (hardened film or the like) excellent in chemical resistance such as solvent resistance or alkali resistance can be obtained. Therefore, in addition to materials for liquid crystal photoresists, it is also used as a constituent component of paints, inks, coating agents, adhesives, and the like, and is particularly suitable for use in the field of electronic materials.

[hardened material]

The cured product of the present invention can be applied, for example, to a curable resin composition by a spin coater or a slit coater. After the coating film is formed on various substrates or substrates, the coating film is cured and obtained. Examples of the substrate or the substrate include glass, ceramics, tantalum wafers, metals, plastics, and the like. This can be carried out by a known method of coating such as a spin coater or a slit coater. The cured product of the present invention is excellent in physical properties such as substrate adhesion, solvent resistance, hardness, film thickness uniformity, line width uniformity, sensitivity, developability, and formed pattern characteristics.

The hardening of the coating film is carried out by heating or irradiation with an active energy ray, or by heating after exposure. In the case where the curable resin composition is cured by heat, the heating temperature is in the range of 50 ° C to 260 ° C, preferably in the range of 80 ° C to 240 ° C. Further, in the case where the curable resin composition is cured by light, light of various wavelengths such as ultraviolet rays, X rays, g lines, i-line, excimer laser or the like is used for exposure. The thickness of the coating film after hardening can be appropriately selected depending on the application, but it is usually 0.1 to 40 μm, preferably 0.3 to 20 μm, more preferably about 0.5 to 10 μm.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to the examples.

Synthesis Example 1

In a 1 L flask equipped with a flow cooler, a dropping funnel, and a stirrer, nitrogen gas was introduced at 0.02 L/min to prepare a nitrogen atmosphere, and 250 parts by mass of dipropylene glycol dimethyl ether was placed, and the mixture was heated to 65 ° C while stirring. Next, 30 parts by mass of methacrylic acid, 60 parts by mass of tricyclo[5.2.1.0 ^2.6 ]癸-8-yl methacrylate, and 200 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were dissolved. A solution was prepared by dissolving 70 parts by mass of dipropylene glycol dimethyl ether, and the solution was added dropwise to a flask kept at 65 ° C for 4 hours using a dropping funnel. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 220 parts by mass of dipropylene glycol dimethyl ether, and another drop was used. The funnel was added dropwise to the flask over 3 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept 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 the copolymer A. The obtained copolymer A solution had a solid content of 30.8 mass%, an acid value of 75 mg-KOH/g (as a solid content), a weight average molecular weight Mw of 11,400, and a degree of dispersion of 2.23.

Synthesis Example 2

In a 1 L flask equipped with a flow cooler, a dropping funnel, and a stirrer, nitrogen gas was introduced at 0.02 L/min to prepare a nitrogen atmosphere, and 250 parts by mass of dipropylene glycol dimethyl ether was placed, and the mixture was heated to 65 ° C while stirring. Next, 30 parts by mass of methacrylic acid, 60 parts by mass of tricyclo[5.2.1.0 ^2.6 ]癸-8-yl methacrylate, and 200 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were dissolved. A solution was prepared by dissolving 70 parts by mass of dipropylene glycol dimethyl ether, and the solution was added dropwise to a flask kept at 65 ° C for 4 hours using a dropping funnel. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 220 parts by mass of dipropylene glycol dimethyl ether, and another drop was used. The funnel was added dropwise to the flask over 3 hours. After completion of the dropwise addition of the solution of the polymerization initiator, it was kept 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. The obtained copolymer A solution had a solid content of 31.1% by mass, an acid value of 71 mg-KOH/g (as a solid content), a weight average molecular weight Mw of 11,800, and a degree of dispersion of 2.22.

Synthesis Example 3

In a 1 L flask equipped with a flow cooler, a dropping funnel, and a stirrer, nitrogen gas was introduced at 0.02 L/min to prepare 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 placed. Heat to 65 ° C while stirring. Next, 30 parts by mass of methacrylic acid, 60 parts by mass of tricyclo[5.2.1.0 ^2.6 ]癸-8-yl methacrylate, and 200 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate were dissolved. A solution was prepared by using 70 parts by mass of propylene glycol monomethyl ether acetate, and the solution was added dropwise to a flask kept at 65 ° C for 4 hours using a dropping funnel. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 230 parts by mass of dipropylene glycol dimethyl ether, and another drop was used. The funnel was added dropwise to the flask over 3 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept 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 the copolymer A. The solid content of the obtained copolymer A solution was 31.2% by mass, the acid value was 73 mg-KOH/g (in terms of solid content), the weight average molecular weight Mw was 10,800, and the degree of dispersion was 2.16.

Synthesis Example 4

In a 1 L flask equipped with a flow cooler, a dropping funnel, and a stirrer, nitrogen gas was introduced at 0.02 L/min to prepare a nitrogen atmosphere, and 250 parts by mass of dipropylene glycol dimethyl ether was placed, and the mixture was heated to 65 ° C while stirring. Next, 30 parts by mass of methacrylic acid and 260 parts by mass of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]癸-8 or 9-yl acrylate are dissolved in 70 parts by mass of dipropylene glycol dimethyl ether. The solution was prepared, and the solution was added dropwise to a flask maintained at 65 ° C for 4 hours using a dropping funnel. On the other hand, 30 parts by mass of a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in a solution of 220 parts by mass of dipropylene glycol dimethyl ether, and another drop was used. The funnel was added dropwise to the flask over 3 hours. After completion of the dropwise addition of the solution of the polymerization initiator, the mixture was kept 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 the copolymer B. The obtained copolymer B solution had a solid content of 29.8% by mass, an acid value of 68 mg-KOH/g (as a solid content), a weight average molecular weight Mw of 11,100, and a degree of dispersion of 2.21.

Comparative Synthesis Example 1

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

Comparative Synthesis Example 2

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

Example 1

In 50 parts by mass of the copolymer solution produced in Synthesis Example 1, 50 parts by mass of trimethylolpropane triacrylate and 2 parts by mass of "Irgacure 907" manufactured by Ciba-Geigy as a starter were blended to prepare a curable resin. Matter 1.

Example 2

The curable resin composition 2 was prepared in the same manner as in Example 1 except that the copolymer solution was changed to the one produced in Synthesis Example 2.

Example 3

The curable resin composition 3 was prepared in the same manner as in Example 1 except that the copolymer solution was changed to the one produced in Synthesis Example 3.

Example 4

The curable resin composition 4 was prepared in the same manner as in Example 1 except that the copolymer solution was changed to the one produced in Synthesis Example 4.

Comparative example 1

The curable resin composition 5 was prepared in the same manner as in Example 1 except that the copolymer solution was changed to the manufacturer of Comparative Synthesis Example 1.

Comparative example 2

The curable resin composition 6 was prepared in the same manner as in Example 1 except that the copolymer solution was changed to the manufacturer of Comparative Synthesis Example 2.

Evaluation test (1) Production of test pieces for evaluation

The copolymer solution (curable resin composition) obtained in each of the examples and the comparative examples was applied to a substrate by a spin coater, and then heated at 80 ° C for 10 minutes under hot pressing, and then heated in an oven at 230 ° C. Test pieces for each evaluation were prepared in minutes. As the substrate, a glass plate and a stainless steel plate are used.

(2) Stability

In each of the examples and the comparative examples, a copolymer test solution which was stored at room temperature for 2 weeks was used, and a test piece for evaluation (base material: glass plate, stainless steel plate) was produced in the same manner as in the above (1).

In comparison with the test piece for evaluation [the above (1)] prepared by using the copolymer solution before storage, the uniform coating film having the same film thickness is ◎, and the film thickness is changed, but the film is almost the same. The change in the film thickness of the large film is Δ, and the film which cannot form a uniform film is ×. In the case of using an evaluation test piece made of a glass plate, the same results as in the case of the test piece for evaluation made of a stainless steel plate were obtained.

(3) Adhesion

Using the test piece for evaluation (base material: glass plate, stainless steel plate) produced in the above (1), the adhesion from the substrate was measured in accordance with JIS K-5600-5-6. In addition, the classification specified in "Classification of Test Results in Table 1" described in 8.3 of JISK5600-5-6 is evaluated based on the following criteria.

◎: The classification of the test results is "0".

○: The classification of the test results is "1".

△: The classification of the test results is "2".

×: The classification of the test results is "3" and "4".

(4) Solvent resistance

In the examples and comparative examples, one drop of isopropyl alcohol (IPA), methyl ethyl ketone (MEK), and N-methylpyrrolidone (NMP) were each added to the test piece for evaluation made of a glass plate. ) and let stand for 10 minutes. After washing with water, the position where the solvent is dropped is not changed at all; ◎; traces of some micro-solvents remain, but disappear after wiping; ○; traces of residual solvent, even if wiping does not disappear, △; . The same results were obtained also in the case of using the test piece for evaluation made of a stainless steel plate.

The results of the evaluation test are shown in Table 1. Further, in Table 1, the unit of the numerical value indicates the parts by weight.

The abbreviations of the solvents in Table 1 are as follows.

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 apparent from the table, the curable resin composition of the examples and the cured coating film obtained from the resin composition are all in the properties of stability, substrate adhesion, and solvent resistance. Excellent. On the other hand, the curable resin composition of the comparative example and the hardened coating film obtained from the resin composition were inferior in stability and adhesion.

[Industry use possibility]

According to the present invention, it is possible to solve the problem of safety in the use of a solvent, and at the same time, it is excellent in resin solubility, stability of composition, and coating property, and sensitivity, developability, and formed pattern in the case of using a material for a photoresist. The physical properties such as properties are excellent curable resin compositions. The coating film obtained by hardening the curable resin composition is uniform in film thickness It is excellent in physical properties such as adhesion to a substrate, solvent resistance, and the like, and can be used as a coating material, a coating agent, an adhesive, etc., and is particularly suitable for use in an electronic material field. .

Claims (5)

A curable resin composition characterized by comprising a copolymer and a solvent, wherein the copolymer is a monomer unit containing (A) a polymerizable unsaturated compound containing an alicyclic epoxy group and (B) an alkali-soluble solution A copolymer of a monomer unit containing 30 to 100% by mass of dipropylene glycol dimethyl ether in the total solvent. The curable resin composition of claim 1, wherein (A) the alicyclic epoxy group-containing polymerizable unsaturated compound is selected from the group consisting of 3,4-epoxycyclohexylmethyl (meth)acrylic acid. A compound of at least one of an ester, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]non-8 or 9-yl(meth)acrylate. The curable resin composition according to claim 1 or 2, wherein the copolymer further contains (C) a monomer unit corresponding to an alicyclic polymerizable unsaturated compound not containing an epoxy group. A method for producing a curable resin composition according to any one of claims 1 to 3, which comprises (1) a step of producing a copolymer using a solvent containing dipropylene glycol dimethyl ether as a polymerization solvent, Or (2) a step of exchanging a solvent of the copolymer with a solvent containing dipropylene glycol dimethyl ether. A cured product obtained by hardening a curable resin composition according to any one of claims 1 to 3.