KR20220038407A - curable composition - Google Patents

Abstract

An object of the present invention is to provide a curable composition exhibiting excellent curing reactivity either by energy ray curing or thermosetting. The present invention is a curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (A) has a structural unit represented by the following general formula (1), , a curable composition having a molecular weight distribution (weight average molecular weight/number average molecular weight) of 1.0 to 4.0.
In the following formula, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n represents an integer of 2 or more.

Description

curable composition

The present invention relates to a curable composition. More specifically, it relates to a curable composition excellent in curing reactivity.

A high molecular compound having a reactive functional group in a side chain causes a crosslinking reaction by an energy ray or heat to provide a good cured product, so it is industrially versatile and useful, and is useful as a point/adhesive agent, a coating agent, a paint, an ink, and a resist. etc., are used for a wide range of applications.

For example, it is known that a polymer compound having a cyclic ether group or (meth)acryloyl group such as an epoxy group is cured in the presence of a compound that generates a cation or a radical by irradiation or heating with an energy ray. . Moreover, it is known that a crosslinking reaction advances by heating a hydroxyl group, an isocyanate group, a carboxyl group, and an oxazolyl group.

By the way, it is known that the high molecular compound which has a vinyl ether group in a side chain also raises a crosslinking reaction by irradiation or heating of an energy ray, and provides hardened|cured material.

For example, Patent Document 1 contains a vinyl ether group-containing polymer having a specific structure and a specific compound that generates cations or radicals upon irradiation with energy rays, so that bubbles are not generated even during curing by irradiation with energy rays. , a curable composition having a remarkably high curing performance by irradiation with an energy ray and obtaining a cured product of good quality is described.

Moreover, in patent document 2, it has sufficient photocurability by including the acrylic resin which has a cationically polymerizable compound, a cationically polymerizable functional group, and a photocationic polymerization initiator in a predetermined range amount in patent document 2, respectively, and is difficult to adhere, for example. A photocurable resin composition having sufficient adhesion to hard plastics typified by phosphorus polycarbonate and PET is disclosed.

Japanese Patent Laid-Open No. 6-298884 Japanese Laid-Open Patent Publication No. 2006-57078

As described above, various curable compositions have been proposed so far. However, in the conventional curable composition, there is still room for improvement in curing reactivity. Moreover, if the said curable composition can fully harden|cure in any of energy-beam hardening and thermosetting, and can provide a desired hardened|cured material, the said curable composition can be applied to a wider range of uses.

The present invention has been made in view of the current situation, and an object of the present invention is to provide a curable composition exhibiting excellent curing reactivity either by energy ray curing or thermal curing.

As a result of various studies on the curable composition, the present inventors have found that by including a polymer having a specific structural unit and a molecular weight distribution (weight average molecular weight/number average molecular weight) in a specific range, and a polymerizable compound and/or a curing catalyst , discovered that a curable composition excellent in curing reactivity was obtained, and completed the present invention.

That is, the present invention is a curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (A) is a structural unit represented by the following general formula (1) It has a molecular weight distribution (weight average molecular weight/number average molecular weight) is 1.0-4.0, It is a curable composition characterized by the above-mentioned.

[Formula 1]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n is 2 or more represents an integer.)

The present invention further provides a curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), wherein the polymer (A) is a vinyl ether group represented by the following general formula (2) It is a curable composition characterized in that it is a group transfer polymer of a monomer component containing (meth)acrylic acid esters.

[Formula 2]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n is 1 or more represents an integer.)

The said curable composition WHEREIN: It is preferable that the weight average molecular weights of the said polymer (A) are 5000-1000000.

The said curable composition WHEREIN: It is preferable that the said curing catalyst (C) is at least 1 sort(s) chosen from the group which consists of a cation curing catalyst and a radical curing catalyst.

In the curable composition, the polymerizable compound (B) is selected from the group consisting of a vinyl ether compound, a cyclic ether compound, (meth)acrylic acid ester, a carboxylic acid compound, a maleimide compound, an alcohol, and a thiol. It is preferable that it is at least 1 type.

Moreover, the said curable composition WHEREIN: It is preferable that the said polymeric compound (B) is at least 1 sort(s) chosen from the group which consists of a methylene malonic acid diester compound and (alpha)-cyanoacrylic acid ester.

Moreover, the said curable composition WHEREIN: It is preferable that the said polymeric compound (B) is an acidic radical containing alkali-soluble resin, and/or resin which has a group which produces|generates an acidic radical by heat or an acid.

The curable composition is preferably at least one selected from the group consisting of a coating agent, an adhesive, an adhesive, a resist, a paint, an ink composition for printing, an electronic component, and an optical component.

This invention is also use of the above-mentioned curable composition for manufacturing at least 1 sort(s) selected from the group which consists of a coating agent, an adhesive, an adhesive agent, a resist, a paint, a printing ink composition, an electronic component, and an optical component.

Since the curable composition of this invention consists of the structure mentioned above, it is excellent in hardening reactivity. The curable composition of the present invention is preferably used for various applications such as a pressure-sensitive adhesive, an adhesive, an ink composition for printing, a composition for a resist, a coating agent, and a molding material.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram of the differential molecular weight distribution curve obtained by measuring by GPC method.
It is a figure which shows the DSC curve of the photocation hardening sample in an Example.
It is a figure which shows the DSC curve of the photoradical hardening sample in an Example.

Hereinafter, the present invention will be described in detail.

Moreover, what combined two or more of each preferable aspect of this invention described below is also a preferable aspect of this invention.

In addition, in this specification, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth)acrylate" means "acrylate and/or methacrylate" .

Curable composition (1)

The first curable composition of the present invention (hereinafter also referred to as "curable composition (1)") contains a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), and the polymer (A) ) has a structural unit represented by the following general formula (1), and molecular weight distribution (weight average molecular weight/number average molecular weight) is characterized in that it is 1.0 to 4.0.

[Formula 3]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n is 2 or more represents an integer.)

The reason why the curable composition (1) of the present invention has excellent curing reactivity is that, in addition to containing a polymer having a very highly reactive vinyl ether group, a sufficient amount of vinyl ether groups for the curing reaction to proceed efficiently is present in the polymer. It is presumed to be because As for the conventional polymer which has a vinyl ether group in a side chain, when manufacturing a polymer, a part of vinyl ether group reacts, Since coupling between polymers occurs from it as a starting point, or a polymer chain is grafted from a main chain, molecular weight distribution increases. In this case, a vinyl ether group is consumed in a polymer, and content of the vinyl ether group in a polymer becomes inadequate. That is, the polymer whose molecular weight distribution was controlled in the above-mentioned predetermined range is a polymer with sufficient content of the vinyl ether group in a polymer, It is thought that curable composition can exhibit the outstanding hardening reactivity by using such a polymer.

In addition, when the polymer (A) is synthesized by radical polymerization, for example, since a gel component is included, a cured product having a desired shape such as a flat coating film cannot be obtained, or the strength of the cured product is reduced. Although there was a concern, since generation|occurrence|production of a gel component is suppressed in the polymer whose molecular weight distribution of the said polymer (A) was controlled to a predetermined range, favorable hardened|cured material can be obtained.

Below, each component contained in the curable composition (1) of this invention is demonstrated.

<Polymer (A)>

The polymer (A) used in the curable composition (1) of the present invention has a structural unit represented by the general formula (1) (hereinafter also referred to as “structural unit (a1)”), and has a molecular weight distribution (weight average molecular weight/number average molecular weight) is 1.0-4.0.

In the said General formula (1), R< ¹ > represents a hydrogen atom or a methyl group.

In the said General formula (1), R< ² > and R< ³ > are the same or different, and represent a hydrogen atom or an organic group.

Examples of the organic group represented by R ² or R ³ include, for example, a chain or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least a part of atoms constituting the hydrocarbon group, a halogen atom, an oxygen atom, What was substituted with a nitrogen atom or a sulfur atom, etc. are mentioned.

Examples of the chain hydrocarbon group include a linear or branched aliphatic hydrocarbon group.

As said aliphatic hydrocarbon group, saturated hydrocarbon groups, such as an alkyl group, and unsaturated hydrocarbon groups, such as an alkenyl group, are mentioned, Preferably, a saturated hydrocarbon group is mentioned.

Specific examples of the aliphatic hydrocarbon group include, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, Neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group , 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-tetramethylbutyl group, Nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, decyl group, undecyl group, alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and eicosyl group; Vinyl group, n-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, an alkenyl group such as 3-methyl-1-butenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, 1-octenyl group, or 2-octenyl group; and the like.

Examples of the cyclic hydrocarbon group include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group. and the like.

Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups such as a phenyl group, a naphthyl group, a biphenyl group, a methoxyphenyl group, a trichlorophenyl group, an ethylphenyl group, a tolyl group, a xylyl group, and a benzyl group.

As said halogen atom, chlorine, bromine, or fluorine is preferable and fluorine is more preferable.

Especially, as said organic group, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, a C1-C5 halogenated alkyl group, and a C6-C12 aromatic hydrocarbon group are preferable, A C1-C6 alkyl group, and a carbon number A 1-5 halogenated alkyl group or a C6-C11 aromatic hydrocarbon group is more preferable, and a C1-C2 alkyl group, a C1-C2 halogenated alkyl group, and a C6-C8 aromatic hydrocarbon group are still more preferable.

In the said General formula (1), R< ⁴ > represents a hydrogen atom or an organic group.

As an organic group represented by ^R4 , the thing similar to the organic group represented by ^{R2 and} R3 mentioned above is mentioned, for example. Among them, R ⁴ is preferably a chain or cyclic hydrocarbon group having 1 to 11 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 11 carbon atoms. And, it is more preferable that it is a C1-C3 alkyl group.

In the said General formula (1), n is an integer of 2 or more.

The polymer having the structural unit (a1) is obtained, for example, by polymerizing a monomer component containing vinyl ether group-containing (meth)acrylic acid esters represented by the following general formula (2).

[Formula 4]

In the general formula (2), R ¹ , R ² , R ³ and R ⁴ are the same as R ¹ , R ² , R ³ and R ⁴ in the general formula (1), respectively. n represents an integer of 2 or more.

Specific examples of the vinyl ether group-containing (meth)acrylic acid esters represented by the general formula (2) include, for example, (meth)acrylic acid 2-(2-vinyloxyethoxy)ethyl and the like. there is.

The said polymer (A) may have 1 type of said structural unit (a1), and may have 2 or more types.

It is preferable that the content rate of the said structural unit (a1) in the said polymer (A) is 1-100 mol% with respect to 100 mol% of all structural units. The content of the structural unit (a1) is more preferably 4 mol% or more, and still more preferably 8 mol% or more, from the viewpoint of increasing the crosslinking density and imparting solvent resistance, hardness, and the like to the cured product. Moreover, 95 mol% or less is preferable and, as for the content rate of the said structural unit (a1), 90 mol% or less is more preferable.

In addition, when 2 or more types are included as said structural unit (a1), the said content rate is the total content rate of 2 or more types.

The said polymer (A) may have another structural unit (a2) further. As said other structural unit (a2), the structural unit derived from other polymerizable monomers other than the said vinyl ether group containing (meth)acrylic acid ester is mentioned.

As said other polymerizable monomer, the polymerizable monomer which has an electron-deficient double bond is mentioned, for example, These can be suitably selected according to the objective of the polymer to manufacture, and a use.

Specifically, as the polymerizable monomer having an electron-deficient double bond, for example, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylic acid i-propyl, ( Meth)acrylic acid n-butyl, (meth)acrylic acid s-butyl, (meth)acrylic acid t-butyl, (meth)acrylic acid n-amyl, (meth)acrylic acid s-amyl, (meth)acrylic acid t-amyl, (meth) Acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isodecyl, (meth)acrylic acid tridecyl, (meth)acrylic acid octyl, (meth)acrylic acid isooctyl, (meth)acrylic acid lauryl, (meth)acrylic acid ) stearyl acrylate, (meth)acrylic acid cyclohexyl, (meth)acrylic acid cyclohexylmethyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid isobornyl, (meth)acrylic acid adamantyl, (meth)acrylic acid tricyclo (meth)acrylic acid esters, such as decanyl, (meth)acrylic-acid benzyl, (meth)acrylic-acid phenyl, (meth)acrylic-acid 2-(acetoacetoxy)ethyl, (meth)acrylic-acid allyl;

(meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, (meth)acrylic acid 4-hydroxybutyl, caprolactone-modified hydroxy (meth)acrylate and hydroxyl group-containing (meth)acrylic acid esters such as (meth)acrylic acid 4-hydroxymethylcyclohexylmethyl;

(meth)acrylic acid glycidyl, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, (meth)acrylic acid tetrahydrofurfuryl, (meth)acrylic acid (3-ethyloxetan-3-yl)methyl, etc. Cyclic ether group containing (meth)acrylic acid esters;

halogen-containing (meth)acrylic acid esters such as (meth)acrylic acid trifluoroethyl, (meth)acrylic acid octafluoropentyl, (meth)acrylic acid heptadecafluorodecyl, and (meth)acrylic acid perfluorooctylethyl;

(meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-methylol (meth)acrylamide, nitrogen atom-containing polymerizable monomers such as (meth)acrylic acid N,N'-dimethylaminoethyl, N-phenylmaleimide, N-cyclohexylmaleimide, and 2-isopropenyl 2-oxazoline;

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, polyfunctional polymerizable monomers such as 1,6-hexanediol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and pentaerythritol tri(meth)acrylate;

isocyanate group-containing polymerizable monomers such as 2-(meth)acryloyloxyethyl isocyanate and (meth)acryloyl isocyanate;

4-(meth)acryloyloxy-2,2,6,6-tetramethylpiperidine, 1-(meth)acryloyl-4-cyano-4-(meth)acryloylamino-2, UV-stable polymerizable monomers such as 2,6,6-tetramethylpiperidine;

polymerizable cyclic lactone monomers such as methylenebutyrolactone and methylmethylenebutyrolactone; (meth)acrylonitrile; maleic anhydride;

1,4-dioxaspiro [4,5] deca-2-yl methacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4- (meth) acryloyloxymethyl-2-methyl -2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl- 2-methyl-2-cyclohexyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, alkoxylated phenylphenol (meth)acrylate; and the like.

It is preferable that carbon number is 1-22, as for the said other polymerizable monomer, it is more preferable that it is 1-18, It is still more preferable that it is 3-15.

The said polymer (A) may have 1 type of said other structural unit (a2), and may have 2 or more types.

It is preferable that the content rate of the said structural unit (a2) in the said polymer (A) is 0-99 mol% with respect to 100 mol% of all structural units. The content of the structural unit (a2) is more preferably 5 mol% or more from the viewpoint of imparting various physical properties derived from the structural unit (a2), such as flexibility, adhesiveness, stability, and heat resistance, to the cured product. and more preferably 10 mol% or more, more preferably 96 mol% or less, and still more preferably 92 mol% or less.

In addition, when 2 or more types are included as said structural unit (a2), the said content rate is the total content rate of 2 or more types.

The content ratio of the structural units (a1) and (a2) is determined by using gas chromatography, liquid chromatography, ¹ H-HMR, etc. It can obtain|require by the comparison method of the applicable integral value of ¹ H-NMR.

It is preferable that the said polymer (A) has the terminal group derived from the silane compound which has a carbon-carbon double bond at the main chain terminal. As described later, when the polymer (A) is produced by group transfer polymerization using a silane compound having a carbon-carbon double bond as a polymerization initiator, at the end of the polymerization initiation side of the main chain of the polymer, the carbon- A group derived from a silane compound having a carbon double bond is formed.

Group transfer polymerization is one type of anionic polymerization in which a monomer is polymerized using the silane compound having a carbon-carbon double bond as a polymerization initiator, as described later, wherein the silane compound having a carbon-carbon double bond is A carbon-carbon double bond as described later by adding to a polymerizable monomer having an electron-deficient double bond giving the (meth)acrylic group of the vinyl ether group-containing (meth)acrylic acid esters or the structural unit (a2) described above. At the same time that a structure derived from a silane compound having And to the formed silyl ketene acetal, vinyl ether group containing (meth)acrylic acid ester or the polymerizable monomer which has an electron-deficient double bond which provides the said structural unit (a2) further superposes|polymerizes. As described above, in polymerization of the monomer component, it is thought that the polymer is obtained by sequentially transferring silyl ketene acetal at the growth terminal to the terminal of the polymer molecule.

As the terminal group derived from the silane compound having a carbon-carbon double bond, a structure represented by the following general formula (3), (4) or (5) is preferably exemplified.

[Formula 5]

(In the formula, R ⁵ and R ⁶ are the same or different, and represent a hydrogen atom or an organic group. R ⁷ represents an organic group.)

[Formula 6]

(In the formula, R ⁵ , R ⁶ and R ^7' are the same or different and represent a hydrogen atom or an organic group.)

[Formula 7]

(In the formula, R ⁵ , R ⁶ and R ^7' are the same or different and represent a hydrogen atom or an organic group.)

Examples of the organic group represented by R ⁵ and R ⁶ in the general formulas (3), (4) and (5) include the same organic groups as those described above, and among them, a hydrocarbon group having 1 to 12 carbon atoms. desirable.

Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, and an aromatic hydrocarbon group. In the hydrocarbon group, at least a part of atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and at least one hydrogen atom constituting the hydrocarbon group is a fluorine atom, a chlorine atom, a bromine atom, etc. halogen atom; hydroxyl group; You may be substituted by substituents, such as an alkoxy group.

Among them, the hydrocarbon group represented by R ⁵ and R ⁶ is more preferably an alkyl group, cycloalkyl group, haloalkyl group or aromatic hydrocarbon group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group, It is still more preferable that they are a 1-6 alkyl group, and it is especially preferable that they are a methyl group and an ethyl group.

Examples of the organic group represented by R ⁷ and R ^7' include the same organic groups as described above, and among them, a hydrocarbon group having 1 to 22 carbon atoms is preferable, and an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group. , more preferably an aromatic hydrocarbon group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a tert-butyl group, an adamantyl group, a cyclohexyl group, a 2-ethylhexyl group, or a phenyl group, a methyl group, an ethyl group, a tert It is especially preferable that it is a -butyl group.

In the hydrocarbon group represented by R ⁷ and R ^7' , at least a part of atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and at least one hydrogen atom constituting the hydrocarbon group is a fluorine atom , a halogen atom such as a chlorine atom or a bromine atom; hydroxyl group; You may be substituted by substituents, such as an alkoxy group.

A plurality of R ^{7 ′} may be the same or different.

In addition, R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ^7' may be bonded to each other to form a ring structure. Examples of the ring structure include alicyclic hydrocarbon structures such as cycloalkyl such as cyclohexyl and cyclopentyl; oxygen-containing heterocyclic structures such as a dihydrofuran ring, a tetrahydrofuran ring, a dihydropyran ring, and a tetrahydropyran ring; and the like.

Further, when producing the polymer (A) using the group transfer polymerization, as a polymerization initiator, a silyl ketene acetal represented by the general formula (7), a vinylsilane compound represented by the general formula (8), and the general formula ( When the allylsilane compound represented by 9) is used, respectively, the obtained polymer has the main chain terminal of the structure represented by the said general formula (3), general formula (4), and general formula (5), respectively.

Among them, the polymer (A) preferably has a terminal group derived from silyl ketene acetal represented by the general formula (3) in the main chain from the viewpoint of easy control of molecular weight distribution when obtained by group transfer polymerization. Do.

The polymer (A) may further have a terminal structure represented by the following general formula (6). When it has a terminal structure represented by the following general formula (6) at one end of a main chain, a desired function can be provided to a polymer. The said polymer (A) has the terminal group derived from the silane compound which has the said carbon-carbon double bond at one terminal (1st terminal) of a main chain, and the following general formula ( It is preferable to have a terminal structure represented by 6).

[Formula 8]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. X is a hydrogen atom , a halogen atom, an alkyl group, a hydroxymethyl group, an allyl group or a propargyl group. n represents an integer of 2 or more.)

In the general formula (6), R ¹ , R ² , R ³ and R ⁴ are the same as R ¹ , R ² , R ³ and R ⁴ in the general formula (1), respectively.

In the general formula (6), X represents a hydrogen atom, a halogen atom, an alkyl group, a hydroxymethyl group, an allyl group or a propargyl group. As said alkyl group, it is preferable that it is a C1-C8 alkyl group, and it is more preferable that it is a C1-C6 alkyl group.

Among them, X is preferably a hydrogen atom from the viewpoint of unifying the terminal groups of the polymer, preferably a propargyl group from the viewpoint of easily imparting a function to the polymer, and an alkyl group from the viewpoint of improving the stability of the polymer It is preferable to be

As for the said polymer (A), molecular weight distribution (weight average molecular weight/number average molecular weight) is 1.0-4.0. When the said polymer (A) has the said structural unit (a1) and has the molecular weight distribution mentioned above, it is excellent in hardening reactivity and can suppress the dispersion|variation of various physical properties as hardened|cured material.

It is preferable that it is 3.5 or less, as for the molecular weight distribution of the said polymer (A), it is more preferable that it is 3.0 or less, It is still more preferable that it is 2.0 or less. In addition, the said molecular weight distribution is also called "dispersion degree".

Although the range suitable for the weight average molecular weight of the said polymer (A) exists in various uses, it is preferable that it is 5000-1000000.

The weight average molecular weight of the polymer (A) is more preferably 10000 or more, more preferably 20000 or more, more preferably 800000 or less, and still more preferably 600000 or less, from the viewpoint of durability. .

The weight average molecular weight and number average molecular weight of the said polymer (A) can be measured using a gel permeation chromatography (GPC) method, Specifically, it can obtain|require by the method as described in the Example mentioned later. Molecular weight distribution can be calculated and calculated|required by dividing a weight average molecular weight by a number average molecular weight.

As for the said polymer (A), it is preferable that the amount of insoluble content is 10 mass % or less with respect to 100 mass % of said polymers, It is more preferable that it is 5 mass % or less, It is more preferable that it is 1 mass % or less, It is 0.5 mass % The following are especially preferable.

When the quantity of an insoluble content increases, there exists a possibility that the shape of the hardened|cured material of a curable composition may worsen or the intensity|strength of hardened|cured material may fall, such as a flat coating film is not obtained.

The said insoluble component is a gel component contained in a polymer, Preferably it is a component insoluble with respect to ethyl acetate, toluene, or tetrahydrofuran, and the solubility at 25 degreeC is ethyl acetate, toluene, or tetrahydrofuran with respect to 100 g. 0.5 g or less, preferably 0.1 g or less.

Ethyl acetate, toluene, or tetrahydrofuran is added to the amount of the insoluble matter so that the concentration of the polymer is about 33 mass %, stirred sufficiently at room temperature, and then passed through a filter having a pore diameter of 4 µm and placed on the filter. When the mass after drying of the remaining insoluble content is set to (b) and the mass of the initial polymer is set to (a), it can be calculated|required as (b)/(a)*100.

In the differential molecular weight distribution curve obtained by measuring the polymer (A) by the gel permeation chromatography (GPC) method, in the polymer (A), the point of the maximum value of the differential molecular weight distribution curve is T, and the differential When the 5% height point of T on the molecular weight distribution curve is L ₀ and L ₁ from the low molecular weight side, the area (X) of the triangle surrounded by TL ₀ -L ₁ and the differential molecular weight distribution curve and L ₀ - It is preferable that ratio (X/Y) of the area (Y) of the part enclosed by the line which connects L< ₁ > is 0.8-2.0. When the polymer satisfies the ratio of the above-mentioned range, it can be said that the gelation of the polymer is suppressed. As for the said ratio (X/Y), it is more preferable that it is 0.8-1.5.

Moreover, in FIG. 1, the schematic of the differential molecular weight distribution curve obtained by measuring by the GPC method, and said T, L ₀ , L ₁ are shown.

The GPC measurement conditions are the same as those described in Examples to be described later.

The content of the polymer (A) is preferably 5 to 100 mass% with respect to 100 mass% of the total solid content of the curable composition, and the crosslinking density is increased to impart solvent resistance, hardness, etc. to the cured product, It is more preferable that it is 10 mass % or more, and it is still more preferable that it is 15 mass % or more. Moreover, it is more preferable that it is 99.9 mass % or less, and, as for content of the said polymer (A), it is more preferable that it is 95 mass % or less with respect to 100 mass % of solid content total amount of curable composition.

In addition, in this specification, "total amount of solid content" means the total amount of the components (components excluding the solvent etc. which volatilize at the time of formation of a hardened|cured material and a curing catalyst) which form the hardened|cured material.

Moreover, when the curable composition of this invention is a curable composition for resists, since solvent resistance can become favorable, content of the said polymer (A) is 1-50 mass % with respect to 100 mass % of solid content total of curable composition. It is preferable that it is 2-40 mass %, It is more preferable that it is 5-30 mass %, and it is still more preferable.

(Method for Producing Polymer (A))

Although it will not specifically limit if it is a method which can manufacture the polymer (A) which has the above-mentioned structure as a method of manufacturing the said polymer (A), From the point which can manufacture the said polymer (A) efficiently, The method of manufacturing by group transfer polymerization of the monomer component containing the vinyl ether group containing (meth)acrylic acid ester mentioned above is preferable. By performing group transfer polymerization, the polymer obtained by polymerization-reacting only the (meth)acryloyl of vinyl ether group containing (meth)acrylic acid esters can be manufactured efficiently. Moreover, according to this method, the quantity of the gel component (insoluble content) contained in the polymer obtained can be suppressed low.

Group transfer polymerization is one type of anionic polymerization in which a monomer is polymerized using a silane compound having a carbon-carbon double bond, such as silyl ketene acetal, as a polymerization initiator. A silane compound having a carbon-carbon double bond is added to the (meth)acryloyl group of (meth)acrylic acid esters containing a vinyl ether group, and silylketene acetal at the growth end of the newly formed polymer is sequentially added to the end of the polymer molecule. The polymer is obtained by transferring to

By using such group transfer polymerization, the polymerization reaction of vinyl ether group containing (meth)acrylic acid esters can be performed in temperature ranges, such as room temperature, control is comparatively easy. Moreover, the polymerization reaction can be carried out without the need to strictly control the amount of moisture in the reaction system. In addition, when the polymerization is used, the generation of impurities is small and a vinyl ether group-containing (meth)acrylic acid ester polymer can be produced with a vinyl ether group remaining at a high conversion rate.

A production method using the group transfer polymerization as a preferred method for producing the polymer (A) will be described below.

In the method for producing the polymer (A), a monomer component containing the above-mentioned vinyl ether group-containing (meth)acrylic acid esters is subjected to group transfer polymerization in the presence of a silane compound having a carbon-carbon double bond and a catalyst. It is preferred to include a process.

Specifically, in the polymerization reaction, any two of the monomer component, the catalyst, and the silane compound having a carbon-carbon double bond are injected into the reaction vessel before the reaction, and polymerization is started by adding the remaining one. The order in which these are added is not particularly limited, and may be added by any method to initiate polymerization.

The silane compound having a carbon-carbon double bond, the catalyst, and the monomer component may each be added in the total amount to be used at a time, may be added continuously in small amounts, or may be added in several times.

The molecular weight of the polymer obtained by polymerizing the monomer component is the type and amount of the monomer component, the type and amount of the silane compound having a carbon-carbon double bond, the type and amount of the catalyst, and the type or amount of the solvent used can be appropriately controlled.

The amount of the silane compound having a carbon-carbon double bond to be used is not particularly limited as long as a desired polymer is obtained, but from 1×10 ^-4 to the monomer component to be used from the viewpoint of more efficient production of the polymer. It is preferable that it is 10 mol%, 1x10 ^-3 - 5 mol% is more preferable, It is still more preferable that it is 1x10 ^-2 - 1 mol%.

The amount of the catalyst used is not particularly limited as long as a desired polymer is obtained, but it is preferably 1 × 10 ^-4 to 10 mol% with respect to the monomer component to be used from the viewpoint of more efficiently producing the polymer, 1x10 ^-3 to 5 mol% is more preferable, and it is still more preferable that it is 1x10 ^-2 to 1 mol%.

Although the said polymerization reaction can also be performed without using a solvent, it is preferable to use a solvent. The solvent to be used is not limited as long as it is a solvent capable of dissolving the raw material, the catalyst, the polymerization initiator, and the polymer, but an aprotic solvent is preferable from the viewpoint that the polymerization reaction can proceed efficiently.

Specific examples of the solvent used in the present invention include aromatic hydrocarbon-based solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane; Ketone solvents, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbon solvents such as chlorobenzene, dichloromethane, chloroform and 1,2-dichloroethane; Nitrile solvents, such as acetonitrile, propionitrile, and valeronitrile; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amide solvents such as dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone; Diethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether ( ether solvents such as diglyme), diethylene glycol ethyl ether (carbitol), and cyclopentyl methyl ether (CPME); fluorine-based solvents such as perfluorohexane, perfluorocyclohexane, pentafluorobenzene, and octafluorotoluene; DMSO, nitromethane, etc. are mentioned.

Among them, since the polymerization reaction can proceed more efficiently, the solvent includes an aromatic hydrocarbon-based solvent, an aliphatic hydrocarbon-based solvent, a ketone-based solvent, a halogenated hydrocarbon-based solvent, an ether-based solvent, an ester-based solvent, and It is preferable that it is at least 1 sort(s) chosen from the group which consists of a nitrile solvent, and it is more preferable that they are an aromatic hydrocarbon solvent, an ether solvent, and an ester solvent.

The said solvent may be used individually by 1 type, or may be used in combination of 2 or more type.

The amount of the solvent used is preferably 10 to 10000 mass%, more preferably 50 to 5000 mass%, still more preferably 100 to 1000 mass% with respect to 100 mass% of the total amount of the monomer components to be used. .

Moreover, in the said polymerization, it is preferable that the oxygen concentration in the solvent at the time of polymerization initiation is 1000 ppm or less. If the oxygen concentration in the solvent at the time of polymerization is in the above-mentioned range, the activity of the silane compound or catalyst having a carbon-carbon double bond is less likely to decrease, so that the polymerization reaction proceeds more favorably and the desired polymer is obtained. It can be manufactured more efficiently. It is more preferable that it is 800 ppm or less, and, as for the said oxygen concentration, it is still more preferable that it is 0-500 ppm.

The said oxygen concentration can be measured with a Polaro system dissolved oxygen meter.

Moreover, in the said polymerization, it is preferable that the water content in the solvent at the time of polymerization initiation is 1000 ppm or less. When the amount of water in the solvent at the time of polymerization is in the above-mentioned range, the silane compound having a carbon-carbon double bond is less likely to be decomposed and the activity of the catalyst or the like is less likely to decrease, so that the polymerization reaction proceeds more favorably, The desired polymer can be produced more efficiently. It is more preferable that it is 500 ppm or less, and, as for the said moisture content, it is still more preferable that it is 300 ppm or less.

The said moisture content can be measured by the Karl Fischer moisture measurement method.

Although the reaction temperature in particular in the said polymerization is not restrict|limited, From the point which can control molecular weight and molecular weight distribution, and maintain catalytic activity, -20-100 degreeC is preferable, -10-50 degreeC is more preferable, , 0-30 degreeC is more preferable. Moreover, it is also one of the preferable aspects of the manufacturing method of this invention to include the process of superposing|polymerizing at room temperature +/-20 degreeC from a viewpoint of manufacturing cost reduction.

Although reaction time in particular is not restrict|limited, 10 minutes - 48 hours are preferable, 30 minutes - 36 hours are more preferable, and 1 - 24 hours are still more preferable.

Although the reaction atmosphere in the said superposition|polymerization may wait, it is preferable that it is an inert gas atmosphere, such as nitrogen and argon.

Moreover, it is preferable that it is 10000 ppm or less, as for the oxygen concentration in the atmosphere in the said superposition|polymerization, it is more preferable that it is 1000 ppm or less, It is still more preferable that it is 100 ppm or less.

The polymer obtained by the polymerization reaction has a silyl ketene acetal structure or an enolate anion structure containing a silyl group of a polymerization initiator at the end of the main chain, and water, alcohol, or acid is added to the reaction system to form one end of the polymer. The polymerization reaction may be stopped by converting the silyl ketene acetal or enolate anion of carboxylic acid or ester.

As said alcohol, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol etc. are mentioned, for example.

As said acid, inorganic acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, and organic acids, such as acetic acid and benzoic acid, are mentioned, for example.

The amount of water, alcohol or acid to be used is not particularly limited, but is preferably from 1 to 1000 mol, more preferably from 1 to 100 mol, further preferably from 1 mol to 1 mol of the silane compound having a carbon-carbon double bond to be used. is 1 to 10 mol.

Moreover, instead of the said water, alcohol, or an acid, you may add a oral agent. By adding the oral agent, a desired functional group can be introduced and the polymerization reaction can be stopped. As said oral agent, halogens, such as iodine and bromine, halogenated succinimide compounds, halogenated alkyl, halogenated allyl, halogenated propargyl, aldehyde, acid chloride, etc. are mentioned, for example.

The amount of the oral agent used is not particularly limited, but is preferably 0.5 to 1.5 mol, more preferably 0.6 to 1.3 mol, still more preferably 0.8 to 1.2 mol, based on 1 mol of silyl ketene acetal to be used. .

The monomer component used in the said manufacturing method, the silane compound which has a carbon-carbon double bond, and a catalyst are demonstrated.

As said monomer component, the monomer which can introduce|transduce the said structural unit (a1), and the monomer which can introduce|transduce the said structural unit (a2) are mentioned. As a monomer into which the said structural unit (a1) can be introduce|transduced, the vinyl ether group containing (meth)acrylic acid ester mentioned above is mentioned. As a monomer into which the said structural unit (a2) can be introduce|transduced, the other polymerizable monomer mentioned above is mentioned.

What is necessary is just to set content of each said monomer suitably so that the polymer which has a structural unit in the range of a desired content ratio may be obtained.

As the silane compound having a carbon-carbon double bond, for example, the following general formula (7):

[Formula 9]

(Wherein, R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or an organic group. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent an organic group. R ⁵ and R ⁶ Alternatively, R ⁶ and R ⁷ may be bonded to form a ring structure. R ⁸ , R ⁹ and R ¹⁰ may be bonded to two or more of these to form a ring structure.)

Silyl ketene acetal represented by the following general formula (8):

[Formula 10]

(Wherein, R ⁵ , R ⁶ and R ^7' are the same or different and represent a hydrogen atom or an organic group. R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent an organic group. R ⁵ and R ⁶ or R ⁶ and R ^7' may be bonded to each other to form a ring structure. R ⁸ , R ⁹ and R ¹⁰ may be bonded to two or more of these to form a ring structure.)

A vinyl silane compound represented by, and the following general formula (9):

[Formula 11]

(Wherein, R ⁵ , R ⁶ and R ^7' are the same or different and represent a hydrogen atom or an organic group. R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent an organic group. R ⁵ and R ⁶ or R ⁶ and R ^7' may be bonded to form a ring structure. R ⁸ , R ⁹ and R ¹⁰ may be bonded to two or more of these to form a ring structure.)

One type or two or more types of the allylsilane compound represented by is mentioned preferably.

Among them, silyl ketene acetal is more preferable from the viewpoint that polymerization easily proceeds efficiently.

In the general formulas (7), (8) and (9), R ⁵ and R ⁶ are the same or different and represent a hydrogen atom or an organic group.

As said R< ⁵ > and R<^{6>, the thing similar to R<5> and R<6 > in} the above-mentioned general formula (3), (4), (5), respectively is mentioned.

As said R< ⁷ > and R<7>, the thing same as R< ⁷ > and R<^{7>' in} the above-mentioned general formulas (3), (4), and (5), respectively is mentioned.

In the general formulas (7), (8) and (9), R ⁸ , R ⁹ , and R ¹⁰ are the same or different and represent an organic group.

Examples of the organic group represented by R ⁸ , R ⁹ and R ¹⁰ include the same organic groups as described above, and among them, a hydrocarbon group having 1 to 12 carbon atoms and an alkoxy group are preferable, and a hydrocarbon group having 1 to 6 carbon atoms; It is more preferable that they are an alkoxy group, and it is still more preferable that they are a methyl group, an ethyl group, isopropyl group, tert- butyl group, a phenyl group, a methoxy group, and an ethoxy group.

Further, in the hydrocarbon group represented by R ⁸ , R ⁹ and R ¹⁰ , at least a part of atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom, and one or more hydrogen atoms constituting the hydrocarbon group Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; hydroxyl group; You may be substituted by substituents, such as an alkoxy group.

Specific examples of the group represented by -SiR ⁸ R ⁹ R ¹⁰ in the general formulas (7), (8) and (9) include, for example, a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group; triisobutylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, methyldiphenylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, etc. are mentioned. Among these, a trimethylsilyl group, a triethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a triethoxysilyl group, and a triphenylsilyl group are preferable from the viewpoints of ease of availability and synthesis.

Specific examples of the silyl ketene acetal represented by the general formula (7) include, for example, methyl (trimethylsilyl) dimethyl ketene acetal, methyl (trimethylsilyl) diisopropyl ketene acetal, and methyl (triethylsilyl) dimethyl. Ketene acetal, methyl (triisopropylsilyl) dimethyl ketene acetal, methyl (tert-butyldimethylsilyl) dimethyl ketene acetal, methyl (trimethylsilyl) diethyl ketene acetal, methyl (triphenylsilyl) dimethyl ketene acetal, methyl (methyldi Phenylsilyl) dimethyl ketene acetal, methyl (dimethylphenylsilyl) dimethyl ketene acetal, methyl (triethoxysilyl) dimethyl ketene acetal, ethyl (trimethylsilyl) dimethyl ketene acetal, 2-ethylhexyl (trimethylsilyl) dimethyl ketene acetal, tert -Butyl(trimethylsilyl)dimethylketeneacetal, 1-[(1-methoxy-2-methyl-1-propenyl)oxy]-1-methylsilacyclobutane, etc. are mentioned.

Among these, methyl (trimethylsilyl) dimethyl ketene acetal, methyl (triisopropylsilyl) dimethyl ketene acetal, and ethyl (trimethylsilyl) dimethyl ketene acetal are preferable from the point of easy availability, synthesis, and stability. .

The said silyl ketene acetal may be used only 1 type, and may be used in combination of 2 or more type.

Specific examples of the vinylsilane compound represented by the general formula (8) include vinyltrimethylsilane, 1-trimethylsilylhexene, 1-trimethylsilyloctene, 1-trimethylsilyl-1-phenylethylene, 1- Trimethylsilyl-2-phenylethylene, vinyl-tert-butyldimethylsilane, 1-tert-butyldimethylsilylhexene, 1-tert-butyldimethylsilyloctene, 1-tert-butyldimethylsilyl-2-phenylethylene, vinyltris ( trimethylsilyl)silane, 1-tris(trimethylsilyl)silylhexene, 1-tris(trimethylsilyl)silyloctene, 1-tris(trimethylsilyl)silyl-2-phenylethylene, etc. are mentioned.

Specific examples of the allylsilane compound represented by the general formula (9) include 3-(trimethylsilyl)-1-propene, 3-(triethylsilyl)-1-propene, 3-( Dimethylethylsilyl)-1-propene, 3-(triisopropylsilyl)-1-propene, 3-(dimethylisopropylsilyl)-1-propene, 3-(trinormalpropylsilyl)-1-propene Pen, 3-(dimethylnormalpropylsilyl)-1-propene, 3-(trinormalbutylsilyl)-1-propene, 3-(dimethylnormalbutylsilyl)-1-propene, 3-(triphenylsilyl) )-1-propene, 3-(dimethylphenylsilyl)-1-propene, 2-methyl-3-(trimethylsilyl)-1-propene, 3-(trimethylsilyl)-2-methyl-1-propene phen, 3-(triphenylsilyl)-2-methyl-1-propene, and the like.

As said catalyst, those which act as basic catalysts, such as a Brenstead base and a Lewis base, are mentioned preferably, Inorganic bases, such as alkali metal hydroxides and alkaline-earth metal hydroxides; organic bases such as trialkylamine and pyridine; and the like.

Among them, the catalyst is an organophosphorus compound, an N-heterocyclic carbene, a fluorine ion-containing compound, At least 1 sort(s) chosen from the group which consists of a type|mold amine compound and an ammonium salt compound is preferable. When these specific catalysts are used, in (meth)acrylic acid esters containing vinyl ether groups, cationic polymerization of vinyl ether groups or decomposition of vinyl ethers are difficult to occur, and (meth)acryloyl groups are polymerized more efficiently. can

Examples of the organophosphorus compound include 1-tert-butyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino)phosphoranylideneamino]-2λ ⁵ , 4λ ⁵ -catenadi(phosphazene) (phosphazene base P4-t-BuP ₄ ), 1-tert-octyl-4,4,4-tris(dimethylamino)-2,2-bis[tris(dimethylamino) Phosphoranylideneamino]-2λ ⁵ ,4λ ⁵ -catenadi(phosphazene) (phosphazene base P4-tOct), 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino) -2λ ⁵ , -4λ ⁵ -catenadi(phosphazene) (phosphazene base P2-t-Bu), 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ ⁵ ,4λ ⁵ -catenadi(phosphazene) (phosphazene base P2-t-Et), tert-butylimino-tris(dimethylamino)phosphorane (phosphazene base P1-t-Bu), tert-butylimino-tri phosphazene bases such as (pyrrolidino)phosphorane (BTPP) and 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine; Tris(2,4,6-trimethoxyphenyl)phosphine, tributylphosphine, tris(dimethylaminophosphine), 2,8,9-triisobutyl-2,5,8,9-tetraaza- 1-Phosphabicyclo[3,3,3]undecane, 2,8,9-trimethyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane, 2 ,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo[3,3,3]undecane; and the like. Among them, the phosphazene base P4-t-BuP ₄ , 2,8,9-triisobutyl-2,5,8,9-tetraaza- has strong basicity and can effectively activate silyl ketene acetal. 1-Phosphabicyclo[3,3,3]undecane is preferred.

Examples of the N-heterocyclic carbene include 1,3-dimethylimidazol-2-ylidene, 1,3-diethylimidazol-2-ylidene, 1,3-di-tert -Butylimidazol-2-ylidene, 1,3-di-cyclohexylimidazol-2-ylidene, 1,3-di-isopropylimidazol-2-ylidene, 1,3-di (1-adamantyl)imidazol-2-ylidene, 1,3-di-mesityylimidazol-2-ylidene, etc. are mentioned. Among them, 1,3-di-tert-butylimidazol-2-ylidene and 1,3-di-isopropylimidazol-2-ylidene are preferred from the viewpoint of effectively activating silyl ketene acetal. desirable.

Examples of the fluorine ion-containing compound include tetra-n-butylammonium fluoride (TBAF), tris(dimethylamino)sulfonium bifluoride (TASHF ₂ ), hydrogen fluoride-pyridine, tetrabutylammonium bifluoride, fluoride Potassium hydrogen etc. are mentioned. Among them, tetra-n-butylammonium fluoride (TBAF), tetrabutylammonium bifluoride, tris(dimethylamino)sulfonium bifluoride (TASHF), from the viewpoint of easy availability and the ability to effectively activate silyl ketene acetal. ₂ ) is preferred.

Examples of the cyclic amine compound include 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 7 -methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene etc. are mentioned.

Examples of the ammonium salt compound include tetrabutylammonium bisacetate, tetrabutylammonium acetate, tetrabutylammonium benzoate, tetrabutylammonium bisbenzoate, tetrabutylammonium metachlorobenzoate, tetrabutylammonium cyanate, tetrabutyl Ammonium methoxide, tetrabutylammonium thiolate, tetrabutylammonium bibromide, and the ammonium cation of these ammonium salt compounds are combined with tetramethylammonium, triethylammonium, benzyltributylammonium, N-methyl-N-butylpiperidinium, What was replaced with N-methyl-N-butylpyrrolidinium cation, the thing replaced with pyridinium cation, etc. are mentioned.

In addition to the above, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 7-methyl-1,5,7 A nitrogen-containing heterocyclic compound with strong basicity such as -triazabicyclo[4.4.0]deca-5-ene can also be used.

Only 1 type may be used for the said catalyst, and it may use it in combination of 2 or more type.

In the said superposition|polymerization, in the range which does not affect the effect of this invention, you may use other components other than the component mentioned above. As said other component, well-known additives, such as a polymerization initiator, a chain transfer agent, a polymerization accelerator, and a polymerization inhibitor, which are normally used in a polymerization reaction, etc. are mentioned, for example. These can be suitably selected as needed.

The said manufacturing method may include other processes other than the said polymerization reaction process. As said other process, an aging process, a neutralization process, the deactivation process of a polymerization initiator or a chain transfer agent, a dilution process, a drying process, a concentration process, a refinement|purification process etc. are mentioned, for example. These processes can be implemented by a well-known method.

It is preferable that the said polymer (A) is manufactured by the manufacturing method mentioned above. That is, it is preferable that the said polymer (A) is a group transfer polymer of the monomer component containing vinyl ether group containing (meth)acrylic acid ester represented by the said General formula (2).

When a polymer (A) is manufactured by the said manufacturing method, the conversion rate of the monomer component used for superposition|polymerization is very high, and the amount of residual monomers can be made very small.

On the other hand, when the polymer (A) is prepared by radical polymerization, even if it is possible to obtain a polymer in which the molecular weight distribution of the polymer is controlled within the predetermined range without gelation, the monomer remains and it is difficult to control the amount. For this reason, there exists a possibility that the reproducibility of the physical property expression of the hardened|cured material obtained may fall.

It is preferable that content of the residual monomer of the said polymer (A) is 10 mass % or less with respect to 100 mass % of polymer, It is more preferable that it is 5 mass % or less, It is still more preferable that it is 0-3 mass %.

Content of a residual monomer can be measured by < ¹ >H-NMR, gas chromatography, liquid chromatography, and gel permeation chromatography.

<Polymerizable compound (B)>

Although it will not specifically limit if it is a compound which can bridge|crosslink the said polymer (A) as a polymeric compound used in this invention, Especially since it can react efficiently with a vinyl ether group, a vinyl ether compound and a ring At least one selected from the group consisting of a type ether compound, (meth)acrylic acid ester, a carboxylic acid compound, a maleimide compound, an alcohol, and a thiol is preferable. Especially, as said polymeric compound, a vinyl ether compound, a cyclic ether compound, and a thiol are more preferable, and a vinyl ether compound and a cyclic ether compound are still more preferable.

Only 1 type may be used for the said polymeric compound, and it may use it in combination of 2 or more type.

Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxy Ethyl vinyl ether, ethoxyethyl vinyl ether, chlorethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl alkyl vinyl ethers such as vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, and tetrahydrofurfuryl vinyl ether; vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorphenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthranyl ether; alicyclic compound-containing vinyl ethers such as cyclohexyl vinyl ether and cyclohexanedimethanol monovinyl ether; allyl group-containing vinyl ethers such as allyl vinyl ether; polyfunctional divinyl ethers such as diethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,4-butanediol divinyl ether, and 1,4-cyclohexanedimethanol divinyl ether; and the like.

It is preferable that the molecular weight of the said vinyl ether compound is 10000 or less.

Examples of the cyclic ether compound include a compound containing an epoxy group, an oxetane compound, a compound having a tetrahydrofuran ring, and (meth)acrylic acid esters containing a cyclic ether group similar to those of the above-mentioned polymerizable monomer. can be heard

Specific examples of the cyclic ether compound include monofunctional epoxy resins such as n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and 1,2-epoxycyclohexane; Hexanediol diglycidyl ether, tetraethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, monoallyl diglycidyl isocyanuric acid, glycidyl methacrylate bifunctional epoxy resins, such as; Trimethylolpropane triglycidyl ether, sorbitol polyglycidyl ether, 1,3-bis(N,N-diglycidylaminoethyl)benzene, novolak-type epoxy resin, tetrakisphenolethane-type epoxy resin, etc. functional epoxy resin; 1,2-epoxy-4-vinylcyclohexane, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylmethylmethacrylate, etc. Epoxy resin having a lan ring; 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl (triethoxysilylpro monofunctional oxetane resins such as poxymethyl)oxetane and 3-cyclohexyloxymethyl-3-ethyl-oxetane; bifunctional oxetane resins such as bis(3-ethyl-3-oxetanylmethyl)ether and 1,4-bisb[(3-ethyl-3-oxetanyl)methoxy]methylbbenzene; Trimethylolpropanetris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritoltris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritoltetrakis(3-ethyl-3-oxeta) Polyfunctional oxetane resins, such as nylmethyl) ether and dipentaerythritol pentakis (3-ethyl-3- oxetanylmethyl) ether, etc. are mentioned.

The molecular weight of the cyclic ether compound is preferably 10000 or less.

As said (meth)acrylic acid ester, For example, methyl (meth)acrylate, butyl (meth)acrylate, isoamyl (meth)acrylate, lauryl (meth)acrylate, isobornyl (meth)acryl Rate, dicyclopentenyl (meth) acrylate, ethoxy-diethylene glycol (meth) acrylate, methoxydipropylene glucose (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hexafluoropropyl ( monofunctional (meth)acrylates such as meth)acrylate, diethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate; 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerin di(meth)acrylate, 9,9-bis[4-(2) -(meth)acryloyloxyethoxy)phenyl]fluorene, dimethyloltricyclodecanedi(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris( polyfunctional (meth)acrylates such as (meth)acryloyloxyethyl)isocyanuric acid, ditrimethylolpropanetetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Macromers which have (meth)acryloyl groups, such as epoxy (meth)acrylate, urethane (meth)acrylate, and polyester (meth)acrylate, etc. are mentioned.

It is preferable that the molecular weight of the said (meth)acrylic acid ester is 10000 or less.

Examples of the carboxylic acid compound include succinic acid, malonic acid, maleic acid, adipic acid, malic acid, tartaric acid, azobenzene-4,4'-dicarboxylic acid, and cyclohexane-1,4-dicarboxyl acid. compound which has 2 or more functional groups in a molecule|numerator, such as an acid, a citric acid, a trimellitic acid, and 1, 3, 5- tricarboxylic-acid benzene; The polymer etc. which contain a carboxyl group in side chains, such as poly(meth)acrylic acid, are mentioned.

It is preferable that the molecular weight of the said carboxylic acid compound is 10000 or less.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N,N'-tetramethylenebismaleimide, bisphenol A bis(4-maleimidephenylether), 4,4 '-diphenylmethanebismaleimide, m-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1, 3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyletherbismaleimide, 4,4'-diphenylsulfonebismalei Maleimide compounds, such as imide and 1, 3-bis (3-maleimide phenoxy) benzene, are mentioned.

It is preferable that the molecular weight of the said maleimide compound is 10000 or less.

Examples of the alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, pentaerythol, trimethylolpropane, Trimethylolethane, dihydroxynaphthalene, 2,4-diethyl-1,5-pentanediol, 4,4'-(hexafluoroisopropylidene)diphenol, 1,3-cyclohexanediol, 1,4 -Cyclohexanediol, cyclohexanedimethanol, 4,4'-biphenyldimethanol, 9,9-bis(4-hydroxyphenyl)fluorene, 2,2-bis(4-hydroxyphenyl)propane, di The compound etc. which have 2 or more hydroxyl groups in a molecule|numerator, such as pentaerythritol, are mentioned.

The molecular weight of the alcohol is preferably 10000 or less.

As the thiol, for example, 1,2-ethanedithiol, 1,3-propanedithiol, 2,4,6-trimercapto-triazine, 2-dibutylamino-4,6-dimer and compounds having two or more thiol groups in the molecule, such as capto-triazine, 1,4-bis(3-mercaptobutyryloxy)butane, and pentaerythritoltetrakis(3-mercaptobutyrate). Moreover, the compound containing at least 1 each of a carboxyl group and a thiol group in a molecule|numerator, such as mercaptoacetic acid and 3-mercaptopropionic acid, may be sufficient.

The molecular weight of the thiol is preferably 10000 or less.

It is also preferable that the said polymeric compound is a methylene malonic acid diester compound at the point which hardening at low temperature is possible.

Examples of the methylene malonic acid diester compound include a diester compound represented by the following general formula (10) and a polyfunctional methylene malonic acid diester in which a plurality of methylene malonic acid diesters are bonded.

[Formula 12]

(In the formula (10), R ¹¹ and R ¹² are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R ¹¹ and R ¹² are one of a divalent having 3 to 15 carbon atoms. A hydrocarbon group is formed. R ¹³ and R ¹⁴ are the same or different and represent a monovalent organic group having 1 to 30 carbon atoms.)

Examples of the polyfunctional methylene malonic acid diester include a reaction product obtained by reacting a diester compound represented by the general formula (10) with a polyhydric alcohol under conditions in which a transesterification reaction occurs between them. For example, the following general The compound represented by Formula (11) or (12) is mentioned.

[Formula 13]

(In formula (11), R ¹¹ and R ¹² are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R ¹¹ and R ¹² are one of each other to form a divalent compound having 3 to 15 carbon atoms. Forms a hydrocarbon group. R ¹³ represents a monovalent organic group having 1 to 30 carbon atoms. R ¹⁵ represents an n-valent organic group. n represents the number of structural units in parentheses included in the formula (11); An integer greater than or equal to 2. In formula (11), a plurality of R ¹¹ , R ¹² , and R ¹³ may be the same or different from each other.)

[Formula 14]

(In formula (12), R ¹¹ and R ¹² are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R ¹¹ and R ¹² are one of each other to form a divalent compound having 3 to 15 carbon atoms. A hydrocarbon group is formed. R ¹³ represents a monovalent organic group having 1 to 30 carbon atoms. R ¹⁶ represents a divalent organic group. R ¹⁷ represents a hydroxyl group or a monovalent organic group. m is a formula ( The number of structural units in parentheses included in 12) is shown, and an integer of 2 or more is represented. A plurality of R ¹¹ , R ¹² and R ¹⁶ may be the same or different from each other.)

In the said general formulas (10), (11) and ( ¹² ), as carbon number of the hydrocarbon group represented by ^R11 and R12, 1-10 are preferable and 1-5 are more preferable.

Examples of the hydrocarbon group represented by R ¹¹ and R ¹² include methyl group, ethyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n- nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, isopropyl group, 2-methylbutyl group, isoamyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, isoheptyl group, isooctyl group, 2-ethylhexyl group, 2-propylpentyl group, neononyl group, 2-ethyl Heptyl group, 2-propylhexyl group, 2-butylpentyl group, isodecyl group, neodecyl group, 2-ethyloctyl group, 2-propylheptyl group, 2-butylhexyl group, isoondecyl group, neoundecyl group, 2 -Ethyl nonyl group, 2-propyloctyl group, 2-butylheptyl group, 2-pentylhexyl group, isododecyl group, neododecyl group, 2-ethyldecyl group, 2-propylnonyl group, 2-butyloctyl group, 2 -pentylheptyl group, isotridecyl group, neotridecyl group, 2-ethylundecyl group, 2-propyldecyl group, 2-butyloctyl group, 2-pentyloctyl group, 2-hexylheptyl group, isotetradecyl group, Neotetradecyl group, 2-ethyldodecyl group, 2-propylundecyl group, 2-butyldecyl group, 2-pentylnonyl group, 2-hexyloctyl group, isopentadecyl group, neopentadecyl group, cyclohexylmethyl group, benzyl group and the like.

In the general formulas (10), (11) and (12), at least one of R ¹¹ and R ¹² may be a hydrogen atom or both may be a hydrogen atom, but both of R ¹¹ and R ¹² are hydrogen atoms it is preferable

Said R ¹¹ and R ¹² may further form a divalent hydrocarbon group having 3 to 15 carbon atoms as one of R ¹¹ and R ¹² . As carbon number of the said divalent hydrocarbon group in this case, 4-12 are preferable and 5-9 are more preferable.

Specific examples of the divalent hydrocarbon group include a 1,3-propylene group, a 1,4-butylene group, a 1,5-pentylene group, a 1,6-hexylene group, and a 1,5-hexylene group. can

In the general formulas (10), (11) and (12), R ¹³ and R ¹⁴ are the same or different, and are monovalent organic groups. Examples of the organic group include a monovalent hydrocarbon group and a monovalent hetero atom-containing group, and these may have one or two or more substituents. Examples of the substituent include an alkoxy group, a hydroxyl group, a nitro group, an azide group, a cyano group, an acyl group, an acyloxy group, a carboxyl group, a heterocyclic group, and an ester group, and these may be further substituted with a substituent.

Although there is no restriction|limiting in the number of substituents which ^R13 and R14 have, It is preferable that it is ⁵ or less, respectively, and it is more preferable that it is 3 or less.

^Carbon number of ^R13 and R14 is 1-30, respectively, It is preferable that it is 1-20, It is more preferable that it is 1-15, It is more preferable that it is 1-10, It is especially preferable that it is 1-6.

When R ¹³ and R ¹⁴ each have 1 or 2 or more substituents, it is preferable that the number of carbon atoms including the substituent is in the range of the carbon number, respectively.

The monovalent hydrocarbon group may be either a monovalent aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be any of a linear aliphatic hydrocarbon group, a branched chain aliphatic hydrocarbon group, and an alicyclic hydrocarbon group. . Moreover, any of a saturated aliphatic hydrocarbon group and an unsaturated aliphatic hydrocarbon group may be sufficient as the said aliphatic hydrocarbon group.

The alicyclic hydrocarbon group is a group having a cyclic aliphatic hydrocarbon moiety, and may have a linear or branched aliphatic hydrocarbon moiety.

The said aromatic hydrocarbon group is a group which has an aromatic ring, and may have an aliphatic part.

As said aliphatic hydrocarbon group, the group similar to the above-mentioned aliphatic hydrocarbon group and alicyclic hydrocarbon group, etc. are mentioned.

Moreover, as said aromatic hydrocarbon group, the group similar to the above-mentioned aromatic hydrocarbon group, etc. are mentioned.

Especially, an aliphatic hydrocarbon group is preferable and a saturated aliphatic hydrocarbon group is more preferable.

A polyalkylene oxide group, a polyester group, etc. are mentioned as said monovalent|monohydric hetero atom containing group.

R ¹³ and R ¹⁴ may be one of R ¹³ and R ¹⁴ to form a divalent organic group having 3 to 30 carbon atoms. As carbon number of the divalent organic group in this case, 3-10 are preferable and 3-6 are more preferable.

Examples of the divalent organic group include a divalent hydrocarbon group, and specific examples of the divalent hydrocarbon group include a 2,2-propylene group, a 1,3-propylene group, a 1,4-butylene group, and 1,5. -pentylene group, 1,6-hexylene group, 1,5-hexylene group, etc. are mentioned.

The divalent organic group may be a contribution in which one or more hydrogen atoms of a divalent hydrocarbon group having 3 to 15 carbon atoms are substituted with a substituent. Examples of the substituent include the same groups as the substituents for R ¹³ and R ¹⁴ described above. It is preferable to have 1-5 substituents, and, as for the said divalent organic group, it is more preferable to have 1-3 pieces.

The divalent organic group may be a divalent hetero atom-containing group, and examples of the divalent hetero atom-containing group include a polyalkylene oxide and a polyester group.

R ¹⁵ in the general formula (11) is preferably an n-valent organic group, a divalent or higher valence organic group, for example, a residue obtained by removing two or more hydroxyl groups from a polyol.

As said polyol, glycerol, polyglycerol, the compound which added alkylene glycol to glycerol, erythritol, xylitol, sorbitol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. are mentioned, for example.

Although the upper limit of n is not specifically limited, It is preferable that it is 100 or less, It is more preferable that it is 12 or less, It is still more preferable that it is 6 or less.

It is preferable that carbon number of the n-valent organic group represented by R< ¹⁵ > is 1-30, It is more preferable that it is 1-20, It is more preferable that it is 1-15, It is especially preferable that it is 1-10.

R ¹⁶ in the general formula (12) is a divalent organic group.

Examples of the divalent organic group represented by R ¹⁶ include the same groups as the divalent organic group described above. Preferably, a residue obtained by removing two hydroxyl groups from diol and two hydroxyl groups from polyalkylene glycol and residues other than .

As said diol or polyalkylene glycol, ethylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol etc. are mentioned, for example.

It is preferable that carbon number is 1-30, as for the divalent organic group represented by R< ¹⁶ >, it is more preferable that it is 1-20, It is still more preferable that it is 1-15, It is especially preferable that it is 1-10.

R ¹⁷ in the general formula (12) represents a hydroxyl group or a monovalent organic group.

The monovalent organic group represented by R ¹⁷ is not particularly limited, and examples thereof include the same groups as the monovalent organic groups represented by R ¹³ and R ¹⁴ described above.

It is preferable that R ¹⁷ is a hydroxyl group or a group represented by the following general formula (13).

[Formula 15]

(In the formula (13), R ¹¹ and R ¹² are the same or different, and represent a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, or R ¹¹ and R ¹² are one and a divalent having 3 to 15 carbon atoms. A hydrocarbon group is formed. R ¹⁴ represents a monovalent organic group having 1 to 30 carbon atoms.)

Examples of R ¹¹ , R ¹² , and R ¹⁴ in the general formula (13) include the same ones as those of R ¹¹ , R ¹² , and R ¹⁴ described above, respectively.

Specific examples of the diester compound represented by the general formula (10) include, for example, methylpropyl methylenemalonate, dihexyl methylenemalonate, dicyclohexylmethylenemalonate, diisopropyl methylenemalonate, butylmethyl methylenemalonate, Ethoxyethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl ethyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethyl methyl methylene malonate, methylene malonate Ethoxyethyl methyl ronate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxyethyl methylene malonate, dimethyl methylene malonate, di-n-propyl methylene malonate, ethylhexyl methylene malonate , penkyl methyl methylene malonate, menthyl methyl methylene malonate, 2-phenylpropyl ethyl methylene malonate, 3-phenylpropyl methylene malonic acid, dimethoxyethyl methylene malonate, and the like.

It is preferable that the molecular weight of the said methylene malonic acid diester compound is 10000 or less.

As the polymerizable compound, α-cyanoacrylic acid ester can also be preferably used.

As the α-cyanoacrylic acid ester, conventionally known α-cyanoacrylic acid ester can be used, and specifically, methyl-α-cyanoacrylic acid ester, ethyl-α-cyanoacrylic acid ester, propyl-α- alkyl and cycloalkyl-α-cyanoacrylic acid esters such as cyanoacrylic acid ester, butyl-α-cyanoacrylic acid ester, and cyclohexyl-α-cyanoacrylic acid ester; alkenyl and cycloalkenyl-α-cyanoacrylic acid esters such as allyl-α-cyanoacrylic acid ester, methallyl-α-cyanoacrylic acid ester, and cyclohexenyl-α-cyanoacrylic acid ester; alkynyl-α-cyanoacrylic acid ester such as propanyl-α-cyanoacrylic acid ester; aryl-α-cyanoacrylic acid esters such as phenyl-α-cyanoacrylic acid ester and toluyl-α-cyanoacrylic acid ester; methoxyethyl-α-cyanoacrylic acid ester, ethoxyethyl-α-cyanoacrylic acid ester, and furfuryl-α-cyanoacrylic acid ester containing a hetero atom; silicon-containing trimethylsilylmethyl-α-cyanoacrylic acid ester, trimethylsilylethyl-α-cyanoacrylic acid ester, trimethylsilylpropyl-α-cyanoacrylic acid ester, and dimethylvinylsilylmethyl-α-cyanoacrylic acid ester; and the like. Among them, from the viewpoint of performance and cost, alkyl and cycloalkyl-α-cyanoacrylic acid esters are preferable, and ethyl-α-cyanoacrylic acid esters are more preferable.

The molecular weight of the α-cyanoacrylic acid ester is preferably 10000 or less.

In addition, as the polymerizable compound, a compound capable of forming a crosslinked structure by reacting with a vinyl ether group may be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl aliphatic alcohols such as -1,5-pentanediol, propylene glycol, dipropylene glycol, polytetraethylene glycol, polycarbonate diol, and glycerol; aromatic alcohols such as 4,4'-biphenol and bisphenol A; acid anhydrides such as maleic anhydride; and the like.

When the curable composition of the present invention contains the polymerizable compound (B), the content of the polymerizable compound (B) is preferably 1 to 95 mass% with respect to 100 mass% of the total solid content of the curable composition, and , more preferably 10 to 90 mass%.

As the polymerizable compound (B), an acid group-containing alkali-soluble resin (b1) and/or a resin (b2) having a group generating an acid group by heat or acid can also be preferably used. By including these resins, the polymer (A) and the acid group contained in the resin can react, and the curable composition of the present invention can sufficiently advance the curing reaction even under relatively low temperature curing conditions of 200°C or less. Moreover, hardened|cured material excellent in solvent resistance can be provided, and various optical members used for liquid crystal, organic EL, quantum dot, micro LED liquid crystal display device, solid-state image sensor, touch panel type display device, etc., electric/electronic equipment, etc. It can be used suitably for various uses, such as a structural member.

Acid group-containing alkali-soluble resin (b1)

Acid group-containing alkali-soluble resin (b1) (hereinafter also referred to as "resin (b1)") is a polymer having an acid group. By having an acidic radical, it becomes alkali-soluble.

Examples of the acid group include a functional group that neutralizes with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic acid anhydride group, a phosphoric acid group, and a sulfonic acid group. you may have Especially, a carboxyl group or a carboxylic anhydride group is preferable, and a carboxyl group is more preferable.

(b1-1) structural unit having an acid group

It is preferable that the said resin (b1) has the structural unit (b1-1) which has the above-mentioned acidic radical.

As a method of obtaining the polymer having the structural unit (b1-1), for example, method (1) of polymerizing a monomer component containing an acid group-containing monomer, or polymerizing a monomer component containing an epoxy group-containing monomer, After obtaining a polymer containing an epoxy group, by subjecting the epoxy group to an addition reaction of the acid group of an acid group-containing monomer, the epoxy group is ring-opened, and a polybasic acid or polybasic acid anhydride is reacted with the hydroxyl group generated at that time to generate a carboxyl group (2), etc. Alternatively, a method combining these may be used.

In the method (1), the structural unit (b1-1) is a structural unit derived from an acid group-containing monomer. In the method (2), the structural unit (b1-1) is a structural unit containing a carboxyl group formed by reacting an acid group-containing monomer with a structural unit derived from an epoxy group-containing monomer and further reacting a polybasic acid or polybasic acid anhydride.

Especially, it is preferable that the said structural unit (b1-1) is a structural unit derived from an acidic radical containing monomer.

As said acidic radical containing monomer, the compound which has the above-mentioned acidic radical and a polymerizable double bond (carbon-carbon double bond) in a molecule|numerator is mentioned. As said polymerizable double bond, a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group etc. are mentioned, for example. Especially, a (meth)acryloyl group is preferable.

As a specific example of the said acidic radical containing monomer, For example, unsaturated monocarboxylic acids, such as (meth)acrylic acid, a crotonic acid, a cinnamic acid, and vinylbenzoic acid; unsaturated polyhydric carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; β-carboxyethyl (meth) acrylate, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), long-chain unsaturated mono which has a chain extension between the carboxyl group and the unsaturated group carboxylic acids; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; Phosphoric acid group-containing unsaturated compounds, such as light ester P-1M (made by Kyoeisha Chemical); and the like. Among these, from a viewpoint of versatility, availability, etc., a carboxylic acid monomer (unsaturated monocarboxylic acids, unsaturated polyhydric carboxylic acids, long-chain unsaturated monocarboxylic acids, unsaturated acid anhydrides) is preferable. From the viewpoints of reactivity and alkali solubility, the acid group-containing monomer is more preferably an unsaturated monocarboxylic acid, and still more preferably (meth)acrylic acid.

As said epoxy-group containing monomer, the compound which has an epoxy group and the said polymerizable double bond in a molecule|numerator is mentioned, Preferably, an epoxy-group containing (meth)acrylate is mentioned.

Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, (meth)acrylic acid β-methylglycidyl, (meth)acrylic acid β-ethylglycidyl, vinylbenzylglycidyl ether, allylglycidyl. Cydyl ether, (meth)acrylic acid (3,4-epoxycyclohexyl)methyl, vinylcyclohexene oxide, etc. are mentioned. Especially, (meth)acrylic-acid glycidyl and (meth)acrylic-acid (3,4-epoxycyclohexyl)methyl are preferable, and (meth)acrylic-acid glycidyl is more preferable.

As said polybasic acid or polybasic acid anhydride, For example, Polybasic acids, such as a succinic acid, a maleic acid, a phthalic acid, tetrahydrophthalic acid; Succinic anhydride (alias: succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endmethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydro Dibasic acid anhydrides, such as phthalic anhydride and itaconic anhydride, and polybasic acid anhydrides, such as trimellitic anhydride, are mentioned. Especially, polybasic acid anhydride is preferable.

The said resin (b1) may have only 1 type of the said structural unit (b1-1), and may have it 2 or more types.

The content of the structural unit (b1-1) is preferably 3 mass% or more, and 5 mass% or more, based on 100 mass% of all structural units of the resin (b1), from the viewpoint of maintaining appropriate developability. It is more preferable, it is more preferable that it is 7 mass % or more, It is more preferable that it is 40 mass % or less, It is more preferable that it is 30 mass % or less, It is still more preferable that it is 20 mass % or less.

(b1-2) Structural unit having a ring structure in the main chain

It is preferable that the said resin (b1) is a polymer which has a ring structure in a principal chain. By having a ring structure in a principal chain, the heat resistance of the said resin (b1) can be improved. Examples of the ring structure include an imide ring, a tetrahydrofuran ring, and a lactone ring. In order to have these ring structures, it is preferable that the said resin (b1) further has a structural unit (b1-2) which has a ring structure in a principal chain.

As the monomer into which the structural unit (b1-2) can be introduced, for example, a monomer having a double bond-containing ring structure in the molecule, or a monomer that is subjected to cyclization polymerization to form a polymer having a ring structure in the main chain; A monomer etc. which form a ring structure after superposition|polymerization are mentioned. Among them, from the viewpoint of good heat resistance, solvent resistance, hardness, dispersibility of color material, etc., N-substituted maleimide-based monomers, dialkyl-2,2'-(oxydimethylene)diacrylate-based monomers, and α-( At least one type of monomer selected from the group consisting of unsaturated alkoxyalkyl) acrylate-based monomers is preferable, and from the viewpoint of further excellent heat-resistant colorability, N-substituted maleimide-based monomers, and dialkyl-2,2'-( At least one type of monomer selected from the group consisting of oxydimethylene) diacrylate-based monomers is more preferable.

Examples of the N-substituted maleimide-based monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and Nt-butylmaleimide. imide, N-dodecyl maleimide, N-benzyl maleimide, N-naphthyl maleimide, etc. are mentioned, These 1 type, or 2 or more types can be used. Among them, from the viewpoint of transparency, N-phenylmaleimide and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable.

As said N-benzyl maleimide, For example, benzyl maleimide; Alkyl-substituted benzyl maleimide, such as p-methylbenzyl maleimide and p-butylbenzyl maleimide; Phenolic hydroxyl group-substituted benzyl maleimide, such as p-hydroxybenzyl maleimide; halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide, and p-dichlorobenzylmaleimide; and the like.

Examples of the dialkyl-2,2'-(oxydimethylene)diacrylate-based monomer include 2,2'-[oxybis(methylene)]bisacrylic acid, dialkyl-2,2'-[ At least one ester moiety contains tertiary carbon, such as oxybis(methylene)]bis-2-propenoate and dialkyl-2,2'-[oxybis(methylene)]bis-2-propenoate compounds and the like. Among these, it is preferable to use, for example, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate etc. from a viewpoint of transparency, dispersibility, ease of industrial availability, etc. .

Examples of the α-(unsaturated alkoxyalkyl)acrylate-based monomer include α-allyloxymethyl acrylic acid, α-allyloxymethyl methyl acrylate, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylic acid n- Propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxymethyl acrylic acid n- and amyl, α-allyloxymethyl acrylic acid s-amyl, α-allyloxymethyl acrylate t-amyl, and α-allyloxymethyl acrylate neopentyl. Among them, an alkyl-(α-allyloxymethyl)acrylate-based monomer is preferable. As the alkyl-(α-allyloxymethyl)acrylate monomer, for example, methyl-(α-allyloxymethyl)acrylate or the like is used from the viewpoint of transparency, dispersibility, and industrial availability. it is preferable

The α- (unsaturated alkoxyalkyl) acrylate-based monomer can be produced, for example, by a production method disclosed in International Publication No. 2010/114077.

As a monomer which provides the said structural unit (b1-2), 2-(hydroxyalkyl) acrylic acid alkylester is mentioned further preferably. 2-(hydroxyalkyl) acrylic acid alkyl ester can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

As said 2-(hydroxyalkyl) acrylic acid alkylester, 2-(1-hydroxyalkyl) acrylic acid alkyl ester, 2-(2-hydroxyalkyl) acrylic acid alkylester, etc. are mentioned, Specifically, Example For example, 2-(1-hydroxymethyl) methyl acrylate, 2-(1-hydroxymethyl) ethyl acrylate, 2-(1-hydroxymethyl) isopropyl acrylate, 2-(1-hydroxymethyl) acrylic acid n-butyl, 2-(1-hydroxymethyl) acrylate t-butyl, 2-(1-hydroxymethyl) acrylate 2-ethylhexyl, etc. are mentioned. Especially, 2-(1-hydroxymethyl) methyl acrylate and 2-(1-hydroxymethyl) ethyl acrylate are preferable.

The said resin (b1) may have 1 type of the said structural unit (b1-2), and may have 2 or more types.

The content ratio of the structural unit (b1-2) is preferably 5 mass% or more, and 8 mass%, based on 100 mass% of all structural units of the resin (b1), from the viewpoint that heat resistance and solvent resistance can be improved. % or more, more preferably 10 mass% or more, preferably 35 mass% or less, more preferably 30 mass% or less, still more preferably 25 mass% or less.

(b1-3) other structural units

The resin (b1) may have other structural units (b1-3) other than the structural units (b1-1) and (b1-2) described above.

As said other structural unit (b1-3), the structural unit derived from the following monomer is mentioned, for example.

(meth)acrylic acid 2-hydroxyethyl, (meth)acrylic acid 2-hydroxypropyl, (meth)acrylic acid 3-hydroxypropyl, (meth)acrylic acid 2-hydroxybutyl, (meth)acrylic acid 3-hydroxybutyl; Hydroxyl group-containing monomers, such as hydroxyalkyl (meth)acrylates, such as (meth)acrylic-acid 4-hydroxybutyl and (meth)acrylic-acid 2,3-hydroxypropyl;

(meth) methyl acrylate, (meth) ethyl acrylate, (meth) acrylate n-propyl, (meth) acrylate i-propyl, (meth) acrylate n-butyl, (meth) acrylate s-butyl, (meth) acrylic acid n- Amyl, (meth)acrylic acid s-amyl, (meth)acrylic acid n-hexyl, (meth)acrylic acid 2-ethylhexyl, (meth)acrylic acid isodecyl, (meth)acrylic acid tridecyl, (meth)acrylate octyl, (meth) Isooctyl acrylate, (meth) acrylic acid lauryl, (meth) acrylate stearyl, (meth) acrylate benzyl, (meth) acrylate phenyl, (meth) acrylate isobornyl, (meth) acrylate adamantyl, (meth) acrylic acid Tricyclodecanyl, (meth)acrylic acid cyclohexyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid 2-methoxyethyl, (meth)acrylic acid 2-ethoxyethyl, (meth)acrylic acid tetrahydrofurfuryl, ( Meth)acrylic acid N,N-dimethylaminoethyl, 1,4-dioxaspiro[4,5]deca-2-ylmethacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl -2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acrylo (meth)acrylic acid esters such as yloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane and 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane monomer;

aromatic vinyl-based monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene;

(meth)acrylic acid glycidyl, (meth)acrylic acid β-methylglycidyl, (meth)acrylic acid β-ethylglycidyl, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth)acrylic acid (3, Epoxy group-containing monomers, such as 4-epoxycyclohexyl)methyl and vinylcyclohexene oxide;

(meth)acrylamides, such as N,N- dimethyl (meth)acrylamide and N-methylol (meth)acrylamide;

macromonomers having a (meth)acryloyl group at one end of a polymer molecular chain, such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam;

conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;

Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether , vinyl ethers such as methoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether;

N-vinyl compounds, such as N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinylimidazole, N-vinyl morpholine, and N-vinyl acetamide;

unsaturated isocyanates such as (meth)acrylic acid isocyanatoethyl and allyl isocyanate; etc.

Among them, the structural unit (b1-3) is a structural unit derived from at least one monomer selected from the group consisting of the hydroxyl group-containing monomer, (meth)acrylic acid ester monomer, aromatic vinyl monomer, and epoxy group-containing monomer. It is preferable to be

The said resin (b1) may have 1 type of said structural unit (b1-3), and may have 2 or more types.

The content of the structural unit (b1-3) is preferably 50 mass% or more, more preferably 60 mass% or more, based on 100 mass% of all structural units of the resin (b1) from the viewpoint of good developability. and more preferably 70 mass% or more, preferably 92 mass% or less, more preferably 90 mass% or less, still more preferably 85 mass% or less.

When the said resin (b1) contains 2 or more types of said structural unit (b1-3), the content rate of each structural unit can be set suitably according to the use of the curable composition of this invention, and the objective.

It is preferable that the said resin (b1) has an epoxy group further. When the said resin (b1) further has an epoxy group, sclerosis|hardenability of the curable composition of this invention can be improved, and the hardened|cured material more excellent in solvent resistance can be provided.

The said resin (b1) which has an epoxy group can be obtained by superposing|polymerizing the monomer component containing the above-mentioned epoxy group containing monomer.

When the resin (b1) has an epoxy group, the epoxy equivalent of the resin (b1) is preferably 100 or more and 20000 or less, more preferably 200 or more and 8000 or less, and 500 or more, It is more preferable that it is 5000 or less. The said epoxy equivalent can be calculated|required by dividing the amount of resin by the number of moles of the epoxy group contained in resin.

It is preferable that the acid value of the said resin (b1) is 20-230 mgKOH/g. Developability becomes favorable as the said acid value is the range mentioned above, and the cured film excellent in solvent resistance can be provided. It is more preferable that it is 30-200 mgKOH/g, and it is still more preferable that it is 40-180 mgKOH/g.

The said acid value is a value obtained by measuring by the neutralization titration method using KOH solution.

The weight average molecular weight of the resin (b1) is not particularly limited, and may be appropriately set according to the purpose and use of the curable composition, preferably from 1000 to 100000, more preferably from 2000 to 50000, and from 4000 to 30000 more preferably.

It is preferable that it is 1.0-4.0, as for the molecular weight distribution (weight average molecular weight/number average molecular weight) of the said resin (b1), it is more preferable that it is 1.1-3.5, It is still more preferable that it is 1.5-3.0.

The said weight average molecular weight and molecular weight distribution are values obtained by measuring by the gel permeation chromatography method (GPC), Specifically, it can obtain|require by the method as described in the Example mentioned later.

The said resin (b1) may have a polymerizable double bond in a side chain. By having a polymerizable double bond in a side chain, sclerosis|hardenability of the said resin (b1) can be improved. As said polymerizable double bond, the polymerizable double bond mentioned above is mentioned. Especially, it is preferable that it is a reactive point that it is a (meth)acryloyl group.

When the said resin (b1) has a polymerizable double bond in a side chain, it is preferable that the double bond equivalent is 200-8000 g/equivalent, It is more preferable that it is 250-5000 g/equivalent, It is 300-1500 g It is more preferable that it is /equivalent.

The said double bond equivalent is the mass of the solid content of the resin solution per 1 mol of double bonds of the said resin (b1). The mass of solid content of the said resin solution sums up the mass of the monomer component which comprises the said resin (b1), and the mass of a polymerization inhibitor. The said double bond equivalent can be calculated|required by dividing the mass (g) of resin solid content of a resin solution by the double bond amount (mol) of resin. The amount of double bonds in the resin can be determined from the amount of the acid group-containing monomer used during polymerization and the compound having a functional group capable of bonding to the acid group and a polymerizable double bond. A hydroxyl group, an epoxy group, etc. are mentioned as a functional group which can couple|bond the said acidic radical. Moreover, it can also measure using various analyzes, such as titration and elemental analysis, NMR and IR, and a differential scanning calorimetry method.

As a method for producing the resin (b1), particularly if it is a method capable of obtaining a polymer having at least the structural unit (b1-1) and optionally the structural units (b1-2) and (b1-3) It is not restrict|limited, The method of superposing|polymerizing by a well-known method the monomer component containing the monomer which can introduce each structural unit (b1-1) - (b1-3) mentioned above by a well-known method is mentioned, for example, The manufacturing method described in paragraphs [0039] - [0062] of Unexamined-Japanese-Patent No. 2015-42697 is mentioned.

The content of the resin (b1) is preferably 10 to 60 mass%, more preferably 20 to 50 mass%, still more preferably 30 to 45 mass%, in 100 mass% of the total solid content of the curable composition. .

Resin having a group that generates an acid group by heat or acid (b2)

Examples of the resin (b2) having a group that generates an acid group by heat or acid include resins having a structure or group in which an acid group is generated by the action of heat or acid.

Examples of the structure or group in which an acid group is generated by the action of heat or acid include a tertiary carbon-containing group, a group in which an acid group is blocked by a vinyl ether compound, or a phenol by a protecting group such as a t-butyl group or an acetyl group. and groups in which the hydroxyl group is protected.

Examples of the tertiary carbon-containing group include groups preferably represented by -COO*R ¹⁸ (R ¹⁸ represents a monovalent organic group, and a carbon atom bonded to O* is a tertiary carbon atom.) there is.

R ¹⁸ of -COO*R ¹⁸ represents a monovalent organic group, and the carbon atom couple|bonded with O* is a tertiary carbon atom. A tertiary carbon atom means the carbon atom whose other carbon atom couple|bonded with the said carbon atom is three.

The monovalent organic group preferably includes a monovalent chain, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 91 carbon atoms. The said organic group may have a substituent.

R ¹⁸ has more preferably 1 to 50 carbon atoms, still more preferably 1 to 35 carbon atoms, still more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and most preferably It has 1 to 9 carbon atoms.

R ¹⁸ may preferably be represented by -C(R ¹⁹ )(R ²⁰ )(R ²¹ ). In this case, R ¹⁹ , R ²⁰ , and R ²¹ are the same or different and are preferably a hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, may have a cyclic structure, or may have a substituent. In addition, R ¹⁹ , R ²⁰ , and R ²¹ may be linked to each other at a terminal site to form a cyclic structure.

Here, in the tertiary carbon-containing group, it is preferable that at least one of the adjacent carbon atoms is bonded to a hydrogen atom in the tertiary carbon atom. For example, when R ¹⁸ is a group represented by -C(R ¹⁹ )(R ²⁰ )(R ²¹ ), at least one of R ¹⁹ , R ²⁰ and R ²¹ represents a carbon atom having one or more hydrogen atoms. It is also preferable that the carbon atom is bonded to a tertiary carbon atom.

R ¹⁹ , R ²⁰ and R ²¹ are the same or different and are preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms. It is a saturated hydrocarbon group, Especially preferably, it is a C1-C3 saturated hydrocarbon group.

R ¹⁸ is preferably a t-butyl group or a t-amyl group.

In order to obtain the polymer which has the said tertiary carbon-containing group, what is necessary is just to use a tertiary carbon-containing monomer as a monomer component. As said tertiary carbon-containing monomer, Preferably, (meth)acrylate t-butyl, (meth)acrylate t-amyl, etc. are mentioned.

Examples of the group in which the acid group is blocked by the vinyl ether compound include a group in which the vinyl ether compound is bonded to the acid group such as a carboxyl group.

Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, i-propyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2 -aliphatic vinyl ether compounds, such as ethylhexyl vinyl ether and cyclohexyl vinyl ether, cyclic ether compounds, such as dihydropyran, which can generate|occur|produce vinyl ether by ring opening are mentioned.

Among the vinyl ether compounds, dihydropyran is preferable at a lower temperature from which the protecting group is easily removed.

The group in which the acid group is blocked by the dihydropyran is preferably a group represented by the following formula.

[Formula 16]

As the group in which the phenolic hydroxyl group was protected by a protecting group such as the t-butyl group or an acetyl group, groups preferably represented by the following formulas are exemplified.

[Formula 17]

(In formula, n represents the number of substituents, and is an integer of 1-5.)

The group represented by the above formula is, for example, reacted in a solvent in the presence of an acid catalyst such as hydrochloric acid or sulfuric acid at a temperature of 50 to 150°C for 1 to 30 hours, whereby the protecting group is detached and an acidic group is generated.

Especially, the group in which the acidic radical is blocked by the said dihydropyran is preferable at the point which can produce|generate an acidic radical at lower temperature.

(b2-1) Structural unit represented by general formula (14)

The resin (b2) preferably includes a resin having a structural unit (b2-1) represented by the following general formula (14).

[Formula 18]

(Wherein, R ²² represents a hydrogen atom or a methyl group. Y represents a direct bond or a divalent organic group. A represents a group in which an acidic group is generated by heat or acid.)

In the general formula (14), R ²² represents a hydrogen atom or a methyl group. Especially, since heat resistance is favorable, it is preferable that R ²² is a methyl group.

Y represents a direct bond or a divalent organic group.

As said divalent organic group, the divalent hydrocarbon group which may have a substituent is mentioned.

As said divalent hydrocarbon group, an alkylene group, a cycloalkylene group, an arylene group, etc. are mentioned.

In the divalent hydrocarbon group, at least one of atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.

A hydroxyl group, an alkoxy group, a halogen atom etc. are mentioned as said substituent.

Y is preferably a direct bond.

In the general formula (14), A represents a group in which an acidic radical is generated by heat or an acid.

Examples of the group in which an acidic radical is generated by heat or acid include the same structure or group in which an acidic radical is generated by the action of heat or acid as described above.

The said resin (b2) may have 1 type of the said structural unit (b2-1), and may have 2 or more types.

The content of the structural unit (b2-1) is preferably 5 mass% or more, more preferably 10 mass% or more, based on 100 mass% of all structural units of the resin (b2) from the viewpoint of good solvent resistance. and more preferably 15 mass% or more, preferably 80 mass% or less, more preferably 70 mass% or less, still more preferably 60 mass% or less.

(b2-2) Structural unit having a ring structure in the main chain

It is preferable that the said resin (b2) is a polymer which has a ring structure in a principal chain. By having a ring structure in a principal chain, the heat resistance of the said resin (b2) can be improved. As said ring structure, the thing similar to the ring structure described in the structural unit (b1-2) mentioned above is mentioned. It is preferable that the said resin (b2) further has a structural unit (b2-2) which has a ring structure in a principal chain.

Examples of the monomer capable of introducing the structural unit (b2-2) include the same monomers as the monomer capable of introducing the structural unit (b1-2) described above.

The said resin (b2) may have 1 type of the said structural unit (b2-2), and may have 2 or more types.

The content of the structural unit (b2-2) is preferably 5 mass% or more, and 8 mass% or more, based on 100 mass% of all structural units of the resin (b2) from the viewpoint of good heat resistance and solvent resistance. It is more preferable, it is more preferable that it is 10 mass % or more, It is preferable that it is 35 mass % or less, It is more preferable that it is 30 mass % or less, It is still more preferable that it is 25 mass % or less.

(b2-3) other structural units

The resin (b2) may further have another structural unit (b2-3) in addition to the structural units (b2-1) and (b2-2) described above.

As said other structural unit (b2-3), the structural unit similar to the other structural unit (b1-3) mentioned above is mentioned.

Among them, the structural unit (b2-3) is a structural unit derived from at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, a (meth)acrylic acid ester monomer, an aromatic vinyl monomer, and an epoxy group-containing monomer. it is preferable

The said resin (b2) may have 1 type of the said structural unit (b2-3), and may have 2 or more types.

The content ratio of the structural unit (b2-3) is preferably 15 mass% or more, and more preferably 20 mass% or more, based on 100 mass% of all structural units of the resin (b2) from the viewpoint of improving developability. It is preferable, and it is more preferable that it is 30 mass % or more, It is preferable that it is 95 mass % or less, It is more preferable that it is 90 mass % or less, It is still more preferable that it is 85 mass % or less.

When the said resin (b2) contains 2 or more types of the said structural unit (b2-3), the content rate of each structural unit can be designed suitably according to the use of the curable composition of this invention, and the objective.

It is preferable that the said resin (b2) has an epoxy group further. When the said resin (b2) further has an epoxy group, sclerosis|hardenability of a curable composition can be improved, and the hardened|cured material more excellent in solvent resistance can be provided.

The said resin (b2) which has an epoxy group can be obtained by superposing|polymerizing the monomer component containing the above-mentioned epoxy group containing monomer.

It is preferable that the acid value of the said resin (b2) is 20-230 mgKOH/g. Developability becomes favorable as the said acid value is the range mentioned above, and the cured film excellent in solvent resistance can be provided. It is more preferable that it is 30-200 mgKOH/g, and it is still more preferable that it is 40-180 mgKOH/g.

The said acid value is a value obtained by measuring by the neutralization titration method using KOH solution.

The weight average molecular weight of the resin (b2) is not particularly limited, and may be appropriately set according to the purpose and use of the curable composition of the present invention, but it is preferably 1000 to 100000, more preferably 2000 to 50000, 4000 It is more preferable that it is -30000.

Although the molecular weight distribution (weight average molecular weight/number average molecular weight) of the said resin (b2) is not restrict|limited in particular, It is preferable that it is 1.0-4.0, It is more preferable that it is 1.1-3.5, It is still more preferable that it is 1.5-3.0.

The weight average molecular weight and molecular weight distribution of the said polymer are values obtained by measuring by the gel permeation chromatography method (GPC), Specifically, it can obtain|require by the method as described in the Example mentioned later.

The said resin (b2) may have a polymerizable double bond in a side chain. By having a polymerizable double bond in a side chain, sclerosis|hardenability of the said resin (b2) can be improved.

As said polymerizable double bond, the thing similar to the thing in resin (b1) mentioned above is mentioned preferably. When the said resin (b2) has a polymerizable double bond in a side chain, the double bond equivalent of the same range as resin (b1) mentioned above is mentioned preferably also for the double bond equivalent.

As a manufacturing method of the said resin (b2), especially if it is a method which can obtain the polymer which has at least the said structural unit (b2-1) and, if necessary, the said structural units (b2-2) and (b2-3), It is not restrict|limited, The method of superposing|polymerizing by a well-known method is mentioned the monomer component containing the monomer which can introduce|transduce each structural unit (b2-1) - (b2-3) mentioned above by a well-known method. Moreover, after superposing|polymerizing the monomer component containing an acidic radical containing monomer, you may add a protecting group to an acidic radical.

The quantity of each monomer can be suitably adjusted so that content of each structural unit in a polymer may become a desired range.

It does not restrict|limit especially as a polymerization method, The method similar to the manufacturing method of the said resin (b1) is mentioned.

The content of the resin (b2) is preferably 10 to 60 mass%, more preferably 20 to 50 mass%, still more preferably 30 to 45 mass%, in 100 mass% of the total solid content of the curable composition. .

When using the resin (b1) and the resin (b2) together, the total content of the resin (b1) and the resin (b2) is preferably 1 to 50 mass% in 100 mass% of the total solid content of the curable composition, It is more preferable that it is 3-40 mass %, and it is still more preferable that it is 5-35 mass %.

The said resin (b2) may have the above-mentioned acidic radical. The said resin (b) may have the group which produces|generates an acidic radical by the said heat|fever or an acid, and the above-mentioned acidic radical.

The polymerizable compound is the vinyl ether compound, a cyclic ether compound, (meth)acrylic acid ester, a carboxylic acid compound, an acid group-containing alkali-soluble resin, a resin having a group generating an acid group by heat or acid, a maleimide compound, At least one selected from the group consisting of alcohols and thiols is preferable.

<Cure catalyst (C)>

Although it does not specifically limit as a curing catalyst used in this invention, Preferably, at least 1 type selected from the group which consists of a cation curing catalyst and a radical curing catalyst is mentioned. Especially, a cation curing catalyst is preferable at the point which the crosslinking reaction of a vinyl ether group advances rapidly.

In either case of the cationic curing catalyst and the radical curing catalyst, depending on the embodiment, it is also possible to use a heat latent or photolatent. Moreover, a Lewis acid or a Brensted acid itself can also be used as a cation curing catalyst. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

(thermal latent cationic curing catalyst)

It does not specifically limit as said heat-latent cationic curing catalyst, A well-known thing can be used. These are compounds that cannot generate a practical amount of cationically active species depending on irradiation with light, and the temperature at which cationically active species is generated is preferably 40°C to 200°C, more preferably 60°C to 180°C, 80 degreeC - 150 degreeC are more preferable. Examples of the heat latent cationic curing catalyst include a nonionic curing catalyst and an ionic curing catalyst.

Among the heat-latent cationic curing catalysts, nonionic curing catalysts include Lewis acid moieties such as organoboron compounds, nitrogen-containing compounds such as amines and pyridines, phosphorus-containing compounds such as phosphine, and sulfur-containing compounds such as sulfides The compound which consists of a combination with Lewis base moieties, such as these is mentioned.

Among the thermal latent cationic curing catalysts, examples of the ionic curing catalyst include (4-hydroxyphenyl)benzylmethylsulfonium, (4-hydroxyphenyl)methyl-o-tolylsulfonium, (4 -Cathions such as acetoxyphenyl)benzylmethylsulfonium and diphenylmethylsulfonium and tetrafluoroborate, hexafluorophosphate, triphenylhexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate , a compound formed in combination with an anion such as tetrakis(pentafluorophenyl)borate, bis(trifluoromethanesulfonyl)imide, or tricyanomethanide.

(Photolatent Cationic Curing Catalyst)

It does not specifically limit as said photolatent cationic curing catalyst, A well-known thing can be used, A nonionic curing catalyst and an ionic curing catalyst are mentioned. Examples of the nonionic curing catalyst include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, and N-hydroxyimide phosphonate. Examples of the ionic curing catalyst include diphenyliodonium, 4-methoxydiphenyliodonium, bis(4-methylphenyl)iodonium, and 4-isopropyl-4'-methyldiphenyliodo nium, bis(4-tert-butylphenyl)iodonium, bis(dodecylphenyl)iodonium, diphenyl-4-thiophenoxyphenylsulfonium, bis[4-(diphenylsulfonio)- phenyl]sulfide, bis[4-(di(4-(2-hydroxyethyl)phenyl)sulfonio)-phenyl]sulfide, 4-chlorophenyldiphenylsulfonium, triphenylsulfonium, η5-2 cations such as ,4-(cyclopentazenyl)[1,2,3,4,5,6-η-(methylethyl)benzene]-Fe(1+), tetrafluoroborate, hexafluorophosphate; and a compound composed of a combination with an anion such as triphenylhexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate and tetrakis(pentafluorophenyl)borate. Moreover, you may add photosensitizers, such as a thioxanthone, as needed.

A photoacid generator can also be used as the photolatent cation curing catalyst, and as such compounds, for example, an onium salt compound, a sulfone compound, a sulfonic acid ester compound, a quinonediazide compound, a sulfonimide compound, and a diazomethane A compound etc. are mentioned.

Especially, it is preferable that it is at least 1 sort(s) selected from the group which consists of an onium salt compound, a sulfonimide compound, and a diazomethane compound, It is more preferable that it is an onium salt compound, It is still more preferable that it is a triarylsulfonium salt.

Examples of the onium salt compound include a diaryliodonium salt, a triarylsulfonium salt, and a triarylphosphonium salt.

Specific examples of the diaryl iodonium salt include Bluesil PI2074 (manufactured by Elkem), diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, and diphenyliodonium hexafluoro. Rhoantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate diphenyl iodonium salts, such as; 4-Methoxyphenylphenyliodoniumtetrafluoroborate, 4-methoxyphenylphenyliodoniumhexafluorophosphonate, 4-methoxyphenylphenyliodoniumhexafluoroantimonate, 4-methoxy Phenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodo 4-methoxyphenylphenyl iodonium salts, such as nium-p-toluenesulfonate; Bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphonate, bis(4-tert-butylphenyl)iodonium hexafluoro Rhoantimonate, bis(4-tert-butylphenyl)iodonium hexafluoroarsenate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butyl and bis(4-tert-butylphenyl)iodonium salts such as phenyl)iodonium trifluoroacetate and bis(4-tert-butylphenyl)iodonium-p-toluenesulfonate.

Examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium hexafluoro triphenylsulfonium salts such as arsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, and triphenylsulfonium-p-toluenesulfonate; 4-Methoxyphenyldiphenylsulfoniumtetrafluoroborate, 4-methoxyphenyldiphenylsulfoniumhexafluorophosphonate, 4-methoxyphenyldiphenylsulfoniumhexafluoroantimonate, 4-methoxy Phenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonate 4-methoxyphenyldiphenylsulfonium salts, such as phonium-p-toluenesulfonate; 4-phenylthiophenyldiphenylsulfoniumtetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 4-phenylthio Phenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonate 4-phenylthiophenyldiphenylsulfonium salts, such as phonium-p-toluenesulfonate, etc. are mentioned.

Examples of the triarylphosphonium salt include triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphonate, triphenylphosphonium hexafluoroantimonate, and triphenylphosphonium hexafluoro triphenylphosphonium salts such as loarsenate, triphenylphosphonium trifluoromethanesulfonate, triphenylphosphonium trifluoroacetate, and triphenylphosphonium-p-toluenesulfonate; 4-Methoxyphenyldiphenylphosphoniumtetrafluoroborate, 4-methoxyphenyldiphenylphosphoniumhexafluorophosphonate, 4-methoxyphenyldiphenylphosphonium hexafluoroantimonate, 4-methoxy Phenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphospho 4-methoxyphenyldiphenylphosphonium salts, such as phonium-p-toluenesulfonate; Tris (4-methoxyphenyl) phosphonium tetrafluoroborate, tris (4-methoxyphenyl) phosphonium hexafluorophosphonate, tris (4-methoxyphenyl) phosphonium hexafluoroantimonate, tris (4-methoxyphenyl) phosphonium hexafluoroarsenate, tris (4-methoxyphenyl) phosphonium trifluoromethanesulfonate, tris (4-methoxyphenyl) phosphonium trifluoroacetate, tris ( and tris(4-methoxyphenyl)phosphonium salts such as 4-methoxyphenyl)phosphonium-p-toluenesulfonate.

Examples of the sulfonimide compound include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulf Ponyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclo-[2,2,1]-hepto-5-ene-2,3-dicarboximide, N-(trifluoro Methylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hepto-5-ene-2,3-dicarboximide, N-(trifluoromethylsulfonyloxy)bicyclo-[2 N-(trifluoromethylsulfonyloxy) such as ,2,1]-heptane-5,6-oxy-2,3-dicarboximide and N-(trifluoromethylsulfonyloxy)naphthylimide sulfonimide compounds having a group; N-(campanylsulfonyloxy)succinimide, N-(campanylsulfonyloxy)phthalimide, N-(campanylsulfonyloxy)diphenylmaleimide, N-(campanylsulfonyloxy)bicyclo-[2 ,2,1]-hepto-5-ene-2,3-dicarboximide, N-(campanylsulfonyloxy)-7-oxabicyclo-[2,2,1]-hepto-5-ene-2 ,3-dicarboximide, N-(campanylsulfonyloxy)bicyclo-[2,2,1]-heptane-5,6-oxy-2,3-dicarboximide, N-(campanylsulfonyloxy) sulfonimide compounds having an N-(campanylsulfonyloxy) group such as naphthylimide; N-(4-methylphenylsulfonyloxy)succinimide, N-(4-methylphenylsulfonyloxy)phthalimide, N-(4-methylphenylsulfonyloxy)diphenylmaleimide, N-(4-methylphenylsulfonyloxy) Ponyloxy)bicyclo-[2,2,1]-hepto-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo-[2,2, 1]-Hepto-5-ene-2,3-dicarboximide, N-(4-methylphenylsulfonyloxy)bicyclo-[2,2,1]-heptane-5,6-oxy-2,3- sulfonimide compounds having an N-(4-methylphenylsulfonyloxy) group such as dicarboximide and N-(4-methylphenylsulfonyloxy)naphthylimide; N-(2-trifluoromethylphenylsulfonyloxy)succinimide, N-(2-trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmalei Mead, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo-[2,2,1]-hepto-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyl) Ponyloxy)-7-oxabicyclo-[2,2,1]-hepto-5-ene-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo-[2 N-(2-trifluoromethylphenyl, such as ,2,1]-heptane-5,6-oxy-2,3-dicarboximide, N-(2-trifluoromethylphenylsulfonyloxy)naphthylimide, etc. and sulfonimide compounds having a sulfonyloxy) group.

Examples of the diazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p- Toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethyl ethylsulfonyl)diazomethane, and the like.

(thermal latent radical curing catalyst)

Examples of the thermal latent radical curing catalyst include cumene hydroperoxide, dicumyl peroxide, diisopropylbenzene peroxide, di-t-butyl peroxide, lauryl peroxide, benzoyl peroxide, t-butyl organic peroxides such as peroxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate, and t-amylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2 azo compounds such as '-azobis(2-methylpropionate); and the like.

(Photolatent Radical Curing Catalyst)

Examples of the photolatent radical curing catalyst include 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy- 2-methyl-1-1phenylpropanone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 2-benzyl-2-(dimethylamino)-4'-morph alkylphenones such as polynobutyrophenone; acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide; methyl benzoyl formate;

2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)- aminoketone compounds such as butan-1-one (“IRGACURE379”, manufactured by BASF); Benzyl ketals such as 2,2-dimethoxy-1,2-diphenylethan-1-one (“IRGACURE651”, manufactured by BASF) and phenylglyoxylic acid methyl ester (“DAROCUR MBF”, manufactured by BASF) compound; 1-Hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", manufactured by BASF), 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy-1-{ 4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl｝-2-methyl-propan-1-one ("IRGACURE127", manufactured by BASF), [1-hydroxyl- Hydroketone compounds, such as cyclohexyl-phenyl- ketone + benzophenone] ("IRGACURE500", the BASF make); 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime)] (“OXE01”, manufactured by BASF), ethanone, 1-[9-ethyl-6 -(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) ("OXE02", manufactured by BASF), 1,2-octanedione, 1-[4-( Phenylthio)-, 2-, (O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-, 1-(O-acetyloxime) ("OXE04", BASF company make)), such as oxime ester type compound; benzophenone compounds; benzoin compounds; thioxanthone-based compounds; halomethylated triazine-based compounds; halomethylated oxadiazole compounds; biimidazole-based compounds; titanocene-based compounds; benzoic acid ester compounds; acridine-based compounds; and the like.

When the curable composition of this invention contains the said curing catalyst (C), it is preferable that content of the said curing catalyst (C) is 0.01-10 mass parts with respect to 100 mass parts of the said polymer (A), 0.1-5 It is more preferable that it is a mass part, and it is still more preferable that it is 0.5-3 mass parts.

Moreover, when using the said photolatent radical curing catalyst especially as said curing catalyst (C), content of the said curing catalyst (C) is 0.3-20 mass with respect to 100 mass % of solid content total of curable composition of this invention. It is preferable that it is %, It is more preferable that it is 0.5-10 mass %, It is more preferable that it is 1-8 mass %.

Moreover, when using the photo-latent cation curing catalyst of the said photo-acid generator especially as said curing catalyst (C), content of the said curing catalyst (C) with respect to 100 mass % of solid content total amount of curable composition of this invention. , It is preferable that it is 0.3-20 mass %, It is more preferable that it is 0.5-10 mass %, It is more preferable that it is 1-8 mass %.

The curable composition (1) of this invention may contain other components other than the component mentioned above further. Examples of the other components include other polymerizable compounds other than those described above, epoxy compounds, solvents, chain transfer agents, dispersants, antioxidants, leveling agents, inorganic fine particles, coupling agents, curing agents, curing aids, plasticizers, polymerizations Inhibitor, UV absorber, defoaming agent, antistatic agent, anti-aging agent, wettability improver, adhesion imparting agent, colorant (pigment, dye), heat resistance improver, developer, filler, thermosetting resin, gloss remover, slip agent, surface modifier, thixotropic (搖變) 1 type, or 2 or more types of arbitrary components, such as an adjuvant, a quinonediazide compound, a polyhydric phenol compound, a cationically polymerizable compound, and a thermal acid generator, are mentioned. What is necessary is just to select these from a well-known thing suitably according to the objective of a curable composition, and a use. Moreover, the usage-amount can also be set suitably.

(Other polymerizable compounds)

It is preferable that the curable composition (1) of this invention contains the said other polymeric compound. By further including the said other polymeric compound, the hardened|cured material excellent also in various physical properties, such as solvent resistance, mechanical strength, heat resistance, in addition to sclerosis|hardenability, can be provided.

The other polymerizable compound is a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. It is a low molecular compound which has, For example, the monofunctional compound which has one polymerizable unsaturated group in a molecule|numerator, and the polyfunctional compound which has two or more are mentioned.

As a specific example of the said other polymeric compound, for example, described in paragraphs [0077] - [0085] of Unexamined-Japanese-Patent No. 2015-42697, other than the above-mentioned polymeric compound (B), monofunctional A polymerizable compound and a polyfunctional polymerizable compound are mentioned.

Among them, the polyfunctional polymerizable compound is preferably a polyfunctional (meth) acrylate compound, a polyfunctional urethane (meth) acrylate compound, (meth) acryl from the viewpoint of reactivity, economy, availability, etc. The compound which has a (meth)acryloyl group, such as a loyl group containing isocyanurate compound, is mentioned, More preferably, a polyfunctional (meth)acrylate compound is mentioned. By including the compound which has a (meth)acryloyl group, a curable composition becomes the thing more excellent in photosensitivity and sclerosis|hardenability, and can obtain the hardened|cured material which is further high hardness and is highly transparent. As said polyfunctional polymeric compound, it is more preferable to use a trifunctional or more than trifunctional polyfunctional (meth)acrylate compound.

The content of the other polymerizable compound is not particularly limited as long as the effect of the present invention is exhibited, and may be appropriately set. Preferably it is 5-60 mass %, More preferably, it is 10-50 mass %.

(epoxy compound)

It is preferable that curable composition (1) of this invention contains an epoxy compound. When an epoxy compound is included, cationic polymerization will advance, a crosslinking reaction will advance more easily, and hardened|cured material excellent in solvent resistance can be provided.

As said epoxy compound, the compound which has an epoxy group and a polymerizable double bond is mentioned, For example, the epoxy group containing monomer mentioned above is mentioned.

To [ content of the said epoxy compound / 100 mass % of solid content total amount of curable composition ], Preferably it is 1-50 mass %, More preferably, it is 2-40 mass %, More preferably, it is 5-30 mass %.

curable composition (2)

The second curable composition of the present invention (hereinafter also referred to as "curable composition (2)") is a curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C), The polymer (A) is a group transfer polymer of a monomer component containing vinyl ether group-containing (meth)acrylic acid esters represented by the following general formula (2).

[Formula 19]

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n is 1 or more represents an integer.)

A curable composition containing such a group transfer polymer also has excellent curing reactivity.

Further, as described above, since the group transfer polymer is obtained by group transfer polymerization, a cured product having a desired shape with a small amount of insoluble content and a cured product having good strength can be obtained. Moreover, since there is little quantity of a residual monomer, the reproducibility of the physical property expression of the hardened|cured material obtained becomes high.

The group transfer polymer preferably has the same structural unit as the structural unit (a1), except that n is an integer of 1 or more in the structural unit (a1) represented by the general formula (1) described above.

The polymer (A) used in the curable composition (2) may further have the same structural unit as the polymer (A) used in the curable composition (1) except for having the structural unit described above. . In addition, physical properties such as various molecular weights, insoluble content, and residual monomer amount of the polymer (A) used in the curable composition (2) and the content in the curable composition are the polymers used in the curable composition (1). The same thing as (A) is preferable.

As a manufacturing method of the polymer (A) used in the said curable composition (2), n is 1 or more in the vinyl ether group containing (meth)acrylic acid ester represented by General formula (2) mentioned above as a monomer component. The method similar to the method of performing group transfer polymerization described in the manufacturing method of the polymer (A) used in the said curable composition (1) is mentioned except using the thing which is an integer.

As vinyl ether group-containing (meth)acrylic acid esters in which n is an integer of 1 or more in the general formula (2), for example, (meth)acrylic acid 2-(2-vinyloxyethoxy)ethyl, (meth) Acrylic acid 2-vinyloxyethyl etc. are mentioned preferably.

As the polymerizable compound (B) used in the curable composition (2) and the curing catalyst (C), the polymerizable compound (B) used in the curable composition (1), and the curing catalyst (C) and the same may be mentioned respectively. Their content is also the same.

Moreover, the said curable composition (2) may contain the other component further. As said other component, the thing similar to the other component used by the said curable composition (1) is mentioned.

<Method for producing curable composition>

It does not specifically limit as a manufacturing method of the curable composition (1) and (2) of this invention, For example, each component mentioned above is well-known various mixers and dispersers, such as a bead mill, a ball mill, a kneader, and a blender. It can be prepared by mixing and dispersing using Moreover, after manufacturing a polymer, another solvent may be added to what desolved the solvent used for manufacture, and you may mix with each component. Moreover, you may further include the other process normally performed. For example, when a color material is included, a color material composition may be previously prepared using a solvent, a dispersing agent, etc., and then, you may mix with each component mentioned above.

<How to use>

As a method of using the curable compositions (1) and (2) of the present invention, for example, the curable composition is applied on a substrate, and the coated material is dried, heated, or irradiated with active energy rays, or these By combination, the method of hardening a coating material, and forming a cured film, etc. are mentioned.

It does not specifically limit as said base material, For example, the well-known base material which consists of wood, glass, various plastics, or these combinations is mentioned.

The coating method is not particularly limited, and can be carried out by known methods such as gravure coating, roll coating, bar coating, applicator and inkjet coating.

The drying or heating method may be appropriately selected from known methods according to the composition, purpose, and use of the curable composition. For example, it is preferable to carry out at 50 to 300°C, and more desirable. It is preferable that they are 1 minute - 72 hours, and, as for dry heating time, it is more preferable that they are 20 minutes - 24 hours.

Active energy ray irradiation can be performed by a well-known method using active energy rays, such as infrared rays, an ultraviolet-ray, X-rays, and an electron beam. The irradiation amount can be appropriately set according to the composition and use of the curable composition.

Moreover, you may use the curable composition (1) and (2) of this invention as a molding material. It does not specifically limit as a shaping|molding method, According to the composition, purpose, or use of a curable composition, it can select suitably from well-known methods, such as injection molding, extrusion molding, and a 3D printer.

When the hardened|cured material of the said curable composition is a cured film, although what is necessary is just to design the thickness suitably according to the objective and a use, it is preferable that they are 1 micrometer - 5 mm normally.

<Use>

Curable compositions (1) and (2) of this invention are excellent in the hardening reactivity by an active energy ray or a heat|fever. Curable compositions (1) and (2) of the present invention are adhesive, adhesive, printing ink composition, 3D printer composition, resist composition, sealing material, releasability, fingerprint adhesion prevention, water repellency, hydrophilicity, hard coat, antifouling, antistatic Various coatings with functions such as prevention and insulation, various functional paints for automobiles, buildings and structures, industrial use, packaging, etc. Various molding materials such as surface protection sheets, substrates, lenses, electronic parts, optical films, and optical parts It can be used suitably for uses, such as.

Curable compositions (1) and (2) of this invention can be used suitably as a composition for resists, and can be used more preferably as a composition for color filters. As a method for producing and using the curable compositions (1) and (2) of the present invention preferable as a composition for a resist, the methods described in paragraphs [0120] to [0140] of JP-A-2015-42697 are exemplified.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited only to these Examples. In addition, unless otherwise indicated, "part" shall mean "part by mass" and "%" shall mean "mass %", respectively.

Various physical properties of the polymer were measured by the following method.

<Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw/Mn)>

The obtained polymer was melt|dissolved and diluted with tetrahydrofuran, and what filtered with a filter with a pore diameter of 0.45 micrometer was measured by the following gel permeation chromatography (GPC) apparatus and conditions.

Device: HLC-8020GPC (manufactured by Toso Corporation)

Elution solvent: tetrahydrofuran

Standard material: standard polystyrene (manufactured by Toso Corporation)

Separation column: TSKgel SuperHM-M, TSKgel SuperH-RC (manufactured by Toso Corporation)

In addition, for polymers B-1 and B-2, TSKgel SuperHZM-M and TSKgel SuperH-RC (manufactured by Tosoh Corporation) were used as separation columns.

< ¹ H-NMR measurement>

About the obtained polymer, ¹ H-NMR measurement was performed on condition of the following.

Device: Nuclear magnetic resonance device manufactured by Agilent Technologies (600 MHz)

Measurement solvent: deuterated chloroform

Sample preparation: Several mg to several tens of mg of the obtained polymer were dissolved in a measurement solvent.

<Insoluble fraction>

Ethyl acetate was added to about 2-3 g of obtained polymers so that solid content might be about 33 mass %, and after fully stirring at room temperature, the obtained solution was passed through the filter whose pore diameter is 4 micrometers. After the residue on the filter was further washed with about 7 to 10 g of ethyl acetate, the residue was dried at room temperature for 5 minutes, and the mass (b) of the residue after drying was measured. The mass of the polymer was taken as (a), and the insoluble fraction was computed from the following formula.

Insoluble fraction (mass %) = (b)/(a) × 100

＜X/Y ratio＞

In the differential molecular weight distribution curve obtained by molecular weight measurement of the polymer by the GPC method, as shown in Fig. 1, the point of the maximum value is T, and the 5% height point of T on the differential molecular weight distribution curve is the low molecular weight side. Calculate the area (X) of the triangle surrounded by TL ₀ -L ₁ and the area (Y) of the portion surrounded by the line connecting the differential molecular weight distribution curve and L ₀ -L ₁ when L ₀ and L ₁ are defined from , the ratio (X/Y) was calculated.

<Solid content>

About 1 g of the polymer solution was weighed into an aluminum cup, and after adding and dissolving about 3 g of acetone, it was dried naturally at room temperature. And after drying at 170 degreeC under vacuum for 1.5 hours using a hot-air dryer (brand name: PHH-101, the SPEC company make), it stood to cool in the desiccator and measured the mass. From the mass decrease, the solid content (mass %) of the polymer solution was calculated.

＜Mountain value＞

3 g of the polymer solution was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N aqueous KOH solution as a titrant. The titration was performed using an automatic titration device (trade name: COM-555, manufactured by Hiranuma Industries, Ltd.), and the acid value (mgKOH/g) per solid content (mgKOH/g) was calculated|required from the acid value of the solution, and the solid content of the solution.

Preparation of polymers

(Production Example 1)

<Production of methacrylic acid 2-(2-vinyloxyethoxy)ethyl polymer>

In a 50 mL shrink flask, dehydrated tetrahydrofuran (230 parts by mass), methyl (trimethylsilyl) dimethyl ketene acetal (0.9 parts by mass), and tetrabutylammonium benzoate (0.02 parts by mass) were placed, and under a nitrogen stream, room temperature While stirring in a methacrylate, 2-(2-vinyloxyethoxy)ethyl (hereinafter referred to as "VEEM") (100 parts by mass) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours, and then the reaction solution was passed through a silica gel column to remove the catalyst. The resulting solution was concentrated to obtain a VEEM polymer. As a result of confirming the obtained polymer by < ¹ >H-NMR, the peak derived from vinyl ether was confirmed around 6.5 ppm, and it turned out that all the vinyl ether groups remain|survives from the integral value.

VEEM as a monomer was not observed, and the insoluble content contained in the polymer was 0%.

The weight average molecular weight of the obtained polymer was 42000, the number average molecular weight was 25000, and molecular weight distribution (Mw/Mn) was 1.7. Moreover, the value of X/Y of the polymer was 1.16.

100 mass parts of ethyl acetate was added to this, and the 50 mass % polymer solution was prepared.

(Production Example 2)

<Production of methacrylic acid 2-(2-vinyloxyethoxy)ethyl-methyl methacrylate copolymer>

In a 500 mL flask, dehydrated tetrahydrofuran (200 parts by mass), methyl(trimethylsilyl)dimethylketeneacetal (1.7 parts by mass), and tetrabutylammonium benzoate (0.02 parts by mass) were placed. Under nitrogen stream, while stirring at 20 degreeC, the monomer liquid mixture (VEEM (20 mass parts) and methyl methacrylate (henceforth "MMA".) (90 mass parts))) was dripped slowly. After stirring for 5 hours, the catalyst was removed by diluting with ethyl acetate and passing through a silica gel shot column. The polymer concentration of the obtained solution was concentrated and adjusted, and the VEEM-MMA copolymer solution with a polymer concentration of 50% was obtained. When the obtained copolymer was confirmed by < ¹ >H-NMR, the peak derived from vinyl ether was confirmed, and it turned out that all the vinyl ether groups remain|survives from the integral value. VEEM and MMA which are monomers were not observed, and the insoluble content contained in a copolymer was 0 %. The ratio of the structural units of the copolymer was VEEM/MMA = 11/89 (mol%). Moreover, the weight average molecular weight of the said copolymer was 15000, the number average molecular weight was 12800, and molecular weight distribution (weight average molecular weight/number average molecular weight) was 1.17. The value of X/Y of the copolymer was 1.37.

(Production Example 3)

<Production of methacrylic acid 2-(2-vinyloxyethoxy)ethyl-methyl methacrylate copolymer>

VEEM (100 parts by mass), MMA (50 parts by mass), dehydrated tetrahydrofuran (350 parts by mass), and methyl (trimethylsilyl) dimethyl ketene acetal (2 parts by mass) were placed in a flask, and stirred at room temperature under a nitrogen stream. Phosphazene base P4-t-Bu (0.8 M toluene solution, 2.5 mass parts) was added. After stirring at room temperature overnight (about 20 hours), a small amount of methanol was added to concentrate the reaction solution to obtain a polymer composition comprising a VEEM-MMA copolymer.

As a result of confirming the obtained polymer composition by < ¹ >H-NMR, the peak derived from vinyl ether was confirmed around 6.5 ppm, and it turned out that all the vinyl ether groups remain|survived from the integral value. From this, it was confirmed that the polymer obtained by superposing|polymerizing only the methacryloyl of VEEM was obtained. On the other hand, the peak of VEEM which is a monomer was not confirmed. The insoluble content contained in the copolymer was 0%. The ratio of the structural units of the copolymer was VEEM/MMA = 50/50 (mol%).

Moreover, the weight average molecular weight of the obtained copolymer was 27600, the number average molecular weight was 10600, and molecular weight distribution (Mw/Mn) was 2.61. The value of X/Y of the copolymer was 1.11.

(Production Example 4)

<Production of acrylic acid 2-(2-vinyloxyethoxy)ethyl polymer>

In a flask, 2-(2-vinyloxyethoxy)ethyl acrylate (hereinafter referred to as "VEEA") (100 parts by mass), dehydrated toluene (180 parts by mass), methyl(trimethylsilyl)dimethylketeneacetal (1 part by mass) ) was added, and the phosphazene base P4-t-Bu (0.8 M toluene solution, 2 parts by mass) was added while stirring at 30°C under a nitrogen stream. After stirring at 30°C overnight (about 24 hours), a small amount of methanol was added to concentrate the reaction solution to obtain a polymer composition containing a VEEA polymer.

As a result of confirming the obtained polymer composition by < ¹ >H-NMR, the peak derived from vinyl ether was confirmed around 6.5 ppm, and it turned out that all the vinyl ether groups remain|survived from the integral value. From this, it was confirmed that the polymer obtained by superposing|polymerizing only the acryloyl of VEEA was obtained. On the other hand, the peaks (peaks around 6.5 ppm, 6.2 ppm, and 5.8 ppm) of VEEA as a monomer were not confirmed. The insoluble content contained in the polymer was 0%. Moreover, the weight average molecular weight of the obtained VEEA polymer was 19400, the number average molecular weight was 7600, and molecular weight distribution (Mw/Mn) was 2.57. The value of X/Y of the VEEA polymer was 1.04.

(Preparation Example 5)

<Production of methacrylic acid 2-(2-vinyloxyethoxy)ethyl-cyclohexyl methacrylate copolymer>

VEEM (100 parts by mass) to a mixture of dehydrated tetrahydrofuran (400 parts by mass), methyl(trimethylsilyl)dimethylketeneacetal (6 parts by mass), and tetrabutylammonium benzoate (0.1 parts by mass) in a flask immersed in a thermostat at 20°C ) and cyclohexyl methacrylate (hereinafter referred to as "CHMA") (100 parts by mass) was added dropwise over 10 minutes under a nitrogen stream. After completion of the dropwise addition, the reaction solution was stirred under the same conditions for 5 hours. The obtained solution was diluted with ethyl acetate, passed through a silica gel shot column, and then concentrated under reduced pressure to obtain a polymer composition containing a VEEM-CHMA copolymer.

As a result of confirming the obtained polymer composition by ¹ H-NMR, VEEM and CHMA used for polymerization were completely consumed. The insoluble content contained in the obtained copolymer was 0 %.

Moreover, the weight average molecular weight of the said copolymer was 6900, the number average molecular weight was 6272, and molecular weight distribution (Mw/Mn) was 1.1. The value of X/Y of the VEEM-CHMA copolymer was 1.20.

(Preparation Example 6)

<Production of glycidyl methacrylate polymer>

In a four-neck flask equipped with a thermometer, an inert gas introduction tube, and a reflux condenser, glycidyl methacrylate (hereinafter referred to as “GMA”) (30 parts by mass), methyl ethyl ketone (hereinafter referred to as “MEK”) .) (70 parts by mass) was added to obtain a reaction solution. After deaeration for 3 hours through nitrogen gas in the reaction solution by bubbling, the temperature of the reaction solution was raised to 70° C. while flowing nitrogen gas from the inert gas introduction tube, and a polymerization initiator (azobisisobutyronitrile: AIBN) ( 0.34 parts by mass) of MEK solution (5 parts by mass) was slowly added to the reaction solution. Then, it stirred at the same temperature for 20 hours, and MEK (100 mass parts) was added after standing to cool to room temperature, and the polymer solution was obtained. The GMA polymer was obtained by reprecipitating this polymer solution using hexane. The weight average molecular weight of the obtained polymer was 125800, the number average molecular weight was 23200, and molecular weight distribution (Mw/Mn) was 5.42.

(Production Example 7)

<Production of Polymer B-1>

81.9 parts of propylene glycol monomethyl ether acetate and 37.7 parts of propylene glycol monomethyl ether were injected into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dropping tank inlet, and after nitrogen substitution, heating to 90 ° C. heated up. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 70.0 parts of methacrylic acid-t-butyl, 20.0 parts of methacrylic acid, 34.2 parts of propylene glycol monomethyl ether acetate, and 14.7 parts of propylene glycol monomethyl ether. parts and 2.0 parts of t-butylperoxy-2-ethylhexanoate were prepared with stirring, and to the dropping tank (B), 1.0 parts of n-dodecyl mercaptan and 6.1 parts of propylene glycol monomethyl ether acetate were stirred and mixed. prepared something. After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition|polymerization was performed. After maintaining 90 degreeC for 30 minutes after completion|finish of dripping, it heated up to 115 degreeC, and aged for 90 minutes. Then, after cooling to room temperature, 16.5 parts of GMA, 0.4 parts of dimethylbenzylamine as a catalyst, and 0.2 parts of topanol as a polymerization inhibitor are injected|poured, it is made to react at 110 degreeC for 7 hours, and polymer solution B-1 (solid content 39.8%) ) was obtained. The weight average molecular weight of the obtained polymer was 15000, molecular weight distribution (Mw/Mn) was 2.5, and the acid value was 60 mgKOH/g.

(Preparation Example 8)

<Production of Polymer B-2>

201.0 parts of propylene glycol monomethyl ether acetate was poured into a reaction tank equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube, and a dripping tank inlet, and after nitrogen substitution, it heated and heated up to 90 degreeC. On the other hand, as the dropping tank (A), in a beaker, 10.0 parts of N-benzylmaleimide, 43.6 parts of CHMA, 30.0 parts of methacrylic acid-2-hydroxyethyl, 16.4 parts of GMA, 30.0 parts of propylene glycol monomethyl ether acetate, and t A mixture of 2.0 parts of -butylperoxy-2-ethylhexanoate was prepared with stirring, and 2.0 parts of n-dodecyl mercaptan and 31.3 parts of propylene glycol monomethyl ether acetate were stirred and mixed in the dropping tank (B). . After the temperature of the reaction tank became 90 degreeC, dripping was started over 3 hours from the dripping tank, maintaining the same temperature, and superposition|polymerization was performed. After holding|maintaining 90 degreeC for 30 minute(s) after completion|finish of dripping, it heated up to 115 degreeC, and aged for 90 minutes. Then, after cooling to room temperature, 0.3 parts of dimethylbenzylamine was inject|poured as 11.5 parts of succinic anhydride and a catalyst, it was made to react at 60 degreeC for 3 hours, and polymer solution B-2 (28.8% of solid content) was obtained. The weight average molecular weight of the obtained polymer was 10000, molecular weight distribution (Mw/Mn) was 2.8, and the acid value was 68 mgKOH/g.

(Examples 1-28, Comparative Examples 1-9)

<Preparation of curable composition>

The polymer solution obtained above, the polymerizable compound, and the curing catalyst were each mixed by a blending as shown in Tables 1-3 to obtain a curable composition. In addition, the compounding quantity in a table|surface is a solid content conversion amount.

<Curability evaluation (acetone rubbing test)>

The obtained curable composition was coated on a PET film (7 cm × 21 cm) subjected to single-sided easy adhesion treatment to a thickness of 25 µm using a bar coater, left at room temperature for about 10 to 20 minutes, and then the coated object was , UV curing was performed under the irradiation energy conditions shown in Table 1 using an ultraviolet irradiation device FUSION UV manufactured by Heraeus, or thermosetting was performed under the curing conditions shown in Tables 2 to 3 to obtain a cured coating film. The obtained cured coating film was rubbed 20 times with Kimwipe (manufactured by Nippon Paper Cresia Co., Ltd.) impregnated with acetone, and the degree of curing was confirmed by the following evaluation criteria. A result is shown to Tables 1-3.

(Evaluation standard)

○: The cured coating film does not dissolve.

(triangle|delta): A rubbing mark remained on the cured coating film, or it swelled.

x: The cured coating film was whitened or melt|dissolved.

In addition, the compound described in Tables 1-3 is as follows.

BMI-2300: Phenylmethane maleimide, manufactured by Daiwa Chemical Industry Co., Ltd.

PI2074: Bluesil ^TM PI2074, manufactured by Elkem

Irg184: IRUGACURE184 (1-hydroxycyclohexyl-phenyl ketone, manufactured by BASF)

Polyacrylic acid (Mw5000): manufactured by Aldrich

FRONZA B5200XP: manufactured by SIRRUS

San-Aid SI150L: Manufactured by Sanshin Chemical Industry Co., Ltd.

San-Aid SI110L: Manufactured by Sanshin Chemical Industry Co., Ltd.

San-Aid SI100L: Manufactured by Sanshin Chemical Industry Co., Ltd.

Organic boron compound: FX-TP-BC-PC-AD-57103, manufactured by Nippon Catalyst Co., Ltd.

From Tables 1-3, it turned out that the curable composition of an Example is excellent in hardening reactivity also in ultraviolet curing or thermosetting, and provides favorable hardened|cured material with little energy.

Moreover, it turned out that the curable composition of an Example was excellent in hardening reactivity also compared with the curable composition containing the polymer (GMA) which has a common epoxy group in a side chain among the cation-curable compound which is a comparative example.

<Evaluation of photocuring reactivity>

The VEEM polymer obtained in Production Example 1 and the VEEM-MMA copolymer obtained in Production Example 2 were evaluated for photocuring reactivity by the following method. As a control, Celoxide 2021P (3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by Daicel Corporation) and trimethylolpropane triacrylate (TMPTA) were used as controls. , the photocuring reactivity was evaluated in the same way.

Device: NETZSCH DSC 204F1 Phoenix

Method: 1 to 2 mg of a sample is weighed into a container, set in an apparatus, and 10 mW/cm2 of light (light source: xenon lamp, no filter) is emitted for 5 minutes while maintaining the sample temperature at 25° C. under a nitrogen atmosphere. It was investigated, and the change of the reaction calorific value during that time was measured.

As a photocationic curing sample, Bluesil ^TM PI2074 (manufactured by Elkem) was added as a photocationic curing catalyst to a propylene carbonate solution of 40% by mass of VEEM-MMA copolymer, or an epoxy compound (Celoxide 2021P) per solid content. What mixed mass % was used.

Moreover, what mixed 2 mass % of Irg184 with respect to solid content as an optical radical initiator with the propylene carbonate solution of 50 mass % of VEEM polymers or TMPTA was used as an optical radical hardening sample. The measurement results are shown in Figs. 2 and 3 .

2 shows the DSC curve of the photocationically cured sample. According to FIG. 2, it turned out that heat_generation|fever started abruptly from 3.5 minutes when light irradiation started, and hardening reaction is advancing. The epoxy compound as a comparative control continued to exotherm due to the curing reaction for a while after the calorific value reached a peak. On the other hand, in the VEEM-MMA copolymer, the exothermic peak was sharp, and the curing reaction was completed in a short time. From this point, it was found that the polymer containing a vinyl ether group was excellent in curing reactivity.

3 shows the DSC curve of the photo-radical cured sample. From FIG. 3 , it was found that the VEEM polymer had photo-radical curability equivalent to that of the polyfunctional acrylate compound.

Although sclerosis|hardenability of a curable composition was evaluated above, the physical property of the coating film formed of a curable composition is also important practically. Therefore, the following method evaluated the adhesiveness of a cured coating film, and pencil hardness further using the curable composition of an Example.

In addition, the cured coating film formed by the method similar to the cured coating film used by the above-mentioned <acetone rubbing test> was used for the cured coating film for evaluation.

<Adhesiveness evaluation (cross-cut test)>

The adhesiveness with respect to the PET film of the cured coating film was evaluated according to old JIS-K5400 using the said cured coating film for evaluation. That is, after putting 11 cuts at intervals of 1 mm from the cured coating film, the 90 degree direction was changed and 11 cuts were similarly put, and the checkerboard of 10 squares was created. The cut was made to the extent that the coating film was penetrated and the PET film was not penetrated. A cellophane tape was affixed so as to completely cover the eyes of the checkerboard, and it was rubbed well to adhere well. After that, the end of the tape was grabbed and peeled off at a 45 degree angle. After the tape was removed, the number of eyes remaining on the PET film was counted. It is judged that the more the number of remaining eyes is, the higher the adhesion is. A result is shown in Table 4.

<Pencil hardness test>

Using the cured coating film for evaluation, the scratch hardness of the coating film was evaluated according to JIS K5600-5-4. Electric pencil hardness tester No.553-M (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) was used as a measuring device, and the pencil made by Mitsubishi Pencil Co., Ltd. was used. Table 4 shows the hardness of the hardest pencil that does not cause scratches (plastic deformation).

From Table 4, it was confirmed that the cured coating film formed using the curable composition of an Example was excellent in the adhesiveness to PET film, the pencil hardness was also favorable, and showed the outstanding performance.

(Examples 29 to 30, Comparative Example 10)

Each component was mixed so that it might become the compounding shown in Table 5, and the curable composition was obtained. In addition, the compounding quantity in a table|surface is a solid content conversion amount. In addition, the pigment dispersion 1 in a table|surface was prepared by the following method.

(Preparation Example 1)

Preparation of Pigment Dispersion 1

12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a dispersant, and C.I. Pigment Green 58 in 2.25 parts, and C.I. 1.5 parts of Pigment Yellow 138 was mixed and the pigment dispersion 1 (solid content 22 mass %) was obtained by making it disperse|distribute with a paint shaker for 3 hours.

The compounds described in Table 5 are as follows.

Irgacure OXE02: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (manufactured by BASF)

The solvent resistance of the obtained curable composition was evaluated by the following method. A result is shown in Table 5.

<solvent resistance>

The curable composition is spin-coated on a glass substrate having a width of 5 cm, dried at 100 ° C. for 3 minutes, exposed at 60 mJ using a high-pressure mercury lamp, and heat-treated at 110 ° C. for 40 minutes (post-curing), A cured film with a film thickness of 5 µm was obtained. Then, the cured film was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 40°C for 10 minutes, then taken out, and spectrophotometer UV3100 (manufactured by Shimadzu Corporation) with respect to the immersion liquid (NMP) after taking out the cured film. ) to measure the absorbance. It showed that many color materials eluted in immersion liquid, so that the value of the absorbance was large, and it evaluated that the solvent resistance of a curable composition is low.

From Table 5, it was confirmed that the curable composition of Examples was excellent in curing reactivity and provided a cured product excellent in solvent resistance.

1: Differential molecular weight distribution curve

Claims (9)

A curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C),
The said polymer (A) has a structural unit represented by following General formula (1), and molecular weight distribution (weight average molecular weight/number average molecular weight) is 1.0-4.0, The curable composition characterized by the above-mentioned.

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n is 2 or more represents an integer.) A curable composition comprising a polymer (A), a polymerizable compound (B) and/or a curing catalyst (C),
The said polymer (A) is a group transfer polymer of the monomer component containing vinyl ether group containing (meth)acrylic acid ester represented by following General formula (2), The curable composition characterized by the above-mentioned.

(Wherein, R ¹ represents a hydrogen atom or a methyl group. R ² and R ³ are the same or different and represent a hydrogen atom or an organic group. R ⁴ represents a hydrogen atom or an organic group. n is 1 or more represents an integer.) 3. The method of claim 1 or 2,
The weight average molecular weight of the said polymer (A) is 5000-1000000, The curable composition characterized by the above-mentioned. 4. The method according to any one of claims 1 to 3,
The said curing catalyst (C) is at least 1 type selected from the group which consists of a cation curing catalyst and a radical curing catalyst, The curable composition characterized by the above-mentioned. 5. The method according to any one of claims 1 to 4,
The polymerizable compound (B) is at least one selected from the group consisting of a vinyl ether compound, a cyclic ether compound, (meth)acrylic acid ester, a carboxylic acid compound, a maleimide compound, an alcohol, and a thiol. A curable composition. 5. The method according to any one of claims 1 to 4,
The polymerizable compound (B) is at least one selected from the group consisting of a methylene malonic acid diester compound and α-cyanoacrylic acid ester. 5. The method according to any one of claims 1 to 4,
The polymerizable compound (B) is at least one selected from the group consisting of an acid group-containing alkali-soluble resin and/or a resin having a group generating an acid group by heat or acid. 8. The method according to any one of claims 1 to 7,
A curable composition comprising at least one selected from the group consisting of coatings, pressure-sensitive adhesives, adhesives, resists, paints, ink compositions for printing, electronic components, and optical components. 8. The curable composition according to any one of claims 1 to 7, for producing at least one selected from the group consisting of a coating agent, a pressure-sensitive adhesive, an adhesive, a resist, a paint, an ink composition for printing, an electronic component, and an optical component. use of.

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