TW202244222A - Curable adhesive composition, cured product, and method for manufacturing cured product - Google Patents

Abstract

Provided are: a curable adhesive composition including a first curing system, in which a cross-linking agent reacts with a binder resin having a reactive functional group and the reaction proceeds at a temperature of 120 DEG C or less, and a second curing system, in which one or more compounds having a carbon-carbon double bond react and the reaction proceeds at a temperature of more than 120 DEG C; a cured product thereof; and a method for manufacturing the cured product.

Description

Curable adhesive composition, cured product, and method for producing cured product

The present invention relates to a curable adhesive composition which is less likely to pollute the surroundings in the following step, a cured product of the curable adhesive composition, and a method for producing the cured product.

In recent years, curable adhesives have sometimes been used as materials for forming insulating resin layers, sealant layers, and adhesive members of electronic components and the like.

For example, Patent Document 1 describes a thermosetting adhesive sheet comprising epoxy resin, and the storage elastic modulus (x1) of the hardened product of the aforementioned thermosetting adhesive sheet at 25°C is 1 GPa or more, and, in The storage elastic modulus (x2) at 100°C is above 1GPa. Moreover, it is also described in this document that the thermosetting adhesive sheet described in this document can effectively suppress the slight deformation or deviation of the adhered body at high temperature, even if it is used for fixing as the adhered body. In the case of the adherend that is repeatedly slightly deformed, it is not easy to cause peeling over time. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-110128.

[Problem to be Solved by the Invention]

When using an adhesive composition, the coating film of an adhesive composition is heat-processed normally. In this case, depending on the processing conditions, there is a possibility that the adhesive components may seep out and cause contamination of the surrounding area.

The present invention is made in view of the above circumstances, and an object of the present invention is to provide a curable adhesive composition, a hardened product of the curable adhesive composition, and a method for producing the hardened product that are less likely to contaminate the surroundings in the following step. [Means to solve the problem]

The inventors of the present invention have intensively studied curable adhesive compositions in order to solve the above-mentioned problems. As a result, it was found that by formulating the hardening components in such a way that there is a first hardening system that reacts at a temperature below 120°C, and a second hardening system that reacts at a temperature exceeding 120°C, it is possible to obtain Pollution of the surrounding curable adhesive composition, so that the present invention has been accomplished.

Thus, according to the present invention, the curable adhesive composition of the following [1] to [10], the cured product of [11] to [14] and [16], and the cured product of [15] and [17] are provided. The manufacturing method.

[1] A curable adhesive composition comprising: a first curing system, which is a curing system in which an adhesive resin having a reactive functional group reacts with a crosslinking agent, and the reaction is performed at a temperature below 120°C; and The second hardening system is a hardening system that reacts with one or two or more compounds having carbon-carbon double bonds, and reacts at a temperature exceeding 120°C. [2] The curable adhesive composition as described in [1], wherein the adhesive resin having a reactive functional group is a polyolefin resin. [3] The curable adhesive composition as described in [1] or [2], wherein the adhesive resin having a reactive functional group is an acid-modified resin. [4] The curable adhesive composition according to any one of [1] to [3], wherein the crosslinking agent is a compound having an isocyanurate skeleton. [5] The curable adhesive composition according to any one of [1] to [4], wherein the crosslinking agent is a compound having two or more isocyanate groups. [6] The curable adhesive composition as described in any one of [1] to [5], wherein the compound having a carbon-carbon double bond is a hydrocarbon group having two or more terminal double bonds and A non-aromatic compound that is liquid at 25°C. [7] The curable adhesive composition according to any one of [1] to [6], wherein the compound having a carbon-carbon double bond is a modified polyphenylene ether having a hydrocarbon group having a double bond at the terminal resin. [8] The curable adhesive composition according to any one of [1] to [7], which further contains a cationic polymerization initiator, and the reaction of the second curing system is initiated by the cationic polymerization initiator. [9] The curable adhesive composition as described in any one of [1] to [8], wherein the curable adhesive composition is cured to form a dielectric tangent value at 23°C and a frequency of 1 GHz. Hardened product up to 0.0050. [10] The curable adhesive composition as described in any one of [1] to [9], wherein the curable adhesive composition is cured to form a relative permittivity at 23°C and a frequency of 1 GHz It is a hardened product below 3.00. [11] A cured product obtained by curing the curable adhesive composition according to any one of [1] to [10], and satisfying the following requirements 1 and 2. - Requirement 1: The gel fraction is 10% by mass or more. ·Requirement 2: It has further thermosetting properties. [12] The cured product as described in [11], wherein the cured product has a sheet shape. [13] The cured product as described in [11] or [12], wherein the cured product is a sheet-like adhesive used for electronic components. [14] The cured product according to [11] or [12], wherein the cured product is a sheet-like adhesive used for a coverlay film. [15] A method for producing the hardened product described in any one of [11] to [14], comprising the following step I. - Step I: A step of curing the curable adhesive composition described in any one of [1] to [10] at a temperature of 120° C. or lower. [16] A cured product obtained by curing the curable adhesive composition according to any one of [1] to [10], and satisfying the following requirement 3. - Requirement 3: The gel fraction is 50% by mass or more. [17] A method for producing the cured product described in [16], comprising the following steps IIa and IIb. · Step IIa: a step of curing the curable adhesive composition described in any one of [1] to [10] at a temperature of 120° C. or lower to form a cured product. • Step IIb: a step of further hardening the cured product formed in Step IIa at a temperature exceeding 120°C. [Efficacy of the invention]

According to the present invention, there are provided a curable adhesive composition which is less likely to contaminate the surroundings in an adhering step, a cured product of the curable adhesive composition, and a method for producing the cured product.

Regarding the numerical range described in this specification, the upper limit and the lower limit can be combined arbitrarily. For example, when "preferably 30 to 100, more preferably 40 to 80" is described as a numerical range, the range of "30 to 80" or the range of "40 to 100" is also included in the description in this specification. the value range. Furthermore, for example, when the numerical range is described as "preferably 30 or more, more preferably 40 or more, and preferably 100 or less, more preferably 80 or less", the range of "30 to 80" or "40 The range from 100 to 100" is also included in the range of numerical values recorded in this specification. Moreover, as a numerical range described in this specification, for example, description of "60 to 100" means the range of "60 or more and 100 or less". Furthermore, in the regulation of the upper limit value and the lower limit value described in this specification, the numerical range from the lower limit value to the upper limit value can be specified by appropriately selecting and arbitrarily combining the respective options. In addition, various requirements described as preferred aspects described in this specification may be combined in plural.

In this specification, the number average molecular weight (Mn) is obtained by gel permeation chromatography (GPC; Gel Permeation Chromatography) using tetrahydrofuran (THF) as a solvent, and in terms of standard polystyrene. For example, it can be found in the following conditions are measured. [Example of measurement conditions] ・Gel permeation chromatography device: manufactured by Tosoh Co., Ltd., product name "HLC-8020" ·Tube column: Connect "TSK guard column HXL-L", "TSK gel G2500HXL", "TSK gel G2000HXL" and "TSK gel G1000HXL" in sequence (all manufactured by Tosoh Co., Ltd.) ·Column temperature: 40℃ Developing solvent: tetrahydrofuran ·Flow rate: 1.0mL/min

Hereinafter, the present invention will be described in detail by dividing the present invention into (1) curable adhesive composition, and (2) cured product and method for producing the cured product.

(1) Hardening adhesive composition The curable adhesive composition of the present invention comprises: a first curing system, which is a curing system in which an adhesive resin having a reactive functional group reacts with a crosslinking agent, and the reaction is carried out at a temperature below 120°C; and a second curing system The hardening system is a hardening system that reacts with one or two or more compounds having carbon-carbon double bonds, and reacts at a temperature exceeding 120°C. Furthermore, the components contained in the curable adhesive composition of the present invention may be classified into one of the first curing system and the second curing system, or may be classified into both the first curing system and the second curing system. The composition of those. Furthermore, the curable adhesive composition of the present invention may contain components that are not classified into either the first curing system or the second curing system within a range that does not impair the effects of the present invention.

[First hardening system] The first curing system contained in the curable adhesive composition of the present invention is a curing system in which the adhesive resin with reactive functional groups reacts with the crosslinking agent, and the reaction is carried out at a temperature below 120°C.

The first hardening system reacts at a temperature below 120°C. Since the first curing system reacts at a temperature below 120°C, when using the curable adhesive composition of the present invention, the reaction of the first curing system can be carried out under relatively mild conditions. Therefore, it is possible to efficiently form a crosslinked structure in the coating film of the curable adhesive composition without proceeding with the reaction of the second curing system.

The first hardening system is preferably a binder resin with reactive functional groups (hereinafter sometimes referred to as "binder resin (A)"), and a crosslinking agent (B) that can react with the binder resin (A) ( Hereinafter, it may be described as a "crosslinking agent (B)") in a hardening system that reacts. Therefore, the first hardening system preferably includes the binder resin (A) and the crosslinking agent (B). The first curing system may contain curable components other than the binder resin (A) and the crosslinking agent (B). Other curable components other than the binder resin (A) and the crosslinking agent (B) contained in the first curing system can be appropriately selected according to the reaction characteristics of the first curing system. Furthermore, other curable components may also be classified into the second curable system.

The reaction temperature of the first curing system can consider the reactivity of the reactive functional group in the binder resin (A) and the crosslinking agent (B), by properly combining the binder resin (A) and the crosslinking agent (B) Use and adjust.

In the curable adhesive composition of one aspect of the present invention, as the first curing system, (A) component and (B ) components can be set to 40% by mass or more, 50% by mass or more, 60% by mass or more, 65% by mass or more, or 70% by mass or more, and can also be 94% by mass or less, 90% by mass or less, or 85% by mass % or less, 80 mass % or less, or 77 mass % or less.

In this specification, the so-called "active ingredient" refers to an ingredient in a composition, and refers to an ingredient other than a solvent.

[Component (A): Binder resin with reactive functional groups] The first hardening system comprises a binder resin (A) having reactive functional groups as a hardening component. Since the first hardening system contains the binder resin (A), it is possible to suppress the surrounding contamination in the following step as described later. Binder resin (A) can be used individually by 1 type or in combination of 2 or more types.

The number average molecular weight (Mn) of the adhesive resin (A) is not particularly limited, but it is usually 10,000 or more, preferably 10,000 to 150,000, and more preferably 10,000 to 100,000. The number average molecular weight (Mn) of the binder resin (A) can be obtained by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and calculated in terms of standard polystyrene. As the specific measurement conditions, the above described in the text.

Relative to the total amount of active ingredients (100% by mass) of the curable adhesive composition, the content of the adhesive resin (A) (the total amount of these ingredients when two or more adhesive resins (A) are included) is relatively small. Preferably at least 50% by mass, more preferably at least 60% by mass, more preferably at least 65% by mass, more preferably at most 95% by mass, more preferably at most 90% by mass, further preferably at most 85% by mass, and even more preferably at most 95% by mass. Preferably, it is 80% by mass or less. When the content of the adhesive resin (A) is 50% by mass or more, it is easy to obtain a curable adhesive composition that does not easily contaminate the surroundings. If the content of the binder resin (A) is 95% by mass or less, it is easy to obtain and form low dielectric properties (in this specification, the so-called "low dielectric properties" means "low dielectric coefficient and low dielectric tangent ”) Excellent cured adhesive composition.

Examples of the binder resin (A) include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamideimide-based resins, polyvinyl butyral-based resins, and polycarbonate resins. Department of resin, etc. Among these, polyolefin-based resins are preferable as the binder resin (A). When the adhesive resin (A) is a polyolefin-based resin, it is easy to obtain a curable adhesive composition capable of forming a cured product excellent in low dielectric properties.

In addition, in the case where the (A) component is a curable adhesive composition of a polyolefin resin, the curable adhesive composition may contain other adhesive resins other than the polyolefin resin as other components. In the aforementioned curable adhesive composition, the content of other adhesive resins is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, relative to 100 parts by mass of the total amount of polyolefin resin , and more preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass.

The polyolefin-based resin refers to a polymer containing repeating units derived from olefin-based monomers. Polyolefin-based resins may be polymers composed only of repeating units derived from olefin-based monomers, or may be composed of repeating units derived from olefin-based monomers and monomers that can be copolymerized with olefin-based monomers A polymer composed of repeating units.

The olefin-based monomer is preferably an α-olefin having 2 to 8 carbon atoms, preferably ethylene, propylene, 1-butene, isobutene or 1-hexene, further preferably ethylene or propylene. These olefinic monomers may be used alone or in combination of two or more. Vinyl acetate, (meth)acrylate, styrene, etc. are mentioned as a monomer copolymerizable with an olefin type monomer. Here, "(meth)acrylic acid" means acrylic acid or methacrylic acid (the same applies hereinafter). These "monomers copolymerizable with olefin-based monomers" can be used alone or in combination of two or more.

Examples of polyolefin-based resins include ultra-low-density polyethylene (VLDPE), low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene, Polypropylene (PP), ethylene-propylene copolymer, olefin-based elastomer (TPO), ethylene-vinyl acetate copolymer (EVA), ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate copolymer things etc.

Examples of reactive functional groups contained in the binder resin (A) include carboxyl groups, carboxylic acid anhydride groups, carboxylate groups, hydroxyl groups, epoxy groups, amido groups, ammonium groups, nitrile groups, amino groups, and imide groups. Amino group, isocyanate group, acetyl group, thiol group, ether group, thioether group, sulfonyl group, phosphonyl group, nitro group, carbamate group, halogen atom, alkoxysilyl group, etc.

The binder resin (A) is preferably a modified resin. The modified resin is a resin with reactive functional groups introduced by using a modifier to modify the resin as a precursor. The modifier used in the modification treatment of the binder resin is a compound having a reactive functional group in the molecule. As a reactive functional group, what was demonstrated above is mentioned.

Examples of the modified resin include resins into which acid groups have been introduced (acid-modified resins), or resins into which hydroxyl groups have been introduced, and acid-modified resins are preferred. Among the acid-modified resins, those introduced with an acid anhydride structure are preferable. By using an acid-modified resin as the binder resin (A), it is easy to obtain a curable adhesive composition capable of forming a cured product excellent in low dielectric properties. Furthermore, by using a resin into which an acid anhydride structure is introduced as an acid-modified resin, it tends to be easy to maintain a long service life.

In the case where the component (A) is a curable adhesive composition of an acid-modified resin, the curable adhesive composition may contain other adhesive resins other than the acid-modified resin as other components. In the aforementioned curable adhesive composition, the content of other adhesive resins is preferably 0 to 50 parts by mass, more preferably 0 to 30 parts by mass, relative to 100 parts by mass of the total amount of the acid-modified resin , and more preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass.

Examples of acid-modified resins include: reacting unsaturated carboxylic acid or unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as "unsaturated carboxylic acid, etc.") with the resin to introduce (graft modification) carboxyl group or carboxylic anhydride base resin.

Examples of unsaturated carboxylic acids that react with resins include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, tetrahydrophthalic acid, and aconitic acid; Unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, etc. These unsaturated carboxylic acids may be used alone or in combination of two or more. Among these, maleic anhydride is preferable also in terms of easily obtaining a curable adhesive composition capable of forming a cured product with higher adhesive strength.

With respect to 100 parts by mass of the resin, the amount of the unsaturated carboxylic acid etc. which reacts with the resin is preferably 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, further preferably 0.2 to 1 part by mass . By curing the curable adhesive composition containing the acid-modified resin thus obtained, it is easy to obtain a cured product with higher adhesive strength.

The method of introducing the unsaturated carboxylic acid unit or the unsaturated carboxylic anhydride unit into the resin is not particularly limited. For example, the method of graft-copolymerizing unsaturated carboxylic acid and the like with the resin by the following method: in the presence of free radical generators such as organic peroxides and azonitriles, resin and unsaturated carboxylic acid A method of heating and melting the acid, etc. above the melting point of the resin and reacting; or a method of dissolving the resin and unsaturated carboxylic acid, etc. in an organic solvent, and then heating and stirring in the presence of a radical generator to react.

The binder resin (A) is preferably a modified polyolefin resin, more preferably an acid modified polyolefin resin. When the adhesive resin (A) is an acid-modified polyolefin resin, it is easy to obtain a curable adhesive composition capable of forming a cured product excellent in low dielectric properties and low contamination.

The modified polyolefin-based resin is a polyolefin-based resin with reactive functional groups introduced therein, which is obtained by modifying the polyolefin-based resin as a precursor with a modifying agent.

In the case where the component (A) is a curable adhesive composition of an acid-modified polyolefin resin, the curable adhesive composition may also contain other adhesive resins other than the acid-modified polyolefin resin. other ingredients. In the aforementioned curable adhesive composition, the content of other adhesive resins is preferably from 0 to 50 parts by mass, more preferably from 0 to 50 parts by mass, relative to 100 parts by mass of the total amount of the acid-modified polyolefin resin. 30 parts by mass, more preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass.

[(B) component: crosslinking agent] The first hardening system contains, as a hardening component, a crosslinking agent (B) capable of reacting with the binder resin (A). Since the first hardening system contains the crosslinking agent (B), it is possible to suppress contamination of the surroundings in the next step as will be described later. In addition, the crosslinking agent (B) can be used individually by 1 type or in combination of 2 or more types.

The molecular weight of the crosslinking agent (B) is preferably 1000 or less, more preferably 800 or less, still more preferably 700 or less, still more preferably 600 or less, especially preferably 500 or less. When the molecular weight of the crosslinking agent (B) is 1000 or less, the probability of collision with the binder resin (A) is increased, and a crosslinked structure is easily formed, making it possible to become a hardening adhesive with a high effect of suppressing surrounding contamination in the adhesion step. agent composition. The lower limit of the molecular weight of the crosslinking agent (B) is not particularly present, and is usually 100 or more, preferably 200 or more. Furthermore, the molecular weight of the crosslinking agent (B) is a formula weight determined by the structural formula of the compound used as the crosslinking agent (B).

The content of the crosslinking agent (B) relative to the total amount of active ingredients (100% by mass) of the curable adhesive composition (when two or more crosslinking agents (B) are included, these crosslinking agents (B) The total amount) is preferably at least 0.1% by mass, more preferably at least 0.2% by mass, more preferably at least 0.3% by mass, still more preferably at least 0.5% by mass, still more preferably at least 0.7% by mass, especially preferably at least 0.9% by mass % or more, and preferably at most 5% by mass, more preferably at most 4% by mass, further preferably at most 3% by mass, even more preferably at most 2% by mass. When the content of the crosslinking agent (B) is 0.1% by mass or more relative to the total amount of active ingredients of the curable adhesive composition, it is easy to obtain a curable adhesive composition that does not easily contaminate the surroundings. Furthermore, when the content of the crosslinking agent (B) is 5% by mass or less with respect to the total amount of active ingredients of the curable adhesive composition, it is easy to obtain a curable adhesive composition capable of forming a cured product excellent in low dielectric properties. things.

The content of the crosslinking agent (B) (the total amount of these crosslinking agents (B) when two or more kinds of crosslinking agents (B) are included) is preferably 0.1 parts by mass relative to 100 parts by mass of the component (A) More than 0.3 parts by mass, more preferably 0.5 parts by mass, more preferably 0.8 parts by mass, more preferably 1.2 parts by mass, more preferably 10 parts by mass or less, more preferably 7 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

The crosslinking agent (B) is a compound that can react with the binder resin (A). Therefore, as the crosslinking agent (B), it is necessary to appropriately select a compound having a reactive group or a reactive site that is reactive to the reactive functional group in the binder resin (A). For example, as a crosslinking agent (B), an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a metal chelate type crosslinking agent, an aziridine type crosslinking agent etc. can be used. Among these, from the viewpoint of storage stability, one or more types selected from isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents are preferred. Moreover, in one aspect of the present invention, for example, when the binder resin (A) is an acid-modified resin, and the reactive functional group in the binder resin (A) is a carboxyl group or a carboxylic acid anhydride group, as a crosslinking The agent (B) is preferably at least one selected from isocyanate-based crosslinking agents, epoxy-based crosslinking agents, and metal chelate-based crosslinking agents.

The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups in the molecule. Examples of isocyanate-based crosslinking agents include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, 1,5-pentamethylene diisocyanate, 1 , 6-hexamethylene diisocyanate, diphenylmethane-4,4-diisocyanate, isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetramethylbenzene Dimethyl diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, adducts of these polyisocyanate compounds and polyol compounds such as trimethylolpropane, and biuret products of these polyisocyanate compounds Or isocyanurate etc.

The epoxy-based crosslinking agent is a compound having two or more epoxy groups in the molecule. Examples of epoxy-based crosslinking agents include: 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-meta Xylylenediamine, ethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, diglycidyl aniline, diglycidylamine, etc.

The metal chelate type crosslinking agent is a chelate compound having a metal ion functioning as a crosslinking point. As a metal chelate type crosslinking agent, the metal chelate compound whose metal ion is aluminum ion, zirconium ion, titanium ion, zinc ion, iron ion, tin ion, etc. can be used, for example. Among these, aluminum chelate compounds are preferred.

Examples of aluminum chelate compounds include: tris(acetylacetonate)aluminum, acetylacetonate bis(ethyl acetate)aluminum, diisopropoxymonoacetylacetate oleyl aluminum, monoisopropoxybis Acetyl oleyl acetate, aluminum, etc.

In one aspect of the present invention, the crosslinking agent (B) is preferably a compound having an isocyanurate skeleton, more preferably a compound having an isocyanurate skeleton and two or more isocyanate groups . When the crosslinking agent (B) is a compound having an isocyanurate skeleton, it is easy to obtain a curable adhesive composition capable of forming a cured product excellent in low dielectric properties. Furthermore, in the case of a curable adhesive composition in which the component (B) is a compound having an isocyanurate skeleton, the curable adhesive composition may contain a compound having an isocyanurate skeleton. other cross-linking agents as other components. In the aforementioned curable adhesive composition, the content of other crosslinking agents is preferably 0 to 100 parts by mass, more preferably 0 parts by mass, relative to 100 parts by mass of the total amount of the compound having an isocyanurate skeleton. Parts to 50 parts by mass, more preferably 0 parts by mass to 30 parts by mass, more preferably 0 parts by mass to 10 parts by mass, especially preferably 0 parts by mass to 5 parts by mass.

In one aspect of the present invention, in terms of easily obtaining a curable adhesive composition capable of forming a cured product having excellent low dielectric properties, as the crosslinking agent (B), it is preferable to have two or more The isocyanate-based crosslinking agent of the isocyanate-based compound is more preferably an isocyanurate product of a polyisocyanate compound, and more preferably an isocyanurate product of 1,5-pentamethylene diisocyanate [1,3 , 5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione] or 1,6-hexamethylene diisocyanate [1 ,3,5-tris(6-isocyanatohexyl)-1,3,5-triazine-2,4,6-trione]. Furthermore, in the case of a curable adhesive composition in which the component (B) is an isocyanate-based cross-linking agent, the curable adhesive composition may contain other cross-linking agents other than the isocyanate-based cross-linking agent as other ingredients. In the curable adhesive composition, the content of other crosslinking agents is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, relative to 100 parts by mass of the total amount of the isocyanate-based crosslinking agent parts, more preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, especially preferably 0 to 5 parts by mass.

In one aspect of the present invention, the cross-linking agent (B) is preferably an epoxy-based cross-linking agent from the viewpoint of easily obtaining a curable adhesive composition capable of suppressing surrounding contamination in the following step. In the case of a curable adhesive composition in which the component (B) is an epoxy-based cross-linking agent, the curable adhesive composition may contain other cross-linking agents other than the epoxy-based cross-linking agent as other components . In the aforementioned curable adhesive composition, the content of other crosslinking agents is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, relative to 100 parts by mass of the total amount of the epoxy-based crosslinking agent. parts by mass, more preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, especially preferably 0 to 5 parts by mass.

The crosslinking agent (B) is a compound that can react with the binder resin (A), so it is possible to combine the binder resin (A) and the crosslinking agent in the coating film obtained by coating the curable adhesive composition of the present invention. (B) Reaction to build a cross-linked structure in the coating film. A coating film with a cross-linked structure inside is difficult to flow even when heated. Therefore, by constructing a crosslinked structure in the coating film before bonding the two adherends, even if heat treatment is performed when the two adherends are bonded, it is possible to keep suppressing the separation of the adhesive components in the coating film. The oozing state makes the coating film completely harden. In this way, in the curable adhesive composition of the present invention, the reaction of the adhesive resin (A) and the crosslinking agent (B) (reaction of the first curing system) can be performed before the adhesion step, and the adhesion step can be suppressed. pollution in and around.

[Second hardening system] The second curing system contained in the curable adhesive composition of the present invention is a curing system that reacts with one or two or more compounds having carbon-carbon double bonds, and reacts at a temperature exceeding 120°C. Since the second curing system reacts at a temperature exceeding 120° C., the curable adhesive composition of the present invention has sufficient adhesive ability even after the reaction of the first curing system is completed.

The second hardening system contains a compound having a carbon-carbon double bond as a hardening component. With regard to the reaction involving the participation of compounds with carbon-carbon double bonds, it is relatively easy to control the reaction start time point, so the reaction of the second hardening system can not be carried out during the reaction of the first hardening system. Reliably carry out the reaction of the second hardening system after the reaction of the system is completed. Furthermore, the cured product of the curable adhesive composition containing a compound having a carbon-carbon double bond tends to have excellent low dielectric properties.

The second hardening system may contain one type of compound having a carbon-carbon double bond, or two or more types.

As a compound having a carbon-carbon double bond of the second hardening system, a compound having two or more hydrocarbon groups having a double bond at the end and being liquid at 25°C (hereinafter sometimes described as "carbon-carbon double bond-containing compound) bonded liquid compound (C)"), or a polymer having a hydrocarbon group having a double bond at the terminal (hereinafter sometimes referred to as "carbon-carbon double bond-containing polymer (D)").

In the curable adhesive composition according to one aspect of the present invention, as the second curing system, the (C) component and (D ) components can be set to 6% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, or 23% by mass or more, and can also be 60% by mass or less, 50% by mass or less, or 40% by mass % or less, 35 mass % or less, or 30 mass % or less.

[(C) component: liquid compound containing carbon-carbon double bond] The carbon-carbon double bond-containing liquid compound (C) has two or more hydrocarbon groups having a double bond at the end. Since the carbon-carbon double bond-containing liquid compound (C) has two or more hydrocarbon groups having a double bond at the end, it is easy to obtain a curable adhesive composition that can form a cured product with superior adhesive strength or heat resistance . The carbon-carbon double bond-containing liquid compound (C) may be used alone or in combination of two or more.

In addition, there is a tendency to suppress the occurrence of cracks in the cured product by appropriately loosening the cross-linked structure formed in the cured product. Therefore, the number of hydrocarbon groups having a double bond at the end of the liquid compound (C) containing a carbon-carbon double bond is preferably 2 to 4, more preferably 2.

The carbon number of the hydrocarbon group having a double bond at the terminal contained in the carbon-carbon double bond-containing liquid compound (C) is preferably 2-10, more preferably 2-5. Examples of the hydrocarbon group having a double bond at the terminal include: vinyl, allyl, 3-butenyl, 4-pentenyl, 5-hexenyl, isopropenyl, 1-methyl-2-propenyl , Vinylbenzyl, vinylnaphthyl, etc. Among these, an allyl group is preferable.

The carbon-carbon double bond-containing liquid compound (C) is a compound that is liquid at 25°C. Since the liquid compound (C) containing a carbon-carbon double bond is a compound that is liquid at 25°C, the curable adhesive composition of the present invention can be used during lamination even after the reaction of the first hardening system. It has good wettability and spreadability, and the layer suitability is more excellent. The term "liquid at 25°C" means fluidity at 25°C. For example, a compound that is liquid at 25°C is a compound having a viscosity of 2 mPa·s to 10000 mPa·s measured at 25°C and 1.0 rpm using an E-type viscometer.

The liquid compound (C) containing a carbon-carbon double bond is preferably a non-aromatic compound. The term "non-aromatic compound" means a compound that does not have an aromatic ring. Since the carbon-carbon double bond-containing liquid compound (C) is a non-aromatic compound, the cured product of the curable adhesive composition containing the carbon-carbon double bond-containing liquid compound (C) has low dielectric Tendency to have better properties.

The liquid compound (C) containing a carbon-carbon double bond is preferably a compound having a heterocyclic skeleton. Since the liquid compound (C) containing a carbon-carbon double bond is a compound having a heterocyclic skeleton, it is easy to obtain a curable adhesive composition capable of forming a cured product with superior adhesive strength and low dielectric properties. In the case of a curable adhesive composition in which component (C) is a compound having a heterocyclic skeleton, the curable adhesive composition may also contain other carbon-carbon double-containing compounds other than the compound having a heterocyclic skeleton. Key liquid compounds as other components. In the above curable adhesive composition, the content of other liquid compounds containing carbon-carbon double bonds is preferably 0 to 50 parts by mass relative to 100 parts by mass of the total amount of the compound having a heterocyclic skeleton, More preferably, it is 0-30 mass parts, More preferably, it is 0-10 mass parts, More preferably, it is 0-5 mass parts. As a heterocyclic skeleton, an isocyanurate skeleton or a glycol urea skeleton is mentioned. The heterocyclic skeleton preferably has an n-th rotation axis as a symmetry element. The cured product of the curable adhesive composition containing the carbon-carbon double bond-containing liquid compound (C) having such a heterocyclic skeleton tends to have better low dielectric properties.

The molecular weight of the carbon-carbon double bond-containing liquid compound (C) is preferably at most 1,000, more preferably at most 800, further preferably at most 650, even more preferably at most 500. Compounds with a molecular weight of 1,000 or less tend to satisfy the requirement of being liquid at 25°C. Furthermore, the molecular weight of the liquid compound (C) containing a carbon-carbon double bond is preferably at least 100, more preferably at least 200, and still more preferably at least 275. If it is a compound with a molecular weight of 100 or more, the liquid compound (C) containing a carbon-carbon double bond is also less likely to volatilize in the drying step or thermal curing step of the curable adhesive composition, and it is easy to obtain a hardened product with the desired physical properties .

As a liquid compound (C) containing a carbon-carbon double bond, the compound which has an isocyanurate skeleton, or the compound which has a glycoluril skeleton is mentioned. Examples of the carbon-carbon double bond-containing liquid compound (C) having an isocyanurate skeleton include compounds represented by the following formula (1) or formula (2).

In formula (1), R ¹ and R ² independently represent a hydrocarbon group having a double bond at the terminal, and R ³ represents a saturated hydrocarbon group with 1 to 15 carbons, or an alkyl group substituted with an alkoxy group with 1 to 15 carbons. In formula (2), R ⁴ to R ⁶ each independently represent a hydrocarbon group having a double bond at the end.

The hydrocarbon group having a double bond at the terminal represented by R ¹ , R ² , R ⁴ , R ⁵ , and R ⁶ is as described above.

The saturated hydrocarbon group represented by R ³ has a carbon number of 1 to 15, preferably 5 to 15, more preferably 8 to 15. Examples of the saturated hydrocarbon group represented by ^R include: methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, second-butyl, isobutyl, n-pentyl, n-hexyl , n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, etc.

The carbon number of the alkoxy-substituted alkyl represented by R ³ is 2-15, preferably 2-12, more preferably 3-10. Examples of the alkoxy-substituted alkyl group represented by ^R3 include methoxymethyl, ethoxymethyl, 2-methoxyethoxymethyl, benzyloxymethyl, and the like.

Examples of the carbon-carbon double bond-containing liquid compound (C) having a glycoluril skeleton include compounds represented by the following formula (3).

In formula (3), R ⁷ to R ¹⁰ each independently represent a hydrocarbon group having 1 to 15 carbon atoms, and at least two of these are hydrocarbon groups having a double bond at the terminal. R ¹¹ and R ¹² represent a hydrogen atom or a saturated hydrocarbon group with 1 to 15 carbons.

Among these, the liquid compound (C) containing a carbon-carbon double bond is preferably one having an isocyanurate The compound of the skeleton is more preferably a compound represented by formula (1), and more preferably a compound represented by the following formula.

In the formula, R represents a saturated hydrocarbon group having 5 to 15 carbons, preferably a saturated hydrocarbon group having 8 to 15 carbons.

When the curable adhesive composition of the present invention contains a carbon-carbon double bond-containing liquid compound (C), relative to the total amount of active ingredients (100% by mass) of the curable adhesive composition, carbon - The content of the liquid compound (C) with a carbon double bond (the total amount of these (C) components when two or more (C) components are included) is preferably at least 5% by mass, more preferably at least 7% by mass , more preferably at least 8.5% by mass, and more preferably at most 25% by mass, more preferably at most 20% by mass, further preferably at most 15% by mass. When the content of the liquid compound (C) containing a carbon-carbon double bond is 5% by mass or more in the total amount of active ingredients of the curable adhesive composition, it is easy to obtain a cured product that can form a cured product with excellent adhesive strength Adhesive composition. When the content of the liquid compound (C) containing a carbon-carbon double bond is 25% by mass or less in the total amount of active ingredients of the curable adhesive composition, it is easy to obtain a cured product with excellent low dielectric properties Hardening adhesive composition.

When the curable adhesive composition of the present invention contains a curable compound (C), the content of the curable compound (C) (when two or more curable compounds ( C) is the total amount of these curable compounds (C)) is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, further preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, and more preferably Preferably, it is 30 mass parts or less, More preferably, it is 25 mass parts or less, More preferably, it is 20 mass parts or less, More preferably, it is 16 mass parts or less.

[Component (D): Polymer containing carbon-carbon double bond] The carbon-carbon double bond-containing polymer (D) is a polymer containing a hydrocarbon group having a double bond at the terminal. By containing the carbon-carbon double bond-containing polymer (D) in the second curing system, it is easy to obtain a curable adhesive composition capable of forming a cured product having superior adhesive strength or heat resistance. The carbon-carbon double bond-containing polymer (D) can be used alone or in combination of two or more.

The number of hydrocarbon groups having a double bond at the terminal contained in the carbon-carbon double bond-containing polymer (D) is preferably 2 to 4, more preferably 2. When the number of hydrocarbon groups having a double bond at the terminal is within the above range, it is easy to obtain a curable adhesive composition that can form a cured product that is superior in adhesive strength and heat resistance and suppresses the occurrence of cracks.

The carbon number of the hydrocarbon group having a double bond at the terminal contained in the carbon-carbon double bond-containing polymer (D) is preferably 2-20, more preferably 2-15. Examples of the hydrocarbon group having a double bond at the terminal include: vinyl, allyl, 3-butenyl, 4-pentenyl, 5-hexenyl, isopropenyl, 1-methyl-2-propenyl , Vinylbenzyl, vinylnaphthyl, etc. Among these, vinylbenzyl is preferable at the point that it is easy to obtain a cured product excellent in low dielectric properties.

The number average molecular weight (Mn) of the carbon-carbon double bond-containing polymer (D) is preferably from 500 to 5,000, more preferably from 500 to 3,000. The number average molecular weight (Mn) of the carbon-carbon double bond-containing polymer (D) can be obtained by performing gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and obtained in terms of standard polystyrene as The specific measurement conditions are as described above.

Examples of the carbon-carbon double bond-containing polymer (D) include polyolefin-based resins, phenoxy-based resins, polyimide-based resins, polyamide-imide-based resins, and polyvinyl butyral. resins, polycarbonate resins, polyphenylene ether resins, etc.

In the case where the curable adhesive composition of the present invention contains a carbon-carbon double bond-containing polymer (D), relative to the total amount (100% by mass) of active ingredients of the curable adhesive composition, the carbon- The content of the carbon double bond polymer (D) (the total amount of these (D) components when two or more (D) components are included) is preferably at least 1% by mass, more preferably at least 5% by mass, and further It is preferably at least 10% by mass, more preferably at least 15% by mass, and is preferably at most 30% by mass, more preferably at most 25% by mass. When the content of the carbon-carbon double bond-containing polymer (D) is 1% by mass or more in the total amount of active ingredients of the curable adhesive composition, it is easy to obtain a curable adhesive that can form a cured product with excellent adhesive strength. agent composition. When the content of the carbon-carbon double bond-containing polymer (D) is 30% by mass or less in the total amount of active ingredients of the curable adhesive composition, it is easy to impart adhesiveness.

When the curable adhesive composition of the present invention contains a carbon-carbon double bond-containing polymer (D), with respect to 100 parts by mass of the component (A), the amount of the carbon-carbon double bond-containing polymer (D) The content (the total amount of these (D) components when two or more components (D) are included) is preferably at least 5 parts by mass, more preferably at least 10 parts by mass, still more preferably at least 15 parts by mass, and even more preferably It is 20 mass parts or more, and is preferably 50 mass parts or less, more preferably 40 mass parts or less, still more preferably 35 mass parts or less, still more preferably 30 mass parts or less.

The carbon-carbon double bond-containing polymer (D) is preferably contained in a polymer (D) having a double bond at the end in terms of easily obtaining a curable adhesive composition capable of forming a cured product having better low dielectric properties. Hydrocarbyl-modified polyphenylene ether resin (hereinafter sometimes referred to as "carbon-carbon double bond-containing polymer (D')"). In the case of a curable adhesive composition in which the component (D) is a polymer (D') containing a carbon-carbon double bond, the curable adhesive composition may contain other than the component (D'). Other polymers containing carbon-carbon double bonds are used as other components. In the aforementioned curable adhesive composition, the content of other carbon-carbon double bond-containing polymers is preferably 0 to 50 parts by mass, more preferably It is 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, still more preferably 0 to 5 parts by mass.

The polyphenylene ether resin refers to a resin having a polyphenylene skeleton in the main chain. The so-called polyphenylene skeleton refers to a skeleton having a repeating unit represented by the following formula, or a repeating unit in which hydrogen atoms in the above formula are substituted.

The carbon-carbon double bond-containing polymer (D') is a compound having a polyphenylene ether skeleton and a hydrocarbon group having a double bond at the end. The carbon-carbon double bond-containing polymer (D') has a polyphenylene ether skeleton, so the curable adhesive composition containing the carbon-carbon double bond-containing polymer (D') has excellent low dielectric properties .

Examples of the polyphenylene ether skeleton in the carbon-carbon double bond-containing polymer (D') include those represented by the following formula (4).

In formula (4), X is a divalent group represented by the following formula (5) or formula (6), Y is independently a divalent group represented by the following formula (7), and a and b are 0 to 100 Integers, at least one of a and b is 1 or more. * indicates a bonding site (the same applies hereinafter).

In formula (5), R ¹³ to R ²⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.

In formula (6), R ²¹ to R ²⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group. A represents a linear, branched or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

In formula (7), R ²⁹ to R ³² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, preferably a hydrogen atom or a methyl group.

Examples of the polyphenylene ether skeleton in the carbon-carbon double bond-containing polymer (D') include those represented by the following formula (8).

(a及b為0至100之整數，a與b的至少任一者為1以上)。

(a and b are integers from 0 to 100, and at least one of a and b is 1 or more).

Examples of the hydrocarbon group having a double bond at the terminal in the carbon-carbon double bond-containing polymer (D') include those described above. Among them, vinylbenzyl is more preferable at the point that it is easy to obtain a cured product having excellent low dielectric properties.

As the carbon-carbon double bond-containing polymer (D'), it is preferable to have a hydrocarbon group having a double bond at the end at both ends of the polyphenylene ether skeleton in terms of easily obtaining a cured product having excellent low dielectric properties. resin. In the case where the component (D) is a curable adhesive composition of a resin having a hydrocarbon group having a double bond at the end at both ends of the polyphenylene ether skeleton, the curable adhesive composition may contain other than the resin Other polymers containing carbon-carbon double bonds as other components. In the aforementioned curable adhesive composition, the content of other polymers containing carbon-carbon double bonds is preferably 0 to 50 parts by mass, more preferably 0 parts by mass, relative to 100 parts by mass of the total amount of the aforementioned resin to 30 parts by mass, more preferably 0 to 10 parts by mass, and more preferably 0 to 5 parts by mass.

The carbon-carbon double bond-containing polymer (D') can be obtained by introducing a "hydrocarbon group having a double bond at the end" at the end after forming a polyphenylene ether skeleton. For example, a carbon-carbon double bond-containing polymer (D') having vinylbenzyl groups at both ends can be obtained by reacting a difunctional phenolic compound with a monofunctional phenolic compound to obtain a polymer having a phenolic compound at both ends. After polymerizing the phenolic hydroxyl groups, the terminal phenolic hydroxyl groups are vinylbenzyl etherified using 4-(chloromethyl)styrene.

Examples of the carbon-carbon double bond-containing polymer (D') include compounds represented by the following formula (9).

[Cationic polymerization initiator] The curable adhesive composition of the present invention preferably contains a cationic polymerization initiator, and the reaction of the second curing system is initiated by the cationic polymerization initiator. In the curable adhesive composition containing a cationic polymerization initiator, the stability or reactivity of the second curing system can be adjusted by appropriately selecting a cationic polymerization initiator having a reactivity corresponding to the target. The cationic polymerization initiators can be used alone or in combination of two or more.

As the cationic polymerization initiator, a thermal cationic polymerization initiator is preferable. Thermal cationic polymerization initiators are compounds that generate cationic species that initiate polymerization by heating. Examples of the thermal cationic polymerization initiator include periumium salts, quaternary ammonium salts, phosphonium salts, diazonium salts, and iodonium salts.

Examples of columium salts include: triphenylcolumbitium tetrafluoroborate, triphenylcolumbitium hexafluoroantimonate, triphenylcolumbitium hexafluoroarsenate, tris(4-methoxyphenyl)columbitium hexafluoroarsenate acid salt, diphenyl(4-phenylthiophenyl) percilium hexafluoroarsenate, etc.

Examples of quaternary ammonium salts include: tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium bisulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluene Sulfonate, N,N-Dimethyl-N-benzylanilinium hexafluoroantimonate, N,N-Dimethyl-N-benzylanilinium tetrafluoroborate, N,N-Dimethyl-N-benzylanilinium tetrafluoroborate -N-benzylpyridinium hexafluoroantimonate, N,N-diethyl-N-benzyl trifluoromethanesulfonate, N,N-dimethyl-N-(4-methoxybenzyl ) pyridinium hexafluoroantimonate, N,N-diethyl-N-(4-methoxybenzyl) toluidine hexafluoroantimonate, etc.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium hexafluoroantimonate, and the like.

Examples of the iodine salt include: diphenyliodonium hexafluoroarsenate, bis(4-chlorophenyl)iodonium hexafluoroarsenate, bis(4-bromophenyl)iodonium hexafluoroarsenate, phenyl( 4-methoxyphenyl)iodonium hexafluoroarsenate, etc.

When the curable adhesive composition of the present invention contains a cationic polymerization initiator, it is preferable that at least a part of the cationic polymerization initiator is such that the peak temperature of the heat generation peak obtained by differential scanning calorimetry under the following conditions exceeds 120°C high temperature reactive thermal cationic polymerization initiator. [Differential scanning calorimetry measurement conditions] A mixture prepared by preparing 0.1 parts by mass of cationic polymerization initiator, 100 parts by mass of bisphenol A diglycidyl ether, and 0.1 parts by mass of γ-butyrolactone as the measurement object is used as a measurement sample, from 30°C to 300°C Differential scanning calorimetry was carried out at a heating rate of 10°C/min to measure the peak temperature of the heating peak.

The curable adhesive composition system containing a high-temperature reactive thermal cationic polymerization initiator makes the reaction temperature of the second hardening system easily exceed 120°C. The peak temperature of the exothermic peak of the high-temperature reactive thermal cationic polymerization initiator is preferably 250° C. or lower from the viewpoint that the temperature when curing the curable adhesive composition does not become too high. As commercially available products of high-temperature reactive thermal cationic polymerization initiators, for example, San-aid SI-B3, San-aid SI-B4, San-aid SI-B5, San-aid SI-150 (all three Manufactured by New Chemical Industry Co., Ltd.), etc.

When the curable adhesive composition contains a cationic polymerization initiator, the content of the cationic polymerization initiator is preferably 0.01 mass parts or more, more preferably 0.05 mass parts or more, still more preferably 0.1 mass parts or more, still more preferably 0.2 mass parts or more, and preferably 6 mass parts or less, more preferably 5 mass parts or less, still more preferably 4 parts by mass or less. When content of a cationic polymerization initiator is 0.01 mass part or more, it becomes easy to prevent reactivity fall. When content of a cationic polymerization initiator is 6 mass parts or less, corrosion of an adherend can be suppressed easily.

When using a thermal cationic polymerization initiator as a cationic polymerization initiator, it is preferable to perform differential scanning calorimetry under the following conditions to grasp the thermal stability and reactivity of the thermal cationic polymerization initiator and adjust the second hardening system The reaction start temperature of the reaction.

[Differential scanning calorimetry measurement conditions] Using a mixture of 0.1 parts by mass of thermal cationic polymerization initiator, 100 parts by mass of bisphenol A diglycidyl ether, and 0.1 parts by mass of γ-butyrolactone as a test sample, the temperature was raised from 30°C to 300°C at a rate of 10°C/min Speed differential scanning calorimetry to detect the peak temperature of the fever peak.

For example, the peak temperature of the exothermic peak of benzyl(4-hydroxyphenyl)(methyl)perjumetetrakis(pentafluorophenyl)borate is 140°C. The thermal cationic polymerization initiator is preferably such that the peak temperature of the exothermic peak obtained from the above measurement is 120°C to 180°C, more preferably 130°C to 160°C.

[Silane coupling agent] The curable adhesive composition of the present invention may also contain a silane coupling agent. The silane coupling agent may participate in the reaction of the first hardening system, may also participate in the reaction of the second hardening system, or may not participate in any of these hardening systems. Whether the silane coupling agent used participates in the reaction of the first hardening system or the reaction of the second hardening system is usually determined by the reactivity of the substituents in the silane coupling agent. A silane coupling agent can be used individually by 1 type or in combination of 2 or more types.

As a silane coupling agent, a well-known silane coupling agent can be used. Among them, organosilicon compounds having at least one alkoxysilyl group in the molecule are preferred. Examples of silane coupling agents include: 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Silane coupling agents with (meth)acryl groups, such as methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. ; Vinyltrimethoxysilane, Vinyltriethoxysilane, Dimethoxymethylvinylsilane, Diethoxymethylvinylsilane, Trichlorovinylsilane, Vinyltris(2-methoxy 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-shrink Silane coupling agents with epoxy groups such as glyceryloxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidyloxyoctyltrimethoxysilane, etc.; Silane coupling agents with styryl groups such as styryltrimethoxysilane and p-styryltriethoxysilane;

N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-( 2-aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilane N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl Silane coupling agents with amino groups such as hydrochloride of 3-aminopropyltrimethoxysilane; 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. have urea silane coupling agents with halogen atoms; 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane and other silane coupling agents with halogen atoms; 3-mercaptopropylmethyldimethoxysilane, 3- Silane coupling agents with mercapto groups such as mercaptopropyltrimethoxysilane; silanes with thioether groups such as bis(trimethoxysilylpropyl)tetrasulfide and bis(triethoxysilylpropyl)tetrasulfide Coupling agent; 3-isocyanate propyl trimethoxysilane, 3-isocyanate propyl triethoxy silane and other silane coupling agents with isocyanate groups; allyl trichlorosilane, allyl triethoxysilane, allyl silane coupling agents with allyl groups such as trimethoxysilane; silane coupling agents with hydroxyl groups such as 3-hydroxypropyltrimethoxysilane and 3-hydroxypropyltriethoxysilane.

A silane coupling agent can be used individually by 1 type or in combination of 2 or more types. When the curable adhesive composition contains a silane coupling agent, relative to the total amount of active ingredients (100 mass %) of the curable adhesive composition, the content of the silane coupling agent (when two or more silane coupling agents are included) (the total amount of these silane coupling agents) is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, further preferably at least 0.08% by mass, and is preferably at most 5% by mass, more preferably at most 1% by mass , and more preferably 0.5% by mass or less. When the content of the silane coupling agent is 0.01% by mass or more in the total active ingredients of the curable adhesive composition, it is easy to maintain the adhesiveness after the high temperature and high humidity test. When the content of the silane coupling agent is 5% by mass or less in the total active ingredients of the curable adhesive composition, it is easy to maintain the adhesiveness after the high temperature and high humidity test.

When the curable adhesive composition of the present invention contains a silane coupling agent, with respect to 100 parts by mass of component (A), the content of the silane coupling agent (when two or more silane coupling agents are included is the total amount of these silane coupling agents) The total amount) is preferably at least 0.01 parts by mass, more preferably at least 0.05 parts by mass, still more preferably at least 0.1 parts by mass, still more preferably at least 0.15 parts by mass, and is preferably at most 3 parts by mass, more preferably at most 1 part by mass 0.7 parts by mass or less, more preferably 0.7 parts by mass or less, even more preferably 0.5 parts by mass or less.

[solvent] The curable adhesive composition of the present invention may also contain a solvent and be in the form of a solution. Examples of solvents include: aromatic hydrocarbon solvents such as benzene and toluene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; n-pentane , n-hexane, n-heptane and other aliphatic hydrocarbon solvents; cyclopentane, cyclohexane, methylcyclohexane and other alicyclic hydrocarbon solvents, etc. These solvents may be used alone or in combination of two or more. When the curable adhesive composition contains a solvent, the content of the solvent can be appropriately determined in consideration of applicability and the like.

[other ingredients] The curable adhesive composition of the present invention may contain components (other components) other than the components described so far within the range that does not hinder the effects of the present invention. Examples of other components include additives such as ultraviolet absorbers, antistatic agents, light stabilizers, antioxidants, resin stabilizers, fillers, pigments, extenders, and softeners. These components may be used alone or in combination of two or more. When the curable adhesive composition of the present invention contains these additives, the content of the additives can be appropriately determined according to the purpose.

[Manufacturing method and usage method of curable adhesive composition] The curable adhesive composition of the present invention can be prepared by mixing and stirring the adhesive resin (A), the crosslinking agent (B), the compound having a carbon-carbon double bond, and other optional components according to a conventional method.

The method of using the curable adhesive composition of the present invention is not particularly limited. For example, the curable adhesive composition of the present invention can be coated on an adherend, and the obtained coating film can be dried, and then the reaction of the first curing system can be carried out to form a cross-linked structure in the coating film. Then, after the coating film overlaps another adherend, the reaction of the second curing system is carried out, whereby these adherends are bonded.

Examples of methods for applying the curable adhesive composition include spin coating, spray coating, bar coating, blade coating, roll coating, knife coating, die coating, and gravure coating. law etc.

As a method of drying a coating film, conventionally known drying methods, such as hot-air drying, hot-roll drying, and infrared-ray irradiation, are mentioned. Conditions for drying the coating film are, for example, 80° C. to 120° C. and 30 seconds to 5 minutes. Furthermore, depending on the drying conditions of the coating film, sometimes the drying treatment of the coating film and the reaction of the first hardening system can be carried out at the same time.

The thickness of the coating film is not particularly limited, and is usually 1 μm to 50 μm, preferably 1 μm to 25 μm, more preferably 5 μm to 25 μm.

Furthermore, an adhesive sheet can be produced using the curable adhesive composition of the present invention, and two adherends can be bonded using the adhesive sheet. For example, the curable adhesive composition of the present invention can be coated on a peeling film, and the resulting coating film is dried, and then the reaction of the first curing system is carried out, thereby obtaining a coating film with a crosslinked structure (adhesive film of the adhesive sheet) adhesive layer). The above methods can be used for the coating method and drying method of the curable adhesive composition. Furthermore, the thickness of the preferable coating film, or the simultaneous drying process of the coating film and the reaction of the first curing system are as described above.

The curable adhesive composition of the present invention is preferably a hardened product having a dielectric tangent of less than 0.0050 at 23° C. and a frequency of 1 GHz by curing the curable adhesive composition, and more preferably forms the above-mentioned dielectric tangent of A cured product having a dielectric tangent of 0.0030 or less is more preferably a cured product having a dielectric tangent of 0.0020 or less, more preferably a cured product having a dielectric tangent of 0.0015 or less, further preferably a cured product having a dielectric tangent of 0.0012 or less , and it is more preferable to form a cured product having a dielectric tangent of 0.0010 or less, and it is more preferable to form a cured product having a dielectric tangent of 0.0008 or less. The lower limit of the dielectric tangent under this condition does not particularly exist, and is usually 0.0001 or more.

The curable adhesive composition of the present invention is preferably a hardened product having a relative dielectric constant of 3.00 or less at 23°C and a frequency of 1 GHz by curing the curable adhesive composition, and it is more preferable to form the above-mentioned relative dielectric A cured product having a constant of 2.75 or less, and more preferably a cured product having a relative dielectric constant of 2.50 or less. The lower limit of the relative permittivity under this condition does not particularly exist, and is usually 2.00 or more.

In addition, as long as the sample used for measuring the above-mentioned dielectric tangent or relative permittivity can be measured, the hardened state of the sample is not limited. As an example of the measurement sample of dielectric tangent and relative permittivity, the coating film which heat-processed at 100 degreeC for 2 minutes as a reaction of drying process and the 1st hardening system is mentioned.

When the curable adhesive composition of the present invention forms a cured product having the above-mentioned dielectric properties through a curing reaction, the curable adhesive composition of the present invention can be preferably used as an adhesive member in an electronic component, Forming materials of protective members, insulating members, etc.

(2) Hardened products and their manufacturing methods The cured product of the present invention is the following cured product (α) or cured product (β).

Cured product (α): The raw material composition is the curable adhesive composition of the present invention, and satisfies the following requirements 1 and 2. - Requirement 1: The gel fraction is 10% by mass or more. ·Requirement 2: It has further thermosetting properties.

Cured product (β): The raw material composition is the curable adhesive composition of the present invention, and satisfies the following requirement 3. - Requirement 3: The gel fraction is 50% by mass or more.

[hardened product (α)] The cured product (α)-based raw material composition is the curable adhesive composition of the present invention, and satisfies the above-mentioned requirements 1 and 2.

The gel fraction of the cured product (α) is at least 10% by mass, preferably at least 15% by mass, more preferably at least 20% by mass, and most preferably at least 25% by mass. A cured product with a gel fraction of 10% by mass or more has a fully cross-linked structure inside. Therefore, even if such a cured product is subjected to heat treatment such as hot pressing, the adhesive components will not bleed out in large quantities, and contamination of the surroundings can be suppressed.

The gel fraction of the cured product (α) is usually 70% by mass or less, preferably 60% by mass or less, more preferably less than 50% by mass. A cured product (α) having a gel fraction of 70% by mass or less tends to be excellent in curability or adhesion to an adherend. The gel fraction of the cured product (α) can be calculated by performing an experiment in which a measurement sample is immersed in toluene at 23° C. for 168 hours as described in Examples.

The cured product (α) has further thermosetting properties. The hardening of the hardening material (α) is usually caused by both the reaction of the first hardening system and the reaction of the second hardening system (the components of the first hardening system partially remain in an unreacted state and remain), or only Caused by the reaction of the second hardening system (when the reaction of the first hardening system has been completed).

The cured product (α) preferably has a sheet shape. Since the cured product (α) has a sheet-like shape, it is possible to efficiently bond two adherends by hot pressing or the like.

The hardened product (α) having a sheet shape (hereinafter sometimes referred to as "thermosetting sheet adhesive") may have protective sheets on one or both sides for protection during storage or transportation.

When the thermosetting sheet adhesive is excellent in low dielectric properties, the thermosetting sheet adhesive can be suitably used as a sheet adhesive for electronic components or a sheet adhesive for coverlay films .

The sheet adhesive used for electronic components is a sheet adhesive used for bonding various parts in electronic components, or protecting or insulating circuits in electronic components. Examples of electronic components include communication devices such as smartphones and tablet terminals.

The sheet-like adhesive used for the coverlay film is a sheet-like adhesive used in the manufacture of the coverlay film. The coverlay film is, for example, a laminated film used to protect the surface of a flexible printed wiring board, and generally has an insulating resin layer and an adhesive layer. A thermosetting sheet-like adhesive is useful as the adhesive layer.

[Manufacturing method of hardened product (α)] The "method for producing a cured product (α)" of the present invention has the following step I. Step I: The step of curing the curable adhesive composition of the present invention at a temperature below 120°C.

As mentioned above, the curable adhesive composition of this invention has the 1st hardening system which reacts at the temperature below 120 degreeC. Step I is to carry out the reaction of the first hardening system to build a cross-linked structure in the hardening adhesive composition.

The heating temperature in step I is below 120°C, preferably below 110°C. The heating temperature in step I is usually above 0°C, preferably above 20°C. The heating time in step I is usually 0.5 minute to 5 minutes, preferably 1 minute to 3 minutes.

[Hardened product (β)] The cured product (β) is a cured product in which the raw material composition is the curable adhesive composition of the present invention and satisfies the above requirement 3.

The gel fraction of the cured product (β) is at least 50% by mass, preferably at least 55% by mass. The cured product (β) can be used, for example, as an adhesive member, a protective member, an insulating member, etc. of electronic components. When the cured product (β) has a gel fraction of 50% by mass or more, it exhibits sufficient performance in these applications.

The upper limit of the gel fraction of the cured product (β) is not particularly present, but is usually 95% by mass or less, preferably 90% by mass or less. The gel fraction of the cured product (β) can be obtained by the same method as the calculation method of the gel fraction of the cured product (α).

[Manufacturing method of hardened product (β)] The "method for producing a cured product (β)" of the present invention has the following steps IIa and IIb. Furthermore, the following step III may also be included. Step IIa: The step of curing the curable adhesive composition of the present invention at a temperature below 120°C to form a hardened product Step IIb: a step of further hardening the cured product formed in step IIa at a temperature exceeding 120°C. Step III: The step of hardening the curable adhesive composition of the present invention under the condition that the reaction start temperature is below 120°C and the reaction end temperature exceeds 120°C.

As mentioned above, the curable adhesive composition of this invention has the 1st hardening system which reacts at the temperature below 120 degreeC, and the 2nd hardening system which reacts at the temperature exceeding 120 degreeC. The "method for producing a cured product (β)" of the present invention is a method of producing a cured product by utilizing the reaction of the first curing system and the reaction of the second curing system.

The production method having step IIa and step IIb is a method for producing a cured product (β) in two stages from a curable adhesive composition. That is, the above-mentioned cured product (α) can be obtained by curing the curable adhesive composition of the present invention at a temperature of 120° C. or lower. Then, by heating the cured product (α) at a temperature exceeding 120° C., the reaction of the second curing system can proceed to obtain the cured product (β).

Step IIa is as described for the production method of the cured product (α). The heating temperature in step IIb exceeds 120°C, preferably above 140°C, more preferably above 150°C, and preferably below 180°C. The heating time in step IIb is usually 0.5 hour to 3 hours, preferably 1 hour to 2 hours.

Step III is a method of producing a cured product (β) in one stage from the curable adhesive composition. That is to say, by curing the curable adhesive composition of the present invention under the condition that the reaction start temperature is 120° C. or lower and the reaction end temperature exceeds 120° C., the first curing can be mainly carried out from the initial stage to the intermediate stage. The reaction of the system, from the middle stage to the final stage, mainly carries out the reaction of the second hardening system to obtain the hardened product (β).

The reaction start temperature of the heating condition in step III is below 120°C, preferably below 110°C. The reaction start temperature of the heating condition in step III is usually above 0°C, preferably above 20°C. The reaction end temperature of the heating condition in step III exceeds 120°C, preferably above 140°C, more preferably 150°C to 180°C. The heating time in step III is usually 0.5 hour to 3 hours, preferably 1 hour to 2 hours. [Example]

Hereinafter, examples are given and the present invention will be described in more detail. However, the present invention is not limited to the following examples at all.

[Compounds used in Examples or Comparative Examples] Binder resin (A1): maleic anhydride modified α-olefin polymer [manufactured by Mitsui Chemicals Co., Ltd., trade name: Unistole H-200, number average molecular weight: 47,000] · Isocyanate-based crosslinking agent (B1): 1,3,5-tris(5-isocyanatopentyl)-1,3,5-triazine-2,4,6-trione [manufactured by Mitsui Chemicals Co., Ltd., Trade name: Stabio D-370N, molecular weight: 462] · Epoxy-based crosslinking agent (B2): 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: TETRAD-C, molecular weight :362] ・Metal chelate crosslinking agent (B3): Tris(acetylacetonate)aluminum [manufactured by Soken Chemical Co., Ltd., trade name: M-5A, molecular weight: 324] · Hardening compound (C1): a compound having an isocyanurate skeleton and two allyl groups [manufactured by Shikoku Chemical Industry Co., Ltd., trade name: L-DAIC] · Polyphenylene ether resin (D1): vinylbenzyl modified polyphenylene ether [manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: OPE-2St 1200, number average molecular weight: 1200] Cationic polymerization initiator (E1): thermal cationic polymerization initiator [manufactured by Sanshin Chemical Industry Co., Ltd., trade name: San-aid SI-B3] · Silane coupling agent (F1): 8-glycidyloxyoctyltrimethoxysilane [manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM4803]

[Evaluation of reactivity of thermal cationic polymerization initiators] Using a mixture of 0.1 parts by mass of a cationic polymerization initiator (E1), 100 parts by mass of bisphenol A diglycidyl ether (manufactured by Mitsubishi Chemical Corporation, jER828), and 0.1 parts by mass of γ-butyrolactone as a measurement sample, at 30°C Differential scanning calorimetry was carried out at a heating rate of 10°C/min up to 300°C, and the peak temperature of the exothermic peak was 140°C.

[Example 1] 100 parts by mass of binder resin (A1), 0.5 parts by mass of isocyanate crosslinking agent (B1), 12.5 parts by mass of hardening compound (C1), 25 parts by mass of polyphenylene ether resin (D1), cationic polymerization initiator (E1 ) and 0.12 parts by mass of the silane coupling agent (F1) were dissolved in toluene to prepare a curable adhesive composition. On the release-treated surface of the release sheet (the first release sheet, manufactured by Lintec Co., Ltd., trade name: SP-PET752150), the obtained curable adhesive composition was applied to form a coating film, and the The obtained coating film was dried at 100° C. for 2 minutes to form an adhesive layer (hardened product (α)) having a thickness of 15 μm. On the exposed surface of the adhesive layer, the release-treated surface of another release sheet (second release sheet, manufactured by Lintec Co., Ltd., trade name: SP-PET381130) was attached to obtain an adhesive sheet.

[Example 2 to Example 5, Comparative Example 1] Except having changed the compounding quantity or kind of a component into Table 1, the curable adhesive composition was prepared similarly to Example 1, and the adhesive sheet was obtained.

[Gel fraction of adhesive layer (hardened product (α))] The adhesive sheet obtained in the example or comparative example was cut into a size of 80 mm in length x 80 mm in width, and both peeling sheets were peeled off to obtain an adhesive layer. Then, the obtained adhesive agent layer was wrapped in the polyester mesh (mesh size 200) whose mass was measured beforehand, and the test sample was produced. After the test sample was left to stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%, the mass of the test sample was weighed with a precision balance. The mass (M1) of the adhesive layer before immersion was computed based on the obtained measured value. Next, the test sample was immersed in 0.2 L of toluene at room temperature (23° C.) for 168 hours. After dipping, take out the test sample, dry the test sample in an oven at 100°C for 2 hours, and then let it stand for 24 hours in an environment with a temperature of 23°C and a relative humidity of 50%. Weigh the mass of the dried test sample with a precision balance. The mass (M2) of the adhesive layer after dipping and drying was calculated based on the obtained measured value. From the value of M1 and the value of M2, the gel fraction of the adhesive layer was calculated from the following formula. ·Gel fraction (mass %)=(M2/M1)×100.

[Gel fraction of hardened product (β)] The adhesive sheet obtained in the example or comparative example was cut into a size of 80 mm in length x 80 mm in width, and heated at 160° C. for 1 hour in an oven. Using the cured product (β) obtained by peeling off the release sheet, the gel fraction of the cured product (β) was calculated in the same manner as above.

[Evaluation of exudation of ingredients] Peel off one piece of the release sheet of the adhesive sheet obtained in the examples or comparative examples, and use a thermal laminator to bond the exposed adhesive layer with a polyimide film (Toray-Dupont) at 100°C. Manufactured, Kapton, thickness 25 μm) crimping to obtain a laminate with a structure of release sheet/adhesive layer/polyimide film. Then, the release sheet of the laminate was peeled off, and the exposed adhesive layer was bonded to the copper foil at 100°C using a thermal laminator to obtain a laminate with a structure of copper foil/adhesive layer/polyimide film body. Furthermore, the area of the copper foil is wider than that of the other two layers, so when the adhesive component of the adhesive layer seeps out, it will be attached to the copper foil. This laminate was subjected to hot press treatment at 171° C. and 1.38 MPa for 20 minutes. After cooling, the length of the adhesive component that oozes out most from the adhesive layer in plan view was measured using a digital microscope [the length of the portion indicated by X in FIG. 1 (μm)]. The results are shown in Table 1. Furthermore, FIG. 1 is a schematic plan view of a laminate used for evaluation of exudation of adhesive components in an example, after hot pressing. As shown in Fig. 1, under the influence of hot pressing treatment, part of the adhesive layer (cured product) sandwiched between the copper foil 1 and the polyimide film 3 of the above-mentioned laminate oozes out, and the oozing adhesive component 2 May be attached to copper foil 1. At this time, as shown in FIG. 1 , the maximum value X of the distance X between the adhesive agent component 2 and the polyimide film 3 that exuded in plan view was set as "the exudation length of the adhesive agent component", and described in Table 1.

[relative permittivity, dielectric tangent] After the adhesive layer of the adhesive sheet obtained in the example or comparative example is laminated to a thickness of about 1mm, it is welded at 100°C using a heat laminator to obtain a release sheet/thickness of about 1mm. A laminate with a structure of adhesive layer/release sheet. The release sheets on both sides of the laminate were peeled off to obtain a measurement sample. The relative permittivity and dielectric tangent at 23° C. and 1 GHz were measured for the obtained measurement sample using an RF impedance-material analyzer (manufactured by Keysight Technologies, E4991A). In addition, in this specification, the so-called high-frequency region refers to the region of 300 MHz to 300 GHz, but in this embodiment, 1 GHz is used as an example of the high-frequency region. The results are shown in Table 1.

[表1]

[Table 1]

The curable adhesive compositions obtained in Examples 1 to 5 have a first curing system and a second curing system. When these curable adhesive compositions are used, by utilizing the reaction of the first curing system to form a cross-linked structure in the coating film and then performing the subsequent step, bleeding of the adhesive components can be suppressed.

1: copper foil 2: Adhesive layer or exuded adhesive ingredients 3: Polyimide film

[ Fig. 1 ] is a schematic diagram (plan view) of a part of a laminate used for evaluating the exudation of adhesive components. [ Fig. 2 ] is a schematic view showing a section A-A of Fig. 1 .

Claims (17)

A curable adhesive composition comprising: The first hardening system is a hardening system in which a binder resin having a reactive functional group reacts with a crosslinking agent, and the reaction is carried out at a temperature below 120°C; and The second hardening system is a hardening system that reacts with one or two or more compounds having carbon-carbon double bonds, and reacts at a temperature exceeding 120°C. The curable adhesive composition as described in claim 1, wherein the adhesive resin having reactive functional groups is a polyolefin resin. The curable adhesive composition as described in claim 1 or 2, wherein the adhesive resin having reactive functional groups is an acid-modified resin. The curable adhesive composition according to any one of claims 1 to 3, wherein the crosslinking agent is a compound having an isocyanurate skeleton. The curable adhesive composition according to any one of claims 1 to 4, wherein the crosslinking agent is a compound having two or more isocyanate groups. The curable adhesive composition as described in any one of Claims 1 to 5, wherein the compound having a carbon-carbon double bond has two or more hydrocarbon groups having a double bond at the end and is liquid at 25°C Non-aromatic compounds. The curable adhesive composition as described in any one of claims 1 to 6, wherein the compound having a carbon-carbon double bond is a modified polyphenylene ether resin having a hydrocarbon group having a double bond at the end. The curable adhesive composition according to any one of claims 1 to 7, further comprising a cationic polymerization initiator, and the second curing system starts to react with the aforementioned cationic polymerization initiator. The curable adhesive composition according to any one of claims 1 to 8, wherein the curable adhesive composition is cured to form a cured product having a dielectric tangent of less than 0.0050 at 23° C. and a frequency of 1 GHz. The curable adhesive composition according to any one of claims 1 to 9, wherein the curable adhesive composition is cured to form a cured product having a relative dielectric constant of 3.00 or less at 23°C and a frequency of 1 GHz by curing . A cured product, which is obtained by curing the curable adhesive composition described in any one of claims 1 to 10, and satisfies the following requirements 1 and 2; Requirement 1: The gel fraction is 10% by mass or more; ·Requirement 2: It has further thermosetting properties. The cured product as described in claim 11, wherein the cured product has a sheet shape. The cured product as described in claim 11 or 12, wherein the cured product is a sheet adhesive for electronic components. The cured product as described in claim 11 or 12, wherein the cured product is a sheet-like adhesive used for a cover film. A method for producing a cured product as described in any one of claims 11 to 14, comprising the following step I; ·Step I: The step of curing the curable adhesive composition described in any one of Claims 1 to 10 at a temperature below 120°C. A cured product, which is obtained by curing the curable adhesive composition described in any one of claims 1 to 10, and satisfies the following requirement 3; - Requirement 3: The gel fraction is 50% by mass or more. A method of manufacturing a cured product as described in claim 16, comprising the following steps IIa and IIb; ·Step IIa: a step of curing the curable adhesive composition described in any one of Claims 1 to 10 at a temperature below 120°C to form a cured product; • Step IIb: a step of further hardening the cured product formed in Step IIa at a temperature exceeding 120°C.

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