JP2023010400A - Curable composition, sealant, and adhesive - Google Patents

Abstract

To provide a curable composition that can provide a cured product having both of high adhesion and high durability.SOLUTION: A curable composition contains a polyisobutylene polymer (A) having methacryloyl groups, the number of which is 0.5-1.0 per molecule, a polyfunctional vinyl monomer (B), and a polymerization initiator (C).SELECTED DRAWING: None

Description

The present invention relates to curable compositions, encapsulants, and adhesives.

For example, in applications such as inks, paints, adhesives, sealants, precision parts for electrical and electronic applications, and molded objects, curable compositions that can be cured by heating or irradiation with active energy (e.g., light) are used. ing.

Properties required for materials used in these fields include, for example, durability and gas barrier properties, and an example of a resin having these properties is a polyisobutylene-based polymer.

For example, Patent Documents 1 and 2 disclose a polyisobutylene-based polymer having 0.8 or more specific functional groups per molecule and a saturated cyclic hydrocarbon group or a linear or branched hydrocarbon having 18 or more carbon atoms. and a (meth)acrylate compound having a group. Patent Document 3 discloses a polyisobutylene-based polymer having a specific molecular weight and molecular weight distribution and having 1.2 or more (meth)acryloyl groups in one molecule, and a polyisobutylene polymer having a specific molecular weight and molecular weight distribution and A curable composition containing a polyisobutylene polymer having 0.5 to 1.0 (meth)acryloyl groups per molecule is disclosed. Patent Document 4 discloses a copolymer of a polyisobutylene-based macromonomer having at least 0.8 specific (meth)acryloyl groups per molecule at one end of the main chain and a vinyl-based monomer. Certain vinyl comb copolymers are disclosed. Patent Document 5 discloses an adhesive tape including a backing layer made of a specific copolymer and a pressure-sensitive adhesive layer made of a polyisobutylene-based polymer.

JP 2019-157029 A JP 2019-157030 A WO2018/155401 WO2018/168992 Japanese Patent Publication No. 2012-528919

However, the conventional techniques as described above are not sufficient from the viewpoint of achieving both durability and adhesiveness, and there is room for further improvement.

One embodiment of the present invention has been made in view of the above problems, and an object thereof is to provide a novel curable composition capable of providing a cured product having both high adhesiveness and durability. is.

The present inventor has completed the present invention as a result of intensive studies in order to solve the above problems.

That is, one embodiment of the present invention includes the following configurations.
[1] Polyisobutylene-based polymer (A) having 0.5 to 1.0 (meth)acryloyl groups per molecule, polyfunctional vinyl-based monomer (B), and polymerization initiator (C) A curable composition comprising:
[2] The curable composition according to [1], wherein the (meth)acryloyl group is a group represented by the following general formula (1).

(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and does not have a heteroatom, and R ³ to R ⁶ each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group.)
[3] The curable composition of [1] or [2], further comprising a monofunctional vinyl monomer (D).
[4] With respect to 100 parts by weight of the polyisobutylene polymer (A), 0.01 to 100 parts by weight of the polyfunctional vinyl monomer (B) and 0.01 to 100 parts by weight of the polymerization initiator (C) 20.0 parts by weight, and 0.1 to 1000 parts by weight of the monofunctional vinyl monomer (D), the curable composition according to [3].
[5] A polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule (i) further contains 20 parts by weight or less per 100 parts by weight of the polyisobutylene-based polymer (A) or (ii) does not contain the curable composition according to any one of [1] to [4].
[6] The polyfunctional vinyl monomer (B) includes 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di( meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, The curable composition according to any one of [1] to [5], which is at least one selected from the group consisting of pentaerythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate.
[7] The polyisobutylene-based polymer (A) according to any one of [1] to [6], having 0.8 to 1.0 (meth)acryloyl groups per molecule. Curable composition.
[8] The curable composition according to any one of [1] to [7], wherein the polymerization initiator (C) is a radical photopolymerization initiator.
[9] A sealing material obtained by curing the curable composition according to any one of [1] to [8].
[10] A pressure-sensitive adhesive obtained by curing the curable composition according to any one of [1] to [8].

ADVANTAGE OF THE INVENTION According to one Embodiment of this invention, it is effective in the ability to provide the curable composition which can provide the hardened|cured material which balances high adhesiveness and durability.

An embodiment of the invention will be described below, but the invention is not limited thereto. The present invention is not limited to each configuration described below, and various modifications are possible within the scope of the claims. Further, embodiments or examples obtained by appropriately combining technical means disclosed in different embodiments or examples are also included in the technical scope of the present invention. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the scientific literatures and patent documents described in this specification are used as references in this specification. In addition, unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)".

[1. Technical idea of the present invention]
A cured product obtained by curing a curable composition containing a polyisobutylene-based polymer as a main component has good gas barrier properties and flexibility. There were cases where sufficient adhesiveness was not obtained, and there was room for improvement. Moreover, in recent years, the performance of electric and electronic parts has been improved, and high-precision devices such as organic EL displays have become more widespread. Therefore, there is a demand for a curable composition capable of providing a cured product having both excellent gas barrier properties and flexibility, as well as higher durability and adhesiveness than ever before.

On the other hand, the techniques described in Patent Documents 1 to 5 have room for improvement as follows. For example, Patent Literatures 1 and 2 evaluate the adhesiveness of the composition for pressure-sensitive adhesives, but do not discuss any improvement in durability.

Further, in Patent Literatures 3 and 4, although the conformability to deformation of the curable composition is evaluated, no consideration is given to adhesiveness and durability, and compatibility therebetween.

Moreover, Patent Document 5 does not discuss a polyisobutylene-based polymer into which a functional group is introduced. Moreover, Patent Document 5 does not consider anything about adhesiveness and durability, and about compatibility between them.

As described above, in Patent Documents 1 to 5, compatibility between adhesiveness and durability is not studied at all, and a curable composition capable of providing a cured product having both high durability and adhesiveness is still in demand. It is Therefore, the present inventors have studied how to further improve the durability and adhesiveness of a cured product mainly composed of a polyisobutylene-based polymer having good gas barrier properties and flexibility. In the course of intensive studies, the present inventors surprisingly found the following new finding: (a) the polyisobutylene-based polymer has 1.0 or less (meth)acryloyl groups per molecule; As the content ratio of the polyisobutylene polymer increases, the adhesiveness increases, but the heat resistance and durability tend to decrease due to the decrease in the crosslink density; and (b) the polyisobutylene polymer, As the content of the polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule increases, the durability tends to increase, but the adhesiveness tends to decrease. Based on such new findings, the present inventors have made further intensive studies on compatibility between durability and adhesiveness, which are in a trade-off relationship. As a result, the present inventor found that a polyisobutylene-based polymer (A) having 0.5 to 1.0 (meth)acryloyl groups per molecule and a polyfunctional vinyl-based monomer (B) The present inventors have newly discovered that the above problems can be solved by using them in combination, and have completed the present invention.

[2. Curable composition]
A curable composition according to one embodiment of the present invention comprises a polyisobutylene-based polymer (A) having 0.5 to 1.0 (meth)acryloyl groups per molecule, and a polyfunctional vinyl-based monomer. (B), and a polymerization initiator (C).

In the present specification, "polyisobutylene-based polymer (A) having 0.5 to 1.0 (meth)acryloyl groups per molecule", "polyfunctional vinyl-based monomer (B)" and " The polymerization initiator (C)" may also be referred to as "(A) component", "(B) component" and "(C) component", respectively. Moreover, "the curable composition according to one embodiment of the present invention" may be referred to as "the curable composition".

Since the present curable composition has the structure described above, it has the advantage of being able to provide a cured product having both high adhesiveness and durability. In addition, the cured product obtained by curing the present curable composition (hereinafter also simply referred to as “the cured product”) contains the polyisobutylene-based polymer (A), and therefore has good gas barrier properties and flexibility. It also has the advantage of having

In the present specification, "excellent adhesiveness" means that an adhesive product having a curable composition or a cured product thereof as an adhesive layer on a substrate is excellent in adhesive strength when it is attached to an adherend. intended to Moreover, "excellent in durability" intends that the compression set of the cured product is small. Moreover, "excellent in gas barrier properties" means that the moisture permeability of the cured product is low. "Flexibility" is evaluated by the tensile physical properties (tensile strength at break (Tb), tensile elongation at break (Eb), and 30% modulus (M30)) and hardness of the cured product. Adhesiveness, durability (compression set), moisture permeability and tensile physical properties are evaluated by the methods described in Examples below.

Since the present curable composition has the advantages described above, it can be particularly suitably used as a sealing material and an adhesive for various uses including electric and electronic parts.

<Polyisobutylene polymer (A)>
The present curable composition contains, as a curable resin, a polyisobutylene-based polymer (A) having 0.5 to 1.0 (meth)acryloyl groups per molecule (component (A)). The component (A) in the present curable composition has a main chain composed of a polyisobutylene polymer and an average of 0.5 to 1.0 (meth)acryloyl groups per molecule.

In this specification, the term "polyisobutylene-based polymer having 0.5 to 1.0 (meth)acryloyl groups in one molecule" differs in the number of (meth)acryloyl groups contained in the molecule. An aggregate of polyisobutylene-based polymer molecules in which the average number of (meth)acryloyl groups per molecule is 0.5 to 1.0 is intended. The aggregate has a polyisobutylene-based polymer molecule having no (meth)acryloyl group (hereinafter also simply referred to as "non-functionalized polymer molecule") and one (meth)acryloyl group per molecule. (For example, having only one end of the main chain) is an aggregate with polyisobutylene-based polymer molecules (hereinafter also simply referred to as "monofunctional polymer molecules"), half of all molecules in the aggregate Assemblies in which the above are monofunctionalized polymer molecules are contemplated. A "polyisobutylene-based polymer having 0.5 to 1.0 (meth)acryloyl groups per molecule" is hereinafter simply referred to as a "monofunctional polymer". In addition, as long as the monofunctional polymer has 0.5 to 1.0 (meth)acryloyl groups in one molecule, two (meth)acryloyl groups in one molecule (for example , both ends of the main chain), or polyisobutylene-based polymer molecules having two or more (hereinafter also simply referred to as "multifunctional polymer molecules").

On the other hand, a "polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule" is an aggregate of monofunctional polymer molecules and polyfunctional polymer molecules. A "polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule" is hereinafter simply referred to as a "polyfunctionalized polymer".

In addition, in this specification, the "(meth)acryloyl group" intends an acryloyl group and/or a methacryloyl group (either one or both of an acryloyl group and a methacryloyl group). Moreover, in this specification, the "main chain" of the component (A) intends the remainder of the component (A) excluding the (meth)acryloyl group.

The average number of (meth)acryloyl groups contained in one molecule of the polyisobutylene polymer is 0.5 to 1.0, more preferably 0.6 to 1.0, It is more preferably 0.7 to 1.0, even more preferably 0.8 to 1.0, and particularly preferably 0.9 to 1.0. When the number of (meth)acryloyl groups contained in one molecule of the polyisobutylene-based polymer is within the above-described range, the curable composition has excellent productivity and excellent rapid curing, and the curable composition is It has the advantage that the cured product obtained by curing exhibits desired physical properties. When the average number of (meth)acryloyl groups contained in one molecule of the polyisobutylene polymer is less than 0.5, the tackiness etc. of the cured product is reduced, and various physical properties (e.g., the desired level of high stickiness) may not be obtained. When the number of (meth)acryloyl groups contained in one molecule of the polyisobutylene-based polymer is 0.5 or more, as the number of (meth)acryloyl groups increases, the tackiness of the cured product improves, and the desired High levels of tack tend to be obtained. Further, when the average number of (meth)acryloyl groups contained in one molecule of the polyisobutylene polymer is larger than 1.0, depending on the ratio between the monofunctional polymer molecule and the polyfunctional polymer molecule, Therefore, there is a trade-off relationship between durability and adhesiveness, and it tends to be difficult to obtain a curable composition having an excellent balance between durability and adhesiveness.

The "number of (meth)acryloyl groups contained in one molecule of the polyisobutylene-based polymer" is also referred to as "the number of (meth)acryloyl groups introduced per molecule of the polyisobutylene-based polymer (or the functionalization rate)." I can say.

The number of (meth)acryloyl groups contained in one molecule of the polyisobutylene-based polymer can be calculated by the following method: (i) performing ¹ H NMR measurement of the polyisobutylene-based polymer; From the results obtained, (ii-1) the relative number of polymer molecules present in the polyisobutylene-based polymer (A ), and (ii-2) the relative number of (meth)acryloyl groups present in the polyisobutylene-based polymer ( B) is calculated; (iii) by calculating the ratio (B/A) of the relative number (B) of the (meth)acryloyl group to the relative number (A) of the polymer molecule contained in one molecule ( The number of meth)acryloyl groups (number of introductions) can be determined.

The polyisobutylene-based polymer constituting the main chain of component (A) may be (a) an isobutylene homopolymer, (b) a block copolymer of isobutylene and a monomer other than isobutylene, or a random It may be a copolymer or graft copolymer, or (c) a mixture of two or more thereof.

When the polyisobutylene-based polymer constituting the main chain of component (A) is a copolymer containing a structural unit derived from a monomer other than isobutylene, the structural unit derived from isobutylene and the monomer other than isobutylene The ratio of the constituent units derived from the body is not particularly limited as long as it does not impair the effects of the present invention. When the main chain of the component (A) is a copolymer, the content of structural units derived from isobutylene is preferably 50% by weight or more, more preferably 60% by weight or more, because of excellent gas barrier properties and flexibility. is more preferable. If the content of structural units derived from isobutylene is 50% by weight or more, good gas barrier properties and flexibility are likely to be exhibited, and good damping properties, adhesiveness, and mechanical properties are likely to be obtained. have advantages.

A monomer other than isobutylene is not particularly limited as long as it is a monomer that can be cationic polymerized with isobutylene. Monomers other than isobutylene include aliphatic olefins such as 1-butene, aromatic vinyls such as styrene, methylstyrene, and α-methylstyrene, dienes such as 1,3-butadiene and isoprene, and butyl vinyl ether. silanes such as vinyltrimethylsilane and allyltrimethylsilane; terpenes such as α-pinene, β-pinene and limonene; vinylcarbazole; and acenaphthylene. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene are monomers other than isobutylene from the viewpoint of copolymerizability with isobutylene and physical properties of the resulting copolymer. , α-methylstyrene, α-pinene, β-pinene, limonene, isoprene, 1-butene and 1,3-butadiene are particularly preferred.

The molecular weight of component (A) is not particularly limited, but the number average molecular weight is preferably 500 to 300,000, more preferably 1,000 to 300,000, from the viewpoint of ease of handling of the curable composition and physical properties of the cured product. It is more preferably 2,000 to 200,000, and even more preferably 3,000 to 100,000. When the number average molecular weight of component (A) is 500 or more, (a) sufficient strength of the cured product is likely to be obtained, and (b) the present curable composition is likely to exhibit a suitable range of tackiness and handleability. and (c) physical properties characteristic of polyisobutylene-based polymers (good gas barrier properties, flexibility, etc.) are likely to be exhibited. Further, when the number average molecular weight of component (A) is 300,000 or less, there is an advantage that good fluidity and workability can be easily obtained.

The molecular weight distribution of the component (A) (number represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw/Mn)) is preferably from 1.00 to 2.00, and from 1.10 to 1.80. more preferred. If the molecular weight distribution is within the above range, the advantages are that (a) the melt viscosity of the resin can be lowered, and the handling property during molding processing can be easily improved, and (b) good physical properties of the cured product can be easily obtained. have

In this specification, the number average molecular weight and weight average molecular weight are values calculated by polystyrene conversion using size exclusion chromatography (also referred to as SEC or gel permeation chromatography (GPC)).

Although there are no particular restrictions on the manner in which the (meth)acryloyl group of component (A) is bonded to the main chain, an ester bond, an ether bond, an amide bond, a urethane bond, a thioether bond, a carbonate bond, a urea bond, and a heteroatom can be used. A bond formed of a hydrocarbon group having a valence of 2 or more is exemplified. Among these, an ester bond, an ether bond, an amide bond, and a urethane bond are preferred because of ease of synthesis.

The bonding position of the (meth)acryloyl group of component (A) is not particularly limited, and may be the terminal of the main chain or the side chain. (a) Synthesis is easy, (b) the physical properties of the resulting cured product are suitable as an elastomer material, (c) the number of functional groups per polymer molecule is easy to control, and (d) raw materials are industrially available. The (meth)acryloyl group of the component (A) is preferably attached to the end of the main chain because it is easily available commercially.

In a particularly preferred embodiment, component (A) preferably has 0.5 to 1.0 (meth)acryloyl groups per molecule, and preferably 0.6 to 1.0 (meth)acryloyl groups at the ends of the main chain. is more preferable, more preferably 0.7 to 1.0, even more preferably 0.8 to 1.0, particularly preferably 0.9 to 1.0. This configuration can further improve the adhesiveness and durability of the cured product.

The structure of the (meth)acryloyl group of component (A) is not particularly limited, but from the viewpoint of the physical properties of the cured product, availability of raw materials, and ease of production, It is preferable that the structure is

In general formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and having no heteroatom. R ³ to R ⁶ each independently represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group. Also, the wavy line represents the bonding portion with the main chain.

R ¹ in general formula (1) represents hydrogen or a methyl group. When R ¹ is a hydrogen atom, general formula (1) becomes an acryloyl group, and when R ¹ is a methyl group, general formula (1) becomes a methacryloyl group.

An acryloyl group or a methacryloyl group can be arbitrarily selected as the (meth)acryloyl group of component (A) according to the combination with other components blended in the present curable composition.

For example, when adding an acrylate-based monomer as component (B) in order to adjust various physical properties of the present curable composition or the resulting cured product, the (meth)acryloyl group of component (A) may be R ¹ It may be preferred to choose an acryloyl group in which is a hydrogen atom. In addition, when adding a methacrylate-based monomer as component (B) for the purpose of improving physical properties such as heat resistance of the present curable composition or the obtained cured product, the (meth)acryloyl group of component (A) As, it may be preferred to choose a methacryloyl group in which R ¹ is a methyl group. These selections have the advantage that the reactivities of the components (A) and (B) are close to each other, making it easier to obtain a cured product having a uniform structure.

Alternatively, if it is preferable that the component (A) and the component (B) have different reactivity, when adding an acrylate-based monomer as the component (B), the (meth)acryloyl group of the component (A) may be selected as a methacryloyl group in which R ¹ is a methyl group. Similarly, when a methacrylate-based monomer is added as component (B), an acryloyl group in which R ¹ is a hydrogen atom may be selected as the (meth)acryloyl group for component (A).

R ² in the general formula (1) is a C 2-6 divalent saturated hydrocarbon group containing no heteroatom. Specific examples of R ² include -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH _{2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 CH 2 - ,} and -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - and the like. Among these, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, and -CH ₂ CH ₂ CH ₂ CH ₂ - are preferred from the viewpoint of raw material availability and reactivity.

R ³ to R ⁶ in general formula (1) are each independently a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group. Specific examples of monovalent hydrocarbon groups having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, 2 -ethylhexyl group, nonyl group, decanyl group, and the like. Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, and butoxy groups. Among these, one or more selected from the group consisting of a hydrogen atom, a methyl group, and a methoxy group is preferable in terms of reactivity, and a hydrogen atom is more preferable in consideration of the availability of raw materials.

In a particularly preferred embodiment, the component (A) preferably has 0.5 to 1.0 groups represented by the general formula (1) per molecule at the end of the main chain, and 0.6 to 1 It is more preferable to have 0.0, more preferably 0.7 to 1.0, even more preferably 0.8 to 1.0, particularly 0.9 to 1.0 preferable. This configuration can further improve the adhesiveness and durability of the cured product.

The method for producing component (A) is not particularly limited, and known methods can be applied. Because the availability and productivity of raw materials are high and can be suitably used industrially, for example, the production methods described in WO2013/047314, JP 2013-216782, and WO2017/099043. can be preferably used. The production method includes, for example, (i) a monofunctional polymerization initiator (such as cumyl chloride, tert-butyl chloride, and 2-chloro-2,4,4-trimethylpentane) and a Lewis acid catalyst (such as TiCl ₄ etc.), living cationic polymerization of isobutylene is performed in the presence of an electron donor component such as a nitrogen-containing compound (e.g., 2-methylpyridine, 2,6-dimethylpyridine, triethylamine, etc.) to obtain a polyisobutylene-based polymer. and (ii) functionalizing the terminal of the main chain with a phenoxyalkyl (meth)acrylate compound or the like. By this method, a polyisobutylene polymer having a (meth)acryloyl group at the terminal of the main chain can be produced. In the method, it is particularly preferable to use methyl chloride, butyl chloride, hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, and the like as the solvent from the viewpoints of availability, solubility of raw materials and polymers, and economy. preferable. Moreover, in the method, the reaction is preferably carried out at a low temperature (eg, -70°C). In step (ii) of the method, the degree of functionalization can be controlled by adjusting the amount of the phenoxyalkyl (meth)acrylate compound used.

Alternatively, for example, (i) a step of producing a monomer having both isobutylene and a cationically polymerizable functional group (cationically polymerizable functional group) and a (meth)acryloyl group, and (ii) isobutylene and ( a step of randomly copolymerizing the monomer obtained in i) by cationic polymerization. By this method, a polyisobutylene-based polymer having (meth)acryloyl groups on the side chains of the main chain can be produced.

<Polyfunctional Vinyl Monomer (B)>
Component (B) is a compound that is polymerized by active species generated from the polymerization initiator (C) (component (C)) described later, and is a vinyl-based monomer having two or more polymerizable functional groups in one molecule. be.

The actions of component (B) in the present curable composition include (a) action to adjust various physical properties of the cured product, (b) action as a reactive diluent, and (c) action to form cross-linking points. is mentioned. In addition, by containing the (B) component in the present curable composition, it is possible to prevent deterioration in heat resistance and durability that tends to occur with the use of the monofunctional polymer of the (A) component. Therefore, by using the component (A) and the component (B) together, it is possible to provide a cured product having both durability and adhesiveness.

Examples of the component (B) include compounds described in WO2013/047314, JP-A-2013-216782, and the like. Among these, (meth)acrylate monomers having an alkyl group having 1 to 30 carbon atoms or an alicyclic group are preferred from the viewpoint of compatibility with component (A) and/or excellent photocurability. These (B) components may be used individually by 1 type, and may be used in combination of 2 or more type.

Preferred examples of component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and glycerin di(meth)acrylate. , 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, di(meth)acrylate of ethylene oxide adduct of bisphenol A, neopentyl glycol hydroxypivalate acrylic Acid adducts, polyethylene glycol (PEG) 200 di(meth)acrylate, polyethylene glycol (PEG) 400 di(meth)acrylate, polyethylene glycol (PEG) 600 di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1 , 4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 ,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-(meth)acryloyloxyethyl acid phosphate, trimethylolpropane tri(meth)acrylate, trimethylolpropane acrylic acid Benzoic acid ester, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene oxide-modified diglycerin tetraacrylate, dipentaneerythritol hexa(meth)acrylate, ethylene glycol di (Meth)acrylic acid adduct of glycidyl ether, (meth)acrylic acid adduct of diethylene glycol diglycidyl ether, (meth)acrylic acid adduct of polyethylene glycol diglycidyl ether, (meth)acrylic acid addition of propylene glycol diglycidyl ether product, (meth)acrylic acid adduct of tripropylene glycol diglycidyl ether, (meth)acrylic acid adduct of polypropylene glycol diglycidyl ether, (meth)acrylic acid adduct of neopentyl glycol diglycidyl ether, 1,6- Hexanediol diglycidyl ether (meth) Acrylic acid adduct, glycerol diglycidyl ether (meth)acrylic acid adduct, trimethylolpropane triglycidyl ether (meth)acrylic acid adduct, bisphenol A diglycidyl ether (meth)acrylic acid adduct, bisphenol A propylene (Meth)acrylic acid adducts of diglycidyl ether of 2-mol oxide adducts, and (meth)acrylic acid adducts of hydrogenated bisphenol A diglycidyl ether.

From the viewpoint of availability and reactivity, component (B) is 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth) ) acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta More preferably, it is at least one selected from the group consisting of erythritol tri(meth)acrylate and pentaerythritol tetra(meth)acrylate.

When isomers exist in the divalent or higher valent alkyl group or alicyclic group of component (B), any isomers can be used in the same manner, and mixtures thereof can also be used.

The number average molecular weight of component (B) is not particularly limited, but is preferably 2000 or less, more preferably 1000 or less. When the number average molecular weight of the component (B) is 2000 or less, the viscosity of the present curable composition is within a suitable range, and there is an advantage that good handleability is likely to be obtained. The lower limit of the number-average molecular weight of the component (B) is not particularly limited, but is preferably 150 or more, and preferably 170 or more, in terms of ease of handling of the present curable composition. more preferred.

The number of polymerizable functional groups in one molecule of component (B) is not particularly limited as long as it is two or more, but is preferably 10 or less per molecule, more preferably 6 or less, and further preferably 3 or less. preferable.

The content of component (B) in the present curable composition is preferably 0.01 to 100 parts by weight, preferably 0.10 to 100 parts by weight, per 100 parts by weight of component (A). It is more preferably 0.50 to 50 parts by weight, still more preferably 0.50 to 30 parts by weight, and particularly preferably 0.50 to 20 parts by weight. When the content of component (B) is 0.01 parts by weight or more per 100 parts by weight of component (A), the above-mentioned effects of component (B) are exhibited satisfactorily. Moreover, when the content of the component (B) is 100 parts by weight or less per 100 parts by weight of the component (A), there is an advantage that the cured product has hardness within a suitable range.

<Polymerization initiator (C)>
Component (C) is a compound that generates active species (eg, radical species) capable of initiating polymerization of monomers by an external stimulus. Component (C) is not particularly limited, but includes known radical photopolymerization initiators and thermal radical polymerization initiators.

Component (C) is preferably a photoradical polymerization initiator that generates radical species upon exposure to active energy rays, because the present curable composition exhibits excellent rapid curability. In the present specification, active energy rays include all light in a broad sense, for example, radiation such as α-rays and β-rays, electromagnetic waves such as γ-rays and X-rays, electron beams (EB), ultraviolet rays (wavelength 100 to 400 nm) and visible light (wavelength 400 to 800 nm), preferably ultraviolet light.

Examples of photoradical polymerization initiators include compounds described in WO2013/047314 and JP-A-2013-216782. Among these, (a) a compound having a hydroxyl group and a phenylketone structure, (b) a compound having a benzophenone structure, and (c) a compound having an acylphosphine oxide structure can be preferably used.

(a) Compounds having a hydroxyl group and a phenylketone structure include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1 -phenyl-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1-one, 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinopropan-1-one and the like.

(b) Compounds having a benzophenone structure include benzophenone, 3-methoxybenzophenone, 4-methylbenzophenone, 4,4′-bis(diethylamino)benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, and 4 -chloro-4'-benzylbenzophenone and the like.

(c) Compounds having an acylphosphine oxide structure include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.

Among these, benzophenone, 4,4'-bis(diethylamino)benzophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1- hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide , are particularly preferred.

The radical photopolymerization initiator may be used alone or in combination of two or more. Moreover, one or more photoradical polymerization initiators may be used in combination with other compounds. When the photoradical polymerization initiator is used in combination with another compound, suitable examples of the other compound include amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine. A radical photopolymerization initiator, the amine described above, and an iodonium salt such as phenyliodonium chloride may be used in combination. Further, the radical photopolymerization initiator, the amine described above, and a dye such as methylene blue may be used in combination.

(C) When using a photoradical polymerization initiator as a component, a polymerization inhibitor can also be added as needed. In the present curable composition, coexistence of a photoradical polymerization initiator and a polymerization inhibitor provides the advantage of preventing unintended curing of the curable composition and facilitating handling. Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, benzoquinone, and p-tert-butylcatechol.

When the present curable composition can be heated for curing, a thermal radical polymerization initiator that generates radical species by heat can also be used as the component (C). Also, as the component (C), a radical photopolymerization initiator and a thermal radical polymerization initiator may be used in combination.

Examples of thermal radical polymerization initiators include azo initiators, peroxides, persulfuric acid, and redox initiators. Among these, azo initiators and peroxides are more preferred.

Azo initiators include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis-2-methylbutyronitrile.

Peroxides include t-butyl peroxypivalate, di(4-t-butylcyclohexyl)peroxydicarbonate, t-butyl peroxyisopropyl monocarbonate, dicumyl peroxide, and benzoyl peroxide. .

A thermal radical polymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more type.

The content of component (C) in the curable composition is preferably 0.01 to 20.0 parts by weight, preferably 0.05 to 20.0 parts by weight, per 100 parts by weight of component (A). More preferably, 0.10 to 20.0 parts by weight, even more preferably 0.10 to 10.0 parts by weight, and 0.10 to 5.0 parts by weight It is particularly preferred to have When the content of component (C) is 0.01 parts by weight or more per 100 parts by weight of component (A), the effect of component (C) is exhibited and good curability is obtained. In addition, since the content of component (C) is 20.0 parts by weight or less with respect to 100 parts by weight of component (A), (a) external stimuli (light, heat, etc.) reach deep , the occurrence of uncured portions can be prevented, and (b) the cured product tends to exhibit good heat resistance.

<Monofunctional Vinyl Monomer (D)>
The curable composition preferably further contains a monofunctional vinyl monomer (D) (component (D)). The action of the component (D) in the present curable composition includes (a) action to adjust physical properties of the cured product (e.g., flexibility, etc.) and (b) action as a reactive diluent. .

Component (D) is a compound polymerized by active species generated from component (C), and is a vinyl-based monomer having one polymerizable functional group per molecule.

Examples of component (D) include compounds described in WO2013/047314, JP-A-2013-216782, and the like. Examples of such compounds include linear or cyclic (meth)acrylate monomers, styrene monomers, conjugated diene monomers, acrylonitrile, N-vinylpyrrolidone, acrylamide monomers, vinyl ketone monomers, monomers, vinyl ester monomers, and the like. These (D) components may be used individually by 1 type, and may be used in combination of 2 or more type.

Among these, (meth)acrylate monomers having an alkyl group having 1 to 30 carbon atoms or an alicyclic group are preferred from the viewpoint of compatibility with component (A) and/or excellent photocurability.

Preferred examples of component (D) from the viewpoint that the physical properties of the resulting cured product are good and the viscosity of the curable composition can be easily adjusted include 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, (meth)acrylic acid dicyclopentenyl, isobornyl (meth)acrylate, adamantyl (meth)acrylate, and the like. Preferred examples of component (D) from the viewpoint of availability include isononyl (meth)acrylate, isostearyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and isobornyl (meth)acrylate. mentioned.

When isomers exist in the alkyl group or alicyclic group of component (D), any isomers can be used in the same manner, and mixtures thereof can also be used.

The number average molecular weight of component (D) is not particularly limited, but is preferably 1,000 or less, more preferably 500 or less. When the number average molecular weight of the component (D) is 1000 or less, the viscosity of the present curable composition is within a suitable range, and there is an advantage that good handleability is likely to be obtained. The lower limit of the number average molecular weight of the component (D) is not particularly limited, but is preferably 50 or more, and 70 or more, for example, from the viewpoint of the ease of handling and safety of the present curable composition. It is more preferable to have

The content of component (D) in the present curable composition is preferably 0.1 to 1000 parts by weight, preferably 0.50 to 1000 parts by weight, per 100 parts by weight of component (A). It is more preferably 1.0 to 1000 parts by weight, even more preferably 1.0 to 500 parts by weight, and particularly preferably 1.0 to 300 parts by weight. When the content of component (D) is 0.1 parts by weight or more per 100 parts by weight of component (A), the above-mentioned effect of component (D) is exhibited satisfactorily. In addition, when the content of component (D) is 1000 parts by weight or less with respect to 100 parts by weight of component (A), the cured product has a hardness within a suitable range and exhibits good mechanical properties. It has the advantage of having physical properties and heat resistance.

<Other ingredients>
The present curable composition may contain other components, if necessary, as long as the effects of the present invention are not impaired. Other components include additives (such as fillers, plasticizers, storage stabilizers, antioxidants, UV absorbers, flame retardants, antistatic agents, and pigments), and elastomers that adjust rubber physical properties of cured products. (For example, photocurable (meth)acryloyl group-containing oligomers different from component (A), styrene-based block copolymers, etc.), thiol-based compounds, tertiary amine compounds, adhesion promoters, etc. is mentioned.

(Additive)
The contents of the filler and plasticizer in the present curable composition are not particularly limited, but from the viewpoint of the balance between the effect obtained by addition and the economy, 0.00% per 100 parts by weight of component (A) is used. It is preferably 1 to 500 parts by weight, more preferably 1.0 to 300 parts by weight.

The contents of storage stabilizers, antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, and pigments in the present curable composition are not particularly limited, but the effects obtained by addition and economic efficiency are well balanced. From the viewpoint, it is preferably 0.01 to 20.0 parts by weight, more preferably 0.10 to 10.0 parts by weight, per 100 parts by weight of component (A).

Examples of these additives include various additives described in WO2013/047314, JP-A-2013-216782, and the like.

((Meth)acryloyl group-containing oligomer)
Examples of (meth)acryloyl group-containing oligomers include compounds having a main chain composed of an oligomer containing no constituent units derived from isobutylene, and one or more (meth)acryloyl groups on average per molecule. . The (meth)acryloyl group-containing oligomers may be used singly or in combination of two or more.

Examples of oligomers constituting the main chain include polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, polyether, polyester, polycarbonate, polyacrylate, polymers of epoxy compounds, castor oil, and silicone polymers. is mentioned.

Among these, the group consisting of polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, polyacrylate, a polymer of an epoxy compound, and castor oil, because of its excellent compatibility with other components of the curable composition. Compounds containing a backbone consisting of more selected oligomers are preferred.

The number average molecular weight of the (meth)acryloyl group-containing oligomer is not particularly limited, but the availability, compatibility with other components of the curable composition, and ease of handling of the curable composition is preferably 200 to 500,000, more preferably 1,000 to 100,000.

The content of the (meth)acryloyl group-containing oligomer in the present curable composition is not particularly limited, but (i) the viscosity of the present curable composition is within a suitable range, and/or (ii) the present Since it is excellent in compatibility with other components of the curable composition, it is preferably 0.1 to 1000 parts by weight, and 1.0 to 300 parts by weight, relative to 100 parts by weight of component (A). is more preferable.

(Styrene-based block copolymer)
Styrenic block copolymers include styrene-butadiene copolymer (SBS), styrene-isoprene copolymer (SIS), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-isobutylene-styrene copolymer (SIBS), acrylonitrile-styrene copolymer (AS), and styrene-butadiene-acrylonitrile copolymer (ABS). These styrenic block copolymers may be used singly or in combination of two or more.

Among these, styrene-butadiene copolymer (SBS) and styrene-isoprene copolymer (SIS) have excellent compatibility with other components of the present curable composition and provide preferable rubber physical properties. , styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), and styrene-isobutylene-styrene copolymer (SIBS) are preferred.

The number average molecular weight of the styrenic block copolymer is not particularly limited, but (i) the viscosity of the curable composition is within a suitable range, and/or (ii) other It is preferably from 10,000 to 500,000, more preferably from 50,000 to 300,000, from the viewpoint of excellent compatibility with the components of .

The content of the styrenic block copolymer in the present curable composition is not particularly limited, but from the viewpoint of the balance between adhesiveness and durability, it is 0.1 to 0.1 parts per 100 parts by weight of component (A). It is preferably 1000 parts by weight, more preferably 1.0 to 300 parts by weight.

(thiol compound)
By containing a thiol-based compound as another component, the curable composition (a) increases the cross-linking points, thereby improving curability and providing a cured product having high hardness and strength. or (b) by reducing cross-linking points by chain transfer action, a cured product having excellent flexibility and adhesiveness can be provided as appropriate.

Thiol compounds include decanethiol, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), and trimethylolethane tris. (3-mercaptobutyrate), trimethylol ethane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoglycolate), butanediol bis (3-mercaptoglycolate), trimethylolpropane tris (3-mercapto glycolate), pentaerythritol tetrakis(3-mercaptoglycolate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3 -mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3, 5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and the like. These thiol compounds may be used singly or in combination of two or more.

The content of the thiol-based compound in the present curable composition is not particularly limited, but since the present curable composition is excellent in curability and ease of handling, the content is 0.00 per 100 parts by weight of component (A). It is preferably 1 to 100 parts by weight, more preferably 0.50 to 30 parts by weight.

(Tertiary amine compound)
By including a tertiary amine compound as another compounding component, the present curable composition has an advantage that photocurability can be improved.

Tertiary amine compounds include trimethylamine, triethylamine, tributylamine, N,N'-diethanolamine, N,N'-dimethyl-p-toluidine, N,N'-dimethyl-aniline, N-methyl-diethanolamine, N-methyl -dimethanolamine, N,N'-dimethylamino-acetophenone, N,N'-dimethylaminobenzophenone, N,N'-diethylamino-benzophenone, triisopropanolamine, and the like. These tertiary amine compounds may be used singly or in combination of two or more.

The content of the tertiary amine compound in the present curable composition is not particularly limited, but since the curability of the present curable composition is excellent, it is 0.1 to 100 parts per 100 parts by weight of component (A). It is preferably parts by weight, more preferably 0.50 to 30 parts by weight.

(Adhesion imparting agent)
By including an adhesion imparting agent (also referred to as an "adhesion imparting agent") as another compounding component, the present curable composition has the advantage that the adhesiveness of the cured product can be improved.

Adhesion imparting agents include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryl Oxypropyltriethoxysilane, (meth)acryloxyoctyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3- glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-chloropropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethyl amino)propyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 2-hydroxyethyl (meth)acrylate phosphate, methacryloxyoxyethyl acid phosphate monoethylamine half salt, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate, and the like. These adhesion imparting agents may be used alone or in combination of two or more.

Among these, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3- (Meth)acryloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-amino propylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, 3-(2-amino ethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propylmethyldiethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 2-hydroxyethyl (meth)acrylate phosphate, 2 - hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are particularly preferred.

The content of the adhesiveness-imparting agent in the present curable composition is not particularly limited, but from the viewpoint of the balance between curability and adhesiveness, it is 0.01-20% per 100 parts by weight of component (A). It is preferably 0 parts by weight, more preferably 0.1 to 10.0 parts by weight.

<Physical properties of the present curable composition>
In a preferred embodiment, the curable composition contains 0.01 to 100 parts by weight of a polyfunctional vinyl monomer (B) per 100 parts by weight of the polyisobutylene polymer (A), and polymerization initiation Contains 0.01 to 20.0 parts by weight of agent (C). This configuration has the advantage that the cured product obtained from the curable composition can achieve both higher adhesiveness and durability.

In a preferred embodiment, the curable composition comprises 0.01 to 100 parts by weight of a polyfunctional vinyl monomer (B), a polymerization initiator ( C) 0.01 to 20.0 parts by weight, and 0.1 to 1000 parts by weight of a monofunctional vinyl monomer (D). With this configuration, the cured product obtained from the curable composition has the advantage of being able to achieve both higher adhesiveness and durability, as well as having desirable physical properties (for example, flexibility and the like).

In the present curable composition, the content of the polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule is 20 parts by weight or less per 100 parts by weight of component (A). It is preferably 15 parts by weight or less, more preferably 10 parts by weight or less, and does not contain a polyisobutylene polymer having more than 1.0 (meth)acryloyl groups in one molecule is particularly preferred. This configuration has the advantage that it is easy to obtain a cured product having an excellent balance between durability and adhesiveness. As the content of the polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule is lower, the content of the polyfunctionalized polymer molecules is reduced, so the balance between durability and adhesiveness is achieved. It tends to be easy to obtain a cured product that is excellent in

From the viewpoint of ease of handling, the curable composition is preferably liquid at room temperature. Further, the appearance of the present curable composition is preferably colorless and transparent, pale yellow transparent, pale yellow translucent, or white translucent, since it is easy to obtain a composition having excellent curability by photocuring.

The viscosity of the present curable composition is not particularly limited, but it is preferable that the viscosity at 25° C. is 0.0001 to 10000 Pa·sec in that it can be applied to various coating methods or filling methods. From the viewpoint of ease of application, it is more preferably 0.001 to 5000 Pa·sec.

When applying or filling the curable composition by a method suitable for applying or filling a low-viscosity composition (e.g., spraying, inkjet, screen printing, caulking gun, spray gun, etc.), the curable composition The viscosity at 25° C. is, for example, preferably 0.0001 to 5000 Pa·sec, more preferably 0.0001 to 3000 Pa·sec. If the viscosity of the present curable composition is within the above range, it is easy to handle and the present curable composition can be easily discharged from the discharge port.

When the curable composition is used in applications such as form-in-place gaskets (FIPG), cured-in-place gaskets (CIPG), mold-in-place gaskets (MIPG), liquid injection molding (LIM), and other dispensing applications, The viscosity of the present curable composition at 25° C. is, for example, preferably 0.001 to 10000 Pa·sec, more preferably 0.001 to 5000 Pa·sec. If the viscosity at 25° C. of the present curable composition is 0.001 Pa·sec or more, good thixotropic properties can be obtained, so there is an advantage that it is easy to mold into a desired shape. Further, when the viscosity of the present curable composition at 25° C. is 10000 Pa·sec or less, it can be discharged at a favorable discharge speed, which has the advantage of preventing a decrease in productivity.

The viscosity of the curable composition can be measured using a cone-plate viscometer TVE-25H manufactured by Toki Sangyo Co., Ltd. at a measurement temperature of 25°C.

<Form of the present curable composition>
The present curable composition may be of a one-component type, a two-component type, or a multi-component type of three or more components.

A one-component curable composition is one that has been sealed and stored after previously blending all of the ingredients. A one-component curable composition eliminates the trouble of mixing and kneading multiple components at the time of application, and at the same time eliminates the measurement error that occurs at that time, so quality defects such as poor curing can be prevented. This is a preferred form from the viewpoint of being able to

A two-component curable composition is one in which the components are divided into two parts, A and B, in consideration of the storage stability of the curable composition, and mixed before use. is. As for the method of dividing into two components, various combinations are possible in consideration of the mixing ratio of the curable composition, storage stability, mixing method, pot life and the like.

If necessary, it is possible to prepare a third component in addition to liquids A and B to form a three-component curable composition. be.

The method of mixing the ingredients is not particularly limited, and hand mixers, static mixers, planetary mixers, dispersers, rolls, kneaders, single-screw extruders, twin-screw extruders, Banbury mixers, Brabenders, high-shear mixers, etc. A method of mixing using Mixing may be performed in the dark, if desired.

The temperature during mixing is preferably 10 to 100°C, more preferably 20 to 80°C. The mixing time is preferably about 0.1 to 5 hours, more preferably about 10 minutes to 3 hours.

<Application method or filling method>
The method of applying or filling the adherend with the present curable composition is not particularly limited, and known methods for applying or filling sealing agents and adhesives are used. Such methods include dispensing using automatic coaters, spraying, inkjet, screen printing, gravure printing, dipping, spin coating, and filling using caulking and spray guns.

If the curable composition has a high viscosity at room temperature and is difficult to handle, the curable composition may be heated to a desired viscosity. The temperature at that time is preferably 100° C. or lower, more preferably 80° C. or lower. By heating the present curable composition at 100° C. or less, components (C) and (D) are difficult to volatilize. Therefore, the advantage of safety, and the advantage of being able to prevent the change of the compounding ratio of each component in a curable composition are acquired.

[3. Cured material]
The cured product according to one embodiment of the present invention is described in [2. Curable composition] is obtained by curing the present curable composition described in the section. The cured product according to one embodiment of the present invention is also simply referred to as the main cured product.

Since the cured product has the above structure, it is possible to achieve both high adhesiveness and durability. In addition, the cured product has good gas barrier properties and flexibility.

<Physical properties of the hardened product>
Since the cured product has good flexibility, it can be applied to various uses. For example, it can be suitably used for uses where rubber-like properties and/or relatively hard properties are required. When the cured product is applied to such uses, the hardness of the cured product is preferably 1 to 90 degrees, more preferably 5 to 85 degrees. If the hardness of the main cured product is 1 degree or more, it is not too soft, and good tackiness and handleability can be easily obtained. In addition, in this specification, the hardness of hardened|cured material intends the value measured based on JISK6253:2012. A method for measuring the hardness of the cured product will be described in detail in Examples below.

The tensile strength at break (Tb) of the cured product is preferably 0.010 to 50 MPa, more preferably 0.10 to 40 MPa. If the tensile breaking strength (Tb) of this cured product is 0.010 MPa or more, the cured product has good strength and is easy to handle, and if it is 50 MPa or less, rubber-like properties are maintained. have advantages. Further, when the tensile strength at break (Tb) of the cured product is within the above range, there is an advantage that it can be easily applied to various uses such as sealing agents, moisture-proof agents, potting agents, and gasket materials. In addition, in this specification, the tensile breaking strength (Tb) of hardened|cured material intends the value measured based on JISK6251:2017. A method for measuring the tensile strength at break (Tb) of the cured product will be described in detail in the examples below.

The compression set of the cured product is preferably 70% or less, more preferably 60% or less, and even more preferably 50% or less. If the compression set of this cured product is 70% or less, it has the advantage of being able to maintain good airtightness, and can be applied to various uses such as sealing agents, moisture-proof agents, potting agents, and gasket materials. It has the advantage of being easy In addition, in this specification, the compression set of a hardened|cured material intends the value measured based on JISK6262:2013. A method for measuring the compression set of the cured product will be described in detail in the examples below.

The moisture permeability of the hardened product is preferably 50 g/m ² ·24 hrs or less, more preferably 25 g/m ² ·24 hrs or less. If the moisture permeability of the cured product is 50 g/m ² · 24 hrs or less, various applications that require high gas barrier properties (e.g., sealing agents, encapsulants, moisture-proof agents, gasket materials, potting agents, conformal coatings, etc.) It has the advantage of being easy to apply to In addition, in this specification, the moisture permeability of a cured product intends the value measured using a 0.5-mm-thick test piece based on JIS Z 0208:1976. A method for measuring the moisture permeability of the cured product will be described in detail in Examples below.

The adhesive strength of the hardened product to a stainless steel plate (SUS304, manufactured by Engineering Test Service) is preferably 0.10 N/25 mm or more, more preferably 1.0 N/25 mm or more. If the adhesive strength of this cured product is 0.10 N/25 mm or more, it is difficult to peel off from the substrate, and various applications that require high adhesiveness (e.g., sealing agents, encapsulants, moisture-proof agents, gasket materials, potting agents, conformal coating, etc.). A method for measuring the adhesive strength of the cured product will be described in detail in Examples below.

<Curing method>
The cured product is obtained by curing the curable composition by applying an external stimulus (light or heat).

When the component (C) is a radical photopolymerization initiator, the external stimulus is irradiation of light (active energy ray). Low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, black light lamp, microwave excited mercury lamp, metal halide lamp, sodium lamp, halogen lamp, xenon lamp, LED, fluorescent lamp, sunlight , an electron beam irradiation device, a laser, and the like.

The irradiation amount of the active energy rays is preferably 1 kJ/m ² or more, more preferably 10 kJ/m ² or more. When the integrated amount of light is 1 kJ/m ² or more, the present curable composition can be sufficiently cured.

Efficient curing can be achieved by matching the wavelength of the active energy ray emitted from the light source with the absorption wavelength (and/or maximum absorption wavelength) of the component (C) as much as possible.

When the component (C) is a thermal radical polymerization initiator, the external stimulus is heat (heating). The heating temperature and heating time are not particularly limited, and vary depending on the type of the thermal radical polymerization initiator used. The heating time (curing time) varies depending on the type of thermal radical polymerization initiator used, additives, heating temperature (reaction temperature), etc., but is usually in the range of 1 minute to 5 hours.

Curing of the present curable compositions can be carried out under various atmospheres such as air, nitrogen, and argon. It is preferable to cure the present curable composition in the air because it does not require special equipment and can be easily carried out. Moreover, when there is concern about curing inhibition due to oxygen in the atmosphere, curing is preferably performed under an inert gas such as nitrogen or argon.

[4. Application]
The present curable composition achieves both high adhesiveness and durability, and can provide a cured product having excellent gas barrier properties and flexibility. It can be suitably used for various uses where flexibility is required. Such applications include electric/electronic parts (LEDs, batteries, sensors, semiconductors, circuit boards, displays, home appliances, optical communication/optical circuits, optical recording, magnetic recording, etc.), pharmaceuticals/medical products, automotive parts/ships. Sealing materials, adhesives, sealing materials, gasket materials, adhesives, coating materials, covering materials, resist materials, anti-vibration materials, damping materials, shock-absorbing materials, and cushioning materials for parts, building parts, acoustic parts, etc. , electrical insulating materials, foams, paints, inks, casting agents, potting agents, mold materials, underfill materials, die bonding materials, fillers, and the like. In addition, the cured product applied to these applications can be used in various forms such as sheet (film), tape, molded body (packing, O-ring, belt, tube, valve, hose, etc.). can be done.

The cured product can be suitably used as a sealing material and an adhesive, in particular. The sealing material and the adhesive according to one embodiment of the present invention are described in [2. Curable composition] is obtained by curing the present curable composition described in the section. The encapsulating material and the adhesive according to one embodiment of the present invention are also simply referred to as the present encapsulating material and the present adhesive, respectively.

Since the present sealing material and the present pressure-sensitive adhesive have the above-described configurations, both high adhesiveness and durability can be achieved. In addition, the present sealing material has good gas barrier properties and flexibility.

The present sealing material and the present pressure-sensitive adhesive can be produced by applying the present curable composition to an adherend or filling between two or more adherends and curing the curable composition. The coating method, filling method and curing method of the present curable composition are described in [2. Curable composition] and [3. Cured product] section is appropriately incorporated.

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

Measurements and evaluations in Examples and Comparative Examples were carried out by the following methods.

<Molecular weight>
"Weight average molecular weight Mw", "number average molecular weight Mn" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight (Mw/Mn))" are standard polystyrene conversion methods using size exclusion chromatography (SEC). Calculated by

Using a GPC system manufactured by Waters as a measurement apparatus, chloroform was used as a mobile phase, and a column temperature of 35° C. was used, and a sample solution having a polymer concentration of 4 mg/ml was used for measurement. As the column (stationary phase), a polystyrene crosslinked gel packed (Shodex GPC K-804 and K-802.5; both manufactured by Showa Denko KK) was used.

<Viscosity>
The viscosity of the sample (curable composition) was measured using a cone-plate viscometer TVE-25H manufactured by Toki Sangyo Co., Ltd. at a measurement temperature of 25°C.

<Tensile properties>
The curable composition was applied onto a PET film to a thickness of 0.5 mm. Thereafter, a curable composition is irradiated with UV light (irradiation conditions: illuminance of 500 mW/cm ² , light intensity of 5000 mJ/cm ² ) using a UV irradiation device (manufactured by Fusion UV Systems Japan Co., Ltd., model: LH6). was cured to obtain a sheet-like cured product. A No. 7 dumbbell-shaped test piece was produced from the obtained cured product.

Using the obtained test piece, in accordance with JIS K 6251: 2017, at room temperature (23 ° C.), a tensile test was performed under the conditions of a tensile speed of 200 mm / min, tensile strength at break (Tb), tensile elongation at break (Eb), and 30% modulus (M30) were measured. Tensile breaking strength (Tb) is the tensile strength (MPa) when the test piece breaks. Tensile elongation at break (Eb) is a relative value (%) of the length of the test piece at the time of breaking, with the length of the test piece at the start of the tensile test being 100%. 30% modulus (M30) is the tensile strength (MPa) when the test piece is elongated by 30%.

<Hardness (Type A)>
The curable composition was cured to a thickness of 0.5 mm to prepare a sheet-like test piece. Then, according to JIS K 6253:2012, the cured test pieces were stacked to a thickness of 6 mm, and hardness (type A) was measured using a type A durometer.

<Compression set>
The curable composition was cured to a thickness of 12.5 mm to prepare a cylindrical test piece. Using the obtained test piece, the compression set was measured under conditions of 25% compression at 120° C. for 24 hours in accordance with JIS K 6262:2013.

<Moisture permeability>
The curable composition was cured to a thickness of 0.5 mm to prepare a sheet-like test piece. Using the obtained test piece, moisture permeability was measured under the conditions of 40° C. and relative humidity of 90% RH in accordance with JIS Z 0208:1976.

<Adhesive strength>
The curable composition was applied to a PET film having a thickness of 25 μm so as to have a thickness of 0.5 mm, and a release PET film was attached to the coated surface. Next, the curable composition was cured by UV irradiation under the same conditions using a UV irradiation apparatus in the same manner as in the method for measuring tensile physical properties. The obtained sheet-like cured product (adhesive) was cut to a width of 25 mm. Next, the release PET film was peeled off, and the surface of the cured product was attached to a stainless steel plate (SUS304, manufactured by Engineering Test Service Co., Ltd.) and pressed with a 2-kg pressing roller. Three days after the application, an autograph (AG-2000A, manufactured by Shimadzu Corporation) was used to perform a 180° peel test at 23°C and a peel rate of 300 mm/min to determine the adhesive strength (N/25 mm). It was measured.

<Functionalization rate>
The number of (meth)acryloyl groups contained in one molecule of the polyisobutylene-based polymer was calculated by the following method: (i) ¹ H NMR measurement of the polyisobutylene-based polymer was performed; From the results, (ii-1) the relative number (A) of the polymer molecules present in the polyisobutylene-based polymer was calculated from the peak area (peak integral value) of the protons attributed to the groups derived from the polymerization initiator. and (ii-2) the relative number (B) of (meth)acryloyl groups present in the polyisobutylene-based polymer from the peak area (integral value of the peak) of the protons attributed to the (meth)acryloyl groups. (iii) Calculate the ratio (B/A) of the relative number (B) of the (meth)acryloyl groups to the relative number (A) of the polymer molecule, and calculate the (meth)acryloyl groups contained in one molecule The number of (introduction number) was obtained.

(Production Example 1) Synthesis of polyisobutylene-based polymer (A-1) having 0.5 to 1.0 (meth)acryloyl groups in one molecule Nitrogen was used as the gas in the container of a 1 L separable flask. replaced. After that, 30 mL of n-hexane (dried over molecular sieves) and 400 mL of butyl chloride (dried over molecular sieves) were added into the vessel. Subsequently, the raw material in the container was cooled to -70°C under a nitrogen atmosphere while stirring. Then, 200 mL (2.12 mol) of isobutylene, 1.56 g (0.0101 mol) of cumyl chloride and 0.378 g (0.00353 mol) of 2,6-lutidine were added into the vessel. After the reaction mixture in the vessel was cooled to −70° C., 1.44 mL (0.0131 mol) of titanium tetrachloride was added into the vessel to initiate polymerization. After the initiation of polymerization, the minimum amount of the reaction mixture required for measurement was removed from the vessel at regular intervals, and the reaction mixture thus removed was subjected to gas chromatography to measure the residual isobutylene concentration in the reaction mixture. consumption was measured. The polymerization of isobutylene was terminated when 99.9% or more of the charged isobutylene was consumed. By such operation, a polyisobutylene-based polymer (main chain) was obtained. Next, without removing the polyisobutylene polymer from the container, 2.44 g (0.0111 mol) of phenoxybutyl acrylate and 4 titanium tetrachloride were added to the container containing the polymerized polyisobutylene polymer. The functionalization reaction was carried out by adding .98 mL (0.0454 mol) and continuing to stir the reaction mixture in the vessel at -75 to -80°C for an additional 3 hours.

After completion of the reaction, the catalyst was deactivated by pouring a large amount of methanol into the reaction mixture. Solvents based on methanol, butyl chloride, and hexane in the reaction mixture were removed to give a sticky precipitate. The resulting precipitate was dissolved in 1000 g of butyl chloride, 20 g of powdered activated carbon (manufactured by Futamura Chemical Co., Ltd., product name "Taiko A") was added to the resulting solution, and the resulting mixture was stirred overnight at room temperature. bottom. Subsequently, the mixture was filtered to remove activated carbon in the mixture to obtain a filtrate. 0.0123 g of 4-methoxyphenol was added to the resulting filtrate, and the solvent in the resulting mixture was distilled off under reduced pressure to obtain a polyisobutylene-based polymer (A-1) having acryloyl groups. rice field. A-1 had a number average molecular weight Mn of 15,100, a molecular weight distribution Mw/Mn of 1.26, and the number of acryloyl groups introduced per molecule was 0.93. That is, the polyisobutylene-based polymer (A-1) is a monofunctional polymer in which polyisobutylene-based polymer molecules having acryloyl groups only at one end of the main chain account for the majority. It can be said that it is an assembly of molecules.

(Production Example 2) Synthesis of polyisobutylene-based polymer (A-2) having 0.5 to 1.0 (meth)acryloyl groups in one molecule The gas in the container of the 2 L separable flask was replaced with nitrogen. replaced. After that, 60 mL of n-hexane (dried over molecular sieves) and 800 mL of butyl chloride (dried over molecular sieves) were added into the vessel. Subsequently, the raw material in the container was cooled to -70°C under a nitrogen atmosphere while stirring. 306 mL of isobutylene, 8.36 g of cumyl chloride and 0.82 g of triethylamine were then added into the vessel. After the reaction mixture in the vessel was cooled to −70° C., 2.84 mL of titanium tetrachloride was added into the vessel to initiate polymerization. After the initiation of polymerization, the minimum amount of the reaction mixture required for measurement was removed from the vessel at regular intervals, and the reaction mixture thus removed was subjected to gas chromatography to measure the residual isobutylene concentration in the reaction mixture. consumption was measured. The polymerization of isobutylene was terminated when 99.9% or more of the charged isobutylene was consumed. By such operation, a polyisobutylene-based polymer (main chain) was obtained. Next, 17.0 g of phenoxybutyl acrylate and 23.7 mL of titanium tetrachloride are added to the container containing the polymerized polyisobutylene polymer without removing the polyisobutylene polymer from the container, and The functionalization reaction was carried out by continuing to stir the reaction mixture in the vessel at 75--80°C for an additional 3 hours.

After completion of the reaction, the catalyst was deactivated by pouring a large amount of methanol into the reaction mixture. Solvents based on methanol, butyl chloride, and hexane in the reaction mixture were removed to give a sticky precipitate. The resulting precipitate was dissolved in 1500 g of butyl chloride, 30 g of powdered activated carbon (manufactured by Futamura Chemical Co., Ltd., product name "Taiko A") was added to the resulting solution, and the resulting mixture was stirred overnight at room temperature. bottom. Subsequently, the mixture was filtered to remove activated carbon in the mixture to obtain a filtrate. 0.0300 g of 4-methoxyphenol was added to the resulting filtrate, and the solvent in the resulting mixture was distilled off under reduced pressure to obtain a polyisobutylene-based polymer (A-2) having acryloyl groups. rice field. A-2 had a number average molecular weight Mn of 5100, a molecular weight distribution Mw/Mn of 1.31, and the number of acryloyl groups introduced per molecule was 0.85. That is, the polyisobutylene-based polymer (A-2) is a monofunctional polymer, and a polyisobutylene-based polymer in which polyisobutylene-based polymer molecules having acryloyl groups only at one end of the main chain account for the majority. It can be said that it is an assembly of molecules.

(Production Example 3) Synthesis of polyisobutylene polymer having more than 1.0 (meth)acryloyl groups in one molecule (comparative component of component (A)) (X-1) Container of 1 L separable flask The gas inside was replaced with nitrogen. After that, 30 mL of n-hexane (dried over molecular sieves) and 350 mL of butyl chloride (dried over molecular sieves) were added into the vessel. Subsequently, the raw material in the container was cooled to -70°C under a nitrogen atmosphere while stirring. 150 mL of isobutylene, 1.76 g of p-dicumyl chloride and 0.29 g of 2,6-lutidine were then added into the vessel. After the reaction mixture in the vessel was cooled to −70° C., 0.85 mL of titanium tetrachloride was added into the vessel to initiate polymerization. After the initiation of polymerization, the minimum amount of the reaction mixture required for measurement was removed from the vessel at regular intervals, and the reaction mixture thus removed was subjected to gas chromatography to measure the residual isobutylene concentration in the reaction mixture. consumption was measured. The polymerization of isobutylene was terminated when 99.9% or more of the charged isobutylene was consumed. By such operation, a polyisobutylene-based polymer (main chain) was obtained. Next, without removing the polyisobutylene polymer from the container, 3.70 g of phenoxybutyl acrylate and 5.00 mL of titanium tetrachloride are added to the container containing the polymerized polyisobutylene polymer, and The functionalization reaction was carried out by continuing to stir the reaction mixture in the vessel at 70 to -80°C for an additional 3 hours.

After completion of the reaction, the catalyst was deactivated by pouring a large amount of methanol into the reaction mixture. Solvents based on methanol, butyl chloride, and hexane in the reaction mixture were removed to give a sticky precipitate. The resulting precipitate was dissolved in 650 g of butyl chloride, 10 g of powdered activated carbon (manufactured by Futamura Chemical Co., Ltd., product name "Taiko A") was added to the resulting solution, and the resulting mixture was stirred overnight at room temperature. bottom. Subsequently, the mixture was filtered to remove activated carbon in the mixture to obtain a filtrate. 0.0160 g of 4-methoxyphenol was added to the resulting filtrate, and the solvent in the resulting mixture was distilled off under reduced pressure to obtain a polyisobutylene-based polymer (X-1) having an acryloyl group. rice field. X-1 had a number average molecular weight Mn of 14200, a molecular weight distribution Mw/Mn of 1.20, and the number of acryloyl groups introduced per molecule was 1.85. That is, the polyisobutylene-based polymer (X-1) is a polyfunctional polymer, and polyisobutylene-based polymer molecules in which polyisobutylene-based polymer molecules having acryloyl groups at both ends of the main chain account for the majority. can be said to be an aggregate of

In the following examples and comparative examples, the following ingredients were used.
<(A) Component>
A-1: Polyisobutylene-based polymer obtained in Production Example 1 A-2: Polyisobutylene-based polymer obtained in Production Example 2 <comparative component for component (A)>
X-1: Polyisobutylene-based polymer obtained in Production Example 3 <Component (B)>
B-1: 1,6-hexanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate 1,6HX-A)
B-2: Trimethylolpropane triacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light acrylate TMP-A)
<(C) Component>
C-1: Photopolymerization initiator 2-hydroxy-2-methyl-1-phenyl-propan-1-one (manufactured by Ciba Specialty Chemicals, Darocure 1173)
C-2: Photopolymerization initiator bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF Japan, Irgacure819)
<(D) Component>
D-1: isononyl acrylate D-2: dicyclopentanyl acrylate (FA-513AS, manufactured by Showa Denko Materials Co., Ltd.)
<Other ingredients>
E-1: Hindered phenolic antioxidant 3-(4'-hydroxy-3',5'-di-tert-butylphenyl)-n-octadecyl propionate (manufactured by ADEKA, ADEKA STAB AO-50)
E-2: Hydrophobic fumed silica (filler) (Evonik, Aerosil R972)
(Examples 1-3)
A-1 as component (A), B-1 as component (B), C-1 and C-2 as components (C), D-1 as component (D), and E-1 as other ingredients were mixed at the weight ratio shown in Table 1 to obtain a pale yellow transparent curable composition. The viscosity of the resulting curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

(Example 4)
A curable composition was obtained in the same manner as in Example 3 except that E-2 was added as another compounding component at the weight ratio shown in Table 1. The viscosity of the resulting curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

(Example 5)
A curable composition was obtained in the same manner as in Example 3, except that B-2 was used as the component (B) instead of B-1 in the weight ratio shown in Table 1. The viscosity of the resulting curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

(Example 6)
A curable composition was obtained in the same manner as in Example 3, except that D-1 and D-2 were used together in the weight ratio shown in Table 1 as the component (D). The viscosity of the obtained curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

(Example 7)
A curable composition was obtained in the same manner as in Example 3, except that D-2 was used as the component (D) instead of D-1 in the weight ratio shown in Table 1. The viscosity of the obtained curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

(Example 8)
A curable composition was obtained in the same manner as in Example 7 except that A-2 was used as the component (A) instead of A-1 in the weight ratio shown in Table 1. The viscosity of the obtained curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

(Comparative Examples 1 to 3)
X-1, A-1, C-1, C-2, D-1, and E-1 were mixed in the weight ratio shown in Table 1 to obtain a pale yellow transparent curable composition. The viscosity of the resulting curable composition was measured. Further, the tensile physical properties, hardness, compression set, moisture permeability and adhesive strength of the colorless and transparent cured product obtained by curing the curable composition were measured. Table 1 shows the measurement results.

In the measurement of the adhesive strength of Examples 6 and 7, since the adhesive strength of Examples 6 and 7 is very high, there is no peeling between the cured product (adhesive) and the substrate (PET film). Therefore, the adhesive force between the cured product and the stainless steel plate could not be measured. Therefore, in Table 1, the adhesive strength of Examples 6 and 7 describes the peel stress at the time when the cured product and the substrate are peeled off.

As shown in Table 1, in Comparative Examples 1 to 3 containing X-1 (polyfunctional polymer) and not containing component (B), as the ratio of A-1 (monofunctional polymer) increases, It can be seen that although the tackiness increases, the compression set increases and the durability decreases. This leads to the following considerations (a) and (b): (a) In a curable composition containing a polyfunctional polymer, adding a monofunctional polymer to increase adhesion (b) If the amount of the monofunctional polymer added is limited in order to suppress deterioration in durability, the effect of improving adhesiveness cannot be sufficiently obtained. Furthermore, from these considerations, we focused on a curable composition containing only a monofunctional polymer and not containing a polyfunctional polymer, and attempted to achieve both adhesion and durability in the curable composition. It can be said that it is difficult to assume.

However, surprisingly, in Examples 1 to 3, in the curable composition containing only the monofunctional polymer, by changing the amount of component (B) added, the adhesiveness and durability are well balanced. It was found that a cured product could be provided. Moreover, all cured products were excellent in flexibility and gas barrier properties.

By including a filler (hydrophobic fumed silica), the curable composition of Example 4 was able to provide a cured product with high strength while maintaining high adhesiveness and durability. The curable composition of Example 5 was able to provide a cured product excellent in flexibility, adhesiveness and durability by using a trifunctional vinyl-based monomer as the component (B). In Examples 6 and 7, it was found that the effects of the present invention can be obtained even when two types of component (D) are used in combination and when the type of component (D) is changed. Moreover, in Example 8, it was found that the effect of the present invention can be obtained even when the molecular weight of the component (A) is changed.

The curable composition of the present invention can be suitably used for applications such as sealing agents, pressure-sensitive adhesives, sealing agents, gasket materials, vibration-proof materials, impact-absorbing materials, cushioning materials, acoustic members, tubes, and the like.

Claims (10)

Curing containing polyisobutylene polymer (A) having 0.5 to 1.0 (meth)acryloyl groups per molecule, polyfunctional vinyl monomer (B), and polymerization initiator (C) sex composition. The curable composition according to claim 1, wherein the (meth)acryloyl group is a group represented by the following general formula (1).

(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and does not have a heteroatom, and R ³ to R ⁶ each independently represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group.) 3. The curable composition according to claim 1, further comprising a monofunctional vinyl monomer (D). 0.01 to 100 parts by weight of the polyfunctional vinyl monomer (B) and 0.01 to 20.0 parts by weight of the polymerization initiator (C) with respect to 100 parts by weight of the polyisobutylene polymer (A). 4. The curable composition according to claim 3, comprising parts by weight and 0.1 to 1000 parts by weight of the monofunctional vinyl monomer (D). A polyisobutylene-based polymer having more than 1.0 (meth)acryloyl groups per molecule (i) further contains 20 parts by weight or less relative to 100 parts by weight of the polyisobutylene-based polymer (A), or The curable composition according to any one of claims 1 to 4, which does not contain (ii). The polyfunctional vinyl monomer (B) includes 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate. , 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri The curable composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of (meth)acrylate and pentaerythritol tetra(meth)acrylate. The curable composition according to any one of claims 1 to 6, wherein the polyisobutylene polymer (A) has 0.8 to 1.0 (meth)acryloyl groups per molecule. The curable composition according to any one of claims 1 to 7, wherein the polymerization initiator (C) is a radical photopolymerization initiator. A sealing material obtained by curing the curable composition according to any one of claims 1 to 8. A pressure-sensitive adhesive obtained by curing the curable composition according to any one of claims 1 to 8.