Photocurable resin composition

Abstract

The purpose of the present invention is to provide a photocurable resin composition which has excellent adhesive strength with respect to various materials, and a cured product of which has excellent resin strength. The present invention relates to a photocurable resin composition which contains the following components (A) to (C). Component (A): a polyisobutylene resin which contains one or more (meth)acryloyl groups and a -[CH2C(CH3)2]- unit Component (B): a compound which has one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, while having a main chain that is composed of an organic chain, and which has a weight average molecular weight of 300 or more (excluding the component (A)) Component (C): a radical photopolymerization initiator

Description

Photocurable resin composition

[0001] The present invention relates to a photocurable resin composition having high adhesive strength to various materials (particularly aluminum, polycarbonate, and acrylic resin).

[0002] In recent years, the automotive industry has been using plastic materials to reduce weight and improve fuel efficiency. Because plastic materials have inert or low-polarity surfaces, they are less compatible with adhesives than metal materials, making it difficult to achieve high adhesive strength. Furthermore, parts made solely of plastic materials have low rigidity, so they are sometimes used in combination with metal materials. Among metals, aluminum is prone to forming oxide films on its surface, making its surface inert like plastics, and high adhesive strength is required for the adhesives and sealants used (see JP 2020-023674 A). Furthermore, when bonding plastics, applying heat can cause deformation of the adherend, depending on the plastic material, so photocurable adhesives and sealants that do not require heat are required for plastic materials.

[0003] Sealant having a polyisobutylene skeleton as the main skeleton is sometimes used because of its low moisture permeability, excellent gas barrier properties, and water resistance. However, such sealants have the problem of low adhesive strength due to the low polarity of the skeleton.

[0004] The present invention has been made in view of the above circumstances, and aims to provide a photocurable resin composition that can be cured by light such as ultraviolet light without applying heat to an adherend, that has high adhesive strength to various materials (particularly aluminum, acrylic resin, and polycarbonate), and that produces a cured product with high resin strength.

[0005] The gist of the present invention is as follows: [1] A photocurable resin composition comprising the following components (A) to (C): Component (A): one or more (meth)acryloyl groups and —[CH ２ C(CH ３ ) ２]- units; Component (B): a compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a main chain composed of an organic chain, and having a weight-average molecular weight of 300 or more (excluding component (A)); and Component (C): a photoradical polymerization initiator. [2] The photocurable resin composition according to [1], which contains 0.01 to 20 parts by mass of component (B) per 100 parts by mass of component (A). [3] The photocurable resin composition according to [1] or [2], wherein component (C) is an acylphosphine oxide-based photoradical polymerization initiator. [4] The photocurable resin composition according to any of [1] to [3], further containing a (meth)acrylic monomer as component (D). [5] The photocurable resin composition according to any of [1] to [4], further containing an inorganic filler as component (E). [6] The photocurable resin composition according to [5], comprising 1 to 50 parts by mass of component (E) per 100 parts by mass of component (A). [7] A sealant or adhesive comprising the photocurable resin composition according to any one of [1] to [6]. [8] The sealant or adhesive according to [7], which is used on an adherend containing at least one material selected from the group consisting of aluminum, acrylic resin, and polycarbonate. [9] A cured product obtained by irradiating the photocurable resin composition according to any one of [1] to [6] with light.

[0006] The following describes embodiments of the present invention. However, the present invention is not limited to only the following embodiments. In this specification, "X to Y" means a range including the numerical values ​​(X and Y) written before and after it as the lower and upper limits, respectively, and means "X or more and Y or less." In the present invention, a compound having a (meth)acryloyl group refers to a (meth)acrylate. The (meth)acryloyl group may have the (meth)acryloyl group in the form of a (meth)acryloyloxy group. Furthermore, the term "(meth)acryloyl" includes both acryloyl and methacryloyl. Therefore, for example, the term "(meth)acryloyl group" refers to an acryloyl group (H ２ C=CH-C(=O)-) and methacryloyl groups (H ２ C=C(CH ３)-C(=O)-). Similarly, the term "(meth)acrylate" includes both acrylate and methacrylate, the term "(meth)acryl" includes both acryl and methacryl, and the term "(meth)acrylamide" includes both acrylamide and methacrylamide.

[0007] One aspect of the present invention relates to a photocurable resin composition containing the following components (A) to (C): Component (A): one or more (meth)acryloyl groups and —[CH ２ C(CH ３ ) ２ ]- units; component (B): a compound (excluding component (A)) having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a main chain composed of an organic chain, and having a weight-average molecular weight of 300 or more; and component (C): a photoradical polymerization initiator.

[0008] According to one aspect of the present invention, a photocurable resin composition can be provided that has excellent adhesive strength to various materials (e.g., aluminum, plastics, etc.) and that produces a cured product with excellent resin strength.

[0009] The component (A) used in the present invention has one or more (meth)acryloyl groups and is —[CH ２ C(CH ３ ) ２ Component (A) is not particularly limited as long as it is a polymer (polyisobutylene resin) having a polyisobutylene skeleton containing a —[CH ２ C(CH ３ ) ２ ]- units (polyisobutylene skeleton), ２ C(CH ３ ) ２ ]-unit, "-[CH ２ C(CH ３ ) ２ The component (A) may be a polymer containing other structural units than the —[CH ]- unit. ２ C(CH ３ ) ２]- units in an amount of, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more, based on the total amount of structural units. ２ C(CH ３ ) ２ ]-units may be contained in an amount of less than 100% by mass, 95% by mass or less, or 90% by mass or less. Component (A) preferably has 1 to 12 (meth)acryloyl groups, more preferably 2 to 8, even more preferably 2 to 4, and particularly preferably 2. In the present invention, a polymer can be defined, without being bound by theory, as a structure having a repeating unit of a monomer in the main chain of a polymer, and a compound consisting of 100 or more repeating units. Furthermore, the (meth)acryloyl group may be present either in the side chain or at the end of the molecule (polyisobutylene skeleton). From the viewpoint of high resin strength and excellent cured product properties, it is preferable that the (meth)acryloyl group be present at the end of the molecule. From the viewpoint of storage stability, component (A) preferably does not contain any reactive functional groups other than (meth)acryloyl groups, more preferably contains only (meth)acryloyl groups, and even more preferably contains only acryloyl groups.

[0010] From the viewpoint of obtaining a cured product having low polarity and excellent low moisture permeability, gas barrier properties, and water resistance, the component (A) according to the present invention is preferably a polymer (polyisobutylene resin) having a polyisobutylene skeleton represented by the following general formula (1). Specific examples of the component (A) include polyisobutylene resins having (meth)acryloyloxyalkoxyphenyl groups. The main skeleton of the component (A) according to the present invention is a polyisobutylene skeleton. Isobutylene may be used primarily as the monomer constituting the polyisobutylene skeleton, and monomers other than isobutylene may also be used as long as the effects of the present invention are not impaired. In other words, the component (A) according to the present invention may be a copolymer of isobutylene and a monomer other than isobutylene. From the viewpoint of wettability with plastic materials, the component (A) is preferably liquid at room temperature (25°C).

[0011]

[0012] In general formula (1), R １ represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group. １ is preferably a polyvalent aromatic hydrocarbon group, and particularly preferably a divalent phenylene group. ２ C(CH ３ ) ２ ]-unit (or -[CH ２ C(CH ３ ) ２ represents a polyisobutylene skeleton consisting of methyl- and methyl- groups. ４ represents a divalent hydrocarbon group having 2 to 6 carbon atoms. ４ is preferably a divalent hydrocarbon group having 2 or 3 carbon atoms. ４ is more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group. ２ and R ３ R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. ２ and R ３ is preferably a hydrogen atom. ５ represents a hydrogen atom, a methyl group, or an ethyl group. ５ is preferably a hydrogen atom or a methyl group. n represents an integer of 1 to 6. n is particularly preferably an integer of 2 to 4.

[0013] The molecular weight of component (A) according to the present invention is not particularly limited. From the viewpoints of compatibility with application by screen printing and excellent cured product properties such as high elongation and high strength, the number average molecular weight of component (A) measured by chromatography is preferably 200 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 3,000 to 50,000. The number average molecular weight can be calculated using size permeation chromatography (SEC) in terms of standard polystyrene.

[0014] The viscosity of the component (A) according to the present invention at 25°C is not particularly limited. From the viewpoint of workability and the like, the viscosity of the component (A) at 25°C is, for example, 5 Pa·s or more, preferably 50 Pa·s or more, and more preferably 100 Pa·s or more. The viscosity of the component (A) at 25°C is, for example, 3000 Pa·s or less, preferably 2500 Pa·s or less, more preferably 2000 Pa·s or less, and particularly preferably 1750 Pa·s or less. Unless otherwise specified, the viscosity is a value measured at 25°C using a cone-plate viscometer.

[0015] The method for producing component (A) according to the present invention is not particularly limited, and known methods can be used. Examples of methods for producing component (A) include the method of reacting hydroxyl-terminated polyisobutylene with acryloyl chloride or methacryloyl chloride, as disclosed in Polymer Bulletin, Vol. 6, pp. 135-141 (1981), by T. P. Liao and J. P. Kennedy, and Polymer Bulletin, Vol. 20, pp. 253-260 (1988), by Puskas et al. Other methods for producing component (A) that can be used include reacting hydroxyl-terminated polyisobutylene with a compound having a (meth)acryloyl group and an isocyanate group, reacting hydroxyl-terminated polyisobutylene with a compound having an isocyanate group and a compound having a (meth)acryloyl group and a hydroxyl group, and reacting hydroxyl-terminated polyisobutylene with (meth)acrylic acid or a lower (meth)acrylic acid ester using a dehydration esterification method or an ester exchange method.

[0016] The method for producing the polymer having a polyisobutylene skeleton represented by the above-mentioned general formula (1) is not particularly limited. The method for producing the polymer having a polyisobutylene skeleton represented by the general formula (1) is preferably the method disclosed in JP 2013-216782 A, in which halogen-terminated polyisobutylene is reacted with a compound having a (meth)acryloyl group and a phenoxy group, as represented by the following general formula (2). The halogen-terminated polyisobutylene can be obtained by known methods. The halogen-terminated polyisobutylene can be obtained, for example, by cationic polymerization, and is preferably obtained by living cationic polymerization.

[0017]

[0018] In general formula (2), R ２ , R ３ , R ４ , and R ５ is as defined in the above formula (1). ４ represents a divalent hydrocarbon group having 2 to 6 carbon atoms. ２ and R ３ R each independently represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. ５ represents a hydrogen atom, a methyl group, or an ethyl group. Examples of the compound represented by the general formula (2) include phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxybutyl (meth)acrylate, and phenoxypentyl (meth)acrylate. The compound represented by the general formula (2) is preferably selected from phenoxyethyl (meth)acrylate, phenoxypropyl (meth)acrylate, phenoxybutyl (meth)acrylate, and phenoxypentyl (meth)acrylate.

[0019] The component (B) according to the present invention is a compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, a main chain consisting of an organic chain, and a weight-average molecular weight of 300 or more. However, the component (B) does not include compounds contained in the component (A). In this specification, the term "main chain" refers to the carbon chain with the largest number of carbon atoms in one molecule. In this specification, the organic chain is composed only of atoms selected from the group consisting of carbon, hydrogen, and oxygen. From the viewpoint of compatibility with the component (A), the organic chain is preferably composed only of carbon and hydrogen. The number of carbon atoms in the organic chain is preferably 5 or more, more preferably 7 or more. The weight-average molecular weight of the component (B) is 300 or more. There is no particular upper limit for the weight-average molecular weight of the component (B), but it is preferably less than 3,000, more preferably less than 2,000, and most preferably less than 1,500. In this specification, the weight-average molecular weight refers to the weight-average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). Tetrahydrofuran is used as the solvent. In the photocurable resin composition according to the present invention, when a compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, a main chain consisting of an organic chain, and a weight-average molecular weight of less than 300 is used, the adhesive strength to the acrylic resin decreases, which is undesirable. Although the reason for this is unclear, when both components (A) and (B) are contained, the adhesive strength to the acrylic resin improves. From the viewpoint of improving adhesive strength to both aluminum and acrylic resin, the functional group equivalent ratio of (meth)acryloyl groups to hydrolyzable silyl groups per molecule of component (B) is preferably 0.8 to 7, more preferably 0.9 to 5, and most preferably 1. From the viewpoint of improving adhesive strength to various materials and providing a cured product with excellent resin strength, when the weight-average molecular weight of component (B) is 300 or more but less than 800, it is preferable that hydrolyzable silyl groups be bonded to both ends of the main chain, and when the weight-average molecular weight of component (B) is 800 or more, it is preferable that hydrolyzable silyl groups be bonded to side chains.

[0020] In this specification, the term "hydrolyzable silyl group" refers to a functional group in which one to three, preferably three, hydrolyzable groups such as alkoxy groups (e.g., methoxy groups and ethoxy groups) are added to a silicon atom. Examples of the hydrolyzable silyl group include a trimethoxysilyl group and a triethoxysilyl group.

[0021] Commercially available products of component (B) include, but are not limited to, X-12-1048, X-12-1050, and KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0022] In the photocurable resin composition according to the present invention, the content (blending amount) of (B) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). When the content of (B) is 0.01 to 20 parts by mass, per 100 parts by mass of component (A), there is no risk of a decrease in the physical properties of the cured product, such as resin strength, and the adhesive strength to various materials, such as aluminum, acrylic resin, and polycarbonate, can be improved.

[0023] The component (C) according to the present invention is a photoradical polymerization initiator. The component (C) is not limited as long as it is a compound that generates radicals upon irradiation with active energy rays. Here, active energy rays include all light in the broad sense, such as radiation such as α-rays and β-rays, electromagnetic waves such as γ-rays and X-rays, electron beams, ultraviolet rays with wavelengths of approximately 100 to 400 nm, and visible light with wavelengths of approximately 400 to 800 nm. The active energy rays are preferably ultraviolet rays. Examples of component (C) include acetophenone-based radical photopolymerization initiators, benzoin-based radical photopolymerization initiators, benzophenone-based radical photopolymerization initiators, thioxanthone-based radical photopolymerization initiators, acylphosphine oxide-based radical photopolymerization initiators, and titanocene-based radical photopolymerization initiators. Among these, from the viewpoint of obtaining high adhesive strength to various adherends, component (C) preferably contains either an acetophenone-based photoradical polymerization initiator or an acylphosphine oxide-based photoradical polymerization initiator, and more preferably contains an acylphosphine oxide-based photoradical polymerization initiator. Component (C) preferably contains only an acylphosphine oxide-based radical polymerization initiator.

[0024] Examples of the acetophenone-based photoradical polymerization initiator include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer. Commercially available acetophenone-based photoradical polymerization initiators include IRGACURE (registered trademark) 184, IRGACURE (registered trademark) 1173, IRGACURE (registered trademark) 2959, IRGACURE (registered trademark) 127 (manufactured by BASF), and ESACURE (registered trademark) KIP-150 (manufactured by Lamberti s.p.a.).

[0025] Examples of acylphosphine oxide-based photoradical polymerization initiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)phenyl-phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, etc. Commercially available acylphosphine oxide-based photoradical polymerization initiators include Omnirad (registered trademark) TPO, Omnirad (registered trademark) 819 (manufactured by IGM Resins B.V.), and IRGACURE (registered trademark) 819DW (manufactured by BASF).

[0026] In the photocurable resin composition according to the present invention, the blending amount (content) of component (C) is not particularly limited. The blending amount of component (C) is, for example, 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, per 100 parts by mass of component (A). By being within the above range, a photocurable resin composition having good adhesive strength to adherends made of various materials can be obtained.

[0027] In one embodiment of the present invention, the photocurable resin composition preferably further includes a compound having a (meth)acryloyl group other than the component (A) as component (D). When the photocurable resin composition according to the present invention includes component (D), the adhesive strength can be further improved. Component (D) is not particularly limited. Examples of component (D) include polybutadiene-based urethane (meth)acrylates, hydrogenated polybutadiene-based urethane (meth)acrylates, polycarbonate-based urethane (meth)acrylates, polyether-based urethane (meth)acrylates, polyester-based urethane (meth)acrylates, castor oil-based urethane (meth)acrylates, isoprene-based (meth)acrylates, hydrogenated isoprene-based (meth)acrylates, epoxy (meth)acrylates, oligomers such as (meth)acrylic group-containing acrylic polymers, and (meth)acrylate monomers. In this specification, the term "oligomer" refers to a polymer in which two to several tens of monomer units are repeated, and the weight-average molecular weight thereof is 1,000 or more. From the viewpoint of improving adhesive strength to various materials, it is preferable that component (D) contains a (meth)acrylate monomer. Examples of the (meth)acrylate monomer include a monofunctional (meth)acrylate monomer having one (meth)acryloyl group in one molecule, and a polyfunctional (meth)acrylate monomer having two or more (meth)acryloyl groups in one molecule. From the viewpoint of improving adhesive strength to various materials, it is preferable that the (meth)acrylate monomer contains a monofunctional (meth)acrylate monomer, and it is preferable that the (meth)acrylate monomer contains only a monofunctional (meth)acrylate monomer.

[0028] Examples of monofunctional (meth)acrylate monomers include methoxydiethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate, methoxytetraethylene glycol mono(meth)acrylate, methoxypentaethylene glycol mono(meth)acrylate, methoxyhexaethylene glycol mono(meth)acrylate, methoxyheptaethylene glycol mono(meth)acrylate, methoxyhexaethylene glycol mono(meth)acrylate, methoxyoctaethylene glycol mono(meth)acrylate, methoxynonaethylene glycol mono(meth)acrylate, methoxydecaethylene glycol mono(meth)acrylate, methoxytripropylene glycol mono(meth)acrylate, methoxytetrapropylene glycol mono(meth)acrylate, methoxypentapropylene glycol mono(meth)acrylate, methoxyhexapropylene glycol mono(meth)acrylate, methoxyheptapropylene glycol mono(meth)acrylate, methoxyhectapropylene glycol mono(meth)acrylate, methacrylate, Octapropylene glycol mono(meth)acrylate, methoxynonapropylene glycol mono(meth)acrylate, methoxydecapropylene glycol mono(meth)acrylate, methoxytributylene glycol mono(meth)acrylate, methoxytetrabutylene glycol mono(meth)acrylate, methoxypentabtylene glycol mono(meth)acrylate, methoxyhexabtylene glycol mono(meth)acrylate, methoxyheptabtylene glycol mono(meth)acrylate, methoxyheptabtylene glycol Lithium mono(meth)acrylate, methoxyoctabutylene glycol mono(meth)acrylate, methoxynonabutylene glycol mono(meth)acrylate, methoxydecabutylene glycol mono(meth)acrylate, ethoxydiethylene glycol mono(meth)acrylate, ethoxytriethylene glycol mono(meth)acrylate, ethoxytetraethylene glycol mono(meth)acrylate, ethoxypentaethylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate,Ethoxyheptaethylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate, ethoxyoctaethylene glycol mono(meth)acrylate, ethoxynonaethylene glycol mono(meth)acrylate, ethoxydecaethylene glycol mono(meth)acrylate, ethoxytripropylene glycol mono(meth)acrylate, ethoxytetrapropylene glycol mono(meth)acrylate, ethoxypentapropylene glycol mono(meth)acrylate, ethoxyhexapropylene glycol mono(meth)acrylate, ethoxyheptapropylene glycol mono(meth)acrylate, ethoxyhexapropylene glycol mono(meth)acrylate, ethoxyoctapropylene glycol mono(meth)acrylate, ethoxynonapropylene glycol mono(meth)acrylate, ethoxydecapropylene glycol mono(meth)acrylate, ethoxytributylene glycol mono(meth)acrylate, ethoxytetrabutylene glycol mono(meth)acrylate, ethoxypentabtylene glycol mono(meth)acrylate, ethoxyhexabtylene glycol mono(meth)acrylate, ethoxyheptabtylene glycol mono(meth)acrylate, ethoxyhexabtylene glycol mono(meth)acrylate, ethoxyoctabtylene glycol mono(meth)acrylate, ethoxynonabtylene glycol mono(meth)acrylate, ethoxydecabutylene glycol mono(meth)acrylate, etc. Among these, from the viewpoint of improving adhesive strength to various adherend materials, it is preferable that the weight average molecular weight of the monofunctional (meth)acrylate monomer is less than 500. The monofunctional (meth)acrylate monomer preferably contains a (meth)acrylate having an alicyclic structure in the molecule, more preferably contains isobornyl (meth)acrylate, and most preferably contains isobornyl acrylate. The monofunctional (meth)acrylate monomer may be used alone or in combination of two or more.

[0029] Examples of polyfunctional (meth)acrylate monomers include tetrafunctional (meth)acrylate monomers such as ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylate monomers such as dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, and dipentaerythritol penta(meth)acrylate; and hexafunctional (meth)acrylate monomers such as dipentaerythritol hexa(meth)acrylate. Among these, the polyfunctional (meth)acrylate monomer is preferably selected from the group consisting of dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and dipentaerythritol penta(meth)acrylate. The polyfunctional (meth)acrylate monomers can be used alone or in combination of two or more.

[0030] In the photocurable resin composition according to the present invention, the blending amount (content) of component (D) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 10 to 30 parts by mass, per 100 parts by mass of component (A). Within the above range, adhesive strength can be further improved.

[0031] In one embodiment of the present invention, the photocurable resin composition preferably further contains an inorganic filler as component (E). Examples of inorganic fillers include glass powder, fumed silica powder, alumina powder, mica powder, ceramic powder, silicone rubber powder, calcium carbonate powder, aluminum nitride powder, carbon powder, kaolin clay, dried clay mineral, and dried diatomaceous earth. From the viewpoint of improving resin strength without inhibiting photocurability, component (E) is preferably fumed silica (powder), and most preferably fumed silica (powder) surface-treated with dimethylsilicone oil. From the viewpoint of improving resin strength when dispersed in component (A), the BET specific surface area of ​​component (E) is 50 to 200 m. ２ / g, and 70 to 130m２ / g, and more preferably 80 to 120m ２ / g is most preferred.

[0032] Commercially available products of component (E) include Aerosil (registered trademark) R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, and R202 manufactured by Nippon Aerosil.

[0033] In the photocurable resin composition according to the present invention, the blending amount (content) of component (E) is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). Within the above range, photocurability is not inhibited and resin strength can be improved.

[0034] In one embodiment of the present invention, the photocurable resin composition preferably further contains an antifoaming agent as component (F). By including an antifoaming agent, air bubbles can be removed from the photocurable resin composition after the photocurable resin composition is applied to an adherend, thereby improving photocurability, resin strength, and the like. The antifoaming agent is not particularly limited. Examples of antifoaming agents include silicone-based antifoaming agents, modified silicone-based antifoaming agents, acetylene alcohol-based antifoaming agents, silica-based antifoaming agents, wax, polyether-modified polydimethylsiloxane, paraffin-based oil, and foam-defoaming aliphatic derivatives. Among these, it is preferable that component (F) contains a silicone-based antifoaming agent.

[0035] In the photocurable resin composition according to the present invention, the content of component (F) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and most preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A). By being within the above range, photocurability can be improved without reducing adhesive strength.

[0036] <Optional Components> Additives such as organic fillers, organic peroxides, storage stabilizers, antioxidants, light stabilizers, and surfactants (excluding components contained in component (F)) can be used in the photocurable resin composition according to the present invention, as long as the object of the present invention is not impaired.

[0037] The organic filler may be an organic powder composed of rubber, elastomer, plastic, polymer (or copolymer), or the like. The organic filler may also be an organic filler having a multilayer structure, such as a core-shell type. The organic filler may be used alone, or two or more types may be used in combination. The amount (content) of the organic filler (the total amount when two or more types are used) is preferably 0.1 to 50 parts by mass per 100 parts by mass of component (A).

[0038] An organic peroxide may be added to the photocurable resin composition of the present invention for the purpose of imparting curability by heating or a redox reaction. By using a redox reaction, radical species can be generated at room temperature. The organic peroxide is not particularly limited. Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide; peroxyketals such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(t-butylperoxy)butane; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, and 2,5-dimethylhexane-2,5 hydroperoxides such as di-t-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; diacyl peroxides such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, and m-toluoyl peroxide;Peroxydicarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis-(4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, and diallyl peroxydicarbonate; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, and t-butylperoxy-2-ethylhexanoate. peroxyesters such as t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctoate, t-hexylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxyneohexanoate, t-hexylperoxyneohexanoate, and cumylperoxyneohexanoate; and acetylcyclohexylsulfonyl peroxide and t-butylperoxyallyl carbonate. The organic peroxides may be used alone or in combination.

[0039] When an organic peroxide is used in the photocurable resin composition according to the present invention, a curing accelerator may be added to accelerate the redox reaction. The curing accelerator is not particularly limited. Preferable curing accelerators include saccharin (o-benzoixulfimide), hydrazine compounds, amine compounds, mercaptan compounds, and transition metal-containing compounds.

[0040] Examples of the hydrazine compound include 1-acetyl-2-phenylhydrazine, 1-acetyl-2(p-tolyl)hydrazine, 1-benzoyl-2-phenylhydrazine, 1-(1',1',1'-trifluoro)acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl)hydrazine, 1-acetyl-2-(p-nitrophenyl)hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), ethyl carbazate, p-nitrophenylhydrazine, and p-trisulfonylhydrazide.

[0041] Examples of the amine compound include heterocyclic secondary amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, and 1,2,3,4-tetrahydroquinaldine; heterocyclic tertiary amines such as quinoline, methylquinoline, quinaldine, and quinoxalinephenazine; aromatic tertiary amines such as N,N-dimethyl-para-toluidine, N,N-dimethyl-anisidine, and N,N-dimethylaniline; and azole compounds such as 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, and 3-mercaptobenzotrizole.

[0042] Examples of mercaptan compounds include n-dodecyl mercaptan, ethyl mercaptan, butyl mercaptan, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, and pentaerythritol tetrakisthioglycolate.

[0043] The transition metal-containing compound is preferably a metal chelate complex salt, such as iron pentadione, cobalt pentadione, copper pentadione, propylenediamine copper, ethylenediamine copper, iron naphthate, nickel naphthate, cobalt naphthate, copper naphthate, copper octate, iron hexoate, iron propionate, and vanadium acetylacetonate.

[0044] Examples of the storage stabilizer include radical absorbers such as benzoquinone, hydroquinone, and hydroquinone monomethyl ether, and metal chelating agents such as ethylenediaminetetraacetic acid or its di-sodium salt, oxalic acid, acetylacetone, and o-aminophenol.

[0045] Examples of antioxidants include quinone compounds such as β-naphthoquinone, 2-methoxy-1,4-naphthoquinone, methylhydroquinone, hydroquinone, hydroquinone monomethyl ether, mono-tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-benzoquinone, 2,5-diphenyl-p-benzoquinone, and 2,5-di-tert-butyl-p-benzoquinone; phenothiazine, 2,2-methylene-bis(4-methyl-6-tert-butylphenol), catechol, tert-butylcatechol, and 2-butyl-4 -hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 3,9-bis[2-[3-(3-tert-butyl N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionamide], benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-tolyl)tri-p-cresol, calcium diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- phenolic compounds such as tris(2,4-di-tert-butylphenyl)phosphite, tris[2-[ [2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphen-6-yl]oxy]ethyl]amine, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetrakis(2,4-di-tert-butylphenyl)[1,1-bisphenyl]-4,4'-diylbisphosphonite, 6-[3-(3-tert-butyl-4-hydroxy-5- Examples of suitable antioxidants include phosphorus-based compounds such as [methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphene; sulfur-based compounds such as dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis(3-laurylthiopropionate), and 2-mercaptobenzimidazole; amine-based compounds such as phenothiazine; lactone-based compounds; and vitamin E-based compounds. Among these, phenol-based compounds are preferred as antioxidants.

[0046] Examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1-[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidine, Lysinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, decanedioic acid bis(2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, N,N',N'',N'''-tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazine- 2-yl)-4,7-diazadecane-1,10-diamine, polycondensate of dibutylamine / 1,3,5-triazine / N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino] ], polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one, β-alanine, N,-(2,2,6,6-tetramethyl-4-piperidinyl)-dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione, 2,2,4,4-Tetramethyl-7-oxa-3,20-diazadispiro[5,1,11,2]heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo-[5,1,11,2]-heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanediol, [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2,2 higher fatty acid esters of 2,2,6,6-tetramethyl-4-piperidinol, 1,3-benzenedicarboxamide, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl), and other hindered amine compounds; benzophenone compounds such as octabenzone; 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-[2 benzotriazole-based compounds such as 2-hydroxy-3-(3,4,5,6-tetrahydrophthalimido-methyl)-5-methylphenyl]benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, reaction products of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol, and 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol; benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol. The light stabilizer is particularly preferably a hindered amine compound.

[0047] The photocurable resin composition according to the present invention can be produced by a conventionally known method. For example, the photocurable resin composition according to the present invention can be produced by blending predetermined amounts of components (A) to (C) and other components and mixing them using a mixing means such as a mixer at a temperature of preferably 10 to 70°C for preferably 0.1 to 5 hours. Furthermore, since the photocurable resin composition according to the present invention has photocurability, it is preferable to produce the photocurable resin composition according to the present invention in a light-shielding environment.

[0048] <Coating Method> Examples of methods that can be used to apply the photocurable resin composition of the present invention to an adherend include dispensing using an automatic coater, spraying, inkjet printing, screen printing, gravure printing, dipping, spin coating, etc. From the viewpoint of coatability, the photocurable resin composition of the present invention is preferably liquid at 25°C.

[0049] <Curing Method> The photocurable resin composition according to the present invention can be cured by irradiation with light such as ultraviolet light or visible light. The light source used for irradiation is not particularly limited. Examples of the light source include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a black light lamp, a microwave-excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, and an electron beam irradiation device. The light source is preferably an LED from the viewpoint of minimizing thermal damage to the adherend. The dose of light irradiation is preferably 3 kJ / m from the viewpoint of the properties of the cured product. ２ More preferably, 5 kJ / m ２ The amount of light irradiation is preferably 70 kJ / m from the viewpoint of the takt time of the curing step. ２ More preferably, 60 kJ / m or less. ２ or less, and particularly preferably 50 kJ / m ２ The following is the result.

[0050] <Cured Product> The cured product according to the present invention is obtained by curing the photocurable resin composition according to the present invention by irradiating it with light such as ultraviolet light or visible light using the above-mentioned curing method. In one embodiment, the cured product according to the present invention is obtained by irradiating the above-mentioned photocurable resin composition with light. The cured product according to the present invention can be obtained by any curing method as long as it is obtained by curing the photocurable resin composition according to the present invention.

[0051] <Applications> The photocurable resin composition according to the present invention can be used as a sealant, adhesive, coating agent, casting agent, potting agent, etc. For use in such applications, the photocurable resin composition according to the present invention is preferably liquid at 25°C. A cured product of the photocurable resin composition according to the present invention is a rubbery elastic body that excels in at least one of low gas permeability, low moisture permeability, heat resistance, acid resistance, and flexibility. Therefore, the cured product according to the present invention can be used in fuel cells, solar cells, dye-sensitized solar cells, lithium ion batteries, electrolytic capacitors, liquid crystal displays, organic EL displays, electronic paper, LEDs, hard disk drives, photodiodes, optical communications / circuits, electric wires / cables / optical fibers, optical isolators, laminates such as IC cards, sensors, substrates, pharmaceutical / medical instruments / devices, etc. The photocurable resin composition according to the present invention has excellent adhesive strength to adherends made of various materials, and is therefore particularly suitable for bonding dissimilar materials, such as bonding metal to plastic materials and bonding different plastic materials to each other.

[0052] One embodiment of the present invention is a sealant or adhesive comprising the above-mentioned photocurable resin composition.

[0053] <Adherend> The photocurable resin composition according to the present invention has excellent adhesive strength to a variety of materials, and can be used as an adherend to various metals, glasses, plastics, etc. In particular, the photocurable resin composition according to the present invention exhibits excellent adhesive strength to aluminum, acrylic resin, and polycarbonate, and is therefore particularly suitable for use with an adherend selected from the group consisting of aluminum, acrylic resin, and polycarbonate.

[0054] In one embodiment, the sealant or adhesive according to the present invention is used on an adherend containing at least one material selected from the group consisting of aluminum, acrylic resin, and polycarbonate.

[0055] <Sealing Method> When the photocurable resin composition according to the present invention is used as a sealant, the sealing method is not particularly limited. Typical sealing methods include form-in-place gasket (FIPG), cure-in-place gasket (CIPG), mold-in-place gasket (MIPG), and liquid injection molding.

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0057] Examples 1 to 4, Comparative Examples 1 to 5 The following components were prepared to prepare photocurable resin compositions.

[0058] <Production of polyisobutylene having acryloyloxyethoxyphenyl groups (component (A))> After replacing the atmosphere inside a 5 L separable flask with nitrogen, 200 mL of n-hexane and 2000 mL of butyl chloride were added and cooled to -70°C while stirring under a nitrogen atmosphere. Next, 840 mL (9 mol) of isobutylene, 12 g (0.05 mol) of p-dicumyl chloride, and 1.1 g (0.012 mol) of 2-methylpyridine were added. After the reaction mixture was cooled to -70°C, 5.0 mL (0.05 mol) of titanium tetrachloride was added to initiate polymerization. Three hours after the start of polymerization, 40 g of phenoxyethyl acrylate (Light Acrylate PO-A, manufactured by Kyoeisha Chemical Co., Ltd.) and 110 mL of titanium tetrachloride were added. Stirring was continued at -70°C for 4 hours, and then 1000 mL of methanol was added to terminate the reaction.

[0059] The supernatant was separated from the reaction solution, and the solvent and other components were distilled off. The resulting product was then dissolved in 3,000 mL of n-hexane, washed three times with 3,000 mL of pure water, and reprecipitated from methanol. The solvent was then distilled off under reduced pressure, and the resulting polymer was vacuum-dried at 80°C for 24 hours to yield polyisobutylene having acryloyloxyethoxyphenyl groups (component (A)).

[0060] The produced component (A) is —[CH ２ C(CH ３ ) ２ ]-unit and contained two acryloyl groups. More specifically, the produced component (A) was a compound represented by the general formula (1) １ is a phenylene group, PIB is a polyisobutylene backbone, and R ４ is a divalent hydrocarbon group having two carbon atoms (ethylene group), and R ２ and R ３ is a hydrogen atom, and R ５ is a hydrogen atom, and n is 2. The number average molecular weight of component (A) (chromatography method (size permeation chromatography), polystyrene equivalent) was 11,100, and the viscosity of component (A) (25°C) was 1550 Pa s.

[0061] Component (B) Component (B-1): A compound in which two or more trimethoxysilyl groups and two or more acryloyl groups are bonded to an organic chain, and the functional group equivalent weight per molecule is trimethoxysilyl groups:acryloyl groups = 1:1. Product name: X-12-1048 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 1172 Component (B-2): 8-methacryloxyoctyltrimethoxysilane Product name: KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 318.5 Component (B') Component (B'-1): 3-methacryloxypropyltrimethoxysilane Product name: KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 234.3 Component (B'-2): 3-acryloxypropyltrimethoxysilane Product name: KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 248.4 Component (B'-3): Vinyltrimethoxysilane Product name: KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 190.3 (B'-4) component: 3-glycidoxypropyltrimethoxysilane Product name: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 236.3 (B'-5) component: 3-mercaptopropyltrimethoxysilane Product name: KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.) Weight average molecular weight: 196.4 (C) component (photoradical polymerization initiator): 2,4,6-trimethylbenzoyldiphenylphosphine oxide Product name: Omnirad (registered trademark) TPO (manufactured by IGM Resin B.V.) (D) component: isobornyl acrylate Product name: Light Acrylate IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.) (E) component: fumed silica surface-treated with dimethyl silicone oil Product name: AEROSIL (registered trademark) RY200 (manufactured by Nippon Aerosil Co., Ltd.) BET specific surface area: 100 m ２ / g Component (F): Silicone-based antifoaming agent, trade name BYK-1799 (manufactured by BYK-Chemie GmbH).

[0062] The components other than component (C) were weighed into a stirring vessel and stirred with a mixer for 30 minutes. Next, component (C) was added in the dark and stirred with a mixer for 30 minutes. The detailed amounts prepared were as shown in Table 1. All values ​​in Table 1 are expressed in parts by mass. All tests were conducted at 25°C.

[0063] The test methods used in the examples and comparative examples in Table 1 are as follows.

[0064] [Shear Adhesion Strength (ADC / PC)] The photocurable resin compositions of the Examples and Comparative Examples were each applied to an aluminum die-cast test piece measuring 25 mm wide x 100 mm long x 1 mm thick. A transparent polycarbonate test piece was then attached to the test piece using a jig so that the overlapping area was 25 mm x 10 mm and the thickness was 1 mm. UV (wavelength: 365 nm, cumulative light intensity: 40 kJ / m) was applied using a belt conveyor-type LED UV irradiator. ２ ) was irradiated from the polycarbonate test piece side to cure the photocurable resin composition. The prepared test pieces were then used to measure the tensile shear adhesive strength (unit: MPa) at 25°C using a universal tensile tester (tensile speed: 50 mm / min) in accordance with JIS K6850:1999. The shear adhesive strength was measured at maximum strength. The values ​​listed in Table 1 are the average values ​​of N = 3. The preferred shear adhesive strength for aluminum die-cast / polycarbonate adherends is 0.40 MPa or greater. Furthermore, the percentage change in Examples 1 to 4 and Comparative Examples 2 to 5 was calculated based on Comparative Example 1, which did not contain components (B) and (B'). Percent change (%) = (shear adhesive strength of each Example or Comparative Example - shear adhesive strength of Comparative Example 1) / shear adhesive strength of Comparative Example 1 × 100.

[0065] [Shear Adhesion Strength (PMMA / PC)] The photocurable resin compositions of the Examples and Comparative Examples were each applied to an acrylic resin test piece measuring 25 mm wide x 100 mm long x 1 mm thick. A transparent polycarbonate test piece was then attached to the PMMA / PC using a jig so that the overlapping area was 25 mm x 10 mm and the thickness was 1 mm. UV (wavelength: 365 nm, cumulative light intensity: 40 kJ / m) was applied using a belt conveyor-type LED UV irradiator. ２) was irradiated from the polycarbonate test piece side to cure the photocurable resin composition. The prepared test pieces were then used to measure the tensile shear bond strength (unit: MPa) at 25°C using a universal tensile tester (tensile speed: 50 mm / min) in accordance with JIS K6850:1999. The tensile shear bond strength was the value at maximum strength. The preferred shear bond strength for acrylic resin / polycarbonate adherends is 0.60 MPa or greater. Furthermore, the percentage change in Examples 1 to 4 and Comparative Examples 2 to 5 was calculated based on Comparative Example 1, which did not contain components (B) and (B'). Percent change (%) = (shear bond strength of each Example or Comparative Example - shear bond strength of Comparative Example 1) / shear bond strength of Comparative Example 1 x 100.

[0066] [Shear Adhesion Strength (PC / PC)] The photocurable resin compositions of the Examples and Comparative Examples were each applied to a transparent polycarbonate test piece measuring 25 mm wide x 100 mm long x 1 mm thick. Then, another polycarbonate test piece was attached to the test piece using a jig so that the overlapping surface was 25 mm x 10 mm and the thickness was 1 mm. UV (wavelength: 365 nm, cumulative light intensity: 40 kJ / m) was applied using a belt conveyor-type LED UV irradiator. ２ ) to cure the photocurable resin composition. The prepared test specimens were then used to measure the tensile shear bond strength (unit: MPa) at 25°C using a universal tensile tester (tensile speed: 50 mm / min) in accordance with JIS K6850:1999. The tensile shear bond strength was the value at maximum strength. A preferred shear bond strength for polycarbonate / polycarbonate adherends is 0.60 MPa or greater. Furthermore, the percentage change in Examples 1 to 4 and Comparative Examples 2 to 5 was calculated based on Comparative Example 1, which did not contain components (B) and (B'). Percent change (%) = (shear bond strength of each Example or Comparative Example - shear bond strength of Comparative Example 1) / shear bond strength of Comparative Example 1 x 100.

[0067]

[0068] As shown in Table 1, the results of the shear adhesive strength using the photocurable resin compositions of Examples 1 to 4 confirmed that the shear adhesive strength was improved for all of the aluminum die-cast, acrylic resin, and polycarbonate materials compared to Comparative Example 1, which did not contain the components (B) and (B'). On the other hand, Comparative Examples 2 to 4, which contained the component (B'), showed a decrease in shear adhesive strength to the acrylic resin compared to Comparative Example 1. Furthermore, for Comparative Example 5, a decrease in shear adhesive strength was observed for all three types of materials compared to Comparative Example 1.

[0069] Furthermore, for Examples 1 to 4 and Comparative Examples 1 to 3, the resin strength was measured.

[0070] [Resin Strength (Tensile Strength)] The photocurable resin composition of each Example and Comparative Example was set to a thickness of 1 mm, and ultraviolet light (wavelength: 365 nm, cumulative light amount: 40 kJ / m ２ The photocurable resin composition was cured by irradiating it with UV light to produce a sheet-like cured product. Test pieces were prepared by punching out using a No. 3 dumbbell. Both ends of the test piece were fixed to the chuck so that the long axis of the test piece was aligned with the center of the chuck. The test piece was pulled at a pulling speed of 500 mm / min, and the maximum load was measured. The "tensile strength (MPa)" was calculated from the maximum load. The results are shown in Table 2. Details are in accordance with JIS K 6251 (2010). It is more preferable that the resin strength of the cured product according to the present invention is 2.2 MPa or greater. Furthermore, the percentage change in Examples 1 to 4 and Comparative Examples 2 and 3 was calculated based on Comparative Example 1, which did not contain components (B) and (B'). Percent change (%) = (resin strength of each Example or Comparative Example - resin strength of Comparative Example 1) / resin strength of Comparative Example 1 x 100.

[0071]

[0072] As shown in Table 2, the cured products of the photocurable resin compositions of Examples 1 to 4 had improved resin strength compared to the cured product of the photocurable resin composition of Comparative Example 1. On the other hand, the cured product of the photocurable resin composition of Comparative Example 2 showed improved resin strength compared to the cured product of the photocurable resin composition of Comparative Example 1, but the improvement in resin strength was not sufficient compared to Examples 1 to 4. The cured product of the photocurable resin composition of Comparative Example 3 showed neither a decrease nor an improvement in resin strength compared to the cured product of the photocurable resin composition of Comparative Example 1.

[0073] From the above, it can be seen that the photocurable resin composition containing components (A) to (C) has high adhesive strength to adherends made of various materials such as aluminum, acrylic resin, polycarbonate, etc. Furthermore, the photocurable resin composition containing components (A) to (C) can produce a tough cured product with excellent resin strength.

[0074] The photocurable resin composition according to the present invention has high adhesive strength to various materials, and the cured product thereof has high resin strength, so that it can be used for various adhesive and sealing applications. In particular, the photocurable resin composition according to the present invention is effective as an adhesive and a sealant for different materials, and is therefore industrially useful.

[0075] This application is based on Japanese Patent Application No. 2023-145146, filed on September 7, 2023, the disclosure of which is incorporated herein by reference in its entirety.

Claims

1. A photocurable resin composition containing the following components (A) to (C): Component (A): one or more (meth)acryloyl groups and a -[CH ２ C (CH ３ ) ２ ]- units; component (B): a compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a main chain composed of an organic chain, and having a weight average molecular weight of 300 or more (excluding component (A)); and component (C): a photoradical polymerization initiator.

2. The photocurable resin composition according to claim 1, comprising 0.01 to 20 parts by mass of component (B) per 100 parts by mass of component (A).

3. The photocurable resin composition according to claim 1 or 2, wherein the component (C) is an acylphosphine oxide-based photoradical polymerization initiator.

4. The photocurable resin composition according to claim 1 or 2, further comprising a (meth)acrylic monomer as component (D).

5. The photocurable resin composition according to claim 1 or 2, further comprising an inorganic filler as component (E).

6. The photocurable resin composition according to claim 5, comprising 1 to 50 parts by mass of the component (E) per 100 parts by mass of the component (A).

7. A sealant or adhesive comprising the photocurable resin composition according to claim 1 or 2.

8. The sealant or adhesive according to claim 7, which is used on an adherend containing at least one material selected from the group consisting of aluminum, acrylic resin and polycarbonate.

9. A cured product obtained by irradiating the photocurable resin composition according to claim 1 or 2 with light.

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