WO2022181565A1

WO2022181565A1 - Curable composition, barrier film-forming composition, and cured product

Info

Publication number: WO2022181565A1
Application number: PCT/JP2022/007042
Authority: WO
Inventors: 拓也松本; 諒子丸山; 智幸岩島
Original assignee: 株式会社Adeka
Priority date: 2021-02-24
Filing date: 2022-02-21
Publication date: 2022-09-01
Also published as: TW202302780A

Abstract

The present invention addresses the problem of providing a curable composition from which it is possible to produce a cured product that has sufficient hardness, and excellent water vapor barrier properties, whitening resistance, and light permeability.　The curable composition according to the present invention contains components (A)-(C). In the total of component (A), component (B), and component (C), the contained amount of component (A) is 20-60 mass%, and the contained amount of component (B) is 5-20 mass%. The curable composition does not contain a softening agent or contains a softening agent in an amount less than 6 parts by mass with respect to 100 parts by mass of the total of component (A), component (B), and component (C). (A) A petrolium resin. (B) A hydrocarbon-based polymer having an acrylic group or a methacrylic group. (C) A monomer having a saturated aliphatic ring and two or more groups selected from the group consisting of acrylic groups and methacrylic groups.

Description

Curable composition, composition for forming barrier film, and cured product

The present invention relates to a curable composition, a composition for forming a barrier film, and a cured product.

Parts that are prone to deterioration due to contact with gases such as low molecular weight compounds, oxygen and water vapor are prevented from deterioration by adopting a structure that covers or seals the surface with a protective film. Glass, plastics, silica, silicon nitride, silicon oxide, metals and the like are known as materials for coating parts to form protective films having gas barrier properties.

Parts such as lighting fixtures, automobiles, and mobile terminals such as smartphones and laptops are being made lighter. Inorganic materials such as metals, glass, silicon nitride, and silicon oxide are heavy, so there is a problem that parts cannot be made lighter. Further, it is difficult to prevent pinholes from forming with glass, and there are other problems such as the inability to completely block the outside from the parts. Therefore, a method of forming a protective film by curing a curable composition containing a compound resin having an epoxy group or an oxetanyl group, a monomer such as an acrylate, a methacrylate and a cyanoacrylate is employed.

For example, in Patent Document 1, an electronic device sealing resin containing a polybutadiene polymer having a (meth)acryloyl group at the end, a photopolymerization initiator, a reactive diluent, a hydrocarbon softener and a hydrocarbon tackifier A composition is proposed.

In Patent Document 2, an acrylate oligomer component selected from the group consisting of polyisoprene-based (meth)acrylate oligomers, polybutadiene-based (meth)acrylate oligomers and polyurethane-based (meth)acrylate oligomers, dicyclopentenyloxyethyl (meth)acrylate , isobornyl (meth)acrylate, tetrahydrofurfuryl methacrylate, benzyl acrylate, lauryl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl acrylate and octyl (meth)acrylate. A photocurable resin composition containing a monomer component, a plasticizer component and a photopolymerization initiator has been proposed.

US2016/362576A1 US2014/290849A1

The protective film obtained using the curable composition sometimes turned white when a load was applied.

Patent Literature 1 describes that the addition of a hydrocarbon-based softening agent and a hydrocarbon-based tackifier to a curable composition improves the water vapor barrier properties of the resulting cured product. However, when a hydrocarbon-based softening agent is blended, the hardness of the cured product is lowered, and the applications for which it can be used are limited.
Patent Document 2 proposes to use the photocurable resin composition described in the same document as a light-transmissive cover member used for an image display member such as a liquid crystal display panel. However, Patent Document 2 does not describe anything about the water vapor barrier property of the cured product, and the invention described in the same document could not impart sufficient water vapor barrier property to the cured product.

In addition, from the viewpoint of emphasizing appearance, the cured product obtained by curing the curable composition is required to have good light transmittance.

Accordingly, an object of the present invention is to provide a curable composition from which a cured product having excellent water vapor barrier properties, sufficient hardness, excellent whitening resistance, and good light transmittance can be produced. .

The inventors have made extensive studies to solve the above problems. As a result, a monomer having two or more groups selected from the group consisting of a petroleum resin, a hydrocarbon polymer having an acrylic group or a methacrylic group, and an acrylic group and a methacrylic group and a saturated alicyclic The present inventors have found that the above-mentioned problems can be solved by using a curable composition containing a certain amount of the curable composition, and have completed the present invention. That is, the present invention provides the following [1] to [15].

[1] A curable composition containing the following components (A) to (C),
The content of component (A) in the total of components (A), (B) and (C) is 20% by mass or more and 60% by mass or less, and the content of component (B) is 5% by mass or more and 20% by mass. % by mass or less,
A curable composition containing no softening agent or containing less than 6 parts by mass of the softening agent per 100 parts by mass of components (A), (B) and (C) combined.
(A) Petroleum resin (B) Hydrocarbon polymer having acrylic or methacrylic group (C) Monomer having two or more groups selected from the group consisting of acrylic group and methacrylic group and a saturated alicyclic ring

[2] The curable composition according to [1], wherein the content of component (C) in the total of components (A), (B) and (C) is 30% by mass or more.

[3] The curable composition according to [1] or [2], wherein component (A) is a polymer having an alicyclic structure and having no acrylic group or methacrylic group.

[4] The curable composition according to any one of [1] to [3], wherein component (A) contains a cyclic olefin polymer (a1) having an alicyclic structure in its main chain.

[5] to [4], wherein the cyclic olefin polymer (a1) has a repeating unit selected from the group consisting of the following general formulas (I), (II), (III), (IV) and (V); A curable composition as described.

(wherein R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an unsubstituted or substituted hydrocarbon group having 1 to 30 carbon atoms, A hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R ¹ and R ² , R ³ and R ⁴ may combine to form a ring,
m represents 0 or a positive integer,
* represents a bond. )

(wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a halogen atom, or an unsubstituted or substituted hydrocarbon group having 1 to 30 carbon atoms, A hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R ⁵ and R ⁶ , R ⁷ and R ⁸ may combine with each other to form a ring,
p and q each independently represent 0 or a positive integer, and * represents a bond. )

(wherein R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted carbon atom represents a hydrocarbon group having a number of 1 to 30, the hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ may combine with each other to form a ring,
* represents a bond. )

(wherein R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted carbon atom having 1 to 30 carbon atoms) represents a hydrogen group, the hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ , R ²¹ and R ²² may combine with each other to form a ring,
* represents a bond. )

(wherein R ²³ , R ²⁴ , R ²⁵ and R ²⁶ each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; and the hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom,
R ²³ and R ²⁴ , R ²⁵ and R ²⁶ may combine with each other to form a ring,
* represents a bond. )

[6] The curable composition according to any one of [1] to [5], wherein component (A) contains a polymer having a repeating unit having an alicyclic structure in its side chain.

[7] The curable composition according to [6], wherein the repeating unit having an alicyclic structure in its side chain is a repeating unit represented by the following general formula (VI).

(Wherein, R ²⁷ represents a hydrogen atom or a methyl group,
R ²⁸ represents an unsubstituted or substituted cycloalkyl group having 3 to 40 carbon atoms,
* represents a bond. )

[8] The curable composition according to any one of [1] to [7], wherein the main chain of component (B) is a hydrocarbon polymer obtained by polymerizing an alkene having 2 to 8 carbon atoms. .

[9] The curable composition according to any one of [1] to [8], wherein the (C) component is a tricyclic compound.

[10] The curable composition according to any one of [1] to [9], further comprising a leveling agent as component (D).

[11] The curable composition according to [10], wherein the leveling agent of component (D) contains a silicone compound.

[12] A barrier film-forming composition containing the curable composition according to any one of [1] to [11].

[13] A cured product of the curable composition according to any one of [1] to [11].

[14] A laminate comprising the cured product according to [13] and a supporting substrate, wherein the cured product is formed on the supporting substrate.

[15] A method for forming a barrier film, comprising a step of curing the curable composition according to any one of [1] to [11].

According to the curable composition of the present invention, it is possible to provide a cured product that has sufficient hardness and has good water vapor barrier properties, whitening resistance and light transmittance.

The curable composition and cured product of the present invention are described below based on preferred embodiments.

In the present specification, the weight average molecular weight and number average molecular weight are measured by gel permeation chromatography (GPC) by the method described in JP-A-2020-059783, the weight average molecular weight calculated in terms of standard polystyrene. and the number average molecular weight.

As used herein, the solid content of the curable composition represents the content of all components in the curable composition excluding the solvent.

(A) Petroleum Resin The curable composition of the present invention contains a petroleum resin as the component (A). Known petroleum resins can be used without particular limitation in the curable composition of the present invention. In the present invention, it is preferable that the petroleum resin contains a polymer that has an alicyclic structure and does not have an acrylic group or a methacrylic group, so that a cured product with even better water vapor barrier properties can be obtained.

An alicyclic structure means a saturated or unsaturated aliphatic hydrocarbon ring. The alicyclic structure may have aliphatic branching. The alicyclic structure may be monocyclic, bicyclic, or tricyclic or polycyclic. Monocyclic alicyclic structures include, for example, monocyclic cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane and cyclododecane; Monocyclic cycloalkenes such as cyclobutene, cyclopropene, cyclohexene, cycloheptene and cyclooctene are included. Bicyclic alicyclic structures include bicyclic alkanes such as spiropentane, spirodecane, bicycloundecane, decahydronaphthalene (decalin), norcanane and norbornane; and bicyclic alkenes such as norbornene, norbornadiene and spirpentadiene. be done. Polycyclic alicyclic structures include dicyclopentadiene, adamantane, twistane, cubane, basketane, and hausan.

Examples of the polymer having an alicyclic structure include polymers described in (A-1) to (A-3) below.
(A-1) A polymer having a repeating unit having an alicyclic structure in its main chain (hereinafter sometimes referred to as "cyclic olefin polymer (a1)")
(A-2) A polymer having a repeating unit having an alicyclic structure in its side chain (hereinafter sometimes referred to as "vinyl alicyclic polymer (a2)")
(A-3) A polymer having a repeating unit having an alicyclic structure in both the main chain and the side chain, that is, a polymer having a repeating unit having an alicyclic structure in the side chain in the cyclic olefin polymer (a1) (Hereinafter, it may be referred to as "polymer (a3)".)

In the present invention, the polymer having an alicyclic structure represents one containing two or more repeating units having an alicyclic structure in the main chain or side chain.

(A-1) Polymer Having a Repeating Unit Having an Alicyclic Structure in its Main Chain The polymer having a repeating unit having an alicyclic structure in its main chain, that is, the cyclic olefin polymer (a1) includes Conventionally known ones can be used without particular limitation as long as they have a repeating unit having an alicyclic structure.
Here, the repeating unit having an alicyclic structure in the main chain means a repeating unit having a structure in which part of the alicyclic structure constitutes the main chain of the polymer.

The cyclic olefin polymer (a1) preferably has, for example, a repeating unit represented by the following general formula (I) or (II), because it will have more excellent water vapor barrier properties.

In the above general formulas (I) and (II), the halogen atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include fluorine atom, chlorine atom and A bromine atom etc. are mentioned.

In the above general formulas (I) and (II), unsubstituted or substituted carbon atom number 1 represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ -30 hydrocarbon groups include, for example, unsubstituted or substituted alkyl groups of 1 to 30 carbon atoms, unsubstituted or substituted aryl groups of 6 to 30 carbon atoms, unsubstituted or substituted groups and an arylalkyl group having 7 to 30 carbon atoms.

The unsubstituted or substituted alkyl group having 1 to 30 carbon atoms may be linear or branched. A hydrogen atom in the alkyl group may be substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom. Further, the alkyl group may have a linking group containing an oxygen atom, sulfur atom, nitrogen atom or silicon atom in its carbon chain.
Examples of alkyl groups having 1 to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, tert-amyl, hexyl, cyclohexyl, heptyl and octyl. , nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl, 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, difluoromethyl , trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichlorodifluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tri decafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, methoxymethyl, 1,2-epoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tert-butylthiomethyl, 4-pentenyloxy methyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl-1-methoxyethyl, ethyldithioethyl, trimethylsilylethyl, tert-butyldimethylsilyloxy methyl, 2-(trimethylsilyl)ethoxymethyl, tert-butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, tert-butoxycarbonylmethyl, acryloyloxyethyl, methacryloyloxyethyl, 2-methyl-2-adamantyloxycarbonylmethyl, Acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl and 1,2-dihydroxyethyl etc. In the present invention, an alkyl group having 1 to 10 carbon atoms is preferred from the viewpoint of low viscosity.

Examples of the unsubstituted or substituted aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4 -vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2 -ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethyl Phenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-pentylphenyl, 2,5- Di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1′-biphenyl)-4-yl, 2,4,5- trimethylphenyl and ferrocenyl, and the like. In the present invention, an aryl group having 6 to 25 carbon atoms is preferred from the viewpoint of further improving the light transmittance of the resulting cured product.

Examples of the unsubstituted or substituted arylalkyl group having 7 to 30 carbon atoms include benzyl, 1-methyl-1-phenylethyl, 1-naphthylmethyl, 9-anthracenylmethyl, 9-fluorenyl, 3-phenylpropyl, methyl-2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, phenethyl, styryl and cinnamyl. In the present invention, an arylalkyl group having 7 to 25 carbon atoms is preferred from the viewpoint that the resulting cured product has good light transmittance.

Hydrocarbon groups having 1 to 30 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the general formulas (I) and (II) Examples of substituents include ethylenically unsaturated groups such as vinyl, allyl, acryl, and methacryl; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl ( benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl, carbamoyl; Acyloxy group; amino, ethylamino, dimethylamino, diethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, chlorophenylamino, toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2- pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonyl amino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfamoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butyl Substituted amino groups such as sulfonylamino and phenylsulfonylamino; Phosphate group, carboxyl group, sulfo group, phosphonic acid group, salt of phosphoric acid group, and the like.

In general formulas (I) and (II) above, the hydrocarbon groups having 1 to 30 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are Examples of the linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom include a carbonyl group, an imino group, an ether bond, a silyl ether bond, a thioether bond, and a divalent linking group such as an ester bond. can be done.

^In general ^formula ⁽ I) above, a ring formed by combining R ¹ and R ² and R ³ and R ⁴ together ^; Examples of the ring formed by combining with each other include cycloalkanes (saturated aliphatic rings) having 5 to 10 carbon atoms such as cyclopentane, cyclohexane and cyclooctane, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene , cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene and cyclononatetraene. Among them, cycloalkanes having 5 to 10 carbon atoms are preferable because the cured product obtained using the curable composition of the present invention has good light transmittance.

In general formula (I) above, when m is a positive integer, m is preferably 1 to 5 from the viewpoint of ease of synthesis.

In general formula (II) above, when p is a positive integer, p is preferably 1 to 5 from the viewpoint of ease of synthesis.
In general formula (II) above, when q is a positive integer, q is preferably 1 to 5 from the viewpoint of ease of synthesis.

In the curable composition of the present invention, component (A) includes R ¹ , R ² , R ³ and R ⁴ in general formula (I), R ⁵ , R ⁶ , R ⁷ in general formula (II) and Each R ⁸ is independently a hydrogen atom or a cyclic olefin polymer (a1) having a repeating unit that is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms. It is more preferable to contain a cyclic olefin polymer (a1) having a repeating unit that is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and the cyclic olefin polymer (a1) that has a repeating unit that is a hydrogen atom. It is more preferable to contain because it is easy to obtain a cured product having excellent water vapor barrier properties.

Here, the cyclic olefin polymer (a1) having a repeating unit represented by general formula (I) or (II) means at least one type of repeating unit represented by general formula (I) or (II). If necessary, those having repeating units other than general formulas (I) and (II) can also be used, and represent any of the following (1) to (6).
(1) homopolymer of repeating unit represented by general formula (I) (2) homopolymer of repeating unit represented by general formula (II) (3) repeating unit represented by general formula (I) and general Copolymers with repeating units represented by formula (II) (4) Copolymers with repeating units represented by general formula (I) and other polymerizable compounds (5) Repeats represented by general formula (II) Copolymers of Units and Other Polymerizable Compounds (6) Copolymers of Repeating Units Represented by General Formula (I), Repeating Units Represented by General Formula (II), and Other Polymerizable Compounds

Examples of the other polymerizable compound capable of polymerizing with the repeating unit represented by the general formula (I) or (II) include, for example, a polymerizable compound having no alicyclic structure and a polymerizable compound having an aromatic ring, which will be described later. and polymeric compounds containing alicyclic and aromatic rings.

Specific examples of repeating units represented by general formula (I) include divalent groups derived from bicyclic cyclic olefins such as norbornene.

Examples of repeating units of the compound represented by general formula (II) include divalent groups derived from monocyclic cyclic olefins such as cyclohexene.

The cyclic olefin polymer (a1) having a repeating unit represented by general formula (I) or (II) is represented by general formula (I) or (II) within a range that does not impair the effects of the present invention. It can have a repeating unit other than the repeating unit (hereinafter referred to as "another repeating unit 1").

Examples of the other repeating unit 1 include repeating units having no alicyclic structure and repeating units having an aromatic ring.

Examples of repeating units having no alicyclic structure include olefins such as ethylene, propylene and butene; conjugated dienes such as butadiene and isoprene; non-conjugated dienes such as ethylidenenorbornene; Repeating units derived from polymerizable compounds having no alicyclic structure, such as linear diene compounds such as maleic anhydride, acrylic acid esters, methacrylic acid esters, maleimide, vinyl acetate and vinyl chloride, can be mentioned.

Examples of repeating units having an aromatic ring include vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene, aromatic acrylates such as benzyl acrylate, and aromatic methacrylates such as benzyl methacrylate. repeating units derived from polymerizable compounds having an aromatic ring such as In addition, repeating units derived from polymerizable compounds containing an alicyclic ring and an aromatic ring such as indene can also be mentioned.

When the cyclic olefin polymer (a1) of the present invention contains other repeating units 1 in addition to repeating units represented by general formula (I) or (II), other repeating units in the cyclic olefin polymer (a1) The content of Unit 1 is preferably less than 50% by mass, more preferably 25% by mass or less, and particularly preferably 10% by mass or less. This is because a cured product having even better water vapor barrier properties can be obtained.

In addition, the cyclic olefin polymer (a1) is a known cyclic olefin polymer that does not have repeating units represented by the general formula (I) or (II) within a range that does not impair the effects of the present invention. may contain.

The curable composition of the present invention includes, as the component (A), those having only repeating units represented by general formula (I), those having only repeating units represented by general formula (II), and those having only repeating units represented by general formula ( It is preferable to contain at least one cyclic olefin polymer (a1) selected from those having repeating units represented by I) and (II), since a cured product having even better water vapor barrier properties can be obtained.

When the cyclic olefin polymer (a1) has repeating units represented by the general formulas (I) and (II), the repeating units represented by the general formula (I) in the cyclic olefin polymer (a1) and the repeating unit represented by the general formula (II), the ratio of the repeating unit represented by the general formula (II) is preferably 40% by mass or more, and is preferably 60% by mass or more. More preferably, it is 80% by mass or more. This is because a cured product having even better water vapor barrier properties can be obtained. The upper limit of the content of the repeating unit represented by formula (II) is not particularly limited as long as it is less than 100% by mass.

When the curable composition of the present invention contains a cyclic olefin polymer (a1) having a repeating unit represented by general formula (I) or (II) as component (A), the component (A) generally includes The content of the cyclic olefin polymer (a1) containing the repeating unit represented by formula (I) or (II) is preferably 10% by mass or more, and is preferably 30% by mass or more. It is more preferable because a cured product having excellent properties can be obtained. There is no upper limit, and it can be 100% by mass.

Further, the curable composition of the present invention contains, as component (A), a cyclic olefin polymer (a1) having a repeating unit represented by the following general formula (III). It is preferable because it gives you a product.

In general formula (III), halogen atoms represented by R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , unsubstituted or substituted carbon atoms having 1 to 30 of the hydrocarbon group, the linking group that the hydrocarbon group may have, R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , R ¹⁵ and R ¹⁶ are formed by bonding to each other Examples of the ring include the same as those described for R ¹ and the like in general formula (I).

In general formula (III), R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen atoms or unsubstituted or a substituted hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, or an unsubstituted or substituted hydrocarbon group having 1 to 4 carbon atoms, hydrogen Atoms are more preferred.

Examples of the repeating unit represented by the general formula (III) include divalent groups derived from bicyclic cyclic olefins such as bicyclononene, and compounds containing both alicyclic and aromatic rings such as indene. and a divalent group in which the aromatic ring portion is hydrogenated.

When the cyclic olefin polymer (a1) has a repeating unit represented by the general formula (III), the cyclic olefin polymer (a1) may optionally contain other repeating units other than the general formula (III). (hereinafter referred to as "another repeating unit 2").

Examples of the other repeating unit 2 include repeating units represented by the above general formula (I) or (II), repeating units having no alicyclic structure, and repeating units having an aromatic ring. .

Examples of repeating units having no alicyclic structure and repeating units having an aromatic ring are the same as those described above.

In addition, the cyclic olefin polymer (a1) may have a known cyclic olefin polymer that does not have the repeating unit represented by the general formula (III).

When the cyclic olefin polymer (a1) of the present invention contains another repeating unit 2 in addition to the repeating unit represented by the general formula (III), the other repeating unit 2 is contained in the cyclic olefin polymer (a1). The amount is preferably less than 50% by mass, more preferably 25% by mass or less, and particularly preferably 10% by mass or less. This is because a cured product having even better water vapor barrier properties can be obtained.

In the curable composition of the present invention, the component (A) preferably contains the cyclic olefin polymer (a1) having only the repeating unit represented by the general formula (III), since it has excellent water vapor barrier properties.

When the curable composition of the present invention contains a cyclic olefin polymer (a1) having a repeating unit represented by general formula (III) as component (A), general formula (III) The content of the cyclic olefin polymer (a1) having a repeating unit represented by is preferably 10% by mass or more, and 30% by mass or more because a cured product having excellent water vapor barrier properties can be obtained. more preferred. There is no upper limit, and it can be 100% by mass.

Further, the curable composition of the present invention contains, as component (A), a cyclic olefin polymer having a repeating unit represented by the following general formula (IV) or (V). It is preferable because it gives you a product.

Halogen atoms represented by R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² in general formula (IV) and R ²³ , R ²⁴ , R ²⁵ and R ²⁶ in general formula (V) , an unsubstituted or substituted hydrocarbon group having 1 to 30 carbon atoms, a linking group which the hydrocarbon group may have, R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹³ and R ¹⁴ , Examples of the ring formed by combining R ¹⁵ and R ¹⁶ include the same ones as those described for R ¹ in general formula (I).

As the cyclic olefin polymer (a1) having a repeating unit represented by general formula (IV) or (V), any one of the following (7) to (12) is represented.
(7) a homopolymer of a repeating unit represented by general formula (IV); (8) a homopolymer of a repeating unit represented by general formula (V); and (9) a repeating unit represented by general formula (IV); Copolymer with a repeating unit represented by the general formula (V) (10) Copolymer with a repeating unit represented by the general formula (IV) and another polymerizable compound (11) Represented by the general formula (V) Copolymers of repeating units and other polymerizable compounds (12) Copolymers of repeating units represented by general formula (IV), repeating units represented by general formula (V), and other polymerizable compounds, etc. Examples of the polymerizable compound include polymerizable compounds having no alicyclic structure, polymerizable compounds having an aromatic ring, and polymerizable compounds containing an alicyclic ring and an aromatic ring.

In the curable composition of the present invention, component (A) includes R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ and R ²² in the repeating unit represented by general formula (IV), and general formula ( R ²³ , R ²⁴ , R ²⁵ and R ²⁶ in the repeating unit represented by V) are each independently a hydrogen atom or an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms; It is preferable to contain a cyclic olefin polymer (a1) having a certain repeating unit, and it is preferable to contain a cyclic olefin polymer (a1) having a repeating unit that is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. More preferably, it contains a cyclic olefin polymer (a1) having repeating units that are hydrogen atoms. This is because a cured product having even better water vapor barrier properties can be obtained.

Examples of repeating units represented by general formulas (IV) and (V) include divalent groups derived from tricyclic cyclic olefins such as dicyclopentadiene.

In the curable composition of the present invention, the cyclic olefin polymer (a1) having a repeating unit represented by the general formula (IV) or (V) is a compound represented by the general formula (IV) within a range that does not impair the effects of the present invention. ) and (V) (hereinafter referred to as “another repeating unit 3”).

Other repeating units 3 include, for example, repeating units represented by the general formula (I), (II) or (III), repeating units having no alicyclic structure, and repeating units having an aromatic ring. mentioned. Examples of repeating units having no alicyclic structure and repeating units having an aromatic ring are the same as those described above.

In the curable composition of the present invention, when the cyclic olefin polymer (a1) has repeating units represented by general formula (IV) or (V), repeating units represented by general formulas (IV) and (V) It is preferable to have units because a cured product having even better water vapor barrier properties can be obtained.

When the cyclic olefin polymer (a1) has repeating units represented by the general formulas (IV) and (V), the repeating units represented by the general formula (IV) in the cyclic olefin polymer (a1) and the repeating unit represented by the general formula (V), the mass ratio of the former to the latter is preferably 99:1 to 1:99, and is preferably 80:20 to 20:80. More preferably, it is 60:40 to 40:60. This is because a cured product having even better water vapor barrier properties can be obtained.

When the cyclic olefin polymer (a1) of the present invention contains 3 other repeating units in addition to the repeating units represented by the general formula (IV) or (V), other repeating units in the cyclic olefin polymer (a1) The content of Unit 3 is preferably less than 50% by mass, more preferably 25% by mass or less, and particularly preferably 10% by mass or less. This is because a cured product having even better water vapor barrier properties can be obtained.

In addition, the cyclic olefin polymer (a1) having repeating units represented by the general formula (IV) or (V) does not have repeating units represented by the general formulas (IV) and (V). It may have a known cyclic olefin polymer.

When the curable composition of the present invention contains a cyclic olefin polymer (a1) having a repeating unit represented by general formula (IV) or (V) as component (A), in component (A), The content of the cyclic olefin polymer (a1) having a repeating unit represented by general formula (IV) or (V) is preferably 10% by mass or more, and is preferably 30% by mass or more. It is more preferable because a cured product having excellent properties can be obtained. The upper limit is not particularly limited, and may be 100% by mass.

Commercially available products can be used as the cyclic olefin polymer (a1) having a repeating unit represented by general formula (IV) or (V). Examples of commercially available products include hydrogenated dicyclopentadiene resins (hydrogenated DCPD, hydrogenated DCPD/C9) such as T-REZ HA085, HA103, HA105, HA125, HB103, and HB125 manufactured by JTXG Energy Co., Ltd. .

(A-2) Polymer having a repeating unit having an alicyclic structure in its side chain represents a repeating unit having an alicyclic structure. The repeating unit having an alicyclic structure in the side chain means a repeating unit having an alicyclic structure in the side chain of the polymer and a part of the alicyclic structure not forming the main chain of the polymer. Examples thereof include a structure obtained by polymerizing ethylenically unsaturated bonds outside the alicyclic structure contained in a vinyl alicyclic compound such as the vinyl group of vinylcyclohexane.

The phrase “the vinyl alicyclic polymer has a repeating unit having an alicyclic structure in its side chain” means that the vinyl alicyclic polymer is (a) a homopolymer of a repeating unit having an alicyclic structure in its side chain. or (b) a copolymer containing a repeating unit having an alicyclic structure in its side chain and a repeating unit derived from another polymerizable compound. Other polymerizable compounds include polymerizable compounds having no alicyclic structure, polymerizable compounds having an aromatic ring, and polymerizable compounds containing an alicyclic ring and an aromatic ring.

Examples of repeating units having an alicyclic structure in the side chain include repeating units represented by the following general formula (VI).

In general formula (VI) above, the cycloalkyl group having 3 to 40 carbon atoms represented by R ²⁸ may be saturated monocyclic or saturated polycyclic. Saturated monocyclic cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like. Saturated polycyclic cycloalkyl groups include, for example, adamantyl, decahydronaphthyl, octahydropentalene, bicyclo[1.1.1]pentanyl, and the like. One, two or more hydrogen atoms of the cycloalkyl group may be substituted with substituents described below.

Examples of substituents for substituting the hydrogen atom in the cycloalkyl group having 3 to 40 carbon atoms represented by R ²⁸ include halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl group, acetyl group, 2-chloroacetyl, propionyl, octanoyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n - acyl groups such as octadecyloxycarbonyl and carbamoyl; acyloxy groups such as acetyloxy and benzoyloxy; toluidino, anisidino, N-methyl-anilino, diphenylamino, naphthylamino, 2-pyridylamino, methoxycarbonylamino, phenoxycarbonylamino, acetylamino, benzoylamino, formylamino, pivaloylamino, lauroylamino, carbamoylamino, N,N-dimethyl aminocarbonylamino, N,N-diethylaminocarbonylamino, morpholinocarbonylamino, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino, phenoxycarbonylamino, sulfur Substituted amino groups such as famoylamino, N,N-dimethylaminosulfonylamino, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino; sulfonamide group, sulfonyl group, carboxyl group, cyano group, sulfo group, hydroxyl group, nitro group , an imide group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group, or salts of a carboxyl group, a sulfo group, a phosphonic acid group, a phosphoric acid group, and the like.

The number of carbon atoms when the hydrogen atoms of the cycloalkyl group having 3 to 40 carbon atoms are substituted refers to the number of carbon atoms after the hydrogen atoms are substituted, and the number of carbon atoms before the hydrogen atoms are substituted. does not refer to the number of carbon atoms in

Examples of repeating units represented by general formula (VI) include divalent groups derived from vinyl alicyclic compounds such as vinylcyclohexane and methylvinylcyclohexane. Also included are divalent groups derived from vinyl aromatic compounds such as styrene and vinyl toluene and having hydrogenated aromatic ring portions.

In the present invention, a compound in which R ²⁸ is a saturated monocyclic alkyl group is preferable, and R ²⁸ is particularly preferably a group having a 6-membered cycloalkyl ring, and the side chain is an alicyclic alkyl group. A repeating unit having a ring structure is preferably a repeating unit represented by the following general formula (VII). This is because a cured product having even better water vapor barrier properties can be obtained.

wherein R ²⁹ represents a hydrogen atom or a methyl group,
R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are each independently a hydrogen atom, unsubstituted or substituted, having 1 carbon atom -30 hydrocarbon groups, halogen atoms, acyl groups, amino groups, sulfonamide groups, sulfonyl groups, carboxyl groups, cyano groups, sulfo groups, hydroxyl groups, nitro groups, imido groups, carbamoyl groups, sulfonamide groups, phosphonic acid groups , represents a phosphate group, a carboxyl group, a phosphonic acid group or a phosphate group,
Any two or more of R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ may combine to form a ring,
* represents a bond.

Halogen atoms represented by R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ in general formula (VII), unsubstituted or substituted Any two or more of a hydrocarbon group having 1 to 30 carbon atoms, R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ are linked to form Examples of the ring include those described in the description of R ¹ and the like in general formula (I).

The curable composition of the present invention contains R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R ³⁹ each independently preferably contains a vinyl alicyclic polymer (a2) having a repeating unit that is a hydrogen atom or an unsubstituted or substituted alkyl group having 1 to 30 carbon atoms, It more preferably contains a vinyl alicyclic polymer (a2) having a repeating unit that is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a repeating unit that is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms Containing a vinyl alicyclic polymer (a2) having units is more preferable because a cured product having excellent water vapor barrier properties can be obtained.

The curable composition of the present invention contains R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and R Vinyl alicyclic polymer (a2) containing repeating units in which all of ³⁹ are hydrogen atoms, or R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ and a vinyl alicyclic polymer (a2) having a repeating unit in which 9 of R ³⁹ are hydrogen atoms and the remaining 1 group is an alkyl group having 1 to 3 carbon atoms. , ^R30 , ^R31 , ^R32 , ^R33 , ^R34 , ^R35 , ^R36 , ^R37 , ^R38 and ^R39 are hydrogen atoms, and the remaining one group is a methyl group. It is more preferable to contain a vinyl alicyclic polymer (a2) containing certain repeating units. This is because a cured product having even better water vapor barrier properties can be obtained, and the synthesis of the vinyl alicyclic polymer (a2) is facilitated.

As the repeating unit represented by the general formula (VII), from the viewpoint of obtaining a cured product having excellent water vapor barrier properties, those represented by the following general formulas (VII-1) and (VII-2), etc. can be preferably used.

In the curable composition of the present invention, the vinyl alicyclic polymer (a2) having a repeating unit represented by the general formula (VII) is other than the general formula (VII) within a range that does not impair the effects of the present invention. It can have another repeating unit (hereinafter referred to as "another repeating unit 4").

Examples of the other repeating units 4 include repeating units having no alicyclic structure, repeating units having an aromatic ring, and the like. Examples of repeating units having no alicyclic structure and repeating units having an aromatic ring are the same as those described above.

When the vinyl alicyclic polymer (a2) of the present invention contains other repeating units 4 in addition to repeating units represented by general formula (VI), other repeating units in the vinyl alicyclic polymer (a2) The content of unit 4 is preferably less than 50% by mass, more preferably 25% by mass or less, and particularly preferably 10% by mass or less. This is because a cured product having even better water vapor barrier properties can be obtained.

In addition, the vinyl alicyclic polymer (a2) includes a known vinyl alicyclic polymer that does not have the repeating unit represented by the general formula (VII) within a range that does not impair the effects of the present invention. You may have

When the curable composition of the present invention contains the vinyl alicyclic polymer (a2) as the component (A), the content of the vinyl alicyclic polymer (a2) is 70% in the component (A). The content is preferably 50% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less because a cured product having excellent water vapor barrier properties can be obtained. Although the lower limit is not particularly limited, it is preferably 1% by mass or more.

(A-3) Polymers Having Repeating Units Having Alicyclic Structures in Their Main Chains and Side Chains Polymers having repeating units having alicyclic structures in their main chains and side chains, i. As a polymer having a repeating unit having an alicyclic structure in its chain (hereinafter sometimes referred to as "polymer (a3)"), a repeating unit having an alicyclic structure in its main chain and an alicyclic structure in its side chain It is sufficient if it contains both a repeating unit having a structure.

As such a polymer (a3), for example, at least one repeating unit selected from the group consisting of repeating units represented by the general formulas (I), (II) and (III), and and a repeating unit having an alicyclic structure.

Further, as the polymer (a3), at least one repeating unit selected from the group consisting of repeating units represented by the above general formulas (I), (II), (III), (IV) and (V) and a repeating unit having an alicyclic structure represented by general formula (VI) in the side chain described above.

In the present invention, the polymer (a3) is a polymer having a repeating unit represented by the general formula (IV) or (V) and a repeating unit having an alicyclic structure in its side chain. It is preferable because a cured product having excellent water vapor barrier properties can be obtained. As the repeating unit having an alicyclic structure in the side chain, a repeating unit represented by general formula (VI) is preferable, and a repeating unit represented by general formula (VII) is more preferable. This is because a cured product having even better water vapor barrier properties can be obtained.

In the present invention, the polymer (a3) is represented by the above general formula (VI) or (VII) as a repeating unit represented by the general formula (III) and a repeating unit having an alicyclic structure in the side chain. The repeating unit represented by the general formula (III) and the repeating unit having an alicyclic structure in the side chain are represented by the general formula (VII). It is more preferable to contain a repeating unit represented by the general formula (VII-1) or (VII-2). This is because a cured product having more excellent water vapor barrier properties and adhesion to the indicator substrate can be obtained.

The curable composition of the present invention comprises a repeating unit represented by the general formula (III) as the component (A) and a repeating unit having an alicyclic structure in the side chain represented by the general formula (VI). When the polymer (a3) having a repeating unit of more preferred. This is because a cured product having excellent water vapor barrier properties and adhesion to a supporting substrate can be easily obtained. The upper limit is not particularly limited, and may be 100% by mass.

The curable composition of the present invention has, as component (A), repeating units represented by the above general formulas (III), (IV) and (V) and repeating units having an alicyclic structure in the side chain. It preferably contains the polymer (a3). This is because it becomes easier to obtain a cured product having even better water vapor barrier properties and adhesion to the supporting substrate. For the same reason, the repeating unit having an alicyclic structure in the side chain is preferably a repeating unit represented by general formula (VI), more preferably a repeating unit represented by general formula (VII).

The curable composition of the present invention has, as component (A), repeating units represented by the above general formulas (III), (IV) and (V) and repeating units having an alicyclic structure in the side chain. When the polymer (a3) is contained, the content of the polymer (a3) in the component (A) is preferably 10% by mass or more, and more preferably 20% by mass or more. . This is because it becomes easier to obtain a cured product having even better water vapor barrier properties and adhesion to the supporting substrate. The upper limit is not particularly limited, and may be 100% by mass.

In the curable composition of the present invention, it is The proportion of repeating units is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. This is because a cured product having even better water vapor barrier properties can be obtained. The upper limit of the ratio of repeating units having an alicyclic structure in the main chain is not particularly limited, and may be less than 100% by mass.

In the curable composition of the present invention, the polymer (a3) is represented by general formulas (I), (II), (III), (IV), (V), ( VI) and (VII) other than repeating units (hereinafter referred to as "another repeating unit 5").

Examples of the other repeating units 5 include repeating units having no alicyclic structure, repeating units having an aromatic ring, and the like. Examples of repeating units having no alicyclic structure and repeating units having an aromatic ring are the same as those described above.

When the polymer (a3) of the present invention contains other repeating units 5 in addition to general formulas (I), (II), (III), (IV), (V), (VI) and (VII) , The content of the other repeating unit 5 in the polymer (a3) is preferably less than 50% by mass, more preferably 25% by mass or less, and particularly preferably 10% by mass or less. This is because a cured product having even better water vapor barrier properties can be obtained.

The polymer (a3) is a repeating unit represented by the general formula (III) and a repeating unit having an alicyclic structure in a side chain represented by the general formula (VI), especially general formulas (VII-1) and (VII- 2) and a repeating unit represented by the general formula (VII), for example, an alicyclic saturated hydrocarbon resin obtained by hydrogenating the aromatic ring portion of an aromatic petroleum resin (when referred to as a hydrogenated petroleum resin There is also.) can be preferably used. This is because a cured product having even better water vapor barrier properties can be obtained.

When the curable composition of the present invention contains the polymer (a3) as the component (A), the content of the vinyl polymer (a3) in the component (A) is 10% by mass or more. More preferably, it is 30% by mass or more because a cured product having excellent water vapor barrier properties can be obtained. The upper limit is not particularly limited, and may be 100% by mass.

Examples of the hydrogenated aromatic petroleum resin include those having structures represented by the following formulas (III-S1), (VI-S1), and (VI-S2).

In the curable composition of the present invention, from the viewpoint of excellent solubility in general-purpose organic solvents such as cyclohexane, methyl ethyl ketone and n-heptane, and excellent freedom in solvent selection, the component (A) is a side chain. It is preferably a polymer having a repeating unit having an alicyclic structure, that is, the above vinyl alicyclic polymer (a2) or polymer (a3).

In addition to the cyclic olefin polymer (a1), vinyl alicyclic polymer (a2) and polymer (a3) described above, component (A) may contain known petroleum resins or hydrogenated petroleum resins. good. Known petroleum resins include, for example, C9 petroleum resins obtained by cationic polymerization of C9 fractions obtained by petroleum refining such as naphtha cracking, and thermally polymerizing C5 fractions such as cyclopentadiene and dicyclopentadiene. and C5 to C9 petroleum resins obtained by polymerizing C5 to C9 fractions. Hydrogenated petroleum resins include alicyclic petroleum resins obtained by hydrogenating double bonds in petroleum resins among the various petroleum resins described above. As the hydrogenated petroleum resin, for example, as described in International Publication No. WO 2004/056882, a low-molecular weight by-product produced during polymerization of cyclopentadiene and a vinyl aromatic compound is treated and hydrogenated. good too.

When component (A) contains known petroleum resins or hydrogenated petroleum resins, the content of petroleum resins and hydrogenated petroleum resins in component (A) is preferably less than 90% by mass, preferably less than 70% by mass. It is more preferably 50% by mass or less, more preferably 50% by mass or less. This is because a cured product having even better water vapor barrier properties can be obtained.

In the curable composition of the present invention, the component (A) is preferably a partially or completely hydrogenated petroleum resin because it has almost no odor and facilitates the formation of a transparent cured product. In the curable composition of the present invention, the preferred hydrogenated petroleum resin is a hydrogenated petroleum resin produced using a cyclopentadiene or dicyclopentadiene monomer as a starting material, since the effect of the present invention is remarkable. Preferred hydrogenated petroleum resins are Idemitsu Kosan Co., Ltd. trade name Imarve; Nippon Zeon trade name Quinton; Arakawa Chemical Co., Ltd. trade name Alcon P-90, P-100, P-115, P-125, P-140 , M-90, M-100, M-115, M135; ENEOS Corporation trade name T-REZ HA085, HA103, HA105, HA125, HB1-3, HB125, OP501, PR801, PR803, etc. can be done.

In the curable composition of the present invention, the weight-average molecular weight of the component (A) is not particularly limited as long as the desired water vapor barrier property and the like can be obtained. It is preferably 300 or more and 3,000 or less, and particularly 350 or more and 1,500 or less is a cured product excellent in durability such as scratch resistance as well as water vapor barrier properties and coatability. is easier to form, which is even more preferable.

In the curable composition of the present invention, the softening point of the component (A) is preferably 40°C to 150°C, more preferably 60°C to 140°C, and 80°C to 130°C. is more preferred. This is because the hardness of the cured product is further improved.
(A) The softening point of the component can be measured by ring and ball softening point measuring method.

In the curable composition of the present invention, the content of component (A) is 20% by mass or more and 60% by mass or less in the total of (A) component, (B) component and (C) component, and the resulting cured 25% by mass or more and 55% by mass is preferable, and 30% by mass or more and 50% by mass or less is more preferable, in order to further improve the vapor barrier property of the product.
The content of component (A) in the curable composition can be measured by preparative GPC.

(B) Hydrocarbon Polymer Having Acrylic Group or Methacrylic Group The curable composition of the present invention contains a hydrocarbon polymer having an acrylic group or a methacrylic group as the component (B). In the present invention, a hydrocarbon-based polymer having an acrylic group or a methacrylic group represents a hydrocarbon-based polymer containing units having an acrylic group or a methacrylic group.

In the curable composition of the present invention, the component (B) may be one in which a hydrocarbon polymer and an acrylic group or a methacrylic group are directly bonded, and a hydrocarbon polymer and an acrylic group or a methacrylic group are It may be bound via a linking group. Examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an arylene group having 6 to 20 carbon atoms, a urethane bond (-NH-CO-O-), a urea bond (-NH-CO-NH-), selected from the group consisting of an ester bond (--CO--O--), an amide bond (--NH--CO--), a sulfonate ester bond ( _--SO.sub.2 --O--), and a sulfonamide bond ( _--SO.sub.2 --NH--); group containing at least one of The hydrocarbon-based polymer and the acrylic group or methacrylic group may be linked via a combination of these linking groups. In the curable composition of the present invention, those having an acrylic group or a methacrylic group on the side chain or both ends of the hydrocarbon polymer are preferable, and an acrylic group or a methacrylic group on both ends of the hydrocarbon polymer via a urethane bond. is more preferable. This is because the effects of the present invention are more pronounced.

Examples of the hydrocarbon-based polymer constituting component (B) include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, and aromatic hydrocarbon polymers. In the curable composition of the present invention, an aliphatic hydrocarbon polymer is preferred because the effects of the present invention are more pronounced.

Examples of the aliphatic hydrocarbon polymer include polymers obtained by polymerizing alkenes having 2 to 8 carbon atoms. Moreover, the unsaturated bond of the polymer obtained by polymerizing the alkene may be hydrogenated. Examples of alkenes include monoolefins such as ethylene, propylene, 1-butene, isobutene, 1-tetradecene and 1-octadecene; -pentadiene, 1,4-pentadiene, 1,5-hexadiene and dienes such as 2,5-dimethyl-1,5-hexadiene. In the present invention, the number of carbon atoms in the alkene is preferably 2-7, more preferably 2-6, since the effect of the present invention becomes more remarkable.

In the curable composition of the present invention, the weight average molecular weight of component (B) is preferably 500 or more and 200,000 or less, more preferably 1,000 or more and 100,000 or less, and 1,500 or more. It is more preferably 50,000 or less. This is because the effects of the present invention are more pronounced.

In the curable composition of the present invention, the number average molecular weight of component (B) is preferably 500 or more and 200,000 or less, more preferably 1,000 or more and 100,000 or less, and 1,500 or more. It is more preferably 50,000 or less. This is because the effects of the present invention are more pronounced.

In the curable composition of the present invention, examples of preferred acrylic or methacrylic-containing hydrocarbon polymers as component (B) include polyisobutylene acrylate, polyisobutylene methacrylate, polybutene acrylate, polybutene methacrylate, poly-4- Methylpentene acrylate, poly-4-methylpentene methacrylate, poly-1-octene acrylate, poly-1-octene methacrylate, ethylene/α-olefin copolymer (meth)acrylate, ethylene/α-olefin copolymer methacrylate and these and the like.
In the curable composition of the present invention, polybutadiene acrylate, polybutadiene methacrylate, hydrogenated polybutadiene acrylate, hydrogenated polybutadiene methacrylate, polyisoprene acrylate, polyisoprene methacrylate, hydrogenated polyisoprene acrylate and hydrogenated polyisoprene methacrylate are preferred. ) is more preferable because the effect of the present invention is remarkable.

In the formula, R ⁴⁰ and R ⁴¹ each independently represent the following (α-1), (α-2), (α-3), (α-4), (α-5), (α-6 ), (α-7) or (α-8), n represents an integer of 20 to 1000, and * represents the position of bonding at R ⁴⁰ or R ⁴¹ .

In the curable composition of the present invention, the content of component (B) is 5% by mass or more and 20% by mass or less in the total of component (A), component (B) and component (C). Since the effect becomes remarkable, it is preferably 6% by mass or more and 18% by mass or less, more preferably 8% by mass or more and 15% by mass or less.
The content of component (B) in the curable composition of the present invention can be measured by preparative GPC.

(C) a monomer having two or more groups selected from the group consisting of an acrylic group and a methacrylic group and a saturated alicyclic ring It contains a monomer having two or more groups selected from the group consisting of and a saturated alicyclic ring. A monomer represents a low-molecular-weight compound that becomes a constituent unit of a polymer. In the curable composition of the present invention, the molecular weight of component (C) is preferably 500 or less, more preferably 100 or more and 450 or less, more preferably 150 or more and 350 More preferably:

The above saturated alicyclic ring may be monocyclic or polycyclic. Monocyclic saturated alicyclic rings include, for example, a cyclohexane ring and a cyclopentane ring.
Polycyclic saturated alicyclic rings include decahydronaphthalene ring, bicyclo[2,2,1]heptane ring, bicyclo[2,2,2]octane ring, bicyclo[3,2,1]octane ring, bicyclo[ Bicyclic saturated alicyclic rings such as 3,3,0]octane ring, bicyclo[3,2,2]nonane ring and bicyclo[3,3,1]nonane ring, and tricycloheptane ring and tricyclooctane ring and tricyclic saturated alicyclic rings such as tricyclodecane ring.

In the curable composition of the present invention, the monomer having two or more groups and a saturated alicyclic ring from the group of acrylic groups and methacrylic groups of the component (C) has 1 to 5 saturated alicyclic rings in the structure. preferably 1 to 4, preferably 2 to 3, and more preferably a tricyclic compound having 3, since the effects of the present invention are more pronounced. Examples of tricyclic compounds include compounds containing a tricycloheptane ring, a tricyclooctane ring and a tricyclodecane ring in the structure.

Examples of monomers having two or more groups selected from the group consisting of acrylic groups and methacrylic groups and a saturated alicyclic ring as component (C) include the compounds shown below.

The curable composition of the present invention preferably contains, as the component (C), a tricyclic compound having a structure in which three saturated alicyclic rings are linked, more preferably tricyclodecanedimethanol diacrylate. This is because the coating property of the curable composition is further improved, and a cured product having a further excellent water vapor barrier property can be obtained.

In the curable composition of the present invention, the content of component (C) in the total of components (A), (B) and (C) is preferably 30% by mass or more, and 30% by mass. It is more preferably 70 mass % or less, and even more preferably 35 mass % or more and 65 mass % or less. This is because a cured product having even better whitening resistance can be obtained.
The content of component (C) in the curable composition can be measured by preparative GPC.

In the curable composition of the present invention, the total amount of component (A) and component (B) is 25% by mass or more and 70% by mass or less in the total amount of component (A), component (B) and component (C). more preferably 30% by mass or more and 68% by mass or less, and even more preferably 35% by mass or more and 65% by mass or less. This is because the effects of the present invention are more pronounced.

In the curable composition of the present invention, the total of component (A), component (B) and component (C) is preferably 50 parts by mass or more in 100 parts by mass of the curable composition, and 55 parts by mass or more. It is more preferably 98 parts by mass or less, and even more preferably 60 parts by mass or more and 96 parts by mass or less. This is because the effects of the present invention are more pronounced.

<Softener>
The curable composition of the present invention does not contain a softening agent, or the content of the softening agent is 100 parts by mass in total of the components (A), (B) and (C). is less than 6 parts by mass with respect to In the present invention, the softening agent refers to a substance that has the function of lowering the hardness and increasing the viscosity of the curable composition and that does not correspond to the above components (A) and (B).
By including a softening agent in the curable composition, the adhesiveness of the curable composition and the water vapor barrier property of the obtained cured product can be enhanced. On the other hand, a cured product of a curable composition containing a softening agent has insufficient curability. Therefore, in the present invention, by setting the content of the softening agent to less than 6 parts by mass, the adhesion of the curable composition is enhanced while the hardness of the cured product is sufficient, and the resulting cured product has water vapor barrier properties. In order to increase the softening agent content is set to less than 6 parts by mass.
The curable composition of the present invention preferably does not contain a softening agent from the viewpoint of the hardness of the resulting cured product.
When the curable composition of the present invention contains a softening agent, from the viewpoint of the hardness of the resulting cured product, the content of the softening agent is more than 0 parts by mass and 4 parts by mass or less in 100 parts by mass of the curable composition. It is preferably more than 0 parts by mass and 1 part by mass or less.

Examples of softening agents that can be used in the curable composition of the present invention include process oils such as paraffinic oils, naphthenic oils and aromatic oils, paraffin waxes, microwaxes, polyethylene waxes, ethylene, conjugated diene compounds, Examples include homopolymers or copolymers of α-olefins having 4 or more carbon atoms, styrene elastomers, and the like. It is preferable because it is possible to improve the properties in a well-balanced manner.

Examples of hydrogenated styrene thermoplastic elastomers include hydrogenated styrene thermoplastic elastomers described in International Publication No. 2019-159953. Examples of commercially available hydrogenated styrene-based thermoplastic elastomers include those described as commercially available polystyrene-based elastomers in JP-A-2018-024204.

(D) Component: Leveling Agent The curable composition of the present invention preferably further contains a leveling agent as component (D). In the present invention, the leveling agent refers to an agent that has the function of adjusting the fluidity of the curable composition and flattening the film obtained by coating the curable composition.
Component (D) can be used without any particular limitation as long as it can reduce the surface tension of the curable composition and impart surface orientation. The curable composition of the present invention preferably contains a silicone compound as component (D). This is because the effect of lowering the surface tension is great, and cissing and denting of the coating film can be easily improved.

Examples of the silicone-based compound include silicone, silicone-modified acrylic, polyether-modified polydimethylsiloxane, polyetherester-modified hydroxyl-containing polydimethylsiloxane, polyester-modified hydroxyl-containing polydimethylsiloxane, and polyether-modified polydimethylsiloxane. .

Examples of commercially available leveling agents containing silicone compounds include Dow Corning Toray Co., Ltd.'s product name: "DOWSIL SH-29 Paint Additive", Evonik's product name: "TEGO Flow 425" and "TEGO Glide 100." ", "TEGO Glide 110", "TEGO Glide 432", International Publication No. 2018/0770227, International Publication No. 2018/168714, and Japanese Patent Application Laid-Open No. 2020-041059.

The content of component (D) is preferably 0.01 parts by mass or more and 5 parts by mass or less in 100 parts by mass of the curable composition of the present invention, and 0.03 parts by mass or more and 4.5 parts by mass or less. more preferably 0.05 parts by mass or more and 4 parts by mass or less, since the influence on the physical properties of the cured product is suppressed and a sufficient leveling effect can be exhibited.
The content of component (D) in the curable composition can be measured by GC-MS.

(E) Component: Photopolymerization Initiator The curable composition of the present invention preferably further contains a photopolymerization initiator as the (E) component. Examples of photopolymerization initiators include acetophenone-based compounds, benzyl-based compounds, benzophenone-based compounds, thioxanthone-based compounds, bisimidazole-based compounds, acridine-based compounds, acylphosphine-based compounds, and oxime ester compounds.

Examples of the acetophenone-based compound include those described in International Publication Nos. 2018/012383 and 2018/0181846.

Examples of the benzylic compounds include those described in International Publication No. 2018/0181846.

Examples of the benzophenone-based compounds include benzophenone-based compounds described in International Publication No. 2018/0181846.

Examples of the thioxanthone-based compounds include thioxanthone-based compounds described in International Publication No. 2018/0181846.

Examples of the bisimidazole-based compound include the bisimidazole-based compounds described in International Publication No. 2018/181846 and International Publication No. 00/52529.

Examples of the acridine-based compound include the acridine-based compound described in International Publication No. 2018/181846.

Examples of the acylphosphine-based compounds include acylphosphine-based compounds described in International Publication No. 2018/181846.

Examples of the oxime ester compounds include oxime ester compounds described in International Publication No. 2018/181846.

In the curable composition of the present invention, the content of the photopolymerization initiator is preferably 0.001 parts by mass or more and 20 parts by mass or less in 100 parts by mass of the curable composition, and 0.01 parts by mass or more and 15 parts by mass. It is more preferably not more than 0.1 part by mass and even more preferably 0.1 part by mass or more and 10 parts by mass or less. This is because the photocuring reaction of the curable composition can be easily controlled.

(F) Other Components The curable composition of the present invention may optionally contain a monomer having an acrylic or methacrylic group, a solvent, a cationic polymerizable compound, a cationic polymerization initiator, a thermal radical polymerization initiator, and the like. may contain.

<Monomer having acrylic group or methacrylic group>
In the present invention, a monomer having an acrylic group or a methacrylic group represents a monomer having an acrylic group or a methacrylic group that does not correspond to the components (A), (B) and (C). Examples of monomers having an acrylic group or a methacrylic group include (meth)acrylic monomers described in International Publication No. 2019/15953. (Meth)acryl is a general term for acryl and methacryl.

In addition, as the monomer having an acrylic group or a methacrylic group, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate are used from the viewpoint of forming a cured product excellent in durability such as scratch resistance as well as water vapor barrier properties. , dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.

Furthermore, as a monomer having an acrylic group or a methacrylic group, a monomer having an acrylic group or a methacrylic group having an alicyclic structure is used from the viewpoint of forming a cured product having excellent transparency. is preferred. The alicyclic structure of the monomer having an acrylic group or methacrylic group is not particularly limited as long as it is a ring structure having no aromaticity, and may be either a hydrocarbon ring or a heterocyclic ring structure. .

Examples of the hydrocarbon ring include cyclohexane ring, isobornyl ring, adamantyl ring, dicyclopentenyl ring, dicyclopentanyl ring, tricycloheptane ring, tricyclooctane ring, and tricyclodecane ring.

Examples of monomers having an acrylic or methacrylic group having a hydrocarbon ring include cyclohexyl acrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, adamantyl acrylate, adamantyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, tricyclodecane methacrylate, tricyclodecane methacrylate and the like.

Examples of the heterocyclic ring include pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydrofuran ring, tetrahydropyran ring, caprolactam ring, isocyanuric ring and hydantoin ring. and saturated polycyclic hydrocarbon rings such as saturated monocyclic heterocycles, tetrahydroquinoline rings, tetrahydroisoquinoline rings, dihydrobenzofuran rings and tetrahydrocarbazole rings.

Monomers having an acrylic or methacrylic group having a heterocyclic ring include, for example, triallyl isocyanurate, diallyl isocyanurate, monoallyl isocyanurate, diallyl monoglycidyl isocyanurate, monoallyl diglycidyl isocyanurate, diallyl monopropyl isocyanurate isocyanuric ring-containing compounds such as nurate, diallyl monomethyl isocyanurate, diallyl monobenzyl isocyanurate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate and ε-caprolactone-modified tris-(2-acryloxyethyl) isocyanurate; mentioned.

The molecular weight of the acrylic group- or methacrylic group-containing monomer is preferably 100 or more and 1,000 or less, and 200 or more and 800 or less, because a curable composition having good compatibility can be obtained. preferable.

The number of functional groups of the monomer having an acrylic group or methacrylic group is preferably 3 to 8 from the viewpoint of forming a cured product having excellent durability such as scratch resistance, and 3 to 8. The number is more preferably 6, and the number 3 is even more preferable because a cured product having an excellent balance of durability such as scratch resistance, improved adhesion, and improved water vapor barrier properties can be formed. When the curable composition of the present invention contains a monomer having an acrylic group or a methacrylic group, the preferred content of the monomer having an acrylic group or a methacrylic group is 1 per 100 parts by mass of the curable composition. It is preferably from 3 to 50 parts by mass, more preferably from 3 to 30 parts by mass, and even more preferably from 5 to 20 parts by mass. This is because the effects of the present invention are more pronounced.

<Solvent>
The curable composition of the invention may contain a solvent in order to adjust fluidity or coatability. Examples of the solvent include those that are liquid at 25° C. under atmospheric pressure and capable of dispersing or dissolving each component in the curable composition. Moreover, the solvent is preferably one that does not react with the components (A), (B) and (C) of the curable composition of the present invention because it has little adverse effect on the cured product of the present invention.

Examples of the solvent include those described in International Publication No. 2019/159953. Also, a mixed solvent in which one or more of these solvents are mixed can be used.

When the curable composition of the present invention contains a solvent, the content of the solvent is 30 parts by mass or more and 90 parts by mass or less in 100 parts by mass of the curable composition, because the effect on the cured product of the present invention is small. preferable.

<Cationically polymerizable compound>
In the curable composition of the present invention, a cationic polymerizable compound can be preferably used because it can contribute to improvement of water vapor barrier properties and adhesion of a cured product.
Examples of the cationic polymerizable compound include epoxy compounds, oxetane compounds and vinyl ether compounds. One of these cationic polymerizable compounds may be used alone, or two or more thereof may be used in combination.

As the epoxy compound, oxetane compound, and vinyl ether compound, for example, compounds described in JP-A-2018-172494 can be used. In the present invention, the cationically polymerizable compound preferably contains an epoxy compound or an oxetane compound, and preferably contains an epoxy compound. This is because a cured product having even better water vapor barrier properties and adhesion can be obtained.

Moreover, the curable composition of the present invention can contain a compound having an alicyclic structure and a compound having no alicyclic structure as the cationic polymerizable compound.
As the alicyclic structure of the compound having the alicyclic structure, any one of the above-described hydrocarbon rings and heterocyclic rings can be used.
In the present invention, the cationically polymerizable compound preferably contains a cationically polymerizable compound having an alicyclic structure, more preferably an epoxy compound having an alicyclic structure or an oxetane compound having an alicyclic structure. It is further preferred to contain an epoxy compound having a structure. This is because a cured product having even better water vapor barrier properties and adhesion can be obtained.

Heterocyclic rings such as epoxy groups in epoxy compounds and oxetane groups in oxetane compounds that function as cationic polymerizable groups do not correspond to the above alicyclic structures.

Examples of epoxy compounds having an alicyclic structure include compounds having an oxiranyl group, which is an epoxy group that does not share a portion of the alicyclic structure and the ring structure, and compounds having an epoxy group that shares a portion of the alicyclic structure and the ring structure. A compound having an epoxycycloalkyl group and the like are included. A compound having both an oxiranyl group and an epoxycycloalkyl group is classified as a compound having an epoxycycloalkyl group.

As the compound having an oxiranyl group, a polyglycidyl etherate of an aliphatic alcohol or an alkylene oxide adduct thereof is preferable, and a compound represented by the following general formula (VIII) is more preferable. This is because a cured product having even better water vapor barrier properties and adhesion can be obtained.

In the formula, X ¹ represents a hydrocarbon group having 1 to 20 carbon atoms having a linear, branched or alicyclic structure, and one or more of the hydrogen atoms in the hydrocarbon group are substituted with hydroxyl groups. one or more of the methylene groups in the hydrocarbon group may be substituted with -O-, -CO- or -NH-CO-, n1 is an integer of 1 to 10 show.

The hydrocarbon group having 1 to 20 carbon atoms having a linear, branched or alicyclic structure represented by X ¹ means a straight chain hydrocarbon group having 1 to 20 carbon atoms, a branched carbon atom It represents a hydrocarbon group of numbers 3 to 20 or a hydrocarbon group having an alicyclic structure.

Linear hydrocarbon groups having 1 to 20 carbon atoms represented by X ¹ include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and Linear alkyl groups having 1 to 20 carbon atoms such as octadecyl can be mentioned.

The branched hydrocarbon group having 3 to 20 carbon atoms represented by X ¹ includes isopropyl, isobutyl, sec-butyl, tert-butyl, isoamyl, tert-amyl, isooctyl, 2-ethylhexyl, tert-octyl and Examples include branched alkyl groups having 3 to 20 carbon atoms such as isononyl.

Examples of the hydrocarbon group having an alicyclic structure represented by X ¹ include groups in which an alicyclic structure group and a linear or branched alkyl group are combined. For example, a group in which one or more hydrogen atoms in a linear or branched alkyl group are substituted with an alicyclic structural group, one methylene group in a linear or branched alkyl group, or two or more of which are substituted with a group from which one hydrogen atom has been removed from the alicyclic structural group; one or two or more of the hydrogen atoms of the alicyclic structural group are substituted with linear or branched alkyl groups and the like.

The alicyclic structural group includes a saturated hydrocarbon ring such as a cyclohexane ring, isobornyl ring, adamantyl ring, dicyclopentenyl ring, dicyclopentanyl ring, tricycloheptane ring, tricyclooctane ring and tricyclodecane ring to hydrogen Groups with one atom removed are included.

When X ¹ is a hydrocarbon group having an alicyclic structure, n1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 3, even more preferably 2. . This is because a cured product having even better water vapor barrier properties and adhesion can be obtained.

X ¹ is preferably a hydrocarbon group having an alicyclic structure having 3 to 20 carbon atoms, more preferably a hydrocarbon group having a hydrocarbon ring having 5 to 20 carbon atoms. A hydrocarbon group having a hydrocarbon ring of 8 to 15 or a hydrocarbon group having a heterocyclic ring of 6 to 10 carbon atoms facilitates obtaining a cured product having excellent water vapor barrier properties and adhesion. , more preferred.

The hydrocarbon group having a hydrocarbon ring having 8 to 15 carbon atoms represented by X ¹ is preferably a hydrocarbon group having a saturated polycyclic hydrocarbon ring having 8 to 15 carbon atoms. A hydrocarbon group having an isobornyl ring or a tricyclodecane ring having 8 to 15 carbon atoms is particularly preferred.

As the hydrocarbon group having a heterocyclic ring having 6 to 10 carbon atoms represented by X ¹ , a hydrocarbon group having an isocyanuric ring having 6 to 10 carbon atoms is preferable because it has excellent water vapor barrier properties and adhesion. It is more preferable because it makes it easier to obtain a cured product.

The above fatty alcohols include monohydric alcohols and polyhydric alcohols, and may be mixtures thereof. Examples of the monohydric alcohol include n-butyl alcohol, n-amyl alcohol, n-octanol, lauryl alcohol, stearyl alcohol and behenyl alcohol. Examples of the polyhydric alcohol include 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, 1,2,3-trimethylolpropane, pentaerythritol and the like.

Examples of the polyglycidyl etherified product of the aliphatic alcohol or its alkylene oxide adduct include, for example, a diglycidyl etherified product of a diol of hydrogenated bisphenol described in International Publication No. 2019/159953, described in International Publication No. 2019/159953. Compounds having a hydrocarbon ring as the alicyclic structure of, compounds having a heterocyclic ring as the alicyclic structure described in International Publication No. 2019/159953, and the like.

As the compound having an epoxycycloalkyl group, a compound having an epoxycycloalkyl group represented by the following general formula (X) is preferable because a cured product having excellent water vapor barrier properties and adhesion can be easily obtained.

In the formula, X2 represents a single bond or a linking group (a ^divalent group having one or more atoms).

The linking group represented by X2 includes, for example, a ^divalent hydrocarbon group, an alkenylene group in which part or all of the carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, and a carbonate group. , an amide group, a group in which a plurality of these are linked, and the like.
The divalent hydrocarbon group includes a straight or branched hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having an alicyclic structure. In the present invention, the hydrocarbon group having a straight chain, branched chain, or alicyclic structure having 1 to 20 carbon atoms means a straight chain hydrocarbon group having 1 to 20 carbon atoms and a branched chain having 1 to 20 carbon atoms. or a hydrocarbon group having an alicyclic structure.

The hydrocarbon group having a straight chain, branched chain, or alicyclic structure having 1 to 20 carbon atoms is an alkyl group having a straight chain, branched chain, or alicyclic structure having 1 to 20 carbon atoms and one hydrogen atom. A group excepted, that is, an alkylene group having a linear, branched or alicyclic structure having 1 to 20 carbon atoms can be used.

Examples of the alkyl group having a linear, branched or alicyclic structure having 1 to 20 carbon atoms include the same groups as those represented by X ¹ in the general formula (VIII).

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized (hereinafter sometimes referred to as "epoxidized alkenylene group") include vinylene group, propenylene group, 1 -butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, octenylene group, and other linear or branched alkenylene groups having 2 to 8 carbon atoms.

In the general formula (X), X ² is preferably a linking group, particularly preferably X ² is a divalent hydrocarbon group, an ester bond, or a group in which these are linked, and X ² is A group in which a divalent hydrocarbon group and an ester bond are linked is more preferable because a cured product having excellent water vapor barrier properties and adhesion can be easily obtained.

Further, in the general formula (X), the divalent hydrocarbon group used for X ² is preferably a linear or branched alkylene group having 1 to 18 carbon atoms. A linear or branched alkylene group of 8 is more preferable, and a linear alkylene group having 1 to 5 carbon atoms facilitates obtaining a cured product having excellent water vapor barrier properties and adhesion. Therefore, it is more preferable.

Examples of the compound having an epoxycycloalkyl group include compounds having an epoxycycloalkyl group described in WO 2019/159953, and 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexane Carboxylates are more preferable because a cured product having excellent water vapor barrier properties and adhesion can be easily obtained.

The content of the cationic polymerizable compound is preferably 5 parts by mass or more and 40 parts by mass or less, and 10 parts by mass or more and 35 parts by mass or less in 100 parts by mass of the solid content of the curable composition of the present invention. More preferably, it is 20 parts by mass or more and 30 parts by mass or less. This is because a cured product having even better water vapor barrier properties and adhesion can be obtained.

The content of the cationic polymerizable compound is preferably 0.5 parts by mass or more and 40 parts by mass or less, more preferably 1 part by mass or more and 35 parts by mass or less in 100 parts by mass of the curable composition of the present invention. It is preferably 2 parts by mass or more and 30 parts by mass or less. This is because a curable composition having even better water vapor barrier properties and coatability can be obtained.

The content of the compound having an oxiranyl group is preferably 10 parts by mass or more and 60 parts by mass or less in a total of 100 parts by mass of the compound having an epoxycycloalkyl group and the compound having an oxiranyl group, and 20 parts by mass. It is more preferably 50 parts by mass or less, and further preferably 30 parts by mass or more and 45 parts by mass or less. This is because a curable composition having even better water vapor barrier properties and coatability can be obtained.

The content of the cationic polymerizable compound having an alicyclic structure is preferably 5 parts by mass or more and 40 parts by mass or less, and 10 parts by mass or more and 35 parts by mass, based on 100 parts by mass of the solid content of the curable composition of the present invention. It is more preferably no more than 20 parts by mass and even more preferably 20 parts by mass or more and 30 parts by mass or less. This is because a curable composition having even better water vapor barrier properties and coatability can be obtained.

The content of the cationic polymerizable compound having an alicyclic structure is preferably 0.5 parts by mass or more and 40 parts by mass or less, and 1 part by mass or more and 35 parts by mass in 100 parts by mass of the curable composition of the present invention. It is more preferably 2 parts by mass or more and 30 parts by mass or less. This is because a curable composition having even better water vapor barrier properties and coatability can be obtained.

The content of the cationically polymerizable compound having an alicyclic structure is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and 90 parts by mass in 100 parts by mass of the cationically polymerizable compound. It is more preferable that it is above. This is because a curable composition having even better water vapor barrier properties and coatability can be obtained.

<Cationic polymerization initiator>
The curable composition of the present invention can contain a cationic polymerization initiator together with the cationic polymerizable compound. Examples of the cationic polymerization initiator include compounds that release a substance that initiates cationic polymerization upon irradiation with light, such as onium salts, more specifically aromatic sulfonium salts.

The above aromatic sulfonium salts include San-Apro product names: CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-410S, and ADEKA Co., Ltd. product name: Adeka Optomer SP-150. , SP-170, SP-171, SP-172 and the like.

When the curable composition of the present invention contains a cationic polymerization initiator, the content of the cationic polymerization initiator is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the curable composition. , more preferably 0.5 to 8 parts by mass, and even more preferably 1 to 5 parts by mass. This is because the polymerization reaction of the curable composition can be easily controlled.

The curable composition of the present invention can contain a thermal polymerization initiator as needed. Examples of the thermal polymerization initiator include thermal cationic polymerization initiators and thermal radical polymerization initiators.

<Thermal cationic polymerization initiator>
The thermal cationic polymerization initiator is not particularly limited as long as it is a compound that generates a cationic species or a Lewis acid by heating, and conventionally known compounds can be used. For example, an onium salt-based initiator can be used. can. Examples of the onium salt-based initiator include aryldialkylsulfonium hexafluoroantimonate, aryldialkylsulfonium hexafluorophosphate, diarylalkylsulfonium hexafluoroantimonate, and aryldialkylsulfonium tetraperfluorophenylborate. Examples include sulfonium salts, iodonium salts such as diaryliodonium hexafluoroantimonate, diaryliodonium hexafluorophosphate and diaryliodonium tetraperfluorophenylborate.

A commercially available product can also be used as the thermal cationic polymerization initiator. For example, Adeka Opton CP-77, Adeka Opton CP-66 (manufactured by ADEKA), CI-2639, CI-2624 (Nippon Soda), San Aid SI-60, San Aid SI-80 and San Aid SI-100 (manufactured by Sanshin Chemical Industry), etc. are mentioned.

<Thermal radical polymerization initiator>
Examples of the thermal radical polymerization initiator include thermal radical polymerization initiators described in International Publication No. 2018/181846. A thermal radical polymerization initiator may be used alone or in combination of two or more.

When the curable composition of the present invention contains a monomer having an acrylic group or a methacrylic group and a thermal polymerization initiator, the content of the thermal polymerization initiator with respect to the monomer having an acrylic group or a methacrylic group is The content of the thermal polymerization initiator is preferably 0.1 parts by mass or more and 10 parts by mass or less, and 0.5 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the monomer having a group or a methacrylic group. and more preferably 1 part by mass or more and 5 parts by mass or less. This is because the polymerization reaction can be easily controlled.

As long as the effects of the present invention are not impaired, the curable composition of the present invention may optionally contain phenolic, sulfur, and phosphorus antioxidants, benzotriazole, benzophenone, triazine, and benzoate ultraviolet rays. Absorbent; surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants; halogen compounds, phosphoric acid ester compounds, phosphoric acid amide compounds, melamine compounds , fluororesins, or metal oxides, melamine (poly) phosphate, piperazine (poly) phosphate flame retardants; hydrocarbons, fatty acids, aliphatic alcohols, aliphatic esters, aliphatic amides, or Lubricants based on metallic soap; pigments, coloring agents such as carbon black; fumed silica, fine particle silica, silica, diatomaceous earths, clay, kaolin, diatomaceous earth, silica gel, calcium silicate, sericite, kaolinite, flint, feldspar powder, Silicic acid-based inorganic additives such as vermiculite, attapulgite, talc, mica, minnesotite, pyrophyllite, silica; fillers such as glass fiber and calcium carbonate; nucleating agents such as clarifying agents and crystallization accelerators; dyes and pigments Colorants such as acid generators; base generators; curing catalysts; silane coupling agents; rubber elasticity-imparting agents such as flexible polymers; chelating agents; Antistatic agents; fluidity modifiers; adhesion promoters; and moisture permeation inhibitors.

The total content of the various additives described above is preferably 50 parts by mass or less per 100 parts by mass of the curable composition of the present invention, because the effects of the present invention will be more pronounced.

The curable composition of the present invention can be produced by mixing each component using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, and a triple roll.

The cured product of the present invention can be produced by irradiating the curable composition of the present invention with active energy rays such as ultraviolet rays, or by curing the curable composition by heating. For example, the curable composition of the present invention is applied to a support substrate or the like to form a coating film, and the coating film is irradiated with active energy rays such as ultraviolet rays, or the coating film is heated. A laminate having the cured product of the present invention and a supporting substrate can be produced by the above.

<Support base>
The material of the support substrate is not particularly limited and can be commonly used, for example, inorganic materials such as glass; vinyl compounds such as polyvinyl acetate and polyvinyl fluoride; and polymeric materials such as cycloolefin polymer (COP).

The support substrate may be subjected to surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.

Examples of active energy rays for curing the curable composition (coating film) applied on the supporting substrate include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, and fluorescent lamps. , tungsten lamp, excimer lamp, germicidal lamp, excimer laser, nitrogen laser, argon ion laser, helium cadmium laser, helium neon laser, krypton ion laser, various semiconductor lasers, YAG laser, light emitting diode, CRT light source, etc. Examples include electromagnetic wave energy having a wavelength of from 7000 angstroms and high energy rays such as electron beams, X-rays and radiation.

The exposure time to the active energy ray is affected by the intensity of the active energy ray, the thickness of the cured product film, the content of the polymerization initiator, etc., but usually 0.1 to 10 seconds is sufficient. However, for relatively thick coatings, irradiation times in excess of 10 seconds may be used to ensure sufficient curing of the coating. 0.1 second to several minutes after the irradiation of the active energy ray, the curable composition of the present invention can be cured to a state of being dry to the touch or insoluble in solvents by radical polymerization. Alternatively, heat energy from a thermal head or the like may be used together.

The curable composition of the present invention may be cured by heating. The conditions for curing the curable composition of the present invention by heating are not particularly limited. It may be cured by PEB (post exposure bake), or may be cured by baking at different temperatures several times.

The heating conditions vary depending on the type and blending ratio of each component, but usually the curable composition of the present invention is prebaked at 50° C. to 180° C. for 1 minute to 15 minutes in an oven or 1 minute to 15 minutes in a hot plate. , Then, in order to cure the coating film, the cured product of the present invention is heated at 100 ° C. to 250 ° C., preferably 150 ° C. to 250 ° C. for 30 minutes to 90 minutes in an oven or 30 minutes to 90 minutes in a hot plate. can be obtained.

The film thickness of the cured product of the present invention is preferably 0.5 μm or more and 30 μm or less, more preferably 0.5 μm or more and 20 μm or less, and 1 μm or more and 15 μm or less. and good visible light transmittance.

Specific applications of the cured product of the present invention are not limited to the following applications, but protective films for polarizing plates, optical compensation films, optical filters, paints, coating agents, lining agents, adhesives, and printing. Plates, insulating varnishes, printed circuit boards, in-vehicle boards, electronic control boards, water vapor barrier coatings for LED lighting, insulating sheets, laminated boards, printed circuit boards, for semiconductor devices, for LED packages, for liquid crystal inlets, for organic EL, for quantum Sealing agents for dot displays, optical elements, electrical insulation, electronic parts, solar cells, separation membranes, etc., molding materials, putty, glass fiber impregnating agents, fillers, semiconductors, solar cells, etc. passivation film, interlayer insulating film, protective film, printed circuit board, or color TV, PC monitor, mobile information terminal, CCD image sensor color filter, electrode material for plasma display panel, printing ink, dental composition, stereolithography resins, both liquid and dry films, micromechanical components, fiberglass cable coatings, holographic recording materials, and the like.

In addition, the curable composition of the present invention is a barrier that imparts water vapor barrier properties to wood, plastics, metals, mirrors, glass, ceramics, inorganic substances, leather, fabrics, paper, electronic/electric parts, and coated articles. It can be suitably used as a film-forming composition.

The method for forming a barrier film of the present invention has a step of curing the curable composition of the present invention. The method and conditions for curing the curable composition are as described above.

The present invention will be described in more detail below with reference to examples, etc., but the present invention is not limited to these examples.

The formulations shown in Tables 1 and 2, in 100 parts by mass of the curable composition, 0.1 parts by mass of the following leveling agent and 5 parts by mass of the following photopolymerization initiator were added until insoluble matter disappeared. Stir to mix to obtain curable compositions 1-18 and comparative curable compositions 1-12. The numbers described in the columns of components (A), (B) and (C) in Tables 1 and 2 are the total of components (A), (B) and (C), and the content of each component The amount (% by mass) is shown, and the numbers described in the column of other components represent the content (parts by mass) per 100 parts by mass of the curable composition.

(A) component: petroleum resin A1: T-REZ (registered trademark) HA085 [hydrogenated dicyclopentadiene petroleum resin manufactured by ENEOS Co., Ltd., component (A); polymer having a repeating unit having an alicyclic structure in its main chain (A-1), a repeating unit represented by general formula (IV), and a repeating unit represented by general formula (V). weight average molecular weight of about 550, softening point of 86.4°C]
A2: T-REZ (registered trademark) HA103 [hydrogenated dicyclopentadiene petroleum resin manufactured by ENEOS Corporation, component (A); polymer (A-1) having a repeating unit having an alicyclic structure in its main chain, general It has a repeating unit represented by formula (IV) and a repeating unit represented by general formula (V). Weight average molecular weight of about 620, softening point of 103.4°C]
A3: T-REZ (registered trademark) HB103 [hydrogenated dicyclopentadiene/C9 petroleum resin manufactured by ENEOS Co., Ltd., component (A); Having a repeating unit represented by general formula (III), a repeating unit represented by general formula (IV), a repeating unit represented by general formula (V), and a repeating unit represented by general formula (VI) . Weight average molecular weight of about 730, softening point of 102.4°C]
A4: Petrotac (registered trademark) 90 [C5-C9 petroleum resin manufactured by Tosoh Corporation, component (A); non-hydrogenated petroleum resin polymerized mainly with styrene, vinyltoluene, indene, piperylene and the like. Weight average molecular weight of about 1,600, softening point of 95°C]

(B) Component: Hydrocarbon polymer having acrylic or methacrylic group B1: TE-2000 (manufactured by Nippon Soda Co., Ltd., polybutadiene urethane-bonded type with terminal acrylic group introduced, having acrylic group, main chain having 4 carbon atoms Hydrocarbon polymer obtained by polymerizing alkene, number average molecular weight of about 2,500, (B) component)
B2: Kuraprene (registered trademark) UC-203M (manufactured by Kuraray Co., Ltd. Polyisoprene Polyisoprene side chain methacrylate, a hydrocarbon polymer having a methacrylic group and a main chain polymerizing an alkene having 5 carbon atoms, weight average molecular weight of about 35,000, (B) component)
B3: CN-307 (Polybutadiene acrylate manufactured by Sartomer Co., a hydrocarbon-based polymer having an acrylic group and a polymerized alkene having a main chain of 4 carbon atoms, a number average molecular weight of about 3,500, component (B))
b-1: UA-306H (Pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane prepolymer manufactured by Kyoei Chemical Co., Ltd., having a (meth) acrylic group, but the main chain is a non-hydrocarbon polymer, weight average molecular weight of about 700, non-(B) component)
b-2: Aronix (registered trademark) M1100 (polyol urethane acrylate manufactured by Toagosei Co., Ltd., main chain is non-hydrocarbon polymer, weight average molecular weight 2,000, non-(B) component)
b-3: Artresin (registered trademark) UN-7600 (polyester urethane acrylate manufactured by Negami Kogyo Co., Ltd., main chain is non-hydrocarbon polymer, weight average molecular weight 11,500, non-(B) component)
b-4: Artresin (registered trademark) UN-9200A (polycarbonate urethane acrylate manufactured by Negami Kogyo Co., Ltd., main chain is non-hydrocarbon polymer, weight average molecular weight 150,000, non-(B) component)
b-5: Artresin (registered trademark) UN-6200 (manufactured by Negami Kogyo Co., Ltd. polyether urethane acrylate, main chain is non-hydrocarbon polymer, weight average molecular weight 6,500, non-(B) component)
b-6: Artresin (registered trademark) UN-5500 (urethane acrylate having a polycarbonate skeleton manufactured by Neagari Kogyo Co., Ltd., main chain is non-hydrocarbon polymer, weight average molecular weight 55,000, non-(B) component)
b-7: New Frontier (registered trademark) BPE-4 (Bisphenol A diglycidyl ether acrylic acid adduct manufactured by Daiichi Kogyo Seiyaku Co., Ltd., monomer, molecular weight 512.6, non-(B) component)
b-8: (trade name) Viscoat #540 (Bis-A type urethane acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd., monomer, molecular weight 480, non-(B) component)
b-9: Acryt (registered trademark) 8KX-078 (acrylic polymer urethane acrylate manufactured by Taisei Fine Chemical Co., Ltd., main chain is non-hydrocarbon polymer, weight average molecular weight 40,000, non-(B) component)

(C) Component: Monomer C1 having two or more groups from the group of acrylic and methacrylic groups and a saturated alicyclic ring: NK Ester (trade name) A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.: Tricyclodecane Methanol diacrylate, molecular weight 304.39, monomer having two acrylic groups and saturated alicyclic ring, (C) component)
c-1: Fancryl (registered trademark) FA-513AS (dicyclopentanyl acrylate manufactured by Hitachi Chemical Co., Ltd., molecular weight 206.28, monomer having one acrylic group and saturated alicyclic ring, non-(C) component)
c-2: Light Acrylate (registered trademark) IB-XA (manufactured by Kyoei Chemical Co., Ltd., isobornyl acrylate, molecular weight 208.3, monomer having one acrylic group and saturated alicyclic ring, non-(C) component)
c-3: Viscoat (trade name) #155 (manufactured by Osaka Organic Chemical Industry Co., Ltd., cyclohexyl acrylate, molecular weight 154.21, monomer having one acrylic group and saturated alicyclic ring, non-(C) component)
c-4: Viscoat (trade name) #295, TMPTA (trimethylolpropane triacrylate manufactured by Osaka Organic Chemical Industry Co., Ltd., molecular weight 296.32, monomer having three acrylic groups and no saturated alicyclic ring, non-(C) component)

(D) component: leveling agent DOWSIL (registered trademark) SH-29 Paint Additive (main component of leveling agent manufactured by Dow Corning Toray Co., Ltd. "octamethylcyclotetrasiloxane")

(E) Component: Photopolymerization initiator Omnirad (registered trademark) 184 (manufactured by IGM Resins B.V.)

(F) Component: Softener F1: Tuftec (registered trademark) H1517 (hydrogenated styrene thermoplastic elastomer manufactured by Asahi Kasei Corporation)
F2: Kuraprene (registered trademark) L-SBR-841 (manufactured by Kuraray Co., Ltd., styrene-butadiene random copolymer)

The curable compositions 1 to 18 produced in Examples 1 to 18 and the comparative curable compositions 1 to 12 produced in Comparative Examples 1 to 12 were dissolved in toluene, and the coating thickness after drying was 7 μm. As described above, a PMMA film (manufactured by Sumitomo Chemical Co., Ltd. Technoloy 125S001) or a TAC film (trade name: FT TD60ULP manufactured by Fuji Film Co., Ltd.) subjected to corona discharge treatment was coated with a bar coater. It was applied to form a coating film. The formed coating film was dried in an oven at 80° C. for 60 seconds. After drying, the coating film was exposed to obtain a cured product. Exposure was performed using a metal halide lamp under the condition of 1,000 mJ/cm ² . The curable compositions and cured products thus obtained were evaluated as follows.

<Light transmittance (turbidity)>
The haze value of the cured product formed on the PMMA film subjected to corona discharge treatment was measured using a haze measuring instrument (manufacturer: Nippon Denshoku Industries Co., Ltd., product name: NDH7000SPII). A haze value of less than 1.0 was evaluated as "A", a case of 1.0 or more and less than 2.0 was evaluated as "B", and a case of 2.0 or more was evaluated as "C". The lower the Haze value, the better the light transmittance of the cured product, and the higher the Haze value, the poorer the light transmittance of the cured product. The results are shown in Tables 3 and 4 below.

<Coatability>
The resulting curable composition was dissolved in toluene and applied to a PMMA film so that the coating thickness after drying was 7 μm using a bar coater. The state of the coating film was visually evaluated. did.
When the coatability is good, specifically, when there are no abnormalities such as repelling, uneven coating, and uneven film thickness in the coating film, it is evaluated as "A". A case where there was an abnormality such as "B" was evaluated. The results are shown in Tables 3 and 4 below.

<Whitening resistance>
A 75 μm-thick PET film (Lumirror #75T60 manufactured by Toray Industries, Inc.) was laminated on the cured product formed on the TAC film subjected to corona discharge treatment, and a load of 4 kg was applied from the top of the PET film and allowed to stand for one day. did. The case where there is no change in the cured product is evaluated as "A", the case where part of the load applied part turns white is evaluated as "B", and the case where the entire surface of the load applied area turns white. Rated as "C". The results are shown in Tables 3 and 4 below.

<Water vapor barrier property>
A cured product formed on a TAC film subjected to corona discharge treatment was cut into a size of 3.3 cm x 3.3 cm, placed on a mask with a 5 ^cm2 hole, and measured with a water vapor permeability measuring device (manufactured by Illinois, model 7002). was used to measure the water vapor permeability under the conditions of 90% relative humidity and 40°C. The smaller the measured value, the smaller the permeation amount of water vapor. When the amount of water vapor permeation is less than 60 g/m ² /day, it is evaluated as "A", and when it is 60 g/m ² /day or more and less than 80 g/m ² /day, it is evaluated as "B", and 80 g/m ² /day or more was evaluated as "C". The results are shown in Tables 3 and 4 below.

<Pencil hardness>
The pencil hardness of the cured product formed on the TAC film was evaluated according to the test method of JIS K5600-5-4. A pencil hardness of 2B or more was evaluated as "A", a case of 4B or more and less than 2B was evaluated as "B", and a case of less than 4B was evaluated as "C". The results are shown in Tables 3 and 4 below.

As is clear from Tables 3 and 4, the curable composition of the present invention has excellent coatability, and the resulting cured product has sufficient hardness, whitening resistance, water vapor barrier properties and light transmission. It was confirmed that the performance was excellent.

Claims

A curable composition containing the following components (A) to (C),
The content of component (A) in the total of components (A), (B) and (C) is 20% by mass or more and 60% by mass or less, and the content of component (B) is 5% by mass or more and 20% by mass. % by mass or less,
A curable composition containing no softening agent or containing less than 6 parts by mass of the softening agent per 100 parts by mass of components (A), (B) and (C) combined.
(A) Petroleum resin (B) Hydrocarbon polymer having acrylic or methacrylic group (C) Monomer having two or more groups selected from the group consisting of acrylic group and methacrylic group and a saturated alicyclic ring
The curable composition according to claim 1, wherein the content of component (C) in the total of components (A), (B) and (C) is 30% by mass or more.
The curable composition according to claim 1 or 2, wherein component (A) is a polymer having an alicyclic structure and having no acrylic group or methacrylic group.
The curable composition according to any one of claims 1 to 3, wherein component (A) contains a cyclic olefin polymer (a1) having an alicyclic structure in its main chain.
Curing according to claim 4, wherein the cyclic olefin polymer (a1) has a repeating unit selected from the group consisting of the following general formulas (I), (II), (III), (IV) and (V) sex composition.

(wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, or an unsubstituted or substituted hydrocarbon group having 1 to 30 carbon atoms, A hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R 1 and R 2 , R 3 and R 4 may combine to form a ring,
m represents 0 or a positive integer,
* represents a bond. )

(wherein R 5 , R 6 , R 7 and R 8 each independently represent a hydrogen atom, a halogen atom, or an unsubstituted or substituted hydrocarbon group having 1 to 30 carbon atoms, A hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R 5 and R 6 , R 7 and R 8 may combine with each other to form a ring,
p and q each independently represent 0 or a positive integer, and * represents a bond. )

(wherein R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are each independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted carbon atom represents a hydrocarbon group having a number of 1 to 30, the hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R 9 and R 10 , R 11 and R 12 , R 13 and R 14 , R 15 and R 16 may combine with each other to form a ring,
* represents a bond. )

(wherein R 17 , R 18 , R 19 , R 20 , R 21 and R 22 are each independently a hydrogen atom, a halogen atom, or an unsubstituted or substituted carbon atom having 1 to 30 carbon atoms) represents a hydrogen group, the hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom,
R 17 and R 18 , R 19 and R 20 , R 21 and R 22 may combine with each other to form a ring,
* represents a bond. )

(wherein R 23 , R 24 , R 25 and R 26 each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; and the hydrocarbon group having 1 to 30 carbon atoms may have a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom,
R 23 and R 24 , R 25 and R 26 may combine with each other to form a ring,
* represents a bond. )
The curable composition according to any one of claims 1 to 5, wherein component (A) contains a polymer having a repeating unit having an alicyclic structure in its side chain.
7. The curable composition according to claim 6, wherein the repeating unit having an alicyclic structure in its side chain is a repeating unit represented by general formula (VI) below.

(Wherein, R 27 represents a hydrogen atom or a methyl group,
R 28 represents an unsubstituted or substituted cycloalkyl group having 3 to 40 carbon atoms,
* represents a bond. )
The curable composition according to any one of claims 1 to 7, wherein the main chain of component (B) is a hydrocarbon polymer obtained by polymerizing an alkene having 2 to 8 carbon atoms.
The curable composition according to any one of claims 1 to 8, wherein the component (C) is a tricyclic compound.
The curable composition according to any one of claims 1 to 9, further comprising a leveling agent as component (D).
The curable composition according to claim 10, wherein the leveling agent of component (D) contains a silicone compound.
A barrier film-forming composition containing the curable composition according to any one of claims 1 to 11.
A cured product of the curable composition according to any one of claims 1 to 11.
A laminate comprising the cured product according to claim 13 and a supporting substrate, wherein the cured product is formed on the supporting substrate.
A method for forming a barrier film, comprising a step of curing the curable composition according to any one of claims 1 to 11.