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 thereof has excellent resin strength. The present invention pertains to a photocurable resin composition containing the following components (A) to (C). Component (A): a polyisobutylene resin containing one or more (meth) acryloyl groups and-[CH2C (CH3) 2]-units; component (B): a compound having one or more (meth) acryloyl groups and one or more hydrolyzable silyl groups, having a main chain comprising an organic chain, and having a weight-average molecular weight of 300 or more (excluding component (A)); and (C) a photoradical polymerization initiator.

Description

Technical Field

[0001] This invention relates to a photocurable resin composition that exhibits high adhesion strength to various materials, particularly aluminum, polycarbonate, and acrylic resins. Background Technology

[0002] In recent years, the automotive industry has achieved weight reduction and improved fuel efficiency through the use of plastic materials. However, the surface of plastic materials is inactive or low-polarity, resulting in poor compatibility with adhesives compared to metals, making it difficult to exhibit high adhesive strength. Furthermore, components made solely of plastic materials have low rigidity, thus they are sometimes used in combination with metals. Among metals, aluminum readily forms an oxide film on its surface, making it similarly inactive to plastics, requiring high adhesive strength from the adhesives and sealants used (Japanese Patent Application Laid-Open No. 2020-023674). Moreover, in plastic bonding, applying heat can cause deformation of the adhered materials due to the plastic's properties; therefore, photocurable adhesives and sealants that do not require heat application to plastic materials are needed. Summary of the Invention

[0003] Due to their excellent low moisture permeability, gas barrier properties, and water resistance, sealants with a polyisobutylene backbone in the main skeleton are sometimes used. However, such sealants suffer from low adhesive strength due to their low-polarity backbone.

[0004] The present invention was made in view of the above-mentioned situation, and its object is to provide a photocurable resin composition that can be cured by using light such as ultraviolet light without applying heat to the adherends, and has higher bonding strength for various materials (especially aluminum, acrylic resins and polycarbonate), and the cured product has high resin strength.

[0005] Next, the main idea of ​​the present invention will be explained.

[0006] [1] A photocurable resin composition, characterized in that it contains the following components (A) to (C): (A) Composition: Polyisobutylene resin containing one or more (meth)acryloyl groups and -[CH2C(CH3)2]- units; (B) Component: A compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a backbone composed of organic chains, and having a weight-average molecular weight of 300 or more (excluding component (A)); and (C) Component: Photoradical polymerization initiator.

[0007] [2] The photocurable resin composition according to [1], wherein, relative to 100 parts by weight of component (A) above, it comprises 0.01 to 20 parts by weight of component (B).

[0008] [3] The photocurable resin composition according to [1] or [2], wherein the above-mentioned component (C) is an acylphosphine oxide photoradical polymerization initiator.

[0009] [4] The photocurable resin composition according to any one of [1] to [3] further comprises (meth)acrylic monomers as (D) component.

[0010] [5] The photocurable resin composition according to any one of [1] to [4] further comprises an inorganic filler as component (E).

[0011] [6] The photocurable resin composition according to [5] comprises, relative to 100 parts by weight of component (A), 1 to 50 parts by weight of component (E).

[0012] [7] A sealant or adhesive comprising any one of the light-curing resin compositions described in [1] to [6].

[0013] [8] The sealant or adhesive according to [7] is used for an adherend containing at least one material selected from aluminum, acrylic resin and polycarbonate.

[0014] [9] A cured product obtained by irradiating the photocurable resin composition described in any one of [1] to [6] with light. Detailed Implementation

[0015] The embodiments of the present invention will be described below. It should be noted that the present invention is not limited to the embodiments described below. In this specification, "X to Y" refers to a range including the values ​​(X and Y) described before and after it as a lower and upper limit value, meaning "above X and below Y". In the present invention, a compound having a (meth)acryloyl group refers to a (meth)acrylate. The (meth)acryloyl group can be in the form of (meth)acryloyloxy group. Furthermore, the term "(meth)acryloyl" includes both acryloyl and methacryloyl. Therefore, for example, the term "(meth)acryloyl" includes both acryloyl (H2C=CH-C(=O)-) and methacryloyl (H2C=C(CH3)-C(=O)-). Similarly, the term "(meth)acrylate" includes both acrylate and methacrylate, the term "(meth)acrylic acid" includes both acrylic acid and methacrylic acid, and the term "(meth)acrylamide" includes both acrylamide and methacrylamide.

[0016] One aspect of the present invention relates to a photocurable resin composition comprising the following components (A) to (C).

[0017] (A) Composition: Polyisobutylene resin containing one or more (meth)acryloyl groups and -[CH2C(CH3)2]- units; (B) Component: A compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a backbone composed of organic chains, and having a weight-average molecular weight of 300 or more (excluding component (A)); and (C) Component: Photoradical polymerization initiator.

[0018] According to one aspect of the present invention, a photocurable resin composition can be provided, which has excellent adhesive strength to various materials (e.g., aluminum, plastics, etc.) and whose cured product has excellent resin strength.

[0019] The component (A) used in this invention is not particularly limited as long as it is a polymer (polyisobutylene resin) having one or more (meth)acryloyl groups and a polyisobutylene backbone containing -[CH2C(CH3)2]- units. As component (A), for example, it can be any polymer having -[CH2C(CH3)2]- units (polyisobutylene backbone), or it can be a polymer containing "other structural units besides -[CH2C(CH3)2]- units". Component (A) contains, for example, 70% by mass or more of -[CH2C(CH3)2]- units relative to the total amount of structural units, preferably 75% by mass or more, and more preferably 80% by mass or more. Furthermore, component (A) may contain less than 100% by mass of -[CH2C(CH3)2]- units, may contain 95% by mass or less, or may contain 90% by mass or less. (A) Component preferably has 1 to 12 (meth)acryloyl groups, more preferably 2 to 8, further preferably 2 to 4, and particularly preferably 2 (meth)acryloyl groups. It should be noted that in this invention, the polymer is not theoretically limited; for example, it can be defined as a compound having a structure with repeating units of monomers in the polymer backbone and containing more than 100 repeating units. Furthermore, (meth)acryloyl groups can be present in either the side chains or the ends of the molecule (polyisobutylene backbone). From the viewpoint of high resin strength and excellent cured product properties, it is preferable that they are present at the ends of the molecule. From the viewpoint of storage stability, component (A) preferably does not contain reactive functional groups other than (meth)acryloyl groups, more preferably only (meth)acryloyl groups, and further preferably only acryloyl groups.

[0020] From the viewpoint of obtaining a cured product with low polarity, excellent low moisture permeability, gas barrier properties, and water resistance, component (A) of the present invention is preferably a polymer (polyisobutylene resin) having a polyisobutylene backbone as shown in the following general formula (1). Specific examples of component (A) include polyisobutylene resin having (meth)acryloyloxyalkoxyphenyl. It should be noted that the main backbone of component (A) of the present invention is a polyisobutylene backbone. As monomers constituting the polyisobutylene backbone, monomers other than isobutylene can be used as long as isobutylene is primarily used and within the scope that does not impair the effects of the present invention. That is, component (A) of the present invention can be a copolymer of isobutylene and monomers other than isobutylene. It should be noted that, from the viewpoint of wettability with plastic materials, component (A) is preferably liquid at room temperature (25°C).

[0021] [Chemical Formula 1]

[0022] In general formula (1), R 1 Represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group. R 1 Preferably, it is a polyvalent aromatic hydrocarbon group, and particularly preferably a divalent phenylene group. PIB represents a polyisobutylene skeleton containing the above-mentioned -[CH2C(CH3)2]- unit (or composed of -[CH2C(CH3)2]- unit). R 4 R represents a divalent hydrocarbon group with 2 to 6 carbon atoms. 4 Preferably, it is a divalent hydrocarbon group with 2 or 3 carbon atoms. 4 More preferably, it is ethylidene or propyleneide, and particularly preferably ethylidene. R 2 and R 3 Each can independently represent a hydrogen atom or a monovalent hydrocarbon group with 1 to 20 carbon atoms. R 2 and R 3 Preferably, it contains hydrogen atoms. R 5 Represents a hydrogen atom, methyl group, or ethyl group. R 5 Preferably, it contains hydrogen atoms or methyl groups. n represents any integer from 1 to 6. n is particularly preferably an integer from 2 to 4.

[0023] The molecular weight of component (A) described in this invention is not particularly limited. However, from the viewpoint of achieving excellent cured product properties such as high elongation and high strength in screen-printed coatings, the number-average molecular weight of component (A), determined by chromatography, is preferably 200 to 500,000, more preferably 1,000 to 100,000, and particularly preferably 3,000 to 50,000. It should be noted that the number-average molecular weight can be calculated using the standard polystyrene conversion method of size exclusion chromatography (SEC).

[0024] The viscosity of component (A) described in this invention at 25°C is not particularly limited. From the viewpoint of operability, the viscosity of 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 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. It should be noted that, unless otherwise specified, the viscosity is a value obtained by measuring the viscosity at 25°C using a cone-plate viscometer.

[0025] There are no particular limitations on the method for manufacturing component (A) of this invention, and known methods may be used. For example, methods for manufacturing component (A) may include those disclosed in Polymer Bulletin, Vol. 6, pp. 135-141 (1981), TPLiao and JP Kennedy, and Polymer Bulletin, Vol. 20, pp. 253-260 (1988), and Puskas et al., such as the method of reacting terminal hydroxyl polyisobutylene with acryloyl chloride or methacryloyl chloride. Other methods for manufacturing component (A) may include methods of reacting terminal hydroxyl polyisobutylene with compounds having (meth)acryloyl and isocyanate groups, methods of reacting terminal hydroxyl polyisobutylene with compounds having isocyanate groups and compounds having (meth)acryloyl and hydroxyl groups, and methods of reacting terminal hydroxyl polyisobutylene with (meth)acrylic acid or lower esters of (meth)acrylic acid using dehydration esterification or transesterification.

[0026] There are no particular limitations on the method for manufacturing the polymer with a polyisobutylene backbone shown in general formula (1). The preferred method for manufacturing the polymer with a polyisobutylene backbone shown in general formula (1) is the method disclosed in Japanese Patent Application Publication No. 2013-216782, which involves reacting a halogen-terminated polyisobutylene with a compound having a (meth)acryloyl group and a phenoxy group as shown in general formula (2). Halogen-terminated polyisobutylene can be obtained by known methods. For example, halogen-terminated polyisobutylene can be obtained by cationic polymerization, preferably by living cationic polymerization.

[0027] [Chemical Formula 2]

[0028] In general formula (2), R 2 R 3 R 4 and R 5 As defined in equation (1) above. Specifically, R 4 R represents a divalent hydrocarbon group with 2 to 6 carbon atoms. 2 and R3 Each group independently represents a monovalent hydrocarbon group with 1 to 20 hydrogen atoms and carbon atoms. R 5 The symbol represents a hydrogen atom, a methyl group, or an ethyl group. Examples of compounds represented by the general formula (2) above include phenoxymethyl methacrylate, phenoxyethyl methacrylate, phenoxypropyl methacrylate, phenoxybutyl methacrylate, and phenoxypentyl methacrylate. The compounds represented by the general formula (2) above are preferably selected from phenoxyethyl methacrylate, phenoxypropyl methacrylate, phenoxybutyl methacrylate, and phenoxypentyl methacrylate.

[0029] The (B) component of this invention is a compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a main chain composed of organic chains, and having a weight-average molecular weight of 300 or more. The compounds contained in component (A) are not included in component (B). In this specification, the main chain refers to the carbon chain with the most carbon atoms in a 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 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 component (B) is 300 or more. There is no particular upper limit to the weight-average molecular weight of component (B), but it is preferably less than 3000, more preferably less than 2000, and most preferably less than 1500. In this specification, the weight-average molecular weight refers to the weight-average molecular weight (Mw) of polystyrene obtained by GPC (gel permeation chromatography). In this case, tetrahydrofuran is used as the solvent. In the photocurable resin composition of the present invention, when a compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a main chain composed of organic chains, and having a weight-average molecular weight of less than 300 is used, the adhesive strength to acrylic resins decreases, which is therefore not preferred. Although the reason is not yet clear, the adhesive strength to acrylic resins is improved when both component (A) and component (B) are contained. From the viewpoint of improving the adhesive strength to both aluminum and acrylic resins, the functional group equivalent ratio of (meth)acryloyl groups to hydrolyzable silyl groups in one 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 the adhesive strength to various materials and enabling the cured product to have excellent resin strength, when the weight-average molecular weight of component (B) is 300 or more and less than 800, it is preferable that hydrolyzable silyl groups are bonded to both ends of the main chain; when the weight-average molecular weight of component (B) is 800 or more, it is preferable that hydrolyzable silyl groups are bonded to the side chains.

[0030] In this specification, hydrolyzable silane refers to a general term for functional groups formed by adding 1 to 3, preferably 3, alkoxy groups (e.g., methoxy, ethoxy) to a silicon atom. Examples of hydrolyzable silanes include trimethoxysilane and triethoxysilane.

[0031] Commercially available products that are components (B) include X-12-1048, X-12-1050, KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.), but are not limited to these.

[0032] In the photocurable resin composition of the present invention, the content (composition amount) of (B) relative to 100 parts by weight of component (A) is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, and most preferably 0.5 to 10 parts by weight. When the content of (B) is 0.01 to 20 parts by weight relative to 100 parts by weight of component (A), the cured property of the resin, such as strength, will not be reduced, and the adhesion to various materials such as aluminum, acrylic resins, and polycarbonate can be improved.

[0033] The component (C) described in this invention is a photoradioactive polymerization initiator. Component (C) is not limited to any compound that generates free radicals by irradiation with active energy rays. Here, active energy rays include all types of light in a broad sense, such as alpha rays, beta rays, electromagnetic waves such as gamma rays and X-rays, electron beams, ultraviolet light with a wavelength of approximately 100-400 nm, and visible light with a wavelength of approximately 400-800 nm. Ultraviolet light is preferred. Examples of components (C) include acetophenone-based photoradioactive polymerization initiators, benzoin-based photoradioactive polymerization initiators, benzophenone-based photoradioactive polymerization initiators, thioxanthone-based photoradioactive polymerization initiators, acylphosphine oxide-based photoradioactive polymerization initiators, and titanium oxide-based photoradioactive polymerization initiators. From the viewpoint of obtaining high adhesion to various adhered materials, component (C) preferably includes either an acetophenone-based photoradioactive polymerization initiator or an acylphosphine oxide-based photoradioactive polymerization initiator, and more preferably includes an acylphosphine oxide-based photoradioactive polymerization initiator. (C) The preferred composition contains only acylphosphine oxide free radical polymerization initiator.

[0034] Examples of acetophenone-based photoradical polymerization initiators include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-one, benzoyladium dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-propyl)one, 1-hydroxy-cyclohexyl-phenyl-one, 2-methyl-2-morpholino(4-thiomethylphenyl)propane-1-one, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone oligomers. Commercially available products that are 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 Spa).

[0035] Examples of acylphosphine oxide-based photoradical polymerization initiators include, but are not limited to, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide. Commercially available acylphosphine oxide-based photoradical polymerization initiators include Omnirad (registered trademark) TPO, Omnirad (registered trademark) 819 (manufactured by IGM Resins BV), and IRGACURE (registered trademark) 819DW (manufactured by BASF).

[0036] In the photocurable resin composition of the present invention, the amount (content) of component (C) is not particularly limited. The amount of component (C) relative to 100 parts by weight of component (A) is, for example, 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, and particularly preferably 0.5 to 5 parts by weight. By falling within the above range, a photocurable resin composition exhibiting good adhesive strength to adherends formed of various materials can be obtained.

[0037] In one embodiment of the present invention, the photocurable resin composition preferably further comprises a compound having a (meth)acryloyl group, other than component (A), as component (D). By including component (D) in the photocurable resin composition of the present invention, the adhesive strength can be further improved. Component (D) is not particularly limited. Examples of component (D) include, for example, urethane (meth)acrylates with a polybutadiene backbone, hydrogenated polybutadiene urethane (meth)acrylates with a polycarbonate backbone, urethane (meth)acrylates with a polyether backbone, urethane (meth)acrylates with a polyester backbone, urethane (meth)acrylates with a castor oil backbone, isoprene (meth)acrylates, hydrogenated isoprene (meth)acrylates, epoxy (meth)acrylates, oligomers such as acrylic polymers containing (meth)acryloyl groups, and (meth)acrylate monomers. In this specification, "oligomery" refers to a polymer obtained by repeating monomer units approximately 2 to several tens of times, with a weight-average molecular weight of 1000 or higher. From the viewpoint of improving the adhesive strength of various materials, component (D) preferably contains a (meth)acrylate monomer. Examples of (meth)acrylate monomers include monofunctional (meth)acrylate monomers having one (meth)acryloyl group per molecule and polyfunctional (meth)acrylate monomers having two or more (meth)acryloyl groups per molecule. From the viewpoint of improving the adhesive strength of various materials, the (meth)acrylate monomer preferably contains a monofunctional (meth)acrylate monomer, and more preferably contains only a monofunctional (meth)acrylate monomer.

[0038] 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, methoxyoctaethylene glycol mono(meth)acrylate, methoxynonethylene glycol mono(meth)acrylate, methoxydeethylene glycol mono(meth)acrylate, methoxytripropylene glycol mono(meth)acrylate, methoxytetrapropylene glycol mono(meth)acrylate, and methoxypentapropylene glycol mono(meth)acrylate. Acrylic esters, methoxyhexapropylene glycol mono(meth)acrylate, methoxyheptapropylene glycol mono(meth)acrylate, methoxyoctanepropylene glycol mono(meth)acrylate, methoxynonpropylene glycol mono(meth)acrylate, methoxydepropylene glycol mono(meth)acrylate, methoxytributylene glycol mono(meth)acrylate, methoxytetrabutylene glycol mono(meth)acrylate, methoxypentabutylene glycol mono(meth)acrylate, methoxyhexabutylene glycol mono(meth)acrylate, methoxyheptabutylene glycol mono(meth)acrylate, methoxyoctanepropylene glycol mono(meth)acrylate, methoxynonbutanepropylene glycol mono(meth)acrylate, methoxydebutanepropylene glycol mono(meth)acrylate (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, ethoxyoctaneethylene glycol mono(meth)acrylate, ethoxynonethylene glycol mono(meth)acrylate, ethoxydeethylene glycol mono(meth)acrylate, ethoxytripropylene glycol mono(meth)acrylate, ethoxytetrapropylene glycol mono(meth)acrylate, ethoxypentapropylene glycol mono(meth)acrylate, ethoxyhexaethylene glycol mono(meth)acrylate Propylene glycol mono(meth)acrylate, ethoxyheptapropylene glycol mono(meth)acrylate, ethoxyoctanepropylene glycol mono(meth)acrylate, ethoxynonpropylene glycol mono(meth)acrylate, ethoxydepropylene glycol mono(meth)acrylate, ethoxytributylene glycol mono(meth)acrylate, ethoxytetrabutylene glycol mono(meth)acrylate, ethoxypentabutylene glycol mono(meth)acrylate, ethoxyhexabutylene glycol mono(meth)acrylate, ethoxyheptabutylene glycol mono(meth)acrylate, ethoxyoctanebutylene glycol mono(meth)acrylate, ethoxynonbutylene glycol mono(meth)acrylate, ethoxydebutanediol mono(meth)acrylate, etc. Among these, from the viewpoint of improving the adhesive strength to various adhered materials, the weight-average molecular weight of the monofunctional (meth)acrylate monomer is preferably less than 500. The monofunctional (meth)acrylate monomer preferably comprises (meth)acrylate having an alicyclic structure in the molecule, more preferably comprises isobornyl (meth)acrylate, and most preferably comprises isobornyl acrylate.Monofunctional (meth)acrylate monomers can be used alone or in combination of two or more.

[0039] Examples of polyfunctional (meth)acrylate monomers include tetrafunctional (meth)acrylate monomers such as di(trimethylolpropane)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. Preferably, the polyfunctional (meth)acrylate monomer is 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. Polyfunctional (meth)acrylate monomers can be used alone or in combination of two or more.

[0040] In the photocurable resin composition of the present invention, the amount (content) of component (D) relative to 100 parts by weight of component (A) is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and most preferably 10 to 30 parts by weight. If it is within the above range, the adhesive strength can be further improved.

[0041] In one embodiment of the present invention, the photocurable resin composition preferably further comprises 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, dried clay minerals, and dried diatomaceous earth. From the viewpoint of not hindering photocurability and improving resin strength, component (E) is preferably fumed silica (powder), and most preferably fumed silica (powder) surface-treated with dimethyl silicone oil. From the viewpoint of improving resin strength when dispersed in component (A), the BET specific surface area of ​​component (E) is preferably 50 to 200 m². 2 / g, more preferably 70~130m 2 / g, the optimal value is 80~120m 2 / g.

[0042] Commercially available products that are part of component (E) include those manufactured by NIPPON AEROSIL CO., LTD. under the trade name AEROSIL (registered trademark) R974, R972, R972V, R972CF, R805, R812, R812S, R816, R8200, RY200, RX200, RY200S, R202, etc.

[0043] In the photocurable resin composition of the present invention, the amount (content) of component (E) relative to 100 parts by weight of component (A) is preferably 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and most preferably 5 to 20 parts by weight. If it is within the above range, it will not hinder photocurability and can improve resin strength.

[0044] In one embodiment of the present invention, the photocurable resin composition preferably further comprises an antifoaming agent as component (F). By including an antifoaming agent, air bubbles can be removed from the photocurable resin composition after it has been applied to the substrate, thereby improving photocurability, resin strength, etc. There are no particular limitations on the antifoaming agent. Examples of antifoaming agents include silicone-based antifoaming agents, modified silicone-based antifoaming agents, alkynyl alcohol-based antifoaming agents, silica-based antifoaming agents, waxes, polyether-modified polydimethylsiloxane, paraffin oils, and defoaming aliphatic derivatives. Component (F) preferably comprises a silicone-based antifoaming agent.

[0045] In the photocurable resin composition of the present invention, the content of component (F) is preferably 0.01 to 10 parts by weight relative to 100 parts by weight of component (A), more preferably 0.1 to 5 parts by weight, and most preferably 0.5 to 3 parts by weight. By falling within the above range, photocurability can be improved without any concern about reducing adhesive strength.

[0046] <Any ingredient>

[0047] For the photocurable resin composition described in this invention, additives such as organic fillers, organic peroxides, preservation stabilizers, antioxidants, light stabilizers, and surfactants (excluding those contained in component (F)) may be used without prejudice to the purpose of this invention.

[0048] Organic fillers can be any powder of organic materials composed of rubber, elastomers, plastics, polymers (or copolymers), etc. Additionally, organic fillers can be multi-layered organic fillers such as core-shell type. Organic fillers can be used alone or in combination of two or more. The amount (content) of the organic filler (or their total amount when there are two or more) relative to 100 parts by weight of component (A) is preferably 0.1 to 50 parts by weight.

[0049] To impart curability based on heating or redox reactions to the photocurable resin composition described in this invention, organic peroxides may be added. If a redox reaction is used, free radicals can be generated at room temperature. There are no particular limitations on the organic peroxide. Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, and acetylacetone peroxide; peroxy ketals such as 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)octane, n-butyl-4,4-bis(tert-butylperoxy)valerate, and 2,2-bis(tert-butylperoxy)butane; and tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-hydroperoxylane, and 2,5-dimethylhexane-2, Hydroperoxides such as 5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide; di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyn-3, etc.; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide Diacyl peroxides such as methyl methacrylate and m-toluyl peroxide; diisopropyl peroxide, di(2-ethylhexyl) peroxide, di-n-propyl peroxide, bis-(4-tert-butylcyclohexyl) peroxide, dimyristyl peroxide, di(2-ethoxyethyl) peroxide, dimethoxyisopropyl peroxide, di(3-methyl-3-methoxybutyl) peroxide, diallyl peroxide; tert-butyl peracetate, tert-butyl peroxide isobutyrate, tert-butyl perpentanoate, tert-butyl peroxyneodecanate, tert-butyl peroxyneodecanate, and peroxyneodecanate. Peroxide esters include cumyl esters, tert-butyl peroxide-2-ethylhexanoate, tert-butyl peroxide-3,5,5-trimethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, di-tert-butyl peroxide isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, tert-butyl peroxide-maleate, tert-butyl peroxyisopropyl carbonate, cumyl peroxide-octanoate, tert-hexyl peroxide-neodecanate, tert-hexyl peroxypentanoate, tert-butyl peroxide-neohexanoate, cumyl peroxide-neohexanoate, and other peroxide esters; as well as acetylcyclohexylsulfonyl peroxide and tert-butyl peroxide-allyl carbonate. Organic peroxides can be used alone or in combination.

[0050] When an organic peroxide is used in the photocurable resin composition described in this invention, a curing accelerator may be incorporated to promote the redox reaction. The curing accelerator is not particularly limited. Preferably, saccharin (o-benzoylsulfonylimide), hydrazine compounds, amine compounds, thiols, or compounds containing transition metals are used as curing accelerators.

[0051] Examples of hydrazine compounds 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-carbonhydrazine, 1-formanoic acid-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl)hydrazine, 1-acetyl-2-(p-nitrophenyl)hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), ethyl hydrazine formate, p-nitrophenylhydrazine, p-trisulfonylhydrazine, etc.

[0052] Examples of amine compounds include heterocyclic secondary amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, and 1,2,3,4-tetrahydroquinazine; heterocyclic tertiary amines such as quinoline, methylquinoline, quinazine, and quinoxaline phenazine; aromatic tertiary amines such as N,N-dimethyl-p-toluidine, N,N-dimethylaniline, 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-mercaptobenzotriazole.

[0053] Examples of thiols include n-dodecyl thiols, ethyl thiols, butyl thiols, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol hexa(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, pentaerythritol tetramercaptoacetate, etc.

[0054] As compounds containing transition metals, metal chelate complex salts are preferred. Examples of metal chelate complex salts include iron pentylene, cobalt pentylene, copper pentylene, copper propylenediamine, copper ethylenediamine, iron naphthenate, nickel naphthenate, cobalt naphthenate, copper naphthenate, copper octoate, iron hexanoate, iron propionate, and vanadium acetylacetonate.

[0055] Examples of preservation stabilizers include free radical absorbers such as benzoquinone, hydroquinone, and hydroquinone monomethyl ether; metal chelating agents such as ethylenediaminetetraacetic acid or its 2-sodium salt, oxalic acid, acetylacetone, and o-aminophenol.

[0056] 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, 2-butyl-4-hydroxyanisole, 2,6-di-tert-butyl-p-cresol, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentyl 4,4'-Butyl bis(6-tert-butyl-3-methylphenol), 4,4'-Thiobis(6-tert-butyl-3-methylphenol), 3,9-Bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[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)propionate] [-tert-butyl-4-hydroxyphenyl)propionamide], phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-,C7-C9 side-chain alkyl ester, 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(trimethylmethyl-2,4,6-tolyl)tri-p-cresol, diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]calcium phosphonate, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[[3-(5-tert-butyl- [4-Hydroxy-m-tolyl)propionate], hexamethylenebis[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)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, reaction products of N-phenylaniline and 2,4,6-trimethylpentene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, picric acid, citric acid and other phenolic compounds;Tris(2,4-di-tert-butylphenyl) phosphite, tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphazene-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, tetra(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate, 6-[3- Phosphorus compounds such as (3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxophosphoric acid cycloheptane; sulfur compounds such as dilaurate 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearate 3,3'-thiodipropionate, pentaerythritol tetra(3-lauryl thiopropionate), and 2-mercaptobenzimidazole; amine compounds such as phenothiazines; lactone compounds; and vitamin E compounds. Among these, phenolic compounds are preferred as antioxidants.

[0057] Examples of light stabilizers include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) 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-piperidinyl-methacrylate, and bis(1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate). -4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-1(octoxy)-4-piperidinyl) sebacate, reaction product of 1,1-dimethylethyl hydroperoxide with octane, N,N',N”,N”'-tetra-(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine / 1,3,5-triazine / N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)amino)-triazin-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine / 1,3,5-triazine / N,N'-bis(2,2,6,6-tetramethyl) Polymers of methyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidinyl)butylamine, poly[[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidinyl)imino]], polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinylethanol, and 2,2,4,4-tetramethyl-20-(β-lauryloxycarbonyl)ethyl -7-oxa-3,20-diazabispiro[5.1.11.2] icosano-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-diazabispiro[5.1.11.2] icosano-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazabicyclo[5.1.11.]2] Dodecyl / tetradecyl ester of dodecyl / 20-propionate, malonic acid [(4-methoxyphenyl)-methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid esters of 2,2,6,6-tetramethyl-4-piperidinol, hindered amines such as N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,3-phenylenediamide; 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-hydroxy-3-(3,4,5,6-tetrahydrophthalimide] Benzotriazole compounds such as (-methyl)-5-methylphenyl[benzotriazole], 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-pentylphenyl)benzotriazole, the reaction product of methyl 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, and benzoate compounds such as 2-(2H-benzotriazole-2-yl)-6-dodecyl-4-methylphenol; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol, etc. Hindered amine compounds are particularly preferred as light stabilizers.

[0058] The photocurable resin composition of the present invention can be manufactured by conventionally known methods. For example, the photocurable resin composition of the present invention can be manufactured by mixing a specified amount of components (A) to (C) and other components using a mixing apparatus such as a mixer, preferably at a temperature of 10°C to 70°C, for 0.1 hours to 5 hours. Furthermore, since the photocurable resin composition of the present invention has photocurability, it is preferably manufactured in a light-shielded environment.

[0059] <Coating Method>

[0060] As a method for applying the photocurable resin composition of the present invention to the substrate, methods such as dispensing, spraying, inkjeting, screen printing, gravure printing, dipping, and spin coating using an automatic coating machine can be used. It should be noted that, from the viewpoint of coatability, the photocurable resin composition of the present invention is preferably in a liquid state at 25°C.

[0061] <Curing Method>

[0062] The photocurable resin composition of this invention can be cured by irradiation with ultraviolet light, visible light, or other light. The light source for irradiation is not particularly limited. Examples of light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, xenon lamps, LEDs, fluorescent lamps, sunlight, and electron beam irradiation devices. From the viewpoint of minimizing thermal damage to the adhered material, LEDs are preferred as the light source. From the viewpoint of curing properties, the irradiation dose is preferably 3 kJ / m². 2 The above, more preferably 5 kJ / m 2 The above. Considering the production cycle time of the curing process, the optimal light irradiation dose is 70 kJ / m². 2 The following is more preferably 60 kJ / m 2 The following is particularly preferred: 50 kJ / m 2 the following.

[0063] <Cured product>

[0064] The cured product of this invention is obtained by irradiating the photocurable resin composition of this invention with ultraviolet light, visible light, or other light using the curing method described above. In one embodiment, the cured product of this invention is obtained by irradiating the photocurable resin composition with light. The curing method is not limited as long as the cured product is a cured product obtained by curing the photocurable resin composition of this invention.

[0065] <Applications>

[0066] The photocurable resin composition of this invention can be used as a sealant, adhesive, coating agent, casting agent, potting compound, etc. It should be noted that, in such applications, the photocurable resin composition of this invention is preferably in a liquid state at 25°C. The cured product of the photocurable resin composition of this invention is a rubber elastomer with excellent at least one of the following characteristics: low air permeability, low moisture permeability, heat resistance, acid resistance, and flexibility. Therefore, the cured product of this invention can be used in laminates, sensors, substrates, and medical / medical devices / equipment for fuel cells, solar cells, pigment-sensitized solar cells, lithium-ion batteries, electrolytic capacitors, liquid crystal displays, organic EL displays, electronic paper, LEDs, hard disk drives, photodiodes, optical communication / circuits, wires / cables / optical fibers, optical isolators, IC cards, etc. The photocurable resin composition of this invention exhibits excellent adhesive strength to various materials, and is therefore particularly suitable for bonding different materials, such as metals and plastics, and different plastics.

[0067] One embodiment of the present invention is a sealant or adhesive comprising the above-described photocurable resin composition.

[0068] <Object to be adhered>

[0069] The photocurable resin composition of this invention exhibits excellent adhesive strength to various materials, thus allowing the use of various metals, glass, plastics, etc., as adherends. In particular, the photocurable resin composition of this invention demonstrates excellent adhesive strength to aluminum, acrylic resins, and polycarbonate, and is therefore especially preferred for adherends selected from aluminum, acrylic resins, and polycarbonate.

[0070] In one embodiment, the sealant or adhesive of the present invention can be used on adherends comprising at least one material selected from the group consisting of aluminum, acrylic resins and polycarbonate.

[0071] <Sealing Method>

[0072] There are no particular limitations on the sealing method when using the photocurable resin composition described in this invention as a sealant. Representative examples of sealing methods include FIPG (In-situ Molded Gasket), CIPG (In-situ Cured Gasket), MIPG (In-mold Molded Gasket), and liquid injection molding.

[0073] Example

[0074] The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples.

[0075] [Examples 1-4, Comparative Examples 1-5]

[0076] To prepare a photocurable resin composition, the following components are prepared.

[0077] <Manufacturing of Polyisobutylene Containing Acryloyloxyethoxyphenyl (Component A)>

[0078] Nitrogen purging was performed on a 5L separable flask, followed by the addition of 200 mL of n-hexane and 2000 mL of butane chloride. The mixture was cooled to -70°C under a nitrogen atmosphere with stirring. 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 cooling the reaction mixture to -70°C, 5.0 mL (0.05 mol) of titanium tetrachloride was added to initiate polymerization. Three hours after polymerization began, 40 g of phenoxyethyl acrylate (LIGHT ACRYLATEPO-A, manufactured by Kyoeisha Chemical Co., Ltd.) and 110 mL of titanium tetrachloride were added. The mixture was then stirred at -70°C for another 4 hours, after which 1000 mL of methanol was added to stop the reaction.

[0079] The supernatant was separated from the reaction solution, and the solvent was distilled off. The product was then dissolved in 3000 mL of n-hexane, washed three times with 3000 mL of pure water, and reprecipitated using methanol. Then, the solvent was distilled off under reduced pressure, and the obtained polymer was vacuum dried at 80 °C for 24 hours to obtain polyisobutylene (component (A)) with acryloyloxyethoxyphenyl.

[0080] The manufactured component (A) comprises -[CH2C(CH3)2]- units containing two acryloyl groups. More specifically, the manufactured component (A) is a polymer in general formula (1), R 1 It is phenylene, PIB is a polyisobutylene backbone, R 4 It is a divalent hydrocarbon group with 2 carbon atoms (ethylene), R 2 and R 3 For hydrogen atoms, R 5 The atom is hydrogen, and n is 2. It should be noted that the number average molecular weight of component (A) (chromatographic method (size exclusion chromatography), polystyrene conversion) is 11100, and the viscosity of component (A) (25℃) is 1550 Pa·s.

[0081] (B) Components

[0082] (B-1) Composition: A compound with two or more trimethoxysilyl and acryloyl groups bonded to an organic chain, wherein the functional group equivalent of one molecule is trimethoxysilyl:acryloyl = 1:1; Trade name X-12-1048 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight 1172

[0083] (B-2) Composition: 8-Methacryloxyoctyltrimethoxysilane; Trade name KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight 318.5

[0084] (B') component

[0085] (B'-1) Composition: 3-Methacryloxypropyltrimethoxysilane; Trade name: KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight: 234.3

[0086] (B'-2) Composition: 3-Acryloyloxypropyltrimethoxysilane; Trade name KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight 248.4

[0087] (B'-3) Composition: Vinyltrimethoxysilane; Trade name KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight 190.3

[0088] (B'-4) Composition: 3-Epoxypropoxypropyltrimethoxysilane; Trade name: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight: 236.3

[0089] (B'-5) Composition: 3-Mercaptopropyltrimethoxysilane; Trade name: KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.); Weight average molecular weight: 196.4

[0090] (C) Component (photoradical polymerization initiator): 2,4,6-trimethylbenzoyl diphenylphosphine oxide; trade name Omnirad (registered trademark) TPO (manufactured by IGM Resin BV).

[0091] (D) Ingredient: Isoborneol acrylate; Trade name: LIGHT ACRYLATE IB-XA (manufactured by Kyoeisha Chemical Co., Ltd.)

[0092] (E) Composition: Fumed silica surface-treated with dimethyl silicone oil; Trade name: AEROSIL (registered trademark) RY200 (manufactured by NIPPON AEROSIL CO., LTD.); BET specific surface area: 100 m² 2 / g

[0093] (F) Ingredients: Organosilicon defoamer; Trade name BYK-1799 (manufactured by BYK-Chemie GmbH).

[0094] Weigh all components except component (C) in a mixing vessel and stir for 30 minutes. Then, add component (C) under light-shielding conditions and stir for 30 minutes. Detailed preparation quantities are as shown in Table 1. All values ​​in Table 1 are expressed in parts by mass. All experiments were conducted at 25°C.

[0095] The test methods used in the examples and comparative examples in Table 1 are described below.

[0096] [Shear bond strength (ADC / PC)]

[0097] The photocurable resin compositions of the examples and comparative examples were coated onto aluminum die-cast test pieces with a width of 25 mm × length of 100 mm × thickness of 1 mm. Then, transparent polycarbonate test pieces were bonded together using a clamp so that the overlap was 25 mm × 10 mm and the thickness was 1 mm. UV (wavelength: 365 nm, cumulative light intensity: 40 kJ / m²) was applied from the polycarbonate test piece side using a conveyor belt LED UV irradiator. 2The photocurable resin composition was then cured. The prepared test specimens were then tested at 25°C using a universal tensile testing machine (tensile speed 50 mm / min) according to JIS K6850:1999 for tensile shear bond strength (in MPa). The shear bond strength was set as the measured value at maximum strength. The values ​​listed in Table 1 are average values ​​for N=3. The preferred shear bond strength for the aluminum die-casting / polycarbonate bond is 0.40 MPa or higher. Furthermore, the rates of change in Examples 1-4 and Comparative Examples 2-5 were calculated based on Comparative Example 1, which does not contain component (B) and component (B').

[0098] Change rate (%) = (Shear bond strength of each embodiment or comparative example - Shear bond strength of comparative example 1) / Shear bond strength of comparative example 1 × 100.

[0099] [Shear bond strength (PMMA / PC)]

[0100] The photocurable resin compositions of the examples and comparative examples were coated onto acrylic resin test pieces measuring 25 mm wide × 100 mm long × 1 mm thick. Then, transparent polycarbonate test pieces were fitted together using clamps to achieve an overlap of 25 mm × 10 mm and a thickness of 1 mm. UV (wavelength: 365 nm, cumulative light intensity: 40 kJ / m²) was applied from the polycarbonate test piece side using a conveyor belt LED UV irradiator. 2 The photocurable resin composition was then cured. The prepared test specimens were then tested at 25°C using a universal tensile testing machine (tensile speed 50 mm / min) according to JIS K6850:1999 for tensile shear bond strength (in MPa). The tensile shear bond strength was set to the value at maximum strength. The preferred shear bond strength for the acrylic resin / polycarbonate bonded material is 0.60 MPa or higher. Furthermore, the rates of change in Examples 1-4 and Comparative Examples 2-5 were calculated based on Comparative Example 1, which does not contain component (B) and component (B').

[0101] Change rate (%) = (Shear bond strength of each embodiment or comparative example - Shear bond strength of comparative example 1) / Shear bond strength of comparative example 1 × 100.

[0102] [Shear bond strength (PC / PC)]

[0103] The photocurable resin compositions of the examples and comparative examples were coated onto transparent polycarbonate test pieces with a width of 25 mm × length of 100 mm × thickness of 1 mm. Then, additional polycarbonate test pieces were attached using a clamp to achieve an overlap of 25 mm × 10 mm and a thickness of 1 mm. UV irradiation (wavelength: 365 nm, cumulative light intensity: 40 kJ / m²) was performed using a conveyor belt LED UV irradiator.2 The photocurable resin composition was then cured. The prepared test specimens were then tested at 25°C using a universal tensile testing machine (tensile speed 50 mm / min) according to JIS K6850:1999 for tensile shear bond strength (in MPa). The tensile shear bond strength was set to the value at maximum strength. The shear bond strength of the polycarbonate / polycarbonate bonded material is preferably 0.60 MPa or higher. Furthermore, the rate of change in Examples 1-4 and Comparative Examples 2-5 was calculated based on Comparative Example 1, which does not contain component (B) and component (B').

[0104] Change rate (%) = (Shear bond strength of each embodiment or comparative example - Shear bond strength of comparative example 1) / Shear bond strength of comparative example 1 × 100.

[0105]

[0106] As shown in Table 1, regarding the shear bond strength results of the photocurable resin compositions used in Examples 1-4, an increase in shear bond strength was confirmed in aluminum die castings, acrylic resins, and polycarbonate compared to Comparative Example 1, which did not contain component (B) or (B'). On the other hand, Comparative Examples 2-4, which contained component (B'), showed a decrease in shear bond strength for acrylic resins compared to Comparative Example 1. Furthermore, in Comparative Example 5, a decrease in shear bond strength was observed in all three materials compared to Comparative Example 1.

[0107] Furthermore, the resin strength of Examples 1-4 and Comparative Examples 1-3 was measured.

[0108] [Resin Strength (Tensile Strength)]

[0109] The thickness of the photocurable resin compositions in each embodiment and comparative example was set to 1 mm, and they were irradiated with ultraviolet light (wavelength: 365 nm, cumulative light intensity: 40 kJ / m²). 2 The photocurable resin composition is cured to produce a sheet-like cured product. A test piece is prepared by punching using a No. 3 dumbbell. The two ends of the test piece are fixed to the chuck with the long axis of the test piece aligned with the center of the chuck. The test piece is stretched at a tensile speed of 500 mm / min, and the maximum load is measured. The tensile strength (MPa) is calculated from this maximum load. The results are shown in Table 2. Details are based on JIS K 6251 (2010). It should be noted that the resin strength of the cured product described in this invention is more preferably 2.2 MPa or higher (or greater than 2.2 MPa). Furthermore, the rate of change in Examples 1-4 and Comparative Examples 2-3 is calculated based on Comparative Example 1, which does not contain component (B) and component (B').

[0110] Change rate (%) = (resin strength of each embodiment or comparative example - resin strength of comparative example 1) / resin strength of comparative example 1 × 100.

[0111]

[0112] As shown in Table 2, the cured products of the photocurable resin compositions of Examples 1-4 showed 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 was insufficient compared to Examples 1-4. No decrease or increase in resin strength was observed in the cured product of the photocurable resin composition of Comparative Example 3 compared to the cured product of the photocurable resin composition of Comparative Example 1.

[0113] As can be seen from the above, the photocurable resin composition containing components (A) to (C) exhibits high bonding strength to various materials such as aluminum, acrylic resins, and polycarbonate. Furthermore, by using the photocurable resin composition containing components (A) to (C), a strong and tough cured product with excellent resin strength can be obtained.

[0114] Industrial applicability

[0115] The photocurable resin composition of this invention exhibits high adhesive strength to various materials, and its cured product possesses high resin strength, thus making it suitable for a wide range of bonding and sealing applications. In particular, the photocurable resin composition of this invention is effective as an adhesive and sealant for dissimilar materials, and is therefore industrially useful.

[0116] This application is based on Japanese Patent Application No. 2023-145146, filed on September 7, 2023, the disclosure of which is referenced and incorporated herein by reference in its entirety.

Claims

1. A photocurable resin composition comprising the following components (A) to (C): (A) Composition: Polyisobutylene resin containing one or more (meth)acryloyl groups and -[CH2C(CH3)2]- units; (B) Components: A compound having one or more (meth)acryloyl groups and one or more hydrolyzable silyl groups, having a backbone composed of organic chains, and having a weight-average molecular weight of 300 or more, wherein, Excluding ingredient (A); and (C) Component: Photoradical polymerization initiator.

2. The photocurable resin composition according to claim 1, wherein, The product contains 0.01 to 20 parts by mass of component (B) relative to 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 (meth)acrylic monomers 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, wherein, The product contains 1 to 50 parts by mass of component (E) relative to 100 parts by mass of component (A).

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

8. The sealant or adhesive according to claim 7, used for adherends comprising at least one material selected from the group consisting of aluminum, acrylic resins and polycarbonate.

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

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