CN116635229A - Curable resin composition and adhesive - Google Patents

Abstract

The present invention addresses the problem of providing a curable resin composition that is a two-component or multi-component epoxy resin composition that is more excellent than conventional curable resin compositions. The curable resin composition comprises an epoxy resin, an epoxy curing agent and polymer particles, (i) further comprises aluminum hydroxide having a specific particle diameter in a specific amount, or (ii) further comprises aluminum hydroxide and the polymer particles have a specific structure, or (iii) further comprises a compound having a specific structure and the epoxy curing agent has a specific structure.

Description

Curable resin composition and adhesive

Technical Field

The present invention relates to a two-component curable resin composition containing an epoxy resin, and an adhesive containing the same.

Background

As the adhesive, various compositions are known (for example, patent document 1). Further, a cured product obtained by curing the epoxy resin composition is excellent in strength, heat resistance, water resistance, chemical resistance, electrical insulation, and the like. Therefore, epoxy resin compositions have been used for a wide variety of applications such as industrial applications and civil engineering and construction applications. Conventionally, various epoxy resin compositions have been developed (for example, patent documents 2 to 4).

Prior art literature

Patent literature

Patent document 1: WO2016-137303

Patent document 2: WO2009-034966

Patent document 3: WO2009-025991

Patent document 4: japanese patent laid-open No. 2017-149887

Disclosure of Invention

Problems to be solved by the invention

However, such prior art as described above is insufficient as a two-component type or a multi-component type epoxy resin composition, and there is still room for further improvement.

In view of the above problems, an object of one embodiment of the present invention is to provide a novel curable resin composition which is more excellent than the conventional one as a two-component or multi-component epoxy resin composition.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above problems, and as a result, have completed the present invention.

That is, the curable resin composition according to one embodiment of the present invention is a two-component curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D), and further comprises polymer particles (B) having a core-shell structure comprising a core layer and a shell layer, and aluminum hydroxide (C), wherein the total weight of the aluminum hydroxide (C) in 100% by weight of the total weight of the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle diameter of the aluminum hydroxide (C) is 11 μm or more and 200 μm or less.

The curable resin composition of another embodiment of the present invention is a two-component curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D), wherein the curable resin composition further comprises polymer particles (B) having a core-shell structure comprising a core layer and a shell layer, wherein the total weight of the aluminum hydroxide (C) in 100wt% of the total weight of the curable resin composition is 55wt% or more and 85 wt% or less, the average particle diameter of the polymer particles (B) is 0.15 μm or more and 0.30 μm or less, the ratio of the weight of the core layer to the weight of the shell layer (the weight of the core layer/the weight of the shell layer) is 65/35 to 92/8, the polymer particles (B) are a copolymer obtained by polymerizing a monomer component containing a monomer having an alkyl ester of from 1 wt% to 80% of carbon atoms in the monomer having from 1 wt% to 100wt% of methyl ester of acrylic acid, and the monomer having from 1 wt% to 80wt% of alkyl ester of carbon atoms in the monomer (methyl ester of 1 wt% of the monomer having 1 carbon atoms).

The curable resin composition according to another embodiment of the present invention is a two-component or multi-component curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D), wherein the curable resin composition further comprises polymer particles (B) having a core-shell structure comprising a core layer and a shell layer, and a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule, wherein the number of tertiary alkyl groups located at the ortho position of the phenolic hydroxyl groups in the compound (G) is 0 or 1 molecule, and wherein the epoxy curing agent (D) is at least 1 selected from the group consisting of aliphatic amines, alicyclic amines, amide amines, amino-terminated polyethers, amino-terminated nitrile rubbers, modified substances of aliphatic amines, modified substances of amide amines, modified substances of amino-terminated polyethers, and modified substances of amino-terminated nitrile rubbers.

ADVANTAGEOUS EFFECTS OF INVENTION

According to one embodiment of the present invention, an effect of providing a curable resin composition that is a two-component or multi-component epoxy resin composition and is more excellent than the conventional one can be exhibited.

Detailed Description

An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope shown in the claims. Further, embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples are also included in the technical scope of the present invention. Further, by combining the technical means disclosed in each of the embodiments, new technical features can be formed. All of the academic documents and patent documents described in the present specification are incorporated by reference into the present specification. In the present specification, "a to B" representing a numerical range means "a or more (including a and more than a) and B or less (including B and less than B)", unless otherwise specified.

[ I ] embodiment 1 ]

Embodiment 1 relates to a two-component curable resin composition containing an epoxy resin, and an adhesive containing the same.

With recent higher functionality of electrical devices such as secondary batteries and semiconductors, the amount of heat generated from the devices increases, and heat dissipation from the devices becomes important. Particularly, in a secondary battery such as a lithium ion battery used in a battery pack of a wireless mobile device or an Electric Vehicle (EV), heat generated in the battery during charge and discharge is accumulated to raise the internal temperature of the battery, and therefore efficient heat dissipation is an important issue concerning the reliability and lifetime of the battery. Patent document 1 discloses a battery module in which a battery cell (cell) is fixed to a module case with a thermally conductive adhesive.

Further, as described in patent document 1, in order to improve safety against fire and other accidents that occur due to accumulation of heat during charge and discharge, it is required that the curable resin composition used in the above-mentioned equipment exhibit flame retardancy, and it is desired that the curable resin composition exhibit V-0 rating according to UL 94V Test (Vertical Burning Test).

Further, as described in patent document 1, since the EV battery has a structure in which a large number of battery cells are connected in parallel, and shear stress is applied due to external impact such as a collision of a vehicle, high adhesive force and impact resistance are required for an adhesive that fixes each battery cell to a battery case.

On the other hand, epoxy resins are excellent in various aspects such as dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, chemical resistance and the like of cured products thereof, and therefore are widely used as curable resin compositions for adhesives, sealants and the like in electric devices.

Patent document 2 discloses a technique for improving toughness and impact resistance of a cured product obtained by dispersing polymer fine particles in a curable resin composition containing a curable resin such as an epoxy resin as a main component.

In addition, lithium ion batteries have a characteristic of poor heat resistance, and it is difficult to use a heat-curable one-component epoxy-based curable resin composition. Patent document 3 and the like disclose a two-component epoxy curable resin composition that can be cured at room temperature or a low temperature near room temperature.

In order to improve heat dissipation of electric devices, it is studied to add a heat conductive filler such as aluminum hydroxide or aluminum oxide to a curable resin composition used for the devices to improve heat conductivity. However, with the addition of the thermally conductive filler, there are cases where the mechanical strength, toughness, and impact resistance of the cured product obtained by curing the curable resin composition are reduced. Further, cured products of epoxy resins widely used in electrical equipment have a problem of exhibiting very brittle properties because of low fracture toughness.

The resin composition described in patent document 1 has insufficient impact resistance and has room for improvement. In addition, patent documents 2 to 3 do not describe a technique for improving impact adhesion resistance of an epoxy curable resin composition in which an epoxy resin is combined with a large amount of aluminum hydroxide.

In view of the above-described circumstances, an object of the invention of embodiment 1 is to provide a two-component curable resin composition which is obtained by blending an epoxy resin and aluminum hydroxide and which is capable of giving a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength and impact peel adhesion resistance and which is curable at room temperature or a low temperature close to room temperature.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength and impact peel adhesion resistance can be obtained by blending a polymer particle (B) having a core-shell structure and an aluminum hydroxide (C) having a specific average particle diameter in a specific weight ratio in a two-component curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D).

That is, the invention according to embodiment 1 relates to a curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D), wherein the first component and/or the second component further contains a polymer particle (B) having a core-shell structure and aluminum hydroxide (C), the total weight of the aluminum hydroxide (C) is 55 wt% or more and 85 wt% or less relative to the total weight of the curable resin composition, the average particle diameter of the aluminum hydroxide (C) is 11 μm or more and 200 μm or less, and the curable resin composition is a two-component or multi-component type.

According to the curable resin composition of embodiment 1, the cured product obtained by the epoxy resin and the aluminum hydroxide in a high addition amount can exhibit excellent heat conductivity, flame retardancy and adhesive strength. In addition, in the curable resin composition of embodiment 1, the use of aluminum hydroxide having a specific average particle diameter can effectively exhibit the toughness improvement effect of the polymer particles having a core-shell structure. As a result, the cured product obtained from the curable resin composition of embodiment 1 can exhibit excellent impact resistance. That is, according to embodiment 1, a two-component curable resin composition which can give a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength and impact peel adhesion resistance and which can be cured at room temperature or a low temperature close to room temperature can be provided.

In other words, embodiment 1 is a curable resin composition containing at least an epoxy resin (a), polymer particles (B) having a core-shell structure, aluminum hydroxide (C), and an epoxy curing agent (D). The curable resin composition according to embodiment 1 is a two-component type or multi-component type curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D) as essential components, and further comprising, if necessary, other components such as a color toner and a curing agent, and being used in combination immediately before use. The curable resin composition according to embodiment 1 further comprises a polymer particle (B) having a core-shell structure and aluminum hydroxide (C). The polymer particles (B) having a core-shell structure and aluminum hydroxide (C) are preferably contained in the first component and/or the second component, respectively. The curable resin composition of embodiment 1 may contain other components in addition to the first component and the second component, if necessary.

In the present specification, "epoxy resin (a)", "polymer particles (B)", "aluminum hydroxide (C)", and "epoxy curing agent (D)" are sometimes denoted as "(a) component", "(B) component", "(C) component" and "(D) component, respectively.

In the present specification, "adhesive strength" and "impact peel adhesion resistance" are collectively referred to as "adhesion".

In the present specification, the adhesive strength is evaluated by shear adhesive strength (MPa). That is, the bonding strength means a value of shear bonding strength (MPa). The larger the value of the shear adhesion strength (MPa) after curing means that the more excellent the adhesion strength of the curable resin composition.

In addition, in the present specification, impact peel adhesion resistance can be evaluated by dynamic cleavage resistance measured at 23 ℃ in accordance with ISO 11343. That is, the impact peel adhesion resistance refers to a value of dynamic cleavage resistance (kN/m). The larger the value of the dynamic cleavage resistance after curing means that the more excellent the impact peel adhesion resistance of the curable resin composition.

Epoxy resin (A) >, and

the curable resin composition of embodiment 1 contains an epoxy resin (a) as a curable resin in a first component. As the epoxy resin, various epoxy resins can be used. Examples thereof include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, bisphenol S type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, novolak type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, flame retardant type epoxy resins such as hydrogenated bisphenol A (or F) type epoxy resins, fluorinated epoxy resins, glycidyl ethers of tetrabromobisphenol A, parahydroxybenzoic acid glycidyl ether ester type epoxy resins, meta aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, various alicyclic epoxy resins, N-diglycidyl aniline, N, examples of the epoxy resin include, but are not limited to, glycidyl ethers of aliphatic polyhydric alcohols having two or more members such as N-diglycidyl-o-toluidine, triglycidyl isocyanurate, divinylbenzene dioxide, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, diglycidyl esters of aliphatic polyhydric acids, and glycidyl ethers of polyhydric aliphatic alcohols having two or more members such as glycerin, chelate-modified epoxy resins, rubber-modified epoxy resins, urethane-modified epoxy resins, hydantoin-type epoxy resins, epoxides of unsaturated polymers such as petroleum resins, amino-containing glycidyl ether resins, and epoxy compounds obtained by addition reaction of bisphenol a (or F) or polybasic acids to the above epoxy resins. These epoxy resins may be used alone or in combination of 2 or more.

Among them, the polyalkylene glycol diglycidyl ether includes polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like. More specific examples of the glycol diglycidyl ether include neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, and cyclohexanedimethanol diglycidyl ether. Examples of the diglycidyl esters of the aliphatic polybasic acids include dimer acid diglycidyl esters, adipic acid diglycidyl esters, sebacic acid diglycidyl esters, and maleic acid diglycidyl esters. Examples of the glycidyl ether of the polyhydric aliphatic alcohol having two or more members include trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil-modified polyglycidyl ether, propoxylated polyglycidyl ether, and sorbitol polyglycidyl ether. Examples of the epoxy compound obtained by an addition reaction of a polybasic acid or the like with an epoxy resin include an addition reaction product of tall oil fatty acid dimer (dimer acid) and bisphenol a-type epoxy resin described in, for example, international publication No. 2010-098950.

The polyalkylene glycol diglycidyl ether, the diglycidyl ester of an aliphatic polyhydric acid, and the glycidyl ether of a polyhydric aliphatic alcohol having two or more members are epoxy resins having relatively low viscosity, and when used in combination with other epoxy resins such as bisphenol a epoxy resins and bisphenol F epoxy resins, they function as reactive diluents, and the balance between the viscosity of the composition and the physical properties of the cured product can be improved. That is, the epoxy resin (a) preferably contains a polyepoxide as a reactive diluent. On the other hand, as described later, the monoepoxide functions as a reactive diluent, but is not contained in the epoxy resin (a). The content of the epoxy resin functioning as a reactive diluent is preferably 0.5 to 30% by weight, more preferably 2 to 20% by weight, and still more preferably 5 to 15% by weight of the component (a).

The chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound having a chelate functional group (chelate ligand), and when the curable resin composition containing the chelate-modified epoxy resin is used as an adhesive for a vehicle, the adhesion to the surface of a metal substrate contaminated with an oily substance can be improved. The chelate functional group is a functional group of a compound having a plurality of coordinating atoms capable of coordinating with metal ions in the molecule, and examples thereof include a phosphate group (e.g., -PO (OH) ₂ ) Carboxylic acid group (-CO) ₂ H) Containing sulfate groups (e.g. -SO) ₃ H) Amino groups, hydroxyl groups (particularly hydroxyl groups adjacent to each other on the aromatic ring), and the like. As chelating ligands, there may be mentioned: ethylenediamine, bipyridine, ethylenediamine tetraacetic acid, phenanthroline, porphyrin, crown ether, and the like. As the commercially available chelate-modified epoxy resin, ADEKA RESIN EP-49-10N manufactured by ADEKA can be mentioned. (A) The amount of the chelate-modified epoxy resin in the component (a) is preferably 0.1 to 10% by weight, more preferably 0.5 to 3% by weight.

The rubber-modified epoxy resin is a reaction product obtained by reacting a rubber with an epoxy group-containing compound and having an average of 1.1 or more, preferably 2 or more epoxy groups per 1 molecule. The rubber may be: rubber polymers such as acrylonitrile butadiene rubber (NBR), styrene Butadiene Rubber (SBR), hydrogenated Nitrile Butadiene Rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), butadiene rubber, polyoxypropylene, polyoxyethylene, and polyoxyalkylene such as polybutylene oxide. The rubber polymer preferably has a reactive group such as an amino group, a hydroxyl group, or a carboxyl group at the terminal. The rubber-modified epoxy resin is a product obtained by reacting the rubber-based polymer and the epoxy resin in a proper compounding ratio by a known method. Among them, from the viewpoints of the adhesive strength and impact peel adhesion resistance of the obtained curable resin composition, acrylonitrile-butadiene rubber modified epoxy resin and polyoxyalkylene modified epoxy resin are preferable, and acrylonitrile-butadiene rubber modified epoxy resin is more preferable. The acrylonitrile-butadiene rubber-modified epoxy resin can be obtained, for example, by reacting a carboxyl terminal NBR (CTBN) with a bisphenol A type epoxy resin.

In the above-mentioned acrylonitrile-butadiene rubber modified epoxy resin, the content of the acrylonitrile monomer component in the acrylonitrile-butadiene rubber is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, and even more preferably 15 to 30% by weight, from the viewpoints of the adhesive strength and impact peel adhesion resistance of the obtained curable resin composition. From the viewpoint of the handleability of the obtained curable resin composition, it is particularly preferably 20 to 30% by weight.

In the present specification, "workability of the curable resin composition" refers to workability of operations (coating, etc.) using the curable resin composition.

In addition, for example, an addition reaction product of an amino-terminal polyoxyalkylene and an epoxy resin (hereinafter also referred to as "adduct") is also included in the rubber-modified epoxy resin. The above-mentioned adducts can be produced easily by a known method, for example, as described in U.S. Pat. No. 5084532 and U.S. Pat. No. 6015865. The epoxy resin used in the production of the adduct may be exemplified by the specific examples of the component (a), and is preferably a bisphenol a type epoxy resin or a bisphenol F type epoxy resin, more preferably a bisphenol a type epoxy resin. As commercially available amino-terminal polyoxyalkylene used in the production of the adduct, there may be mentioned, for example, jeffamine D-230, jeffamine D-400, jeffamine D-2000, jeffamine D-4000, jeffamine T-5000, etc. manufactured by Huntsman corporation.

The number of epoxide-reactive end groups per 1 molecule on average in the rubber is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. The term "epoxide-reactive terminal group" refers to a terminal group having reactivity with an epoxide group.

The number average molecular weight of the rubber is preferably 1000 to 10000, more preferably 2000 to 8000, particularly preferably 3000 to 6000 in terms of polystyrene as measured by GPC.

The method for producing the rubber-modified epoxy resin is not particularly limited, and for example, the rubber-modified epoxy resin can be produced by reacting a rubber with an epoxy-containing compound in a large amount. Specifically, it is preferable to produce the rubber by reacting 2 equivalents or more of the epoxy group-containing compound with 1 equivalent of the epoxy-reactive terminal group in the rubber. More preferably, a sufficient amount of the epoxy-containing compound is reacted such that the resulting product becomes a mixture of the rubber and the adduct of the epoxy-containing compound and the free epoxy-containing compound. For example, the rubber-modified epoxy resin can be produced by heating to a temperature of 100 to 250℃in the presence of a catalyst such as phenyldimethylurea or triphenylphosphine. The epoxy group-containing compound used in the production of the rubber-modified epoxy resin is not particularly limited, but is preferably a bisphenol a-type epoxy resin or a bisphenol F-type epoxy resin, more preferably a bisphenol a-type epoxy resin. In the case where an excessive amount of the epoxy group-containing compound is used in the production of the rubber-modified epoxy resin, the unreacted epoxy group-containing compound remaining after the reaction is not contained in the rubber-modified epoxy resin described in the present specification.

In the case of rubber-modified epoxy resins, the epoxy resin can be modified by pre-reacting with a bisphenol component. The bisphenol component used for the modification is preferably 3 to 35 parts by weight, more preferably 5 to 25 parts by weight, based on 100 parts by weight of the rubber component in the rubber-modified epoxy resin. A cured product obtained by curing a curable resin composition containing a modified rubber-modified epoxy resin is excellent in adhesion durability after exposure to high temperatures and also excellent in impact resistance at low temperatures.

The glass transition temperature (Tg) of the rubber-modified epoxy resin is not particularly limited, but is preferably-25℃or lower, more preferably-35℃or lower, further preferably-40℃or lower, particularly preferably-50℃or lower.

The number average molecular weight of the rubber-modified epoxy resin is preferably 1500 to 40000, more preferably 3000 to 30000, particularly preferably 4000 to 20000 in terms of polystyrene as measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, particularly preferably 1.5 to 2.5.

The rubber-modified epoxy resin may be used alone or in combination of 2 or more.

(A) The amount of the rubber-modified epoxy resin in the component (A) is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, still more preferably 5 to 30% by weight, particularly preferably 10 to 20% by weight.

The urethane-modified epoxy resin is a reaction product obtained by reacting a compound having a group reactive with an isocyanate group and an epoxy group with a urethane prepolymer having an isocyanate group, and has an average of 1.1 or more, preferably 2 or more epoxy groups per 1 molecule. For example, a urethane-modified epoxy resin can be obtained by reacting a hydroxyl-containing epoxy compound with a urethane prepolymer.

The number average molecular weight of the urethane-modified epoxy resin is preferably 1500 to 40000, more preferably 3000 to 30000, particularly preferably 4000 to 20000 in terms of polystyrene as measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, particularly preferably 1.5 to 2.5.

The urethane-modified epoxy resin may be used alone or in combination of 2 or more.

(A) The urethane-modified epoxy resin is used in an amount of preferably 1 to 50% by weight, more preferably 2 to 40% by weight, still more preferably 5 to 30% by weight, particularly preferably 10 to 20% by weight.

Among these epoxy resins, epoxy resins having at least 2 epoxy groups in one molecule are preferable from the viewpoints of high curability, excellent flexibility after curing, excellent effect of improving impact peel resistance by blending the core-shell polymer particles (B), and the like. Particularly preferred are compounds having 2 epoxy groups in one molecule.

As the component (a), the cured products obtained from the bisphenol a epoxy resin and the bisphenol F epoxy resin have a high elastic modulus, excellent heat resistance and adhesion, and relatively low cost. Accordingly, the epoxy resin (a) is preferably bisphenol a type epoxy resin and/or bisphenol F type epoxy resin. In addition, the epoxy resin (a) is particularly preferably a bisphenol a type epoxy resin, since a curable resin composition which can provide a cured product excellent in heat resistance can be obtained at low cost.

Among various epoxy resins, the cured product obtained from an epoxy resin having an epoxy equivalent of less than 220 has a high elastic modulus and heat resistance, and therefore, the epoxy equivalent is preferably 90 or more and less than 210, and more preferably 150 or more and less than 200.

In particular, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins having an epoxy equivalent of less than 220 are preferred because they are liquid at ordinary temperature and the resulting curable resin composition is excellent in handleability.

(A) When the component (a) contains a bisphenol a-type epoxy resin and a bisphenol F-type epoxy resin having an epoxy equivalent of 220 or more and less than 5000 in a range of preferably 40 wt% or less, more preferably 20 wt% or less, based on 100 wt% of the component (a), the resulting cured product is excellent in impact resistance, and is therefore preferred.

Polymer particle (B) having core-shell Structure

The curable resin composition according to embodiment 1 contains polymer particles having a core-shell structure as the component (B) in the first component and/or the second component. Here, "the polymer particles (B) have a core-shell structure" means that the polymer particles (B) have a core layer and a shell layer.

When the curable resin composition contains the component (B), the cured product (e.g., adhesive layer) obtained by the toughness improvement effect of the component (B) is excellent in impact peel adhesion resistance. In addition, when the curable resin composition contains the component (B), the obtained cured product tends to have excellent adhesive strength. (B) The component may be contained in only the first component, may be contained in only the second component, or may be contained in both the first component and the second component. (B) The component (c) may be swollen by a low molecular compound contained in the component (D) or the like in the second component. Therefore, from the viewpoint of storage stability of the composition, the component (B) is preferably contained in at least the first component, more preferably in only the first component. Hereinafter, the "polymer particles (B) having a core-shell structure" will also be referred to as "core-shell polymer particles (B)".

The core-shell polymer particles (B) may or may not have an epoxy group in the shell layer. In other words, the shell layer of the core-shell polymer particle (B) may or may not have an epoxy group. From the viewpoint of excellent impact peel adhesion of the resulting cured product, the core-shell polymer particles (B) preferably have epoxy groups in the shell layer. When the shell layer of the core-shell polymer particle (B) has an epoxy group, the content of the epoxy group in the shell layer is preferably greater than 0mmol/g and 2.0mmol/g or less, more preferably 0.1mmol/g or more and 2.0mmol/g or less, still more preferably 0.3mmol/g or more and 1.5mmol/g or less, relative to the total weight of the shell layer of the core-shell polymer particle (B), from the viewpoint of the impact peel adhesion resistance of the resulting cured product. As a result, the core-shell polymer particles (B) can be dispersed in the cured product in the form of primary particles, and as a result, the impact peel adhesion resistance of the cured product can be improved. When the shell layer has an epoxy group, the component (B) is preferably contained only in the first component. In addition, from the viewpoint of storage stability of the curable resin composition, the core-shell polymer particles (B) preferably have no epoxy group in the shell layer. When the core-shell polymer particles (B) are added to the second component containing the epoxy curing agent (D) having reactivity with an epoxy group, which will be described later, the component (B) preferably has no epoxy group in the shell layer.

The curable resin composition may contain (i) core-shell polymer particles (B) having an epoxy group in a shell layer in a first component, and (ii) core-shell polymer particles (B) having no epoxy group in a shell layer in a second component.

In embodiment 1, the particle diameter of the core-shell polymer particles (B) is not particularly limited. In view of industrial productivity, the volume average particle diameter (Mv) of the core-shell polymer particles (B) in embodiment 1 is preferably 0.01 μm to 2.00 μm (10 nm to 2000 nm), more preferably 0.03 μm to 0.60 μm (30 nm to 600 nm), more preferably 0.05 μm to 0.40 μm (50 nm to 400 nm), more preferably 0.10 μm to 0.30 μm (100 nm to 300 nm), more preferably 0.15 μm to 0.30 μm, more preferably 0.16 μm to 0.28 μm, more preferably 0.17 μm to 0.27 μm, and still more preferably 0.18 μm to 0.25 μm. In the case where the volume average particle diameter (Mv) of the core-shell polymer particles (B), (a) is 0.01 μm or more, the viscosity of the curable resin composition is reduced, and thus the handleability is improved, and in the case where (B) is 2.00 μm or less, the polymerization time of the component (B) is shortened, and the industrial productivity is improved. In the present specification, the volume average particle diameter (Mv) of the polymer particles can be measured using Microtrac UPA150 (manufactured by daily nectar corporation) to measure the latex of the polymer particles.

In the curable resin composition, the core-shell polymer particles (B) preferably have a half width of 0.5 to 1 times the volume average particle diameter in the number distribution of the particle diameters, because the obtained curable resin composition is easy to handle with low viscosity.

From the viewpoint of easy realization of the above-described specific particle size distribution, it is preferable that 2 or more maxima exist in the particle size distribution of the core-shell polymer particles (B), and from the viewpoint of labor and cost at the time of production, it is more preferable that 2 to 3 maxima exist, and it is still more preferable that 2 maxima exist. It is particularly preferable that the polymer contains 10 to 90% by weight of core-shell polymer particles having a volume average particle diameter of 10nm or more and less than 150nm, and 90 to 10% by weight of core-shell polymer particles having a volume average particle diameter of 150nm or more and 2000nm or less.

The core-shell polymer particles (B) are preferably dispersed in the curable resin composition in the form of primary particles. The term "core-shell polymer particles are dispersed in the form of primary particles" (hereinafter also referred to as primary dispersion) in the present specification means that the core-shell polymer particles are dispersed substantially independently of each other (without contact), and the dispersion state can be confirmed, for example, by dissolving a part of the curable resin composition in a solvent such as methyl ethyl ketone and measuring the particle diameter thereof by a particle diameter measuring device or the like based on laser light scattering.

The value of the volume average particle diameter (Mv)/number average particle diameter (Mn) obtained by the particle diameter measurement is not particularly limited, but is preferably 3.0 or less, more preferably 2.5 or less, further preferably 2.0 or less, and particularly preferably 1.5 or less. When the volume average particle diameter (Mv)/number average particle diameter (Mn) is 3.0 or less, it is considered that the core-shell polymer particles (B) are well dispersed, and the physical properties such as impact resistance and adhesiveness of the obtained cured product are good.

The volume average particle diameter (Mv)/number average particle diameter (Mn) can be determined by measuring using Microtrac UPA (manufactured by daily necessaries corporation) and dividing Mv by Mn.

The term "stable dispersion" of the core-shell polymer particles means a state in which the core-shell polymer particles are stably dispersed for a long period of time under normal conditions without aggregation, separation, or precipitation in the continuous layer. In addition, it is preferable that the distribution of the core-shell polymer particles in the continuous layer is not substantially changed, and that "stable dispersion" can be maintained even if the composition is stirred by heating the composition in a range where there is no danger to reduce the viscosity.

The core-shell polymer particles (B) may be used alone or in combination of 1 or more than 2.

The core-shell polymer particles (B) are not particularly limited in structure, and preferably have 2 or more layers. In addition, the core layer may have a structure of 3 or more layers including an intermediate layer covering the core layer and a shell layer further covering the intermediate layer.

The layers of the core-shell polymer particles (B) will be specifically described below.

Nuclear layer

In order to improve the toughness of the cured product of the curable resin composition, the core layer is preferably an elastic core layer having properties as rubber. In order to have the property as a rubber, the gel content of the elastic core layer is preferably 60% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more. The gel content as used herein refers to a ratio of insoluble components to the total amount of insoluble components and soluble components when 0.5g of chips (crumbs) obtained by solidification and drying is immersed in 100g of toluene and allowed to stand at 23℃for 24 hours, and then separated into insoluble components and soluble components.

The core layer preferably contains 1 or more selected from diene rubbers, (meth) acrylate rubbers, and organosiloxane rubbers. The core layer preferably contains a diene rubber from the viewpoint of high effect of improving impact peel adhesion of the obtained cured product and the viewpoint of less tendency to cause an increase in viscosity over time due to swelling of the core layer by the component (a) due to low affinity with the epoxy resin (a).

(diene rubber)

Examples of the conjugated diene monomer constituting the diene rubber include: 1, 3-butadiene, isoprene, 2-chloro-1, 3-butadiene, 2-methyl-1, 3-butadiene, and the like. These conjugated diene monomers may be used alone or in combination of 2 or more.

The content of the conjugated diene monomer is preferably in the range of 50 to 100% by weight of the core layer, more preferably in the range of 70 to 100% by weight, and still more preferably in the range of 90 to 100% by weight. When the content of the conjugated diene monomer is 50% by weight or more, the impact peel adhesion resistance of the resulting cured product can be further improved.

Examples of the vinyl monomer copolymerizable with the conjugated diene monomer include: vinyl aromatic hydrocarbons such as styrene, α -methylstyrene, monochlorostyrene, dichlorostyrene, etc.; vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; halogenated vinyl groups such as vinyl chloride, vinyl bromide and chloroprene; vinyl acetate; olefins such as ethylene, propylene, butene, and isobutene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and divinylbenzene. These vinyl monomers may be used alone or in combination of 2 or more. Styrene is particularly preferred.

The content of the vinyl monomer copolymerizable with the conjugated diene monomer is preferably in the range of 0 to 50% by weight, more preferably in the range of 0 to 30% by weight, and still more preferably in the range of 0 to 10% by weight of the core layer. When the content of the vinyl monomer copolymerizable with the conjugated diene monomer is 50% by weight or less, the impact peel adhesion resistance of the resulting cured product can be further improved.

The diene rubber is preferably butadiene rubber using 1, 3-butadiene and/or styrene-butadiene rubber as a copolymer of 1, 3-butadiene and styrene, more preferably butadiene rubber, from the viewpoint of high effect of improving impact peel adhesion and the viewpoint of less tendency to cause an increase in viscosity with time due to swelling of the core layer due to low affinity with the epoxy resin (a). In addition, styrene-butadiene rubber is preferable from the viewpoint of improving the transparency of the cured product obtained by adjusting the refractive index.

((meth) acrylate rubber)

The (meth) acrylate rubber is preferably a rubber elastomer obtained by polymerizing a monomer mixture containing 50 to 100% by weight of at least 1 monomer selected from (meth) acrylate monomers and 0 to 50% by weight of other vinyl monomers copolymerizable with the (meth) acrylate monomers.

Examples of the (meth) acrylic acid ester monomer include: (i) Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate; (ii) Aromatic ring-containing (meth) acrylates such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate; (iii) Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; (iv) Glycidyl (meth) acrylates such as glycidyl (meth) acrylate and glycidyl alkyl (meth) acrylate; (v) alkoxyalkyl (meth) acrylates; (vi) Allyl (meth) acrylate esters such as allyl (meth) acrylate and allyl alkyl (meth) acrylate; (vii) And polyfunctional (meth) acrylates such as monoethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate. These (meth) acrylic acid ester monomers may be used alone or in combination of 1 or more than 2. The (meth) acrylic acid ester monomer is preferably ethyl (meth) acrylate, butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate.

Examples of the other vinyl monomer copolymerizable with the (meth) acrylic acid ester monomer include: (i) Vinyl aromatic hydrocarbons such as styrene, α -methylstyrene, monochlorostyrene, dichlorostyrene, etc.; (ii) vinylcarboxylic acids such as acrylic acid and methacrylic acid; (iii) vinyl cyanides such as acrylonitrile and methacrylonitrile; (iv) Halogenated vinyl groups such as vinyl chloride, vinyl bromide and chloroprene; (v) vinyl acetate; (vi) olefins such as ethylene, propylene, butene, and isobutylene; (vii) And polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and divinylbenzene. These vinyl monomers may be used alone or in combination of 2 or more. Styrene is particularly preferred from the viewpoint of being able to easily increase the refractive index.

(organosiloxane rubber)

Examples of the organosiloxane rubber include: (i) Polysiloxane polymers comprising alkyl or aryl disubstituted siloxy units such as dimethylsiloxy, diethylsiloxy, methylphenylsiloxy, diphenylsiloxy and dimethylsiloxy-diphenylsiloxy; (ii) And polysiloxane polymers comprising an alkyl group or aryl group-substituted siloxy unit, such as organohydrogensiloxy wherein a part of the alkyl group in the side chain is substituted with a hydrogen atom. These polysiloxane polymers may be used alone or in combination of 1 or more than 2. Among them, dimethylsiloxy, methylphenylsiloxy, and dimethylsiloxy-diphenylsiloxy are preferable from the viewpoint of imparting heat resistance to the cured product, and dimethylsiloxy is most preferable from the viewpoint of being easily obtainable. In the embodiment in which the core layer is formed of an organosiloxane rubber, the polysiloxane polymer site is preferably contained in an amount of 80 wt% or more (more preferably 90 wt% or more) based on 100 wt% of the whole organosiloxane rubber so as not to impair the heat resistance of the cured product.

In order to improve toughness of the obtained cured product, the glass transition temperature (hereinafter, sometimes simply referred to as "Tg") of the core layer is preferably 0℃or lower, more preferably-20℃or lower, further preferably-40℃or lower, particularly preferably-60℃or lower.

The volume average particle diameter of the core layer is not particularly limited, but is preferably 0.03 μm to 2 μm, more preferably 0.05 μm to 1 μm, still more preferably 0.12 μm to 0.50 μm, still more preferably 0.12 μm to 0.28 μm, and still more preferably 0.14 to 0.25 μm. When the volume average particle diameter of the core layer is within this range, the core layer can be stably produced, and the heat resistance and impact resistance of the cured product can be improved. In the present specification, the volume average particle diameter of the core layer may be measured using Microtrac UPA150 (manufactured by daily nectar corporation).

In the core-shell polymer particle (B) of embodiment 1, the proportion of the core layer is not particularly limited. The core-shell polymer particles (B) are preferably 40 to 97 wt%, more preferably 60 to 95 wt%, still more preferably 70 to 93 wt%, and particularly preferably 80 to 90 wt% of the core layer based on 100 wt% of the core layer. When the proportion of the core layer is 40% by weight or more, the impact peel adhesion resistance of the resulting cured product can be further improved. When the proportion of the core layer is 97% by weight or less, the core-shell polymer particles are less likely to aggregate, and the curable resin composition has a lower viscosity, so that the handleability is improved.

In the core-shell polymer particle (B) of embodiment 1, the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer/weight of the shell layer) is not particularly limited. The ratio (weight of core layer/weight of shell layer) is preferably 65/35 to 92/8, more preferably 68/32 to 91/9, and still more preferably 70/30 to 90/10, from the viewpoint that the workability of the curable resin composition becomes more excellent and the impact-resistant adhesion of the cured product becomes more excellent.

The core layer is often a single-layer structure, but may be a multilayer structure formed of a layer having rubber elasticity. In addition, in the case where the core layer is a multilayer structure, the polymer compositions of the respective layers may be different from each other within the scope of the above disclosure.

Intermediate layer

An intermediate layer may be formed between the core layer and the shell layer as needed. In particular, the following rubber surface crosslinked layer may be formed as the intermediate layer. From the viewpoint of improving the toughness of the cured product obtained and improving the impact peel adhesion, it is preferable that the intermediate layer is not contained, and it is particularly preferable that the following rubber surface crosslinked layer is not contained.

When the intermediate layer is present, the proportion of the intermediate layer to 100 parts by weight of the core layer is preferably 0.1 to 30 parts by weight, more preferably 0.2 to 20 parts by weight, still more preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight.

The rubber surface crosslinked layer is formed of an intermediate layer polymer obtained by polymerizing a rubber surface crosslinked layer component containing 30 to 100% by weight of a polyfunctional monomer having 2 or more radical polymerizable double bonds in one molecule and 0 to 70% by weight of other vinyl monomers, and has an effect of reducing the viscosity of the curable resin composition and an effect of improving the dispersibility of the core-shell polymer particles (B) in the component (A). In addition, increasing the crosslinking density of the core layer also has the effect of increasing the grafting efficiency of the shell layer.

Specific examples of the polyfunctional monomer include allyl (meth) acrylate esters such as allyl (meth) acrylate esters and allyl alkyl (meth) acrylate esters excluding conjugated diene monomers such as butadiene; allyloxyalkyl (meth) acrylates; multifunctional (meth) acrylates having 2 or more (meth) acrylic groups such as (poly) ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and tetraethylene glycol di (meth) acrylate; diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, etc., preferably allyl methacrylate, triallyl isocyanurate. In the present specification, (meth) acrylate means acrylate and/or methacrylate.

Shell layer

The shell layer present on the outermost side of the core-shell polymer particle is a polymer obtained by polymerizing a shell layer-forming monomer. The polymer (shell polymer) constituting the shell layer functions to improve the compatibility between the core-shell polymer particles (B) and the component (a) and to disperse the core-shell polymer particles (B) in the form of primary particles in the curable resin composition or cured product thereof.

Such shell polymers are preferably grafted to the core layer and/or the intermediate layer described above. In the following, the term "grafted to the core layer" also includes a method of grafting to the intermediate layer when forming the intermediate layer on the core layer. More specifically, it is preferable that the monomer component used for forming the shell layer is graft-polymerized to the core polymer forming the core layer (in the case where the intermediate layer is formed, the core polymer also contains the intermediate layer polymer forming the intermediate layer the same applies hereinafter), and the shell polymer is substantially chemically bonded to the core polymer (in the case where the intermediate layer is formed, the shell polymer is also preferably chemically bonded to the intermediate layer polymer). That is, the shell polymer is preferably formed by graft-polymerizing the shell-forming monomer in the presence of the core polymer, and thereby graft-polymerized to the core polymer to coat a part or the whole of the core polymer. The polymerization operation may be performed by adding a shell polymer layer-forming monomer to a latex of a core polymer prepared in an aqueous polymer latex state and polymerizing it.

In the core-shell polymer particles (B), at least a part of the shell polymer forming the shell layer may be graft polymerized (graft-bonded) to the core polymer, and the core layer and the shell layer may not form a complete layer structure. In other words, the shell polymer may not coat the entire core layer. In the core-shell polymer particles (B), a part of the shell polymer may enter the core layer. In the core-shell polymer particles (B), it is preferable that a part of the shell polymer coats the core layer, in other words, it is preferable that a part of the shell polymer exists on the outermost surface (forming the outermost layer) of the core-shell polymer particles (B).

The composition of the monomer for forming a shell layer, that is, the kind and the content ratio of the monomer contained in the monomer for forming a shell layer are not particularly limited. The shell layer forming monomer is preferably an aromatic vinyl monomer, a vinyl cyanide monomer, or a (meth) acrylate monomer, and more preferably a (meth) acrylate monomer, from the viewpoints of compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition. Particularly preferably, the shell-forming monomer contains methyl methacrylate. These shell layer forming monomers may be used alone or in combination of 1.

In other words, the type and content ratio of the structural units contained in the shell layer are not particularly limited. From the viewpoints of compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition, the shell layer preferably contains structural units derived from 1 or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and (meth) acrylate monomers, and more preferably contains structural units derived from (meth) acrylate monomers. It is particularly preferred that the shell layer comprises structural units derived from methyl methacrylate.

The total amount of the aromatic vinyl monomer, vinyl cyanide monomer, and (meth) acrylate monomer is preferably 10.0 to 99.5 wt%, more preferably 50.0 to 99.0 wt%, even more preferably 65.0 to 98.0 wt%, particularly preferably 67.0 to 80.0 wt%, and most preferably 67.0 to 85.0 wt% in 100 wt% of the shell layer forming monomer.

In other words, the shell layer preferably contains 10.0 to 99.5 wt% in total of the structural units derived from 1 or more monomers selected from the group consisting of aromatic vinyl-containing monomers, vinyl cyanide monomers and (meth) acrylate monomers in the shell layer (shell polymer) 100 wt%, more preferably 50.0 to 99.0 wt%, still more preferably 65.0 to 98.0 wt%, particularly preferably 67.0 to 80.0 wt%, and most preferably 67.0 to 85.0 wt%.

Specific examples of the aromatic vinyl monomer include: vinyl benzenes such as styrene, α -methylstyrene, p-methylstyrene, divinylbenzene, etc.

Specific examples of the vinyl cyanide monomer include: acrylonitrile, methacrylonitrile, and the like.

Specific examples of the (meth) acrylate monomer include: alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; hydroxyalkyl (meth) acrylates, and the like.

Specific examples of the hydroxyalkyl (meth) acrylate include, for example: hydroxy linear alkyl (meth) acrylates (especially hydroxy linear C1-6 alkyl (meth) acrylates), such as 2-hydroxyethyl (meth) acrylate, hydroxy propyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; caprolactone-modified hydroxy (meth) acrylates; hydroxyl group-containing (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, etc., alpha- (hydroxymethyl) acrylate, hydroxyl group-containing (meth) acrylates such as mono (meth) acrylates of polyester diols (especially saturated polyester diols) obtained from dicarboxylic acids (phthalic acid, etc.) and diols (propylene glycol, etc.), etc.

The shell layer of embodiment 1 is preferably a copolymer obtained by polymerizing a shell layer-forming monomer containing 55% by weight or more of an alkyl ester having 1 to 4 carbon atoms of (meth) acrylic acid in 100% by weight of the shell layer-forming monomer. In other words, the shell layer in embodiment 1 preferably contains 55% by weight or more of the structural unit derived from the alkyl ester having 1 to 4 carbon atoms in (meth) acrylic acid in 100% by weight of the shell layer. The shell layer of embodiment 1 is preferably a copolymer obtained by polymerizing 65% by weight or more of a monomer component containing an alkyl ester having 1 to 4 carbon atoms of (meth) acrylic acid in 100% by weight of the monomer for forming the shell layer, more preferably a copolymer obtained by polymerizing 75% by weight or more of a monomer component, still more preferably a copolymer obtained by polymerizing 78% by weight or more of a monomer component, and particularly preferably a copolymer obtained by polymerizing 83% by weight or more of a monomer component. When the shell layer-forming monomer contains an alkyl ester of 1 to 4 carbon atoms of (meth) acrylic acid in the above-mentioned range, there is an advantage that the curable resin composition has good handleability.

Specific examples of the alkyl (meth) acrylate having 1 to 4 carbon atoms include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, and the like.

The monomer for forming a shell layer in embodiment 1 preferably contains 10 to 100% by weight of an alkyl ester of (meth) acrylic acid having 1 carbon atom and 0 to 80% by weight of an alkyl ester of (meth) acrylic acid having 4 carbon atoms in 100% by weight of the monomer for forming a shell layer. In other words, the shell layer of embodiment 1 preferably contains 10 to 100% by weight of the structural unit derived from the alkyl ester of (meth) acrylic acid having 1 carbon atom and 0 to 80% by weight of the structural unit derived from the alkyl ester of (meth) acrylic acid having 4 carbon atoms.

The monomer for forming a shell layer in embodiment 1 more preferably contains 11 to 95% by weight, still more preferably 12 to 92% by weight, still more preferably 13 to 55% by weight, and particularly preferably 14 to 50% by weight of the alkyl (meth) acrylate having 1 carbon atom in 100% by weight of the monomer for forming a shell layer. The monomer for forming a shell layer in embodiment 1 preferably contains 1 to 89% by weight, more preferably 1 to 88% by weight, preferably 1 to 87% by weight, preferably 1 to 86% by weight, more preferably 1 to 78% by weight, more preferably 2 to 76% by weight, more preferably 5 to 76% by weight, more preferably 8 to 76% by weight, more preferably 20 to 74% by weight, more preferably 35 to 72% by weight, more preferably 35 to 60% by weight, and particularly preferably 35 to 50% by weight of the alkyl ester having 4 carbon atoms in the monomer for forming a shell layer in 100% by weight. When the shell layer forming monomer constituting the shell layer of the core-shell polymer particle (B) contains an alkyl ester of (meth) acrylic acid having 1 carbon atom and/or an alkyl ester of (meth) acrylic acid having 4 carbon atoms in the above-mentioned range, the interaction between the core-shell polymer particle (B) and the component (C) can be appropriately controlled, and therefore, the viscosity of the curable resin composition is suppressed to a very low level, and there is an advantage that the workability becomes good.

Methyl methacrylate and methyl acrylate can be used as the alkyl ester of (meth) acrylic acid having 1 carbon atom. As the alkyl ester of (meth) acrylic acid having 4 carbon atoms, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, and t-butyl methacrylate can be used.

From the viewpoint of improving the handleability of the curable resin composition, the shell layer-forming monomer of embodiment 1 preferably has both an alkyl ester having 1 carbon atom (meth) acrylate and an alkyl ester having 4 carbon atoms (meth) acrylate, and more preferably contains 13 to 55 wt% of the alkyl ester having 1 carbon atom (meth) acrylate and 20 to 74 wt% of the alkyl ester having 4 carbon atoms (meth) acrylate. In other words, the shell layer of embodiment 1 preferably has both a structural unit derived from an alkyl ester having 1 carbon atom of (meth) acrylic acid and a structural unit derived from an alkyl ester having 4 carbon atoms of (meth) acrylic acid, and preferably contains 13 to 55 wt% of a structural unit derived from an alkyl ester having 1 carbon atom of (meth) acrylic acid and 20 to 74 wt% of a structural unit derived from an alkyl ester having 4 carbon atoms of (meth) acrylic acid.

The shell layer forming monomer of embodiment 1 is not required to be such that the total of the alkyl ester having 1 carbon atom (meth) acrylate and the alkyl ester having 4 carbon atoms (meth) acrylate in 100% by weight of the shell layer forming monomer is 100% by weight. In other words, the total of (a) the alkyl ester having 1 carbon atom of (meth) acrylic acid, (b) the alkyl ester having 4 carbon atoms of (meth) acrylic acid, and (c) the monomer other than the alkyl ester having 1 carbon atom of (meth) acrylic acid and the alkyl ester having 4 carbon atoms of (meth) acrylic acid in 100% by weight of the monomer for forming a shell layer in embodiment 1 is 100% by weight of the monomer for forming a shell layer. That is, the shell layer forming monomer of embodiment 1 may contain a monomer other than the alkyl ester of (meth) acrylic acid having 1 carbon atom and the alkyl ester of (meth) acrylic acid having 4 carbon atoms.

When the shell layer-forming monomer contains an aromatic vinyl monomer and/or a vinyl cyanide monomer, that is, when the shell layer contains a structural unit derived from an aromatic vinyl monomer and/or a structural unit derived from a vinyl cyanide monomer, the compatibility and dispersibility of the core-shell polymer particles (B) in the curable resin composition become good. On the other hand, in embodiment 1, the content of the aromatic vinyl monomer in 100 wt% of the shell-forming monomer may be 30 wt% or less, 20 wt% or less, 10 wt% or less, 8 wt% or less, or 6 wt% or less, in view of the fact that the curable resin composition can be improved in handleability by reducing the interaction between the component (B) and the component (C). In other words, in embodiment 1, the content of the structural unit derived from the aromatic vinyl monomer in 100 wt% of the shell layer may be 30 wt% or less, may be 20 wt% or less, may be 10 wt% or less, may be 8 wt% or less, and may be 6 wt% or less. In addition, from the viewpoint of improving the handleability of the curable resin composition, in embodiment 1, the content of the vinyl cyanide monomer in 100 wt% of the shell-forming monomer may be 10 wt% or less, 8 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, or 2 wt% or less. In other words, in embodiment 1, the content of the structural unit derived from the vinyl cyanide monomer in the shell layer 100 wt% is preferably 10 wt% or less, may be 8 wt% or less, may be 5 wt% or less, may be 4 wt% or less, may be 3 wt% or less, and may be 2 wt% or less.

The shell layer-forming monomer may further contain a (meth) acrylate monomer having 5 or more carbon atoms. In other words, the shell layer may further have a structural unit derived from a (meth) acrylate monomer having 5 or more carbon atoms. Specific examples of the (meth) acrylic acid ester monomer having 5 or more carbon atoms include 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, and the like.

In order to maintain the core-shell polymer particles (B) in a good dispersion state without aggregation in the cured product or the curable resin composition, the shell-forming monomer is preferably a monomer containing a reactive group selected from the group consisting of an epoxy group, an oxetane group, a hydroxyl group, an amino group, an imide group, a carboxylic acid anhydride group, a cyclic ester, a cyclic amide, and a benzo group, from the viewpoint of chemical bonding with the component (A)More than 1 kind of oxazinyl group and cyanate ester group are particularly preferable monomers having epoxy groups.

The shell layer is preferably a polymer obtained by graft polymerizing a shell layer forming monomer containing a monomer component having an epoxy group to a core layer (core polymer). With this configuration, the cured product obtained has an advantage of excellent impact peel adhesion resistance.

From the viewpoints of impact-resistant peel adhesion and storage stability, the monomer for forming a shell layer is preferably contained in an amount of 0 to 90% by weight, more preferably 1 to 50% by weight, still more preferably 2 to 35% by weight, and particularly preferably 3 to 20% by weight, based on 100% by weight of the monomer for forming a shell layer.

In other words, the shell layer preferably has a structural unit derived from a monomer having an epoxy group. The shell layer preferably contains 0 to 90 wt%, more preferably 1 to 50 wt%, still more preferably 2 to 35 wt%, and particularly preferably 3 to 20 wt% of the structural unit derived from the monomer having an epoxy group in 100 wt% of the shell layer.

The monomer having an epoxy group is preferably used for the formation of a shell layer, more preferably used only for the formation of a shell layer.

In addition, when a polyfunctional monomer having 2 or more radical polymerizable double bonds is used as the shell layer-forming monomer, it is preferable because the core-shell polymer particles in the curable resin composition can be prevented from swelling, and the curable resin composition tends to have low viscosity and good handleability. On the other hand, from the viewpoint of improving the toughness effect and the impact peel adhesion resistance effect of the obtained cured product, it is preferable not to use a polyfunctional monomer having 2 or more radical polymerizable double bonds as the shell layer forming monomer.

The monomer for forming a shell layer may be contained in an amount of, for example, 0 to 20% by weight, preferably 1 to 20% by weight, and more preferably 5 to 15% by weight, based on 100% by weight of the monomer for forming a shell layer.

Specific examples of the monomer having a hydroxyl group of the reactive group-containing monomer include, for example: hydroxy linear alkyl (meth) acrylates (especially hydroxy linear C1-6 alkyl (meth) acrylates), such as 2-hydroxyethyl (meth) acrylate, hydroxy propyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; caprolactone-modified hydroxy (meth) acrylates; hydroxyl group-containing (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, etc., alpha- (hydroxymethyl) acrylate, hydroxyl group-containing (meth) acrylates such as mono (meth) acrylates of polyester diols (especially saturated polyester diols) obtained from dicarboxylic acids (phthalic acid, etc.) and diols (propylene glycol, etc.), etc.

Specific examples of the monomer having an epoxy group include: glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether and allyl glycidyl ether.

Specific examples of the polyfunctional monomer having 2 or more radical polymerizable double bonds include the same monomers as those described above, and allyl methacrylate and triallyl isocyanurate are preferable.

The shell layer of embodiment 1 is preferably a polymer of, for example, the following shell layer forming monomer: a shell layer forming monomer (total 100 wt%) obtained by combining (a) 0 to 50 wt% (preferably 1 to 50 wt%, more preferably 2 to 48 wt%) of an aromatic vinyl monomer (particularly styrene), (b) 0 to 50 wt% (preferably 0 to 30 wt%, more preferably 10 to 25 wt%) of a vinyl cyanide monomer (particularly acrylonitrile), (c) 0 to 100 wt% (preferably 5 to 100 wt%, more preferably 70 to 95 wt%) of a (meth) acrylic ester monomer (particularly methyl methacrylate), and (d) 1 to 50 wt% (preferably 2 to 35 wt%, more preferably 3 to 20 wt%) of a monomer having an epoxy group (particularly glycidyl methacrylate). Thus, a desired toughness improvement effect and mechanical properties can be achieved in a well-balanced manner.

The shell layer of embodiment 1 is preferably a polymer of, for example, the following shell layer forming monomer: a shell layer forming monomer (total 100 wt%) obtained by combining (a) 10 to 100 wt% (preferably 11 to 95 wt%, particularly preferably 14 to 50 wt%) of an alkyl ester monomer having 1 carbon atom (meth) acrylic acid (particularly methyl methacrylate), (b) 0 to 80 wt% (preferably 1 to 78 wt%, particularly preferably 35 to 72 wt%) of an alkyl ester monomer having 4 carbon atoms (meth) acrylic acid (particularly butyl acrylate), (c) 30 wt% or less (preferably 10 wt% or less, more preferably 0 wt%) of an aromatic vinyl monomer (particularly styrene), (d) 10 wt% or less (preferably 5 wt% or less, more preferably 0 wt%) of a vinyl cyanide monomer (particularly acrylonitrile), and (e) 0 to 45 wt% (preferably 0 to 25 wt%, more preferably 3 to 20 wt%) of a monomer having an epoxy group (particularly glycidyl methacrylate). Thus, the desired effect of improving toughness and operability can be achieved in a well-balanced manner.

These monomer components may be used alone or in combination of 2 or more. The shell layer may be formed to contain other monomer components in addition to the above-mentioned monomer components.

From the viewpoint of improving the handleability of the curable resin composition, the glass transition temperature (hereinafter, sometimes simply referred to as "Tg") of the shell layer is preferably from-45 ℃ to 110 ℃, more preferably from-40 ℃ to 100 ℃, still more preferably from-35 ℃ to 50 ℃, particularly preferably from-30 ℃ to 10 ℃.

The grafting ratio of the shell layer is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. When the grafting ratio is 70% or more, the curable resin composition can have a lower viscosity.

The method for calculating the grafting ratio is as follows. First, an aqueous latex containing core-shell polymer particles is coagulated/dehydrated, and finally, dried to obtain a powder of core-shell polymer particles. Next, 2g of the powder of the core-shell polymer particles was immersed in 100g of Methyl Ethyl Ketone (MEK) at 23 ℃ for 24 hours, and then the MEK-soluble component was separated from the MEK-insoluble component, and the methanol-insoluble component was further separated from the MEK-soluble component. Then, the grafting ratio was calculated by determining the ratio of the MEK insoluble component to the total amount of the MEK insoluble component and the methanol insoluble component.

Method for producing core-shell Polymer particles

(method for producing Nuclear layer)

The formation of the core layer constituting the core-shell polymer particles (B) can be carried out by, for example, emulsion polymerization, suspension polymerization, or microsuspension polymerization, and for example, the methods described in international publication nos. 2005/028546 and 2006/070664 can be used.

(method for forming Shell layer and intermediate layer)

The intermediate layer can be formed by polymerizing an intermediate layer-forming monomer by known radical polymerization. In the case of obtaining the rubber elastomer constituting the core layer in the form of an emulsion, the polymerization of the monomer for forming the intermediate layer is preferably performed by an emulsion polymerization method.

The shell layer can be formed by polymerizing a shell layer-forming monomer by known radical polymerization. In the case of obtaining the core layer as an emulsion or the polymer particle precursor composed of the core layer coated with the intermediate layer, the polymerization of the monomer for forming the shell layer is preferably performed by an emulsion polymerization method, and can be produced, for example, according to the method described in International publication No. 2005/028546.

Examples of the emulsifier (dispersant) that can be used in the emulsion polymerization include: anionic emulsifiers (dispersants) such as alkyl or aryl sulfonic acids represented by dioctyl sulfosuccinate, dodecylbenzenesulfonic acid, alkyl or aryl ether sulfonic acids, alkyl or aryl sulfuric acids represented by dodecylsulfuric acid, alkyl or aryl ether sulfuric acids, alkyl or aryl substituted phosphoric acids, alkyl or aryl ether substituted phosphoric acids, N-alkyl or aryl sarcosins represented by dodecylsarcosins, alkyl or aryl carboxylic acids represented by oleic acid, stearic acid, etc., alkyl or aryl ether carboxylic acids, alkali metal salts or ammonium salts of these acids, etc.; nonionic emulsifiers (dispersants) such as alkyl or aryl substituted polyethylene glycols; and dispersing agents such as polyvinyl alcohol, alkyl substituted cellulose, polyvinylpyrrolidone, polyacrylic acid derivatives, and the like. These emulsifiers (dispersants) may be used alone or in combination of 2 or more.

The amount of the emulsifier (dispersant) used is preferably reduced as long as the dispersion stability of the aqueous latex of the polymer particles is not impaired. In addition, the higher the water solubility of the emulsifier (dispersant), the more preferable. When the water solubility is high, the removal of the emulsifier (dispersant) by washing with water becomes easy, and adverse effects on the finally obtained cured product can be easily prevented.

In the case of emulsion polymerization, a known initiator, namely, 2' -azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate, or the like can be used as the thermal decomposition initiator.

In addition, a redox initiator may be used, and the redox initiator may be an organic peroxide such as t-butyl peroxyisopropyl carbonate, terpene hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, or t-hexyl peroxide; and a peroxide such as hydrogen peroxide, inorganic peroxide such as potassium persulfate and ammonium persulfate, a reducing agent such as sodium formaldehyde sulfoxylate and glucose added as needed, a transition metal salt such as iron (II) sulfate added as needed, a chelating agent such as disodium ethylenediamine tetraacetate further added as needed, and a phosphorus-containing compound such as sodium pyrophosphate further added as needed.

In the case of using a redox initiator, polymerization can be carried out even at a low temperature at which substantially no thermal decomposition of the peroxide occurs, and the polymerization temperature can be set in a wide range, which is preferable. Among them, organic peroxides such as cumene hydroperoxide, diisopropylbenzene peroxide and t-butyl hydroperoxide are preferably used as redox initiators. In the case of using the redox initiator, the amount of the reducing agent, the transition metal salt, the chelating agent, and the like may be used in a known range. In addition, when a monomer having 2 or more radical polymerizable double bonds is polymerized, the monomer may be used in a known range. A surfactant may be additionally used, and this is also a known range.

The polymerization temperature, pressure, deoxidation and other conditions in the polymerization may be within known ranges. The polymerization of the intermediate layer-forming monomer may be performed in 1 step or 2 or more steps. For example, it is possible to use: a method of adding the intermediate layer forming monomer to the emulsion of the rubber elastomer constituting the elastic core layer at one time, a method of continuously adding the intermediate layer forming monomer, a method of adding the emulsion of the rubber elastomer constituting the elastic core layer to a reactor in which the intermediate layer forming monomer is previously charged, and then polymerizing the mixture.

When the core-shell polymer particles are used as the component (B), the content of the core-shell polymer particles in the curable resin composition is preferably 1 to 100 parts by weight, more preferably 5 to 90 parts by weight, still more preferably 10 to 80 parts by weight, still more preferably 20 to 70 parts by weight, and particularly preferably 30 to 60 parts by weight, relative to 100 parts by weight of the epoxy resin (a), from the viewpoint of balance between the ease of handling the obtained curable resin composition and the effect of improving toughness of the obtained cured product.

< aluminium hydroxide (C) >)

In the curable resin composition according to embodiment 1, aluminum hydroxide having an average particle diameter of 11 μm or more and 200 μm or less is contained as the component (C) in the first component and/or the second component. When the curable resin composition of embodiment 1 contains the component (C), the obtained cured product has the advantage of excellent thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical burning test (UL 94)).

In embodiment 1, the total weight of aluminum hydroxide (C) must be 55 wt% or more and 85 wt% or less with respect to the total weight of the curable resin composition.

(C) The component may be contained in only the first component, may be contained in only the second component, or may be contained in both the first component and the second component. From the viewpoint of blending a large amount of the component (C) into the curable resin composition, the component (C) is preferably contained in at least the first component, more preferably in both the first component and the second component.

Aluminum hydroxide is prepared from Al (OH) ₃ Or Al ₂ O ₃ ·3H ₂ The white powder crystal represented by the chemical formula of O is generally produced by the bayer process using bauxite as a raw material. Aluminum hydroxide exists in products having various average particle diameters by classification.

The aluminum hydroxide used in embodiment 1 has an average particle diameter of 11 μm or more and 200 μm or less, which is very important.

(C) The component (a) may be subjected to a coupling treatment for improving the adhesion with the component (a). This can improve the physical properties such as impact resistance, strength, and water resistance of the cured product obtained. These coupling agents are not particularly limited, and examples thereof include: among them, a silane-based coupling agent, a chromium-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, and the like are preferable, and an epoxy silane coupling agent is more preferable. The coupling agent may be used alone or in combination of 2 or more kinds.

In embodiment 1, the average particle diameter of the component (C) in the curable resin composition before curing is required to be 11 μm or more and 200 μm or less, preferably 12 μm or more and 150 μm or less, more preferably 13 μm or more and 100 μm or less, still more preferably 15 μm or more and 50 μm or less, particularly preferably 17 μm or more and 30 μm or less, from the viewpoint of both the impact resistance and adhesive strength of the obtained cured product and the viewpoint of suppressing the sedimentation with time of the component (C) in the curable resin composition before curing.

In the present specification, the average particle diameter of the component (C) can be obtained from measurement using a laser scattering particle size analyzer, and is the particle diameter (Dp 50) corresponding to 50% by volume of the cumulative particle size distribution ratio.

When a plurality of components (C) having different average particle diameters are used, the average particle diameter of the total of components (C) can be calculated by a weighted average of the values obtained by multiplying the weight% of each component (C) relative to the total amount of components (C) by the respective average particle diameters.

In embodiment 1, from the viewpoint of improving the properties (thermal conductivity, flame retardancy, adhesive strength, and impact resistance) of the obtained cured product and from the viewpoint of improving the handleability of the composition before curing, the total weight of aluminum hydroxide (C) must be 55% by weight or more and 85% by weight or less, preferably 57% by weight or more and 80% by weight or less, more preferably 60% by weight or more and 76% by weight or less, still more preferably 62% by weight or more and 73% by weight or less, particularly preferably 65% by weight or more and 70% by weight or less, relative to the total weight of the curable resin composition.

The content (amount of the aluminum hydroxide) is preferably 250 parts by weight or more and 750 parts by weight or less, more preferably 300 parts by weight or more and 700 parts by weight or less, still more preferably 350 parts by weight or more and 650 parts by weight or less, particularly preferably 400 parts by weight or more and 600 parts by weight or less, based on 100 parts by weight of the epoxy resin (a), from the viewpoint of improving the properties (heat conductivity, flame retardancy, adhesive strength and impact resistance) of the obtained cured product and improving the handleability of the composition before curing. (C) The components may be used alone or in combination of 1 or more than 2.

As described above, the polymer particles (B) and aluminum hydroxide (C) having a core-shell structure are preferably contained in the first component and/or the second component, respectively. In this case, the polymer particles (B) and the aluminum hydroxide (C) may or may not be contained in the same component, and when the polymer particles (B) and the aluminum hydroxide (C) are contained, the polymer particles (B) and the aluminum hydroxide (C) are preferably contained as the first component and the aluminum hydroxide (C) is preferably contained as the second component.

In embodiment 1, the component (C) is blended in a large amount in the curable resin composition in a range of 55 wt% to 85 wt%. However, in embodiment 1, the effect of improving impact resistance by the above-mentioned component (B) can be maintained at a high level by setting the average particle diameter of the component (C) to 11 μm or more and 200 μm or less, for reasons which will be described below, and which are presumed to be appropriate based on the theory of the plastic deformation region associated with the rubber particle addition system (refer to Jim and the like, "Japanese society of adhesion, vol.40, no.5,177-183").

Plastic deformation region r of plane strain field _p Use of resin toughness value K by Irwin _IC And tensile yield stress sigma is expressed as r _p ＝1/6π×(K _IC /σ) ² . Here, K is the K of a two-component epoxy adhesive which is to be toughened with core-shell polymer particles _IC And sigma are respectively assumed to be 1.5 Mpa.m ^1/2 And r at 50MPa _p 48 μm, plastic deformation region r _p Approximately several tens to 100 μm in size.

On the other hand, in the curable resin composition of embodiment 1, aluminum hydroxide (C) is highly filled in a range of 55 wt% or more and 85 wt% or less, and when aluminum hydroxide having a small particle diameter of about several μm is used, the distance between aluminum hydroxide particles is about several μm, and a sufficient plastic deformation region cannot be ensured, and by aluminum hydroxide particles larger than 10 μm, a certain degree of plastic deformation region can be gradually ensured, and it is estimated that the toughness improvement effect by the core-shell polymer particles (B) is exhibited.

< thermally conductive filler other than aluminum hydroxide >

The curable resin composition according to embodiment 1 may contain a thermally conductive filler other than aluminum hydroxide. Examples may include: silicon dioxide, aluminum oxide, aluminum nitride, boron nitride, silicon nitride, znO, siC, beO, and the like.

The content of the thermally conductive filler other than aluminum hydroxide in the curable resin composition is preferably 1 to 300 parts by weight, more preferably 2 to 200 parts by weight, particularly preferably 5 to 100 parts by weight, relative to 100 parts by weight of the epoxy resin (a).

< flame retardant other than aluminum hydroxide >

The curable resin composition of embodiment 1 may contain a flame retardant other than aluminum hydroxide. Examples may include: magnesium hydroxide, ammonium polyphosphate, tricresyl phosphate, triethyl phosphate, triphenyl phosphate, tris (chloropropyl) phosphate, dimethyl methylphosphonate, brominated polyether polyol, ammonium carbonate, melamine cyanurate, and the like.

The content of the flame retardant other than aluminum hydroxide in the curable resin composition is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, particularly preferably 5 to 50 parts by weight, relative to 100 parts by weight of the epoxy resin (a).

Epoxy curing agent (D)

The curable resin composition of embodiment 1 contains an epoxy curing agent as the component (D) in the second component.

(D) The component (c) is a compound (including an oligomer or a polymer) containing an active hydrogen group which can react with the epoxy resin (a) to form a crosslink even at a low temperature of the order of room temperature.

The epoxy curing agent (D) has reactivity with an epoxy group in the vicinity of room temperature (for example, 5 to 50 ℃ C. Or less). The epoxy curing agent (D) has reactivity with an epoxy group at a low temperature as compared with an epoxy curing agent for heat curing. The epoxy curing agent (D) has an effect of combining the polymer particles (B) and the compound (G) described later, thereby achieving both excellent quick curability and good adhesive strength without requiring a heat treatment at a high temperature exceeding 50 ℃.

The epoxy curing agent (D) of embodiment 1 is not particularly limited, and various epoxy curing agents can be used. As the epoxy curing agent (D) of embodiment 1, for example, there can be mentioned: (a) (a-1) aromatic amines, aliphatic amines, alicyclic amines, amide amines, amine-terminated polyethers and amine-terminated nitrile rubbers, and (a-2) their modified products, namely amine curing agents; and (b) a thiol curing agent; etc. Among them, the epoxy curing agent (D) of embodiment 1 is more preferably an amine curing agent from the viewpoint of the adhesive strength of the cured product obtained.

In the epoxy curing agent (D) according to embodiment 1, from the viewpoint of curability (quick curability) at room temperature, the amine curing agent (a) preferably contains 1 or more selected from the group consisting of aliphatic amines, alicyclic amines, amide amines, amine-terminated polyethers, amine-terminated nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amide amines, modified amine-terminated polyethers, and modified amine-terminated nitrile rubbers, and (b) more preferably contains 1 or more selected from the group consisting of aliphatic amines, alicyclic amines, amide amines, amine-terminated polyethers, amine-terminated nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amide amines, modified amine-terminated polyethers, and modified amine-terminated nitrile rubbers. In the epoxy curing agent (D) of embodiment 1, (a) is preferably 1 or more selected from the group consisting of amino terminated polyethers and amino terminated nitrile rubbers from the viewpoint of impact resistance of the cured product obtained, (a-1) is more preferably 1 or more selected from the group consisting of amino terminated polyethers and amino terminated nitrile rubbers, and (a-2) is more preferably 1 or more selected from the group consisting of amino terminated polyethers and amino terminated nitrile rubbers, and (b) is more preferably amino terminated nitrile rubbers from the viewpoint of curability. In the epoxy curing agent (D) according to embodiment 1, (a) preferably contains 1 or more selected from the group consisting of alicyclic amine, amide amine, amine terminated polyether, amine terminated nitrile rubber, modified alicyclic amine, modified amide amine, modified amine terminated polyether, and modified amine terminated nitrile rubber, among the amine curing agents, (a-1) more preferably contains 1 or more selected from the group consisting of alicyclic amine, amide amine, amine terminated polyether, amine terminated nitrile rubber, modified alicyclic amine, modified amide amine, modified amine terminated polyether, and modified amine terminated nitrile rubber, (b) more preferably contains 1 or more selected from the group consisting of alicyclic amine and amine terminated nitrile rubber, and (b-2) more preferably contains 1 or more selected from the group consisting of alicyclic amine and amine terminated nitrile rubber, from the viewpoint of curability. From the viewpoints of the adhesive strength and curability of the cured product obtained, the epoxy curing agent (D) of embodiment 1 more preferably contains at least 1 or more selected from the group consisting of alicyclic amines, amino-terminated nitrile rubbers, modified products of alicyclic amines and modified products of amino-terminated nitrile rubbers, and still more preferably contains at least 1 or more selected from the group consisting of alicyclic amines, amino-terminated nitrile rubbers, modified products of alicyclic amines and modified products of amino-terminated nitrile rubbers.

The aromatic amine may be exemplified by: meta-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.

The aliphatic amine may be: aliphatic aromatic amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine and the like.

The alicyclic amine may be exemplified by: n-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, menthanediamine, isophoronediamine, 4' -diaminodicyclohexylmethane, 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane as one of spiroacetal diamines, norbornanediamine, tricyclodecanediamine, 1, 3-diaminomethylcyclohexane, and the like.

The amide amine is a compound produced by condensing a dimer (dimer acid) of tall oil fatty acid with a polyamine such as triethylenetetramine and tetraethylenepentamine, and examples of the amide amine that are commercially available include Versamid140 and Versamid 115.

The amino-terminated polyether is preferably an amino-terminated polyether having a polyether main chain and preferably having 1 to 4 amino groups and/or imino groups per 1 molecule (more preferably having 1.5 to 3 amino groups), and examples of commercially available amino-terminated polyethers include Jeffamine D-230, jeffamine D-400, jeffamine D-2000, jeffamine D-4000, jeffamine T-5000, etc. manufactured by Huntsman corporation.

The above-mentioned amino-terminated nitrile rubber is a polybutadiene/acrylonitrile copolymer having an average of preferably 1 to 4 (more preferably 1.5 to 3) amino groups and/or imino groups per 1 molecule and an acrylonitrile monomer content of the main chain of 5 to 40% by mass (more preferably 10 to 35% by mass, further preferably 15 to 30% by mass). Examples of commercially available amino-terminated rubbers include Hypro 1300X16 ATBN, manufactured by CVC company.

Examples of the modified product of the amine curing agent include polyamine-epoxy resin adducts as a reactant of the above-mentioned various polyamines such as aliphatic amine and alicyclic amine with less than the same amount of epoxy resin, and ketimines as dehydration reaction products of polyamines with ketones such as methyl ethyl ketone and isobutyl methyl ketone.

More specifically, the thiol curing agent includes: pentaerythritol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutoxy) butane, 1,3, 5-tris (2- (3-sulfonylbutanoyloxy) ethyl) -1,3, 5-triazine-2, 4, 6-trione, trimethylol propane tris (3-mercaptobutyrate), thiol-terminated polyethers, thiol-terminated polysulfides, and the like.

From the viewpoints of the quick curability of the curable resin composition and the adhesive strength and impact resistance of the resulting cured product, the ratio of the number of moles of the epoxy groups of the epoxy resin (a) to the number of moles of the active hydrogen groups of the epoxy curing agent (D) (the number of moles of the epoxy groups/the number of moles of the active hydrogen groups) is preferably 0.5 or more and 1.6 or less, more preferably 1.1 or more and 1.6 or less, still more preferably 1.1 or more and 1.5 or less, particularly preferably 1.2 or more and 1.4 or less.

The content (blending amount) of the epoxy curing agent (D) is preferably 15 parts by weight or more and 300 parts by weight or less, more preferably 20 parts by weight or more and 200 parts by weight or less, still more preferably 30 parts by weight or more and 150 parts by weight or less, particularly preferably 40 parts by weight or more and 100 parts by weight or less, relative to 100 parts by weight of the epoxy resin (a), from the viewpoint of both the adhesive strength and impact resistance of the obtained cured product and the ease of mixing when the first component and the second component are mixed. (D) The components may be used alone or in combination of 1 or more than 2.

The curable resin composition of embodiment 1 may or may not contain an aromatic amine. The curable resin composition of embodiment 1 preferably contains substantially no aromatic amine, because the resulting cured product has excellent tensile properties when heated. In the present specification, "substantially free of aromatic amine" means that the content of aromatic amine in 100 parts by weight of the curable resin composition is 1000ppm or less. Examples of the aromatic amine include m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

Epoxy curing agent exhibiting activity at high temperature other than component (D)

The curable resin composition of embodiment 1 may contain an epoxy curing agent that exhibits activity at high temperature in addition to an epoxy curing agent (such as the amine curing agent and the thiol curing agent) containing an active hydrogen group that can react with an epoxy resin at low temperature, within a range that does not impair the curing rate of the curable resin composition. As the epoxy curing agent exhibiting activity at high temperature, there may be mentioned: anhydride curing agents; boron trifluoride-amine complexes; dicyandiamide; organic acid hydrazides, and the like.

Compared with the amine curing agent, the anhydride curing agent needs high temperature, has long pot life and has good balance of physical properties such as electric property, chemical property and mechanical property of the cured product. The acid anhydride-based curing agent may be more specifically exemplified by: polysebacic polyanhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, alkenyl substituted succinic anhydride, dodecenyl succinic anhydride, maleic anhydride, tricarballylic anhydride, nadic anhydride (nadic anhydride), methylnadic anhydride, maleic anhydride-based linoleic acid adducts, alkylated terminal alkylene tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, phthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dichloromaleic anhydride, chloronadic anhydride, and chlorobacterial anhydride (chlorendic anhydride), and maleic anhydride-grafted polybutadiene, and the like.

More specific examples of the boron trifluoride-amine complex include: boron trifluoride-monoethylamine, boron trifluoride-piperidine, boron trifluoride-triethylamine, boron trifluoride-aniline, and the like.

The organic acid hydrazide is more specifically exemplified by: adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide (semicarbazide), and the like.

The content (blending amount) of the epoxy curing agent other than the component (D) in the curable resin composition, which exhibits activity at high temperature, is preferably 0.1 part by weight or more and 30 parts by weight or less, more preferably 0.5 part by weight or more and 20 parts by weight or less, still more preferably 1 part by weight or more and 15 parts by weight or less, particularly preferably 2 parts by weight or more and 10 parts by weight or less, relative to 100 parts by weight of the epoxy resin (a).

Epoxy curing accelerator (E)

The curable resin composition according to embodiment 1 may contain an epoxy curing accelerator (E) in the first component and/or the second component. (E) The component (c) is a compound which is not easily reacted with the epoxy resin (a) to form a crosslink, but can accelerate the curing reaction by the epoxy resin (a) and the epoxy curing agent (D). Particularly, the component (E) is preferably one which exhibits a remarkable accelerating effect by being used in combination with an epoxy curing agent having high curability at room temperature, such as an aliphatic amine, alicyclic amine, amide amine, amine-terminated polyether, amine-terminated nitrile rubber, or a modified product thereof.

(E) The component may be contained in only the first component, may be contained in only the second component, or may be contained in both the first component and the second component. From the viewpoint of storage stability of the curable resin composition, the component (E) is preferably contained only in the second component.

Examples of the component (E) include: C1-C12 Alkylimidazole, N-arylimidazole, 2-methylimidazole, 2-ethyl-2-methylimidazole, N-butylimidazole, 1-cyanoethyl-2-undecylimidazoleImidazoles such as trimellitates, adducts of epoxy resins and imidazoles; tertiary amines such as N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononene, triethylenediamine, benzyldimethylamine, and triethylamine; phenols such as 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol introduced into a poly (p-vinylphenol) matrix, p-t-butylphenol, phenol, 4-methoxyphenol, resorcinol, catechol, and 4-t-butylcatechol; etc. Among them, phenols are preferable from the viewpoint of the effect of improving curability, and dihydric phenols such as resorcinol, catechol, and 4-t-butylcatechol are more preferable. (E) The components may be used alone or in combination of 2 or more.

The amount of the epoxy curing accelerator (E) to be blended is preferably 0.1 parts by weight or more and 30 parts by weight or less, more preferably 1 parts by weight or more and 20 parts by weight or less, still more preferably 2 parts by weight or more and 15 parts by weight or less, particularly preferably 3 parts by weight or more and 10 parts by weight or less, based on 100 parts by weight of the epoxy resin (a), from the viewpoint of improving the effect of curability and storage stability.

Silane coupling agent (F) >)

The curable resin composition according to embodiment 1 may contain a silane coupling agent (F) in the first component and/or the second component.

When the curable resin composition contains the component (F), the component (F) functions as an adhesion promoter for assisting both the surface of the adherend such as glass and metal and the curable resin composition.

Specific examples of the silane coupling agent (F) include: isocyanate group-containing silanes such as gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl triethoxysilane, gamma-isocyanatopropyl methyldimethoxysilane; amino-containing silanes such as gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, gamma-aminopropyl methyldimethoxysilane, gamma- (2-propylethyl) aminopropyl trimethoxysilane, gamma- (2-propylethyl) aminopropyl methyldimethoxysilane, gamma- (2-propylethyl) aminopropyl triethoxysilane, and N-phenyl-gamma-aminopropyl trimethoxysilane; ketimine silanes such as N- (1, 3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine; mercaptosilanes such as gamma-mercaptopropyl trimethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-mercaptopropyl methyldimethoxysilane; epoxy group-containing silanes such as gamma-glycidoxypropyl trimethoxysilane, gamma-glycidoxypropyl triethoxysilane, gamma-glycidoxypropyl methyldimethoxysilane, beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and beta- (3, 4-epoxycyclohexyl) ethyltriethoxysilane; isocyanurate silanes such as tris (3-trimethoxysilylpropyl) isocyanurate; etc. Among them, epoxy-containing silanes are preferred from the viewpoint of the adhesive strength of the cured product obtained.

In the present specification, the silane coupling agent (F) as the epoxy group-containing silane is sometimes referred to as "epoxy silane coupling agent (F1)".

(F) The component may be contained in only the first component, may be contained in only the second component, or may be contained in both the first component and the second component. From the viewpoint of the storage stability of the curable resin composition, (a) when the component (F) is 1 or more selected from isocyanate group-containing silanes, epoxy group-containing silanes (epoxy silane coupling agent (F1)) and isocyanurate silanes, it is preferable that the component (F) is contained only in the first component, and (b) when the component (F) is 1 or more selected from aminosilanes, ketimine-type silanes and mercapto silanes, it is preferable that the component (F) is contained only in the second component.

From the viewpoint of improving the effect of adhesion and storage stability, the amount of the silane coupling agent (F) to be blended is preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 1 parts by weight or more and 15 parts by weight or less, still more preferably 2 parts by weight or more and 10 parts by weight or less, particularly preferably 3 parts by weight or more and 7 parts by weight or less, relative to 100 parts by weight of the epoxy resin (a).

The curable resin composition preferably further contains an epoxy silane coupling agent (F1) as the component (F) in view of excellent storage stability of the obtained curable resin composition and excellent adhesive strength of a cured product obtained by curing the curable resin composition.

< enhancer >)

In order to further improve the properties such as toughness, impact resistance, adhesive strength (shear adhesion strength)), and peel adhesion, the curable resin composition may contain a block urethane or an epoxy unmodified rubber-based polymer as a reinforcing agent, if necessary. The reinforcing agent may be used alone or in combination of 2 or more.

< Block carbamate >)

The blocked urethane is an elastomer type, and is a compound having urethane groups and/or urea groups and having isocyanate groups at the terminal, wherein all or part of the terminal isocyanate groups of the compound are blocked with various blocking agents having active hydrogen groups. Particularly preferred are compounds in which all of the terminal isocyanate groups are blocked with a blocking agent. Such a compound can be obtained, for example, by: after or while reacting an excessive amount of a polyisocyanate compound with an organic polymer having an active hydrogen-containing group at the end to prepare a polymer having a urethane group and/or urea group in the main chain and an isocyanate group at the end (urethane prepolymer), all or a part of the isocyanate groups are blocked with a blocking agent having an active hydrogen group.

Specific examples of the blocked urethane include compounds described in International publication No. 2016/163491.

The number average molecular weight of the block urethane is preferably 2000 to 40000, more preferably 3000 to 30000, particularly preferably 4000 to 20000 in terms of polystyrene as measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, particularly preferably 1.5 to 2.5.

The block urethanes may be used alone or 2 or more kinds may be used in combination.

The amount of the blocked urethane is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, particularly preferably 5 to 30 parts by weight, relative to 100 parts by weight of the epoxy resin (a). When the amount is 1 part by weight or more, the effect of improving toughness, impact resistance, adhesion and the like is good, and when it is 50 parts by weight or less, the elastic modulus of the obtained cured product is increased.

< epoxy unmodified rubber Polymer >)

The rubber-based polymer may be contained (blended) in the curable resin composition as needed in an unmodified state in which the rubber-based polymer is not reacted with the epoxy resin.

The rubber-based polymer may be: rubber polymers such as acrylonitrile butadiene rubber (NBR), styrene Butadiene Rubber (SBR), hydrogenated Nitrile Butadiene Rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), butadiene rubber, polyoxypropylene, polyoxyethylene, and polyoxyalkylene such as polybutylene oxide. The rubber polymer preferably has a reactive group such as an amino group, a hydroxyl group, or a carboxyl group at the terminal. Among them, NBR and polyoxyalkylene are preferable from the viewpoints of the adhesiveness and impact peel resistance adhesiveness of the obtained curable resin composition, NBR is more preferable, and carboxyl terminal NBR (CTBN) is particularly preferable.

The glass transition temperature (Tg) of the rubber-based polymer is not particularly limited, but is preferably-25℃or lower, more preferably-35℃or lower, further preferably-40℃or lower, particularly preferably-50℃or lower.

The number average molecular weight of the rubber polymer is preferably 1500 to 40000, more preferably 3000 to 30000, and particularly preferably 4000 to 20000 in terms of polystyrene as measured by GPC. The molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) is preferably 1 to 4, more preferably 1.2 to 3, particularly preferably 1.5 to 2.5.

The rubber-based polymer may be used alone, or 2 or more kinds may be used in combination.

The amount of the rubber-based polymer is preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, particularly preferably 5 to 10 parts by weight, based on 100 parts by weight of the epoxy resin (a). When the amount is 1 part by weight or more, the effect of improving toughness, impact resistance, adhesion and the like is good, and when it is 50 parts by weight or less, the elastic modulus of the obtained cured product is increased.

Inorganic filler other than component (C)

The curable resin composition may contain an inorganic filler other than aluminum hydroxide (C). Examples of the inorganic filler other than the component (C) include silicic acid and/or silicate, and specific examples thereof include: dry silica, wet silica, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, talc, and the like.

The dry silica is also called fumed silica, and examples thereof include: the hydrophilic fumed silica having no surface treatment and the hydrophobic fumed silica produced by chemically treating the silanol moiety of the hydrophilic fumed silica with silane or siloxane are preferable from the viewpoint of dispersibility in the component (a) and the component (D). The fumed silica can impart thixotropic properties by being added to the first component and the second component, and exhibits an effect of preventing sagging.

Specific examples of the inorganic filler other than the component (C) include: reinforcing fillers such as dolomite and carbon black; heavy calcium carbonate, colloidal calcium carbonate, wollastonite, magnesium carbonate, titanium oxide, ferric oxide, aluminum micropowder, zinc oxide, active zinc white, etc.

(C) The inorganic filler other than the components is preferably surface-treated with a surface-treating agent. The dispersibility of the inorganic filler other than the component (C) in the curable resin composition is improved by the surface treatment, and as a result, various physical properties of the obtained cured product are improved.

(C) The inorganic filler other than the components may be used alone or in combination of 1 or more than 2.

(C) The content (amount) of the inorganic filler other than the component (a) is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, still more preferably 5 to 40 parts by weight, particularly preferably 7 to 20 parts by weight, relative to 100 parts by weight of the component (a).

< monoepoxide >)

The curable resin composition may contain a monoepoxide as needed. The monoepoxide may function as a reactive diluent. Specific examples of the monoepoxide include, for example: aliphatic glycidyl ethers such as butyl glycidyl ether, aromatic glycidyl ethers such as phenyl glycidyl ether and tolyl glycidyl ether, ethers composed of an alkyl group having 8 to 10 carbon atoms and a glycidyl group such as 2-ethylhexyl glycidyl ether, ethers composed of a phenyl group having 6 to 12 carbon atoms and a glycidyl group which may be substituted with an alkyl group having 2 to 8 carbon atoms such as p-t-butylphenyl glycidyl ether, and ethers composed of an alkyl group having 12 to 14 carbon atoms and a glycidyl group such as dodecyl glycidyl ether; aliphatic glycidyl esters such as glycidyl (meth) acrylate and glycidyl maleate; glycidyl esters of aliphatic carboxylic acids having 8 to 12 carbon atoms such as glycidyl versatate, glycidyl neodecanoate and glycidyl laurate; and glycidyl p-tert-butylbenzoate.

When the monoepoxide is used, the content (amount) of the monoepoxide in the curable resin composition is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the component (A). When the amount is 0.1 parts by weight or more, the effect of lowering the viscosity is good, and when the amount is 20 parts by weight or less, the physical properties such as adhesiveness are good.

< other ingredients >

The curable resin composition may contain other compounding ingredients (additives) as needed. The other compounding ingredients include: radical curable resins, thermal radical polymerization initiators, photocurable resins, photopolymerization initiators, azo-type chemical blowing agents, expanding agents such as thermally expandable microspheres, fiber pulp such as aromatic polyamide pulp, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (gelation inhibitors), plasticizers, leveling agents, antifoaming agents, antistatic agents, lubricants, adhesion promoters, low shrinkage agents, organic fillers, thermoplastic resins, drying agents, dispersants, solvents, and the like.

The "content" of each component in the curable resin composition may also be referred to as "amount of each component.

Method for producing curable resin composition

The method for producing the curable resin composition is not particularly limited. When the first component of the curable resin composition contains a composition containing the epoxy resin (a) as the curable resin and the core-shell polymer particles as the component (B) (hereinafter also referred to as "polymer particle-containing composition"), the polymer particle-containing composition is preferably a composition in which the core-shell polymer particles (B) are dispersed in the form of primary particles.

As a method for obtaining such a composition (polymer particle-containing composition) in which the core-shell polymer particles (B) are dispersed in the form of primary particles, various methods can be used, and examples thereof include: a method in which the core-shell polymer particles (B) obtained in the form of an aqueous latex are brought into contact with the component (A) and then unnecessary components such as water are removed; the method of temporarily extracting the core-shell polymer particles (B) into an organic solvent, mixing the extracted core-shell polymer particles (B) with the component (a), and then removing the organic solvent is preferably used as described in international publication No. 2005/028546. The specific method for producing the polymer particle-containing composition preferably includes the following steps in order: step 1, mixing an aqueous latex containing core-shell polymer particles (B) (specifically, a reaction mixture obtained after the production of core-shell polymer particles (B) by emulsion polymerization) with an organic solvent having a solubility of 5 wt% or more and 40 wt% or less with respect to water at 20 ℃, and then mixing the obtained mixture with an excessive amount of water to coagulate the core-shell polymer particles (B); step 2, separating/recovering the aggregated core-shell polymer particles (B) from the liquid phase, and then mixing the obtained aggregate of the core-shell polymer particles (B) with an organic solvent again to obtain an organic solvent dispersion of the core-shell polymer particles (B); and 3 a step of further mixing the organic solvent dispersion with the component (A) and then distilling off the organic solvent from the obtained mixture.

(A) When the component is in a liquid state at 23 ℃, the above step 3 is preferred because it is easy. "liquid at 23 ℃ means having a softening point of 23 ℃ or less and exhibiting fluidity at 23 ℃.

The first component of the curable resin composition in which the core-shell polymer particles (B) are dispersed in the form of primary particles can be obtained by mixing the component (C), and optionally the component (a) and other components ((E) component and/or (F) component, etc.) with the composition in which the core-shell polymer particles (B) are dispersed in the component (a) in the form of primary particles (composition containing polymer particles) using a stirrer such as a planetary stirrer. The second component of the curable resin composition can be obtained by mixing the component (D), the component (C), and other components ((B), the component (E), and/or the component (F)) added as needed using a stirrer such as a planetary stirrer.

In the above description, the method of producing the curable resin composition by mixing the first component containing the core-shell polymer particles (B) with the second component containing or not containing the core-shell polymer particles (B) after the first component is produced has been described. However, the curable resin composition may be produced by mixing the first component containing no core-shell polymer particles (B) with the second component containing core-shell polymer particles (B) after the first component containing no core-shell polymer particles (B) is produced.

As described above, the first component containing the epoxy resin (a) and the second component containing the epoxy curing agent (D) are preferably prepared separately. The first component and the second component are preferably mixed immediately before use (may also be referred to as immediately before the bonding operation of the adherend or immediately before curing of the curable resin composition).

On the other hand, the powdery core-shell polymer particles (B) obtained by solidifying by a method such as salting out and drying may be redispersed in the component (a) or the component (D) using a disperser having a high mechanical shearing force such as a three-roll mill, a roll mill, or a kneader. In this case, the redispersion of the component (B) can be efficiently performed by applying a mechanical shearing force at a high temperature. The temperature at which the component (B) is redispersed in the component (A) or the component (D) is preferably 50 to 200 ℃, more preferably 70 to 170 ℃, still more preferably 80 to 150 ℃, particularly preferably 90 to 120 ℃.

< cured object >)

The first component and the second component of the curable resin composition are uniformly mixed using a static mixer or the like, and the resultant mixture is cured at a curing temperature described later, whereby a cured product can be obtained. It is considered that the core-shell polymer particles (B) are uniformly dispersed in the first component obtained by the above method, and therefore it is considered that the core-shell polymer particles (B) are uniformly dispersed in the cured product obtained by using such first component.

The cured product obtained by curing the curable resin composition is also an embodiment of the present invention (for example, embodiment 1 to embodiment 3). The cured product according to one embodiment of the present invention (for example, embodiment 1 to embodiment 3) has an advantage of excellent adhesive strength. The cured product according to one embodiment of the present invention (for example, embodiment 1 to embodiment 3) also has an advantage of excellent impact peel adhesion resistance.

Coating method

The curable resin composition may be applied to the substrate by any method. According to a preferred embodiment, the coating may be performed at a low temperature of the order of room temperature, or may be performed by heating as needed.

The first component and the second component of the curable resin composition may be applied while being uniformly mixed by a static mixer connected to the front end of the device after being discharged from the quantitative discharge device. Further, the first component and the second component of the curable resin composition may be filled in the respective cylinders of the double-cylinder caulking gun having a static mixer connected to the tip thereof, and the coating may be performed by manual extrusion. Coating robots can also be used to extrude onto a substrate in the form of beads, monofilaments or swirls (swirls). The viscosity of the curable resin composition at the application temperature is not particularly limited, but is preferably about 150 to 600pa·s in the extrusion bead method, about 100pa·s in the swirl (swirl) coating method, and about 20 to 400pa·s in the high-volume coating method using a high-speed flow device.

< adhesive >

The obtained cured product is excellent in adhesive strength and impact resistance, and therefore is preferably used as a material for adhesives. The adhesive containing the curable resin composition is also an embodiment of the present invention (for example, embodiment 1 to embodiment 3). The adhesive according to one embodiment of the present invention (for example, embodiment 1 to embodiment 3) has advantages of excellent quick curability and excellent adhesive strength and impact resistance of the resulting cured product (adhesive layer).

In the case of bonding various substrates to each other using the curable resin composition as an adhesive, for example, substrates such as metal, wood, plastic, glass, etc. such as aluminum plate, steel plate, etc. may be bonded. As the base material, there may be mentioned: various plastic substrates such as steel materials including cold rolled steel, hot dip galvanized steel, aluminum materials including aluminum and coated aluminum, general-purpose plastics, engineering plastics, CFRP, GFRP, and other composite materials.

Further, since the cured product of the curable resin composition is excellent in heat conductivity and flame retardancy, it is preferably used as an adhesive for fixing the EV battery cell to the module case. In other words, the adhesive according to one embodiment of the present invention (for example, embodiment 1 to embodiment 3) is preferably an adhesive for a secondary battery. As a method for manufacturing a battery module using an adhesive containing a curable resin composition, and a method for applying the adhesive to a part of the module and a method for applying the adhesive, a method described in international publication 2016/137303 may be mentioned.

The curable resin composition has excellent adhesion. Therefore, the curable resin composition is preferably used as an adhesive for bonding (joining) 2 substrates. The laminate thus obtained comprises 2 substrates and an adhesive layer formed by curing an adhesive containing a curable resin composition between the 2 substrates. The adhesive layer is also an embodiment of the present invention (for example, embodiment 1 to embodiment 3). The laminate according to one embodiment of the present invention (for example, embodiment 1 to embodiment 3) can be obtained by, for example, the following method: (1) Coating an adhesive comprising a curable resin composition on one substrate or both substrates; (2) Contacting the substrates with each other in such a manner that the adhesive is disposed between 2 substrates to be joined; (3) In this state, the adhesive is cured to join 2 substrates. The laminate according to one embodiment of the present invention (for example, embodiment 1 to embodiment 3) thus obtained is preferable because it exhibits high adhesive strength.

The curable resin composition and the adhesive containing the curable resin composition are excellent in toughness and therefore suitable for bonding between dissimilar substrates having different coefficients of linear expansion.

The curable resin composition and an adhesive containing the curable resin composition can also be used for joining structural materials for aerospace, particularly exterior metal structural materials.

< curing temperature >

The curing temperature of the curable resin composition is not particularly limited, but is preferably 5 to 60 ℃, more preferably 10 to 50 ℃, still more preferably 15 to 40 ℃, particularly preferably 20 to 30 ℃ from the viewpoint of being easily curable at around normal temperature.

< usage >

The curable resin composition can be preferably used for applications such as adhesives for vehicles and aircraft construction, adhesives for secondary batteries such as EV battery cells, adhesives for wind power generation construction, paints, materials for lamination with glass fibers and/or carbon fibers to obtain composite materials, materials for printed wiring boards, solder resists, interlayer insulating films, build-up (build-up) materials, adhesives for FPCs, electrical insulating materials such as sealing materials for electronic components such as semiconductors and LEDs, die bonding materials, underfills, mounting materials for semiconductors (for example ACF, ACP, NCF, NCP, etc.), sealing materials for display devices (for example, liquid crystal panels and OLED displays, etc.), and lighting devices (for example, OLED lighting, etc.), and composite materials for repairing concrete. The curable resin composition is particularly useful as an adhesive for secondary batteries.

In the case of using the curable resin composition for a composite material, a wide range of molding methods can be used without particular limitation. Specifically, the molding can be performed by a known molding method such as a paste molding method, a spray molding method, a squeeze-and-pull molding method, a filament winding molding method, a die molding method, a prepreg method, a centrifugal molding method, a liquid molding method, a hot pressing method, a casting method, an injection molding method, a continuous lamination method, a Resin Transfer Molding (RTM) method, a vacuum bag molding method, or a cold pressing method. The curable resin composition is suitable as a material for a composite material with glass fibers and carbon fibers, BMC (bulk molding compound), and SMC (sheet molding compound). The application site is not particularly limited, and specifically, the present invention is suitable for use as a sheet material such as piping, motor parts, automobile parts, railway vehicle parts, ship parts, aircraft parts, industrial machine parts, construction materials, structural members for furniture, musical instruments, etc., decorative sheets, etc., in an oil field pump extraction system such as kitchen cabinets, wash-basins, bathtubs, wall materials, etc., resin concrete, tanks, pressure vessels, industrial pipelines, factory piping, joints, pipes, corrugated boards, helmets, poles, blades for wind power generation, sucker rods/pumps, etc.

[ II ] embodiment 2

Embodiment 2 relates to a two-component curable resin composition containing an epoxy resin, and an adhesive containing the same.

The heat-curable one-component curable resin composition can reduce the viscosity of the composition by increasing the temperature at the time of application, but a two-component curable resin composition curable at a low temperature is desired to be a low temperature at the time of application, and a two-component curable resin composition having a low viscosity and good handleability is desired.

In order to improve heat dissipation from electrical equipment, it is studied to add a heat conductive filler such as aluminum hydroxide or aluminum oxide to a curable resin composition used for the equipment to improve heat conductivity. However, with the addition of the thermally conductive filler, the viscosity of the curable resin composition increases and the handleability may decrease. Further, cured products of epoxy resins widely used in electrical equipment have a problem of exhibiting very brittle properties because of low fracture toughness.

The resin composition described in patent document 1 has insufficient impact resistance and has room for improvement. Further, patent documents 2 to 3 do not describe a technique for improving the operability of an epoxy curable resin composition in which an epoxy resin is combined with a large amount of aluminum hydroxide.

In view of the above-described current situation, an object of the invention of embodiment 2 is to provide a two-component curable resin composition which comprises an epoxy resin and aluminum hydroxide, has a low viscosity and good handleability, and can give a cured product exhibiting excellent thermal conductivity, flame retardancy and adhesive strength, and can be cured at room temperature or a low temperature close to room temperature.

The present inventors have made intensive studies to solve the above problems, and as a result, have found that a cured product having a low viscosity and excellent thermal conductivity, flame retardancy and adhesive strength can be obtained by blending a polymer particle (B) having a core-shell structure and an aluminum hydroxide (C) having a specific average particle diameter and a specific composition in a specific weight ratio into a two-component curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D).

That is, the invention of embodiment 2 relates to a curable resin composition comprising a two-component curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D), wherein the curable resin composition further comprises a core-shell structured polymer particle (B) and aluminum hydroxide (C), the total weight of the aluminum hydroxide (C) is 55wt% or more and 85 wt% or less relative to the total weight of the curable resin composition, the average particle diameter of the core-shell structured polymer particle (B) is 0.15 μm or more and 0.30 μm or less, the core layer/shell weight ratio of the core-shell structured polymer particle (B) is 65/35 to 92/8, the shell layer of the core-shell structured polymer particle (B) is a copolymer containing an alkyl ester having 1 to 4 carbon atoms of (meth) and 55wt% or more of a monomer component, and the core-shell structured polymer particle (B) is a copolymer containing an alkyl ester having 1 to 4 carbon atoms of (meth) and the alkyl ester having 1 to 80wt% of carbon atoms of (meth) and the alkyl ester having 1 to 10 wt% carbon atoms of (meth) and 100wt% or more relative to the total weight of the monomer component constituting the core-shell.

According to the curable resin composition of the present invention having the above-described structure, the cured product obtained from the epoxy resin and the aluminum hydroxide having a high addition amount can exhibit excellent heat conductivity, flame retardancy and adhesive strength. In addition, by using polymer particles having a core-shell structure with a specific average particle diameter and a specific composition, the viscosity of the curable resin composition can be reduced. That is, according to embodiment 2, a two-component curable resin composition which can give a cured product exhibiting excellent thermal conductivity, flame retardancy and adhesive strength, has low viscosity and good handleability, and can be cured at room temperature or a low temperature close to room temperature can be provided.

In other words, embodiment 2 is a curable resin composition containing at least an epoxy resin (a), polymer particles (B) having a core-shell structure, aluminum hydroxide (C), and an epoxy curing agent (D). The curable resin composition according to embodiment 2 is a two-component type curable resin composition comprising a first component containing an epoxy resin (a) and a second component containing an epoxy curing agent (D) as essential components, and further comprising, if necessary, other components such as a color toner and a curing agent, and being used in combination immediately before use. The curable resin composition according to embodiment 2 further contains polymer particles (B) having a core-shell structure and aluminum hydroxide (C). The polymer particles (B) having a core-shell structure and aluminum hydroxide (C) are preferably contained in the first component and/or the second component, respectively. The curable resin composition of embodiment 2 may contain other components in addition to the first component and the second component, if necessary.

According to the curable resin composition of embodiment 2, the cured product obtained by the epoxy resin and the aluminum hydroxide in a high addition amount can exhibit excellent heat conductivity, flame retardancy and adhesive strength. In addition, in the curable resin composition of embodiment 2, the use of polymer particles having a core-shell structure with a specific average particle diameter and a specific composition can reduce the viscosity of the curable resin composition.

In the following, embodiments related to embodiment 2 will be described, and the description of embodiment 1 will be appropriately referred to except for the following details.

Epoxy resin (A) >, and

the modes (types, contents, preferable modes thereof, and the like) of the epoxy resin (a) in embodiment 2 are the same as those of the description of the item < epoxy resin (a) > in embodiment 1, and thus the description thereof is incorporated herein by reference, and the description thereof is omitted.

Polymer particle (B) having core-shell Structure

The curable resin composition according to embodiment 2 contains polymer particles having a core-shell structure as the component (B) in the first component and/or the second component.

In embodiment 2, the core-shell polymer particles (B) must have an average particle diameter of 0.15 μm or more and 0.30 μm or less, preferably 0.16 μm or more and 0.28 μm or less, more preferably 0.17 μm or more and 0.27 μm or less, still more preferably 0.18 μm or more and 0.25 μm or less, from the viewpoints of industrial productivity and handleability of the curable resin composition. In embodiment 2, the viscosity of the curable resin composition is further reduced by setting the average particle diameter (a) of the core-shell polymer particles (B) to 0.15 μm or more, so that the handleability is further improved, the polymerization time of the component (B) is further shortened by setting the average particle diameter (B) to 0.30 μm or less, and the industrial productivity is further improved.

In the core-shell polymer particles (B) of embodiment 2, the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer/weight of the shell layer) must be 65/35 to 92/8, preferably 68/32 to 91/9, more preferably 70/30 to 90/10, from the viewpoint that the handleability of the curable resin composition becomes better and the impact-resistant adhesion of the cured product becomes better.

In the core-shell polymer particles (B) according to embodiment 2, the shell layer must be a copolymer obtained by polymerizing 55 wt% or more of a monomer component (shell layer forming monomer) containing an alkyl ester having 1 to 4 carbon atoms of (meth) acrylic acid in an amount of 100 wt% of the monomer component (shell layer forming monomer), preferably a copolymer obtained by polymerizing 65 wt% or more of the monomer component, more preferably a copolymer obtained by polymerizing 75 wt% or more of the monomer component, still more preferably a copolymer obtained by polymerizing 78 wt% or more of the monomer component, and particularly preferably a copolymer obtained by polymerizing 83 wt% or more of the monomer component, from the viewpoint of improving the handleability of the curable resin composition.

In other words, the shell layer of embodiment 2 must contain 55 wt% or more, preferably 65 wt% or more, more preferably 75 wt% or more, still more preferably 78 wt% or more, and particularly preferably 83 wt% or more of the structural unit derived from the alkyl (meth) acrylate having 1 to 4 carbon atoms in 100 wt% of the shell layer.

In embodiment 2, the monomer component (monomer for forming a shell layer) constituting the shell layer of the polymer particle (B) must contain 10 to 100% by weight, preferably 11 to 95% by weight, more preferably 12 to 92% by weight, still more preferably 13 to 55% by weight, and particularly preferably 14 to 50% by weight of the alkyl ester having 1 carbon atom of (meth) acrylic acid in 100% by weight of the monomer component. In embodiment 2, the monomer component (shell layer forming monomer) constituting the shell layer of the core-shell polymer particle (B) must contain 0 to 80 wt%, preferably 1 to 89 wt%, more preferably 1 to 88 wt%, preferably 1 to 87 wt%, preferably 1 to 86 wt%, more preferably 1 to 78 wt%, more preferably 2 to 76 wt%, more preferably 5 to 76 wt%, more preferably 8 to 76 wt%, more preferably 20 to 74 wt%, more preferably 35 to 72 wt%, even more preferably 35 to 60 wt%, and particularly preferably 35 to 50 wt% of the alkyl ester having 4 carbon atoms in 100 wt% of the monomer component. When the shell layer forming monomer constituting the shell layer of the core-shell polymer particle (B) contains an alkyl ester of (meth) acrylic acid having 1 carbon atom and/or an alkyl ester of (meth) acrylic acid having 4 carbon atoms in the above-mentioned range, the interaction between the core-shell polymer particle (B) and the component (C) can be appropriately controlled, and therefore, the viscosity of the curable resin composition can be controlled to a low level, and there is an advantage that the workability becomes good.

In embodiment 2, the content of aluminum hydroxide (C) in the curable resin composition is, as will be described later, 55 wt% or more and 85 wt% or less in 100 wt% of the total weight of the curable resin composition, and therefore, the probability of contact between the component (B) and the component (C) is high. Therefore, in embodiment 2, it is very important to suppress the viscosity of the curable resin composition to a low level by setting the shell polymer of the component (B) to a monomer composition having reduced interaction with the surface of the component (C) having high polarity, so that the workability is improved. In embodiment 2, the shell layer of the core-shell polymer particle (B) has the above-described specific constitution. The shell layer of the core-shell polymer particles (B) mixed with the epoxy resin is generally of a composition capable of improving compatibility with the epoxy resin, and it is considered that the specific average particle diameter and specific composition of the component (B) in embodiment 2 are specifically designed so as to be optimized in combination with the compounding composition of embodiment 2 containing a large amount of aluminum hydroxide (C). The specific average particle diameter and specific composition of the component (B) in embodiment 2 are unique structures found by the present inventors in intensive studies concerning embodiment 2.

From the viewpoint of improving the handleability of the curable resin composition, the shell layer-forming monomer of embodiment 2 preferably has both an alkyl ester having 1 carbon atom (meth) acrylate and an alkyl ester having 4 carbon atoms (meth) acrylate, and more preferably contains 13 to 55 wt% of the alkyl ester having 1 carbon atom (meth) acrylate and 20 to 74 wt% of the alkyl ester having 4 carbon atoms (meth) acrylate. In other words, the shell layer of embodiment 2 preferably has both the structural unit derived from the alkyl ester having 1 carbon atom (meth) acrylic acid and the structural unit derived from the alkyl ester having 4 carbon atoms (meth) acrylic acid, and preferably contains 13 to 55 wt% of the structural unit derived from the alkyl ester having 1 carbon atom (meth) acrylic acid and 20 to 74 wt% of the structural unit derived from the alkyl ester having 4 carbon atoms (meth) acrylic acid.

The monomer component of embodiment 2 is not required to be such that the total of the alkyl ester having 1 carbon atom (meth) acrylate and the alkyl ester having 4 carbon atoms (meth) acrylate in 100% by weight of the monomer component is 100% by weight. In other words, the monomer component of embodiment 2 may be such that the total of (a) the alkyl ester having 1 carbon atom of (meth) acrylic acid, (b) the alkyl ester having 4 carbon atoms of (meth) acrylic acid, and (c) the sum of the monomers other than the alkyl ester having 1 carbon atom of (meth) acrylic acid and the alkyl ester having 4 carbon atoms of (meth) acrylic acid is 100% by weight of the monomer component. That is, the monomer component of embodiment 2 may contain a monomer other than the alkyl ester of (meth) acrylic acid having 1 carbon atom and the alkyl ester of (meth) acrylic acid having 4 carbon atoms.

In embodiment 2, the core-shell polymer particles (B) may further contain an aromatic vinyl monomer and/or a vinyl cyanide monomer as a shell layer forming monomer, for example, in order to improve compatibility and dispersibility in the curable resin composition. From the point that the curable resin composition can be improved in handleability by reducing the interaction between the component (B) and the component (C), the content of the aromatic vinyl monomer in the 100 wt% of the shell-forming monomer in embodiment 2 is preferably 30 wt% or less, more preferably 20 wt% or less, more preferably 10 wt% or less, more preferably 8 wt% or less, more preferably 6 wt% or less, still more preferably 5 wt% or less, and particularly preferably 0 wt% or less (i.e., no aromatic vinyl monomer is contained). Similarly, from the viewpoint of improving the handleability of the curable resin composition, in embodiment 2, the content of the vinyl cyanide monomer in 100 wt% of the shell-forming monomer is preferably 10 wt% or less, more preferably 8 wt% or less, more preferably 5 wt% or less, more preferably 4 wt% or less, more preferably 3 wt% or less, more preferably 2 wt% or less, more preferably 1 wt% or less, and particularly preferably 0 wt% or less (i.e., no vinyl cyanide monomer is contained).

In embodiment 2, for example, a shell layer is preferably formed from a copolymer obtained by polymerizing (a) 10 to 100% by weight (preferably 11 to 95% by weight, particularly preferably 14 to 50% by weight) of an alkyl ester monomer having 1 carbon atom (meth) in (meth) acrylic acid (particularly methyl methacrylate), (b) 0 to 80% by weight (preferably 1 to 78% by weight, particularly preferably 35 to 72% by weight) of an alkyl ester monomer having 4 carbon atoms in (meth) in (butyl acrylate) (particularly preferably) and (c) 30% by weight or less (preferably 20% by weight, more preferably 10% by weight or less, more preferably 8% by weight or less, more preferably 6% by weight or less) of an aromatic vinyl monomer (particularly styrene) (preferably 5% by weight or less), and (d) 10% by weight (preferably 8% by weight or less, more preferably 5% by weight or less, more preferably 4% by weight or less, particularly preferably 3% by weight or less) of an epoxy monomer (particularly preferably 0% by weight) and (particularly preferably 0 to 3% by weight) of a glycidyl ester. Thus, the desired effect of improving toughness and operability can be achieved in a well-balanced manner.

< aluminium hydroxide (C) >)

In the curable resin composition according to embodiment 2, aluminum hydroxide is contained as the component (C) in the first component and/or the second component. When the curable resin composition of embodiment 2 contains the component (C), the obtained cured product has the advantage of excellent thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical burning test (UL 94)).

In embodiment 2, the total weight of aluminum hydroxide (C) must be 55 wt% or more and 85 wt% or less with respect to the total weight of the curable resin composition.

In embodiment 2, the average particle diameter of the component (C) is not particularly limited. In embodiment 2, the average particle diameter of the component (C) is preferably 11 μm or more and 200 μm or less, more preferably 12 μm or more and 150 μm or less, still more preferably 13 μm or more and 100 μm or less, still more preferably 15 μm or more and 50 μm or less, particularly preferably 17 μm or more and 30 μm or less, from the viewpoint of both the impact resistance and the adhesive strength of the obtained cured product and the viewpoint of suppressing the sedimentation over time of the component (E) in the curable resin composition before curing.

In embodiment 2, from the viewpoint of improving the properties (thermal conductivity, flame retardancy, adhesive strength, and impact resistance) of the obtained cured product and from the viewpoint of improving the handleability of the composition before curing, the total weight of aluminum hydroxide (C) must be 55 wt% or more and 85 wt% or less, preferably 57 wt% or more and 80 wt% or less, more preferably 60 wt% or more and 76 wt% or less, still more preferably 62 wt% or more and 73 wt% or less, and particularly preferably 65 wt% or more and 70 wt% or less, relative to the total weight of the curable resin composition.

Regarding the aluminum hydroxide (C) of embodiment 2, the description of embodiment 1 is appropriately cited for other than the above matters.

The curable resin composition according to embodiment 2 may contain a thermally conductive filler other than aluminum hydroxide (other than component C) and/or a flame retardant other than aluminum hydroxide (other than component C). The modes (types, contents, preferable modes thereof, and the like) of the "heat conductive filler other than aluminum hydroxide" and the "flame retardant other than aluminum hydroxide" in embodiment 2 are the same as those of the "heat conductive filler other than aluminum hydroxide > and the" flame retardant other than aluminum hydroxide "in embodiment 1, and therefore, the descriptions thereof are incorporated herein by reference.

Epoxy curing agent (D)

The curable resin composition according to embodiment 2 contains an epoxy curing agent as the component (D) in the second component. Each mode (type, content, preferable mode thereof, and the like) of the "epoxy curing agent (D)" in embodiment 2 is the same as the description of the < epoxy curing agent (D) > in embodiment 1, and thus the description thereof is incorporated herein by reference, and the description thereof is omitted.

Epoxy curing agent exhibiting activity at high temperature other than component (D)

The curable resin composition of embodiment 2 may contain an epoxy curing agent that exhibits activity at high temperature in addition to an epoxy curing agent (such as the amine curing agent and the thiol curing agent) containing an active hydrogen group that can react with an epoxy resin at low temperature, within a range that does not impair the curing rate of the curable resin composition. The modes (types, contents, preferable modes thereof, and the like) of the epoxy curing agent exhibiting activity at high temperature other than the "(D) component" in embodiment 2 are the same as those of the epoxy curing agent exhibiting activity at high temperature other than the "< (D) component" in embodiment 1, and therefore, the description thereof is incorporated herein by reference.

Epoxy curing accelerator (E)

The curable resin composition according to embodiment 2 may contain an epoxy curing accelerator (E) in the first component and/or the second component. Each mode (type, content, preferable mode thereof, and the like) of the "epoxy curing accelerator (E)" in embodiment 2 is the same as the description of the item < epoxy curing accelerator (E) > in embodiment 1, and thus the description thereof is incorporated herein by reference.

Silane coupling agent (F) >)

The curable resin composition according to embodiment 2 may contain a silane coupling agent (F) in the first component and/or the second component. Each mode (type, content, preferable mode thereof, and the like) of the "silane coupling agent (F)" in embodiment 2 is the same as the explanation of < silane coupling agent (F) > in embodiment 1, and thus the description thereof is incorporated herein by reference, and the explanation thereof is omitted.

[ III ] embodiment 3

Embodiment 3 relates to a curable resin composition, a cured product, an adhesive, and a laminate.

A two-part epoxy resin composition using an aliphatic amine-based curing agent is cured at a low temperature. Therefore, the two-part epoxy resin composition does not require a heating device or the like for curing. The cured product obtained by curing the two-component epoxy resin composition is used for a wide variety of applications such as industrial applications and civil engineering and construction applications, because of its excellent strength, heat resistance, water resistance, chemical resistance, electrical insulation, and the like. Conventionally, as a two-component epoxy resin composition, various compositions have been developed (for example, patent document 4 and the like).

As described above, although the strength of a cured product obtained by curing a two-component epoxy resin composition is excellent, there is a problem that the curing speed of the two-component epoxy resin composition tends to be low.

In particular, in the field where productivity (tact time) is important for automobiles and the like, rapid curability of a two-component type adhesive is important. In addition, a two-component type adhesive used for fixing a battery of an Electric Vehicle (EV) is also required to have rapid curability.

However, such a conventional technique (for example, the technique described in patent document 4) is insufficient from the viewpoint of rapid curability, and there is still room for further improvement.

Embodiment 3 has been completed in view of the above problems, and an object thereof is to provide a novel curable resin composition of two-component type or multi-component type excellent in quick curability.

The present inventors have made intensive studies to solve the above problems, and as a result, have completed the invention of embodiment 3.

The present inventors have made intensive studies to solve the above problems, and as a result, have found the following findings independently, and have completed the present invention according to embodiment 3: in addition to the epoxy resin (a) and the specific epoxy curing agent, a compound having 1 aromatic ring and at least 2 phenolic hydroxyl groups in 1 molecule and having 0 or 1 tertiary alkyl groups in the ortho position to the phenolic hydroxyl groups in 1 molecule is used in combination, whereby a two-component or multi-component curable resin composition excellent in rapid curability can be obtained.

The curable resin composition according to embodiment 3 is a two-component or multi-component curable resin composition comprising a first component comprising an epoxy resin (a) and a second component comprising an epoxy curing agent (D), wherein the curable resin composition further comprises polymer particles (B) having a core-shell structure comprising a core layer and a shell layer, and a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule, wherein the number of tertiary alkyl groups located in the ortho position to the phenolic hydroxyl groups in the compound (G) is 0 or 1 in 1 molecule, and wherein the epoxy curing agent (D) is at least 1 selected from the group consisting of aliphatic amines, alicyclic amines, amidoamines, amino-terminated polyethers, amino-terminated nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amino-terminated polyethers, and modified amino-terminated nitrile rubbers.

The "curable resin composition according to embodiment 3" may be referred to as "curable resin composition 3".

According to embodiment 3, there is an effect that a two-component type or multi-component type curable resin composition excellent in quick curability can be provided.

Embodiments related to embodiment 3 will be described below, and descriptions of embodiments 1 and 2 will be appropriately referred to, except for the details described below.

The 3 rd curable resin composition has the above-described structure, and therefore has an advantage of exhibiting excellent rapid curability. In the present specification, "rapid curability" means a property that can be cured in a short time (for example, about several minutes to several hours) in the vicinity of room temperature (for example, 5 to 50 ℃). That is, the 3 rd curable resin composition has an advantage of being cured in a short time (for example, about several minutes to several hours) at a temperature of 5 ℃ to 50 ℃ or less without requiring a heat treatment at a high temperature exceeding 50 ℃.

The 3 rd curable resin composition contains the epoxy resin (a) in the first component, in other words, may also be referred to as a two-component epoxy resin composition or a multicomponent epoxy resin composition. Therefore, the 3 rd curable resin composition also has an advantage of excellent adhesive strength.

As a two-part type adhesive, a two-part urethane composition containing a urethane resin as a main component is known in addition to a two-part type epoxy resin composition. The two-part urethane composition has a quick curability capable of curing in a short time, as compared with the two-part epoxy resin composition. However, the two-part urethane composition tends to have insufficient strength, heat resistance, and the like of the resulting cured product as compared with the two-part epoxy resin composition.

In many cases, a two-component adhesive used for fixing a battery of an Electric Vehicle (EV) is required to have both rapid curability and strength.

As described above, the 3 rd curable resin composition is excellent in adhesive strength and rapid curability. Therefore, the 3 rd curable resin composition is particularly preferably used as a two-component type adhesive for fixing a battery of an Electric Vehicle (EV).

Further, since the 3 rd curable resin composition contains the polymer particles (B) having a core-shell structure including a core layer and a shell layer, the 3 rd curable resin composition also has an advantage of excellent impact peel adhesion resistance.

Epoxy resin (A) >, and

the modes (types, contents, preferable modes thereof, and the like) of the epoxy resin (a) in embodiment 3 are the same as those of the description of the item < epoxy resin (a) > in embodiment 1, and thus the description thereof is incorporated herein by reference, and the description thereof is omitted.

Polymer particle (B) having core-shell Structure

In the curable resin composition according to embodiment 3, the first component and/or the second component contains polymer particles having a core-shell structure as the component (B). Each mode of the polymer particles (B) having a core-shell structure in embodiment 3 (for example, the composition of the core layer, the composition of the shell layer, and preferred modes thereof) is the same as the explanation in the item < polymer particles (B) having a core-shell structure > in embodiment 1, and therefore, this description is incorporated herein by reference.

< Compound (G) >)

The curable resin composition according to embodiment 3 contains, as the (G) component, a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule in the first component and/or the second component. In this compound (G), the number of tertiary alkyl groups located at the ortho position to the phenolic hydroxyl group is 0 or 1 in 1 molecule.

The compound (G) has an effect of improving the curing speed of the curable resin composition while maintaining good adhesive strength by using the polymer particles (B) and the epoxy curing agent (D) described later in combination. Further, the curable resin composition of embodiment 3 contains the compound (G) together with the polymer particles (B) and the epoxy curing agent (D) described later, and does not require a heat treatment at a high temperature exceeding 50 ℃, and thus exhibits excellent rapid curability, and can be cured in a shorter time than a curable resin composition containing no compound (G).

(G) The component may be contained in only the first component, may be contained in only the second component, or may be contained in both the first component and the second component. From the viewpoint of storage stability of the curable resin composition, the (G) component is preferably contained only in the second component.

In the present specification, an aromatic ring refers to a cyclic hydrocarbon and a heterocyclic compound satisfying the shock rule. Specific examples of the aromatic ring include: benzene, naphthalene, azulene, anthracene, pyrrole, pyridine, furan, thiophene and the like. Among them, benzene is particularly preferred from the viewpoints of the effect of improving the quick curability, the ease of obtaining, and the like.

In the present specification, a phenolic hydroxyl group means a hydroxyl group bonded to a carbon atom of an aromatic ring. In the compound (G), the positions of 2 phenolic hydroxyl groups are not particularly limited, and may be located on any carbon atom of the aromatic ring.

When the aromatic ring is benzene, the 2 phenolic hydroxyl groups may be in any positional relationship of ortho-position, meta-position or para-position, and more preferably in any positional relationship of ortho-position or meta-position, and still more preferably in any positional relationship of meta-position, from the viewpoint of exhibiting an excellent rapid curability improving effect.

The compound (G) may have at least 1 further substituent on the aromatic ring in addition to 2 phenolic hydroxyl groups within a range not to impair the effect of one embodiment of the present invention. The substituent is not particularly limited, and examples thereof include: alkyl groups having 8 or less carbon atoms (methyl, ethyl, propyl, 1-methylethyl (isopropyl), butyl, 1-dimethylethyl (t-butyl), etc.), halogens (chlorine, bromine, iodine), etc.

In the case where the compound (G) has a tertiary alkyl group (for example, a tertiary butyl group or the like) as a further substituent, the number of tertiary alkyl groups located at the ortho position to the phenolic hydroxyl group is 0 or 1 in 1 molecule. When the number of tertiary alkyl groups located at the ortho position to the phenolic hydroxyl group in the molecule of the compound (G1) is 2 or more, the effect of improving the quick curability cannot be obtained, and the time taken for curing increases, which is not preferable. The reason for this is not determined, but it is assumed that this is because the effect of improving the quick curability is hindered by the steric hindrance of the tertiary alkyl group.

The compound (G) preferably has no substituent other than 2 phenolic hydroxyl groups on the aromatic ring. This structure has an advantage of increasing the effect of improving the quick curability.

As the compound (G), there may be mentioned: 1, 3-dihydroxybenzene (alias; resorcinol), 1, 2-dihydroxybenzene (alias; catechol), 1, 4-dihydroxybenzene (alias; hydroquinone), 4-tert-butylcatechol, methylhydroquinone, tert-butylhydroquinone, chlorohydroquinone, 2, 5-dichlorohydroquinone, 2, 5-dibromohydroquinone, pyrogallol, hydroxyquinoline, phloroglucinol, and the like. Among them, resorcinol, catechol, hydroquinone and methylhydroquinone are more preferable, resorcinol and catechol are further preferable, and resorcinol is particularly preferable, from the viewpoint of exhibiting an excellent rapid curability improving effect.

The compound (G) may be used in an amount of 1 or 2 or more.

The curable resin composition according to embodiment 3 contains 1 to 25 parts by weight of the compound (G), more preferably 2 to 20 parts by weight, still more preferably 3 to 15 parts by weight, and particularly preferably 4 to 10 parts by weight, per 100 parts by weight of the epoxy resin (a). When the content of the compound (G) is 1 part by weight or more based on 100 parts by weight of the epoxy resin (a), the effect of improving the quick curability of the compound (G) can be exhibited satisfactorily, and when the content of the compound (b) is 25 parts by weight or less, the storage stability of the curable resin composition is improved and the handling is easy.

As a curing aid for accelerating the curing rate of the epoxy curing agent (D) described later, compounds having a phenolic hydroxyl group such as bisphenol a and 2,4, 6-tris (dimethylaminomethyl) phenol are known. Compounds having 2 aromatic rings and 2 phenolic hydroxyl groups in 1 molecule such as bisphenol a are limited in use due to environmental regulations and the like, and thus are difficult to handle. Therefore, in the curable resin composition of embodiment 3, the smaller the content of the compound having 2 aromatic rings and 2 phenolic hydroxyl groups (bisphenol a) in 1 molecule, the more preferable is, for example, 3 parts by weight or less relative to 100 parts by weight of the epoxy resin (a). However, the curable resin composition of embodiment 3 may contain a compound having 2 aromatic rings and 2 phenolic hydroxyl groups in 1 molecule (e.g., bisphenol a) within a range that does not impair the effects of one embodiment of the present invention.

In the curable resin composition of embodiment 3, the content of the compound having 2 aromatic rings and 2 phenolic hydroxyl groups (bisphenol a) in 1 molecule may be 2 parts by weight or less, may be 1 part by weight or less, may be 0.5 parts by weight or less, and may be less than 0.1 part by weight relative to 100 parts by weight of the epoxy resin (a).

In embodiment 3, the present inventors have found that, independently, a compound having 1 phenolic hydroxyl group in 1 molecule such as 2,4, 6-tris (dimethylaminomethyl) phenol is used as a curing agent instead of the epoxy curing agent (D) described later, and as a result, the effect of improving the quick curability is not sufficient. However, the curable resin composition of embodiment 3 may contain a compound having 1 phenolic hydroxyl group in 1 molecule (e.g., 2,4, 6-tris (dimethylaminomethyl) phenol) within a range that does not impair the effect of one embodiment of the present invention.

< aluminium hydroxide (C) >)

The curable resin composition of embodiment 3 may or may not further contain aluminum hydroxide (C). In the curable resin composition according to embodiment 3, the first component and/or the second component preferably contains aluminum hydroxide (C). When the curable resin composition of embodiment 3 contains the component (C), the obtained cured product has the advantage of excellent thermal conductivity and flame retardancy (for example, flame retardancy evaluated by a vertical burning test (UL 94)).

In embodiment 3, the average particle diameter of the component (C) is not particularly limited. In embodiment 3, the average particle diameter of the component (C) in the curable resin composition before curing is preferably 11 μm or more and 200 μm or less, more preferably 12 μm or more and 150 μm or less, still more preferably 13 μm or more and 100 μm or less, still more preferably 15 μm or more and 50 μm or less, and particularly preferably 17 μm or more and 30 μm or less, from the viewpoint of both the impact resistance and the adhesive strength of the obtained cured product and the suppression of the sedimentation with time of the component (C).

In embodiment 3, the total weight of aluminum hydroxide (C) is not particularly limited with respect to the total weight of the curable resin composition. In embodiment 3, from the viewpoint of improving the properties (thermal conductivity, flame retardancy, adhesive strength, and impact resistance) of the obtained cured product and from the viewpoint of improving the handleability of the composition before curing, the total weight of aluminum hydroxide (C) is preferably 55% by weight or more and 85% by weight or less, more preferably 57% by weight or more and 80% by weight or less, still more preferably 60% by weight or more and 76% by weight or less, still more preferably 62% by weight or more and 73% by weight or less, particularly preferably 65% by weight or more and 70% by weight or less, relative to the total weight of the curable resin composition.

Regarding the aluminum hydroxide (C) of embodiment 3, the description of embodiment 1 is appropriately cited for other than the above matters.

The curable resin composition according to embodiment 3 may contain a thermally conductive filler other than aluminum hydroxide (other than component C) and/or a flame retardant other than aluminum hydroxide (other than component C). The modes (types, contents, preferable modes thereof, and the like) of the "heat conductive filler other than aluminum hydroxide" and the "flame retardant other than aluminum hydroxide" in embodiment 3 are the same as those of the "heat conductive filler other than aluminum hydroxide > and the" flame retardant other than aluminum hydroxide "in embodiment 1, and therefore, the descriptions thereof are incorporated herein by reference.

Epoxy curing agent (D)

The curable resin composition according to embodiment 3 contains an epoxy curing agent as the component (D) in the second component. In embodiment 3, as the epoxy curing agent (D), an amine curing agent is preferably used.

In embodiment 3, the amine curing agent is at least 1 selected from the group consisting of aliphatic amines, alicyclic amines, amide amines, amine terminated polyethers, amine terminated nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amide amines, modified amine terminated polyethers, and modified amine terminated nitrile rubbers. In embodiment 3, the epoxy curing agent (D) may be at least 1 or more selected from the group consisting of aliphatic amines, alicyclic amines, amidoamines, amine terminated polyethers, amine terminated nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amidoamines, modified amine terminated polyethers, and modified amine terminated nitrile rubbers, or may be at least 1 or more selected from the group. When the epoxy curing agent (D) is at least 1 or more selected from the above group, or is composed of only 1 or more selected from the group, the curable resin composition has an advantage of excellent curability (quick curability) at room temperature. In embodiment 3, 1 kind of epoxy curing agent (D) may be used alone, or 2 or more kinds may be used in combination.

In the epoxy curing agent (D) according to embodiment 3, (a) is preferably 1 or more selected from the group consisting of an amino terminated polyether and an amino terminated nitrile rubber from the viewpoint of impact resistance of the cured product obtained, (a-1) is more preferably 1 or more selected from the group consisting of an amino terminated polyether and an amino terminated nitrile rubber, and (b) is more preferably an amino terminated nitrile rubber from the viewpoint of curability. In the epoxy curing agent (D) according to embodiment 3, (a) preferably contains 1 or more selected from the group consisting of alicyclic amine, amide amine, amine terminated polyether, amine terminated nitrile rubber, modified alicyclic amine, modified amide amine, modified amine terminated polyether, and modified amine terminated nitrile rubber, among the amine curing agents, (a-1) more preferably contains 1 or more selected from the group consisting of alicyclic amine, amide amine, amine terminated polyether, amine terminated nitrile rubber, modified alicyclic amine, modified amide amine, modified amine terminated polyether, and modified amine terminated nitrile rubber, (b) more preferably contains 1 or more selected from the group consisting of alicyclic amine and amine terminated nitrile rubber, and (b-2) more preferably contains 1 or more selected from the group consisting of alicyclic amine and amine terminated nitrile rubber, from the viewpoint of curability. From the viewpoints of the adhesive strength and curability of the cured product obtained, the epoxy curing agent (D) according to embodiment 3 more preferably contains at least 1 or more selected from the group consisting of alicyclic amines, amino-terminated nitrile rubbers, modified products of alicyclic amines and modified products of amino-terminated nitrile rubbers, and still more preferably contains at least 1 or more selected from the group consisting of alicyclic amines, amino-terminated nitrile rubbers, modified products of alicyclic amines and modified products of amino-terminated nitrile rubbers.

Regarding the epoxy curing agent (D) of embodiment 3, the description of embodiment 1 is appropriately cited for other than the above matters.

Epoxy curing agent exhibiting activity at high temperature other than component (D)

The curable resin composition of embodiment 3 may contain an epoxy curing agent which exhibits an activity at a high temperature in addition to an epoxy curing agent (such as the amine curing agent and the thiol curing agent) containing an active hydrogen group capable of reacting with an epoxy resin at a low temperature, within a range not impairing the curing rate of the curable resin composition. The modes (types, contents, preferable modes thereof, and the like) of the epoxy curing agent exhibiting activity at high temperature other than the "(D) component" in embodiment 3 are the same as those of the epoxy curing agent exhibiting activity at high temperature other than the "< (D) component" in embodiment 1, and therefore, the description thereof is incorporated herein by reference.

Epoxy curing accelerators (H) other than Compound (G)

The first component and/or the second component of the curable resin composition according to embodiment 3 may contain an epoxy curing accelerator (H) (hereinafter, also referred to as "H component") other than the compound (G).

(H) The component (c) is a compound which is not easily reacted with the epoxy resin (a) to form a crosslink, but can accelerate the curing reaction by the epoxy resin (a) and the epoxy curing agent (D). Particularly, the component (H) is preferably a component which exhibits a remarkable curing acceleration effect by being used in combination with the component (D), i.e., an epoxy curing agent having high curability at room temperature.

(H) The component may be contained in only the first component, may be contained in only the second component, or may be contained in both the first component and the second component. From the viewpoint of storage stability of the curable resin composition, the (H) component is preferably contained only in the second component.

Examples of the component (H) include: an alkylidene imidazole having 1 to 12 (C1-C12) carbon atoms as an alkylene group, an N-arylimidazole,2-methylimidazole, 2-ethyl-2-methylimidazole, N-butylimidazole, 1-cyanoethyl-2-undecylimidazoleImidazoles such as trimellitates, adducts of epoxy resins and imidazoles; tertiary amines such as N, N-dimethylpiperazine, diazabicycloundecene, diazabicyclononene, triethylenediamine, benzyldimethylamine, and triethylamine; phenols such as 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (dimethylaminomethyl) phenol introduced into a poly (p-vinylphenol) matrix, p-tert-butylphenol, phenol, and 4-methoxyphenol; etc. Among them, imidazoles and phenols are preferable from the viewpoint of the effect of improving curability, and phenols such as 2,4, 6-tris (dimethylaminomethyl) phenol are more preferable. (H) The components may be used alone or in combination of 1 or more than 2.

From the viewpoint of both the effect of improving curability and the storage stability, the content of the epoxy curing accelerator (H) in the curable resin composition according to embodiment 3 is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, still more preferably 2 to 15 parts by weight, and particularly preferably 3 to 10 parts by weight, based on 100 parts by weight of the epoxy resin (a).

One embodiment of the present invention may have the following configuration.

[ A1 ] A curable resin composition comprising a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D),

the curable resin composition further comprises polymer particles (B) having a core-shell structure and aluminum hydroxide (C), wherein the total weight of the aluminum hydroxide (C) is 55 to 85 wt% inclusive and the average particle diameter of the aluminum hydroxide (C) is 11 to 200 [ mu ] m inclusive, relative to the total weight of the curable resin composition.

The curable resin composition according to [ A1 ], wherein the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C) are contained in the first component and/or the second component, respectively.

The curable resin composition according to [ A1 ] or [ A2 ], wherein the ratio of the number of moles of the epoxy groups of the epoxy resin (A) to the number of moles of the active hydrogen groups of the epoxy curing agent (D) is 0.5 to 1.5.

The curable resin composition according to any one of [ A1 ] to [ A3 ], wherein the epoxy resin (A) is a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin.

The curable resin composition according to any one of [ A1 ] to [ A4 ], wherein the epoxy curing agent (D) is at least 1 amine curing agent selected from the group consisting of aliphatic amines, alicyclic amines, amide amines, amine-terminated polyethers and amine-terminated nitrile rubbers, or a modified product thereof.

The curable resin composition according to any one of [ A1 ] to [ A5 ], wherein the amount of the core-shell polymer particles (B) is 1 to 100 parts by weight based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ A1 ] to [ A6 ], wherein the amount of the aluminum hydroxide (C) to be blended is 250 parts by weight or more and 750 parts by weight or less based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ A1 ] to [ A7 ], wherein the amount of the epoxy curing agent (D) to be added is 15 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ A1 ] to [ A8 ], wherein the first component and/or the second component further contains an epoxy curing accelerator (E).

The curable resin composition according to any one of [ A1 ] to [ A9 ], wherein the first component and/or the second component further contains a silane coupling agent (F).

The curable resin composition according to any one of [ A1 ] to [ A10 ], wherein the polymer particles (B) having a core-shell structure have 1 or more core layers selected from diene rubbers, (meth) acrylate rubbers and organosiloxane rubbers.

The curable resin composition according to [ A11 ], wherein the polymer particles (B) having a core-shell structure have a diene rubber, and the diene rubber is butadiene rubber and/or styrene-butadiene rubber.

The curable resin composition according to any one of [ A1 ] to [ A12 ], wherein the polymer particles (B) having a core-shell structure have a shell layer obtained by graft-polymerizing 1 or more monomer components selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth) acrylate monomer onto a core layer.

The curable resin composition according to any one of [ A1 ] to [ A13 ], wherein the polymer particles (B) having a core-shell structure have an epoxy group in a shell layer.

The curable resin composition according to any one of [ A1 ] to [ A14 ], wherein the polymer particles (B) having a core-shell structure have a shell layer obtained by graft-polymerizing a monomer component having an epoxy group to a core layer.

The curable resin composition according to any one of [ A1 ] to [ A15 ], wherein the polymer particles (B) having a core-shell structure have an epoxy group in a shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0mmol/g or less based on the total amount of the shell layers.

The curable resin composition according to any one of [ A1 ] to [ A13 ], wherein the polymer particles (B) having a core-shell structure do not contain an epoxy group in the shell layer.

[ A18 ] is a cured product obtained by curing the curable resin composition according to any one of [ A1 ] to [ A17 ].

[ A19 ] an adhesive comprising the curable resin composition according to any one of [ A1 ] to [ A17 ].

The adhesive according to [ A19 ], wherein the adhesive is an adhesive for a secondary battery.

[ A21 ] a laminate comprising:

2-piece substrate

An adhesive layer formed by curing the adhesive described in [ A19 ] or [ A20 ] of the 2 substrates.

One embodiment of the present invention may have the following configuration.

A curable resin composition comprising a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D), wherein the curable resin composition further comprises a core-shell polymer particle (B) and aluminum hydroxide (C), the total weight of the aluminum hydroxide (C) is 55 to 85 wt% inclusive relative to the total weight of the curable resin composition, the average particle diameter of the core-shell polymer particle (B) is 0.15 to 0.30 mu m, the core-shell polymer particle (B) has a core/shell weight ratio of 65/35 to 92/8, the core-shell polymer particle (B) is a copolymer of a monomer component having a shell containing an alkyl ester having 1 to 4 carbon atoms and having 10 to 80 carbon atoms including an alkyl ester having 1 to 1 carbon atom atoms.

The curable resin composition according to [ B1 ], wherein the polymer particles (B) having a core-shell structure and the aluminum hydroxide (C) are contained in the first component and/or the second component, respectively.

The curable resin composition according to [ B1 ] or [ B2 ], wherein the ratio of the number of moles of the epoxy groups of the epoxy resin (A) to the number of moles of the active hydrogen groups of the epoxy curing agent (D) is 0.5 to 1.5.

The curable resin composition according to any one of [ B1 ] to [ B3 ], wherein the epoxy resin (A) is a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin.

The curable resin composition according to any one of [ B1 ] to [ B4 ], wherein the epoxy curing agent (D) is at least 1 amine curing agent selected from the group consisting of aliphatic amines, alicyclic amines, amide amines, amine-terminated polyethers and amine-terminated nitrile rubbers, or a modified product thereof.

The curable resin composition according to any one of [ B1 ] to [ B5 ], wherein the amount of the core-shell polymer particles (B) is 1 to 100 parts by weight based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ B1 ] to [ B6 ], wherein the amount of the aluminum hydroxide (C) to be blended is 250 parts by weight or more and 750 parts by weight or less based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ B1 ] to [ B7 ], wherein the amount of the epoxy curing agent (D) to be added is 15 parts by weight or more and 300 parts by weight or less based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ B1 ] to [ B8 ], wherein the first component and/or the second component further contains an epoxy curing accelerator (E).

The curable resin composition according to any one of [ B1 ] to [ B9 ], wherein the first component and/or the second component further contains a silane coupling agent (F).

The curable resin composition according to any one of [ B1 ] to [ B10 ], wherein the polymer particles (B) having a core-shell structure have 1 or more core layers selected from diene rubbers, (meth) acrylate rubbers and organosiloxane rubbers.

The curable resin composition according to [ B11 ], wherein the polymer particles (B) having a core-shell structure have a diene rubber, and the diene rubber is butadiene rubber and/or styrene-butadiene rubber.

The curable resin composition according to any one of [ B1 ] to [ B12 ], wherein the polymer particles (B) having a core-shell structure have a shell layer obtained by graft-polymerizing 1 or more monomer components selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer, and a (meth) acrylate monomer onto a core layer.

The curable resin composition according to any one of [ B1 ] to [ B13 ], wherein the polymer particles (B) having a core-shell structure have an epoxy group in a shell layer.

The curable resin composition according to any one of [ B1 ] to [ B14 ], wherein the polymer particles (B) having a core-shell structure have a shell layer obtained by graft-polymerizing a monomer component having an epoxy group to a core layer.

The curable resin composition according to any one of [ B1 ] to [ B15 ], wherein the polymer particles (B) having a core-shell structure have an epoxy group in a shell layer, and the content of the epoxy group in the shell layer is 0.1 to 2.0mmol/g or less based on the total amount of the shell layers.

The curable resin composition according to any one of [ B1 ] to [ B13 ], wherein the polymer particles (B) having a core-shell structure do not contain an epoxy group in a shell layer.

[ B18 ] is a cured product obtained by curing the curable resin composition according to any one of [ B1 ] to [ B17 ].

[ B19 ] an adhesive comprising the curable resin composition according to any one of [ B1 ] to [ B17 ].

The adhesive according to [ B19 ], wherein the adhesive is an adhesive for a secondary battery.

[ B21 ] A laminate comprising:

2-piece substrate

An adhesive layer formed by curing the adhesive described in [ B19 ] or [ B20 ] for joining the 2 substrates.

One embodiment of the present invention may have the following configuration.

The curable resin composition (C1) is a two-component or multi-component curable resin composition comprising a first component comprising an epoxy resin (A) and a second component comprising an epoxy curing agent (D), wherein the curable resin composition further comprises polymer particles (B) having a core-shell structure comprising a core layer and a shell layer, and a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule, wherein the number of tertiary alkyl groups located in the ortho position to the phenolic hydroxyl groups in the compound (G) is 0 or 1 molecule, and wherein the epoxy curing agent (D) is at least 1 selected from the group consisting of aliphatic amine, alicyclic amine, amide amine, amino-terminated polyether, amino-terminated nitrile rubber, modified aliphatic amine, modified alicyclic amine, modified amino-terminated polyether, and modified amino-terminated nitrile rubber.

The curable resin composition according to [ C1 ], wherein the ratio of the number of moles of the epoxy groups contained in the epoxy resin (A) to the number of moles of the active hydrogen groups contained in the epoxy curing agent (D) (the number of moles of the epoxy groups/the number of moles of the active hydrogen groups) is 0.5 to 1.6.

The curable resin composition according to [ C1 ] or [ C2 ], wherein the epoxy resin (A) is a bisphenol A type epoxy resin and/or a bisphenol F type epoxy resin.

The curable resin composition according to any one of [ C1 ] to [ C3 ], wherein the epoxy curing agent (D) is at least 1 or more selected from the group consisting of alicyclic amines, amino terminated nitrile rubbers, modified products of alicyclic amines and modified products of amino terminated nitrile rubbers.

The curable resin composition according to any one of [ C1 ] to [ C4 ], wherein the content of the polymer particles (B) is 1 to 100 parts by weight based on 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ C1 ] to [ C5 ], wherein the first component and/or the second component further contains aluminum hydroxide (C).

The curable resin composition according to any one of [ C1 ] to [ C6 ], wherein the content of the epoxy curing agent (D) in the curable resin composition is 15 parts by weight or more and 300 parts by weight or less relative to 100 parts by weight of the epoxy resin (A).

The curable resin composition according to [ C6 ], wherein the content of the aluminum hydroxide (C) in the curable resin composition is 250 parts by weight or more and 750 parts by weight or less relative to 100 parts by weight of the epoxy resin (A).

The curable resin composition according to any one of [ C1 ] to [ C8 ], wherein the first component and/or the second component further contains a silane coupling agent (F).

The curable resin composition according to any one of [ C1 ] to [ C9 ], wherein the first component further contains an epoxy silane coupling agent (F1).

The curable resin composition according to any one of [ C1 ] to [ C10 ], wherein the shell layer has an epoxy group.

The curable resin composition according to any one of [ C1 ] to [ C11 ], wherein the shell layer is a polymer obtained by graft-polymerizing a monomer component having an epoxy group to the core layer.

The curable resin composition according to any one of [ C1 ] to [ C12 ], wherein the shell layer has an epoxy group,

the epoxy group content of the shell layer is greater than 0mmol/g and 2.0mmol/g or less relative to the total weight of the shell layer.

The curable resin composition according to any one of [ C1 ] to [ C13 ], wherein the shell layer does not have an epoxy group.

The curable resin composition according to any one of [ C1 ] to [ C14 ], wherein the compound (G) has no substituent other than the phenolic hydroxyl group on the aromatic ring.

[ C16 ] a cured product obtained by curing the curable resin composition according to any one of [ C1 ] to [ C15 ].

[ C17 ] an adhesive comprising the curable resin composition according to any one of [ C1 ] to [ C15 ].

The adhesive according to [ C18 ], wherein the adhesive is an adhesive for a secondary battery.

[ C19 ] A laminate comprising:

2-piece substrate

An adhesive layer formed by curing the adhesive described in [ C17 ] or [ C18 ] between the 2 substrates.

One embodiment of the present invention may have the following configuration.

A curable resin composition comprising a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D), wherein the curable resin composition further comprises polymer particles (B) and aluminum hydroxide (C), the polymer particles (B) have a core-shell structure comprising a core layer and a shell layer, the total weight of the aluminum hydroxide (C) in 100% by weight of the curable resin composition is 55% by weight or more and 85% by weight or less, and the average particle diameter of the aluminum hydroxide (C) is 11 [ mu ] m or more and 200 [ mu ] m or less.

The curable resin composition according to [ X2 ], wherein the polymer particles (B) have an average particle diameter of 0.15 μm or more and 0.30 μm or less, the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer/weight of the shell layer) in the polymer particles (B) is 65/35 to 92/8, and the shell layer of the polymer particles (B) is a copolymer obtained by polymerizing a monomer component containing 55wt% or more of an alkyl ester having 1 to 4 carbon atoms in (meth) acrylic acid in 100wt% of the monomer component and 10 to 100wt% of an alkyl ester having 1 carbon atoms in (meth) acrylic acid and 0 to 80wt% of an alkyl ester having 4 carbon atoms in (meth) acrylic acid in 100wt% of the monomer component.

The curable resin composition according to [ X1 ] or [ X2 ], wherein the epoxy curing agent (D) is 1 or more selected from the group consisting of aliphatic amines, alicyclic amines, amidoamines, amine terminated polyethers, amine terminated nitrile rubbers, modified aliphatic amines, modified alicyclic amines, modified amidoamines, modified amine terminated polyethers, and modified amine terminated nitrile rubbers.

The curable resin composition according to [ X1 ] or [ X2 ], wherein the curable resin composition further comprises a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule, wherein the number of tertiary alkyl groups located at the ortho position of the phenolic hydroxyl groups in the compound (G) is 0 or 1 in 1 molecule, and the epoxy curing agent (D) is at least one selected from the group consisting of aliphatic amines, alicyclic amines, amidoamines, amine-terminated polyethers, amine-terminated nitrile rubbers, aliphatic amine-modified substances, alicyclic amine-modified substances, amidoamine-modified substances, amine-terminated polyether-modified substances and amine-terminated nitrile rubbers-modified substances.

The curable resin composition according to any one of [ X1 ] to [ X4 ], wherein a ratio of the number of moles of the epoxy groups of the epoxy resin (A) to the number of moles of the active hydrogen groups of the epoxy curing agent (D) (the number of moles of the epoxy groups of the epoxy resin (A)/the number of moles of the active hydrogen groups of the epoxy curing agent (D)) is 0.5 to 1.5.

The curable resin composition according to any one of [ X1 ] to [ X5 ], wherein the polymer particles (B) have a diene rubber in the core layer, and the diene rubber is butadiene rubber and/or styrene-butadiene rubber.

The curable resin composition according to any one of [ X1 ] to [ X6 ], wherein the polymer particles (B) having a core-shell structure have an epoxy group in a shell layer.

The curable resin composition according to any one of [ X1 ] to [ X7 ], wherein the polymer particles (B) have epoxy groups in the shell layer, and the content of the epoxy groups in the shell layer is 0.1 to 2.0mmol/g or less based on the total amount of the shell layer.

The curable resin composition according to any one of [ X1 ] to [ X6 ], wherein the polymer particles (B) do not contain an epoxy group in the shell layer.

[ X10 ] is a cured product obtained by curing the curable resin composition according to any one of [ X1 ] to [ X9 ].

[ X11 ] an adhesive comprising the curable resin composition according to any one of [ X1 ] to [ X9 ].

The adhesive according to [ X11 ], wherein the adhesive is an adhesive for a secondary battery.

[ X13 ] A laminate comprising 2 substrates and an adhesive layer obtained by curing the adhesive agent [ X12 ], wherein the adhesive layer bonds the 2 substrates together.

[ X14 ] A curable resin composition which is a two-component curable resin composition comprising a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D),

the curable resin composition further comprises a polymer particle (B) having a core-shell structure comprising a core layer and a shell layer, wherein the total weight of the aluminum hydroxide (C) in 100% by weight of the curable resin composition is 55% by weight or more and 85% by weight or less, the average particle diameter of the polymer particle (B) is 0.15 [ mu ] m or more and 0.30 [ mu ] m or less, the ratio of the weight of the core layer to the weight of the shell layer (the weight of the core layer/the weight of the shell layer) in the polymer particle (B) is 65/35 to 92/8, the shell layer of the polymer particle (B) is a copolymer obtained by polymerizing a monomer component containing 55% by weight or more of an alkyl ester having 1 to 4 carbon atoms of (meth) acrylic acid and containing 10 to 100% by weight of an alkyl ester having 1 to 80% by weight of carbon atoms of (meth) acrylic acid in 100% of the monomer component.

A curable resin composition comprising a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D), wherein the curable resin composition further comprises polymer particles (B) having a core-shell structure comprising a core layer and a shell layer, and a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule, wherein the number of tertiary alkyl groups located at the ortho position of the phenolic hydroxyl groups in the compound (G) is 0 or 1 molecule, and wherein the epoxy curing agent (D) is at least 1 selected from the group consisting of aliphatic amines, alicyclic amines, amidoamines, amine-terminated polyethers, amine-terminated nitrile rubbers, amine-modified substances, amine-terminated polyether-modified substances and amine-terminated nitrile rubbers.

Examples

[ example A ]

Hereinafter, embodiment 1 will be described in further detail with reference to example a, but the present invention is not limited to these example a.

(measurement of volume average particle diameter)

The average particle diameters of the polybutadiene rubber particles in the polybutadiene rubber latex described in the production example and the core-shell polymer particles (B) in the core-shell polymer latex were measured by the following methods. The volume average particle diameter (Mv) of the particles dispersed in the aqueous latex was measured using Microtrac UPA150 (manufactured by Nikkin corporation). The sample diluted with deionized water was used as a measurement sample. The refractive index of the input water and the refractive index of each core-shell polymer particle (B) were measured by adjusting the sample concentration so that the measurement time was 600 seconds and the Signal Level was in the range of 0.6 to 0.8.

A1. Formation of a Nuclear layer

Production example A1; preparation of polybutadiene rubber latex (R-2)

200 parts by weight of water, 0.03 part by weight of tripotassium phosphate, 0.002 part by weight of disodium ethylenediamine tetraacetate (EDTA), 0.001 part by weight of ferrous sulfate heptahydrate (FE) and 1.55 parts by weight of Sodium Dodecylbenzenesulfonate (SDBS) were charged into a pressure-resistant polymerizer, and after removing oxygen by sufficiently performing nitrogen substitution with stirring, 100 parts by weight of butadiene (Bd) was charged into the system and heated to 45 ℃. The polymerization was initiated by successively adding 0.03 parts by weight of terpene hydroperoxide (PHP) and 0.10 parts by weight of Sodium Formaldehyde Sulfoxylate (SFS). PHP was added in an amount of 0.025 parts by weight in each of the 3 rd, 5 th and 7 th hours from the initiation of polymerization. Further, 0.0006 parts by weight of EDTA and 0.003 parts by weight of FE were added at the 4 th, 6 th and 8 th hours from the initiation of polymerization, respectively. The residual monomer was removed by devolatilization under reduced pressure at 15 hours of polymerization, and the polymerization was terminated to obtain a polybutadiene rubber latex (R-1) containing a polybutadiene rubber as a main component. The volume average particle diameter of polybutadiene rubber particles contained in the obtained latex was 80nm.

21 parts by weight of polybutadiene rubber latex (R-1) (containing 7 parts by weight of polybutadiene rubber), 185 parts by weight of deionized water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of EDTA and 0.001 parts by weight of FE were charged into a pressure-resistant polymerizer, and after removing oxygen by sufficiently performing nitrogen substitution with stirring, 93 parts by weight of Bd was charged into the system and the temperature was raised to 45 ℃. 0.02 part by weight of PHP and 0.10 part by weight of SFS are added in sequence to initiate polymerization. PHP 0.025 weight parts, EDTA 0.0006 weight parts, and FE 0.003 weight parts were added every 3 hours from the initiation of polymerization to 24 hours. The residual monomer was removed by devolatilization under reduced pressure at 30 hours of polymerization, and the polymerization was terminated to obtain a polybutadiene rubber latex (R-2) containing a polybutadiene rubber as a main component. The volume average particle diameter of polybutadiene rubber particles contained in the obtained latex was 200nm.

A2. Preparation of core-shell Polymer latex (formation of Shell)

Production example A2-1; preparation of core-shell Polymer latex (AL-1)

262 parts by weight (including 87 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-2) prepared in production example A1 and 57 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, and stirred at 60℃while nitrogen substitution was performed. After 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added, a mixture of 4 parts by weight of Methyl Methacrylate (MMA), 6 parts by weight of Styrene (ST), 2 parts by weight of Acrylonitrile (AN), 1 part by weight of Glycidyl Methacrylate (GMA), and 0.04 parts by weight of Cumene Hydroperoxide (CHP) was continuously added over 120 minutes. After the completion of the addition, 0.04 parts by weight of CHP was added and the stirring was continued for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (AL-1) containing core-shell polymer particles. The polymerization conversion rate of the monomer component is more than 99%. The core-shell polymer particles contained in the aqueous latex (AL-1) had a volume average particle diameter of 0.21. Mu.m. The content of epoxy groups was 0.5mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production example A2-2; preparation of core-shell Polymer latex (AL-2)

AN aqueous latex (AL-2) containing core-shell polymer particles was obtained in the same manner as in production example A2-1 except that the shell monomer was changed to 5 parts by weight of MMA, 6 parts by weight of ST, and 2 parts by weight of AN. The conversion rate of the monomer component is more than 99%. The core-shell polymer particles contained in the aqueous latex (AL-2) had a volume average particle diameter of 0.21. Mu.m. The content of epoxy groups was 0.0mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples A2-3; preparation of core-shell Polymer latex (AL-3)

AN aqueous latex (AL-3) containing core-shell polymer particles was obtained in the same manner as in production example A2-1 except that the shell monomer was changed to 3 parts by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 2 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The core-shell polymer particles contained in the aqueous latex (AL-3) had a volume average particle diameter of 0.21. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples A2 to 4; preparation of core-shell Polymer latex (AL-4)

AN aqueous latex (AL-4) containing core-shell polymer particles was obtained in the same manner as in production example A2-1 except that the shell monomer was changed to 1 part by weight of MMA, 6 parts by weight of ST, 2 parts by weight of AN, and 4 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The core-shell polymer particles contained in the aqueous latex (AL-4) had a volume average particle diameter of 0.21. Mu.m. The epoxy group content was 2.2mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples A2 to 5; preparation of core-shell Polymer latex (AL-5)

An aqueous latex (AL-5) containing core-shell polymer particles was obtained in the same manner as in production example A2-1 except that 13 parts by weight of MMA was changed to the shell monomer. The conversion rate of the monomer component is more than 99%. The core-shell polymer particles contained in the aqueous latex (AL-5) had a volume average particle diameter of 0.21. Mu.m. The content of epoxy groups was 0.0mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

A3. Preparation of Dispersion (M) of core-shell Polymer particles (B) dispersed in curable resin

Production example A3-1; preparation of the Dispersion (AM-1)

132g of the core-shell polymer latex (AL-1) obtained in production example A2-1 (corresponding to 40g of core-shell polymer particles) was introduced into a 1L mixing tank at 25℃with 132g of Methyl Ethyl Ketone (MEK) and stirred. After uniformly mixing, 200g of water was fed at a feed rate of 80 g/min. After the completion of the supply, stirring was rapidly stopped to obtain a slurry liquid composed of a floatable aggregate and a part of an aqueous phase containing an organic solvent. Then, aggregates containing a part of the aqueous phase remained, and 360g of the aqueous phase was discharged from a discharge port in the lower part of the tank. To the obtained aggregate, MEK 90g was added and uniformly mixed to obtain a dispersion in which core-shell polymer particles were uniformly dispersed. To this dispersion, 60g of an epoxy resin (A-1; manufactured by Mitsubishi chemical Co., ltd., JER 828:828, liquid bisphenol A type epoxy resin) was mixed as the component (A). MEK was removed from the mixture using a rotary evaporator. Thus, a dispersion (AM-1) in which core-shell polymer particles were dispersed in an epoxy resin was obtained.

Production example A3-2; preparation of the Dispersion (AM-2)

A dispersion (AM-2) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in production example A3-1, except that (AL-2) obtained in production example A2-2 was used in place of (AL-1) as the core-shell polymer latex in production example A3-1.

Production examples A3-3; preparation of the Dispersion (AM-3)

A dispersion (AM-3) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in production example A3-1, except that (AL-3) obtained in production example A2-3 was used in place of (AL-1) as the core-shell polymer latex in production example A3-1.

Production examples A3 to 4; preparation of the Dispersion (AM-4)

A dispersion (AM-4) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in production example A3-1, except that (AL-4) obtained in production example A2-4 was used in place of (AL-1) as the core-shell polymer latex in production example A3-1.

Production examples A3 to 5; preparation of the Dispersion (AM-5)

In production example A3-1, a dispersion (AM-5) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in production example A3-1, except that (AL-5) obtained in production example A2-5 was used instead of (AL-1) and 60g of an epoxy resin (A-2; manufactured by Hexion corporation, EPON863: liquid bisphenol F type epoxy resin) was used instead of 60g of the epoxy resin (A-1).

Examples A1 to 17 and comparative examples A1 to 8

The respective components were measured and sufficiently mixed according to the formulations shown in tables 1 to 3, to obtain a first component and a second component of the two-component curable resin composition.

For each of the two-component curable resin compositions in tables 1 to 3, dynamic cleavage resistance (impact peel adhesion resistance), shear adhesion strength, thermal conductivity, and flame retardancy (UL-94) were evaluated in the following manner.

Dynamic cleavage resistance (impact-resistant peel adhesion) >

Each of the compositions obtained by sufficiently mixing the first component and the second component in tables 1 to 3 was applied to 2 cold rolled steel sheets (SPCC-SD), and the resultant was laminated so that the thickness of the adhesive layer was 0.25mm, and cured under the conditions of 23 ℃ x 7 days to obtain a laminate. Using this laminate, dynamic cleavage resistance (impact peel adhesion) was measured at 23 ℃ in accordance with ISO 11343. The results are shown in tables 1 to 3.

< shear bond Strength >

Each composition obtained by thoroughly mixing the first component and the second component in table 2 was applied to a 2-sheet cold-rolled steel sheet (SPCC-SD) or an aluminum sheet (a-5052P) having a width of 25mm×a length of 100mm×a thickness of 1.6mm, and bonded so that the adhesive layer had a width of 25mm×a length of 12.5mm×a thickness of 0.13mm, and cured under conditions of 23 ℃ ×7 days, to obtain a laminate.

The shear adhesion strength in MPa was measured under the measurement conditions that the measurement temperature was 23℃and the measurement speed was 1.3 mm/min. The results are shown in Table 2.

< Heat conductivity coefficient >)

The first component and the second component of Table 3 were mixed and then deaerated, and each of the compositions was poured between 2 glass plates sandwiching a spacer having a thickness of 3mm, and cured at 23℃for 7 days to obtain a cured plate having a thickness of 3 mm. The cured plate was cut to obtain 2 disk-shaped samples having a diameter of 20 mm. The thermal conductivity of the cured product was measured by sandwiching a 4. Phi. Size sensor with 2 samples using a Hot Disk method thermal conductivity measuring apparatus TPA-501 (manufactured by Kyoto electronics Co., ltd.).

< flame retardance >)

The first component and the second component of Table 3 were mixed and then deaerated, and each of the compositions was poured between 2 glass plates sandwiching a spacer having a thickness of 3mm, and cured at 23℃for 7 days to obtain a cured plate having a thickness of 3 mm. The cured plate was cut into a rectangle of 127mm by 12.7mm by 3mm thickness and evaluated according to the UL-94 20mm vertical burning test (V test). The test results were shown in the order of "V-0", "V-1" and "V-2" from those having good flame retardancy, and those having failed the UL-94V test were regarded as "non-conforming to the standard".

The following ingredients were used as the compounding ingredients in tables 1 to 3.

Epoxy resin (A) >, and

a-1: JER828 (bisphenol A type epoxy resin, liquid at ordinary temperature, epoxy equivalent: 184-194 manufactured by Mitsubishi chemical Co., ltd.)

A-2: EPON863 (bisphenol F type epoxy resin, which is liquid at ordinary temperature, manufactured by Hexion Co., ltd., epoxy equivalent: 165-174)

A-3: YED216M (alkyl diglycidyl ether, epoxy equivalent: 140-160, manufactured by Mitsubishi chemical Co., ltd.)

Dispersion (M) of polymer particles (B) dispersed in epoxy resin (A)

AM-1-5: the dispersions obtained in the above production examples A3-1 to 5

< aluminium hydroxide (C) >)

C-1: b303 (untreated aluminum hydroxide, manufactured by light metals Co., ltd., average particle diameter (Dp 50): 26 μm)

C-2: b303STE (aluminum hydroxide treated with epoxy silane coupling agent, manufactured by Japanese light metals Co., ltd., average particle diameter (Dp 50): 17 μm)

C-3: b53 (untreated aluminum hydroxide, manufactured by light metals Co., ltd., average particle diameter (Dp 50): 57 μm)

C-4: SB93 (untreated aluminum hydroxide, manufactured by Japanese light metals Co., ltd., average particle size (Dp 50): 114 μm)

C-5: BE033 (untreated aluminum hydroxide, manufactured by Japanese light metals Co., ltd., average particle diameter (Dp 50): 3.2 μm)

C-6: BE043STE (manufactured by Japanese light metals Co., ltd., epoxy silane coupling agent treated aluminum hydroxide, average particle diameter (Dp 50): 3.7 μm)

C-7: BF013 (untreated aluminum hydroxide, manufactured by Japanese light metals Co., ltd., average particle diameter (Dp 50): 1.2 μm)

C-8: BF013ST (aluminum hydroxide treated with epoxy silane coupling agent, manufactured by Japanese light metals Co., ltd., average particle diameter (Dp 50): 1.2 μm)

Epoxy curing agent (D)

D-1:1, 3-bis (aminomethyl) cyclohexane (manufactured by FUJIFILM Wako Pure Chemical Co., ltd., active hydrogen equivalent: 35.5 g/eq)

D-2: jeffamine T-5000 (manufactured by Huntsman Co., ltd., glycerol poly (propylene oxide) triamine, molecular weight: about 5000, active hydrogen equivalent: 952 g/eq)

D-3: hypro ATBN 1300x16 (manufactured by Huntsman Co., ltd., amino terminated butadiene-acrylonitrile copolymer, molecular weight: about 3800, active hydrogen equivalent weight: 800-1000 g/eq)

D-4: isophoronediamine (manufactured by FUJIFILM Wako Pure Chemical Co., active hydrogen equivalent: 41 g/eq)

Epoxy curing accelerator (E)

E-1: resorcinol (manufactured by FUJIFILM Wako Pure Chemical company)

Epoxy silane coupling agent (F) >)

F-1: DOWSIL Z-6040Silane (manufactured by Dow Toray Co., ltd.)

As is clear from table 1, the two-component curable resin compositions of examples A1 to 8, in which the first component contains the (a) component, the (B) component, and the (C) component, and the second component contains the (C) component, have large values of dynamic cleavage resistance and good impact peel adhesion of the cured product obtained.

The compositions of examples A1, 3 to 8 and comparative examples A1 to 5 were different in the type of the component (C) to be added only, and were identical in the blending composition except for the component (C). The average particle size of aluminum hydroxide used in the compositions of examples A1 and 3 to 8 was large, whereas the average particle size of aluminum hydroxide used in the compositions of comparative examples A1 to 5 was small, and the impact peel adhesion resistance was low as compared with examples A1 and 3 to 8.

The composition of example A2 was a composition obtained by adding the epoxy curing accelerator (E) to the composition of example A1, and it was found that the impact peel adhesion was also excellent.

As is clear from table 2, the two-component curable resin compositions of examples A9 to 14, in which the first component contains the (a), the (B) and the (C) components, and the second component contains the (C) and the (D) components, maintain the shear adhesion to steel sheets and aluminum sheets at a high level, and the resulting cured product has good impact peel adhesion.

The compositions of examples A9 to 11 and comparative example A6 were different in the type of the component (C) to be added only, and were identical in the blending composition except for the component (C). The average particle size of the aluminum hydroxide used in the compositions of examples A9 to 11 was large, compared with the average particle size of the aluminum hydroxide used in the composition of comparative example A6 was small, and the impact peel adhesion resistance was low compared with examples A9 to 11.

The compositions of examples A9 and 12 to 14 were different in the component (B) alone and were identical in the composition except for the component (B). The epoxy group content of the shell layer of the component (B) used in the compositions of examples A9 and 12 to 14 was different. When the shell layer does not contain an epoxy group (example A12), and when the epoxy group content of the shell layer is 0.5mmol/g (example A9) and 1.1mmol/g (example A13), the impact peel adhesion is relatively good.

As is clear from Table 3, the two-component curable resin compositions of examples A15 to 17, in which the first component contains the component (A), the component (B) and the component (C), and the second component contains the component (C) and the component (D), have high thermal conductivity and excellent flame retardancy, and the cured product obtained has good impact peel adhesion.

The compositions of examples A15 to 17 and comparative example A7 were different in the amount of the component (C) alone, and were identical in the composition except for the amount of the component (C). In comparative example A7 in which the total weight of the component (C) was small relative to the total weight of the curable resin composition, the heat conductivity was low, and the flame retardancy test of UL-94 was not satisfactory (does not meet the standard). In comparative example A8 which does not contain the component (C), the heat conductivity is low, and the flame retardancy test of UL-94 is not satisfactory (does not meet the standard).

[ example B ]

Hereinafter, embodiment 2 will be described in further detail with reference to example B, but the present invention is not limited to these example B.

(measurement of volume average particle diameter)

The method for measuring the average particle diameter of the polybutadiene rubber particles in the polybutadiene rubber latex described in production example B and the core-shell polymer particles in the core-shell polymer latex is the same as the method described in one of the above [ example A ] (measurement of volume average particle diameter). Therefore, the description of one item (measurement of volume average particle diameter) of the above [ example a ] is cited, and the description thereof is omitted here.

B1. Formation of a Nuclear layer

In example B, as the core layer, the "production example A1 by the above [ example a ] was used; preparation of polybutadiene rubber latex (R-2) R-2 obtained by the method described in "one item. Thus, reference is made to "manufacturing example A1" of the above [ example a ]; the preparation of polybutadiene rubber latex (R-2) is described in the item "A", and the description thereof is omitted here.

B2. Preparation of core-shell Polymer latex (formation of Shell)

Production example B2-1; preparation of core-shell Polymer latex (BL-1)

271 parts by weight (including 90 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-2) prepared in production example A1 and 51 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition apparatus, and stirred at 60℃while nitrogen substitution was performed. After 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added, a mixture of 9 parts by weight of Methyl Methacrylate (MMA), 1 part by weight of Glycidyl Methacrylate (GMA), and 0.14 parts by weight of Cumene Hydroperoxide (CHP) was continuously added over 120 minutes. After the completion of the addition, 0.04 parts by weight of CHP was added and the stirring was continued for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (BL-1) containing core-shell polymer particles. The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-1) was 0.21. Mu.m. The content of epoxy groups was 0.7mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production example B2-2; preparation of core-shell Polymer latex (BL-2)

262 parts by weight (including 87 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-2) prepared in production example A1 and 57 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, and stirred at 60℃while nitrogen substitution was performed. After 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added, a mixture of shell monomer (MMA 11 parts by weight, GMA 2 parts by weight) and 0.06 parts by weight of CHP was continuously added over 120 minutes. After the completion of the addition, 0.04 parts by weight of CHP was added, and the mixture was stirred for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (BL-2) containing core-shell polymer particles. The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-2) was 0.21. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2-3; preparation of core-shell Polymer latex (BL-3)

An aqueous latex (BL-3) containing core-shell polymer particles was obtained in the same manner as in production example B2-2 except that the shell monomer was changed to 2 parts by weight of MMA, 9 parts by weight of Butyl Acrylate (BA), and 2 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-3) was 0.21. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 4; preparation of core-shell Polymer latex (BL-4)

223 parts by weight (including 74 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-2) prepared in production example A1 and 83 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, and stirred at 60℃while nitrogen substitution was performed. After 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added, a mixture of shell monomers (MMA 4 parts by weight, BA 18 parts by weight, GMA 4 parts by weight), and CHP 0.12 parts by weight was continuously added over 120 minutes. After the completion of the addition, 0.04 parts by weight of CHP was added and the stirring was continued for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (BL-4) containing core-shell polymer particles. The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-4) was 0.22. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 5; preparation of core-shell Polymer latex (BL-5)

An aqueous latex (BL-5) containing core-shell polymer particles was obtained in the same manner as in production example B2-2 except that the shell monomer was changed to 11 parts by weight of BA and 2 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-5) was 0.21. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 6; preparation of core-shell Polymer latex (BL-6)

AN aqueous latex (BL-6) containing core-shell polymer particles was obtained in the same manner as in production example B2-2 except that the shell monomer was changed to 1 part by weight of MMA, 6 parts by weight of ST 2, 2 parts by weight of AN, and 4 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-6) was 0.21. Mu.m. The epoxy group content was 2.2mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 7; preparation of core-shell Polymer latex (BL-7)

An aqueous latex (BL-7) containing core-shell polymer particles was obtained in the same manner as in production example B2-1 except that the shell monomer was changed to 8 parts by weight of MMA and 2 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-7) was 0.21. Mu.m. The content of epoxy groups was 1.4mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 8; preparation of core-shell Polymer latex (BL-8)

An aqueous latex (BL-8) containing core-shell polymer particles was obtained in the same manner as in production example B2-1 except that the shell monomer was changed to 6 parts by weight of MMA and 4 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-8) was 0.21. Mu.m. The epoxy group content was 2.8mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 9; preparation of core-shell Polymer latex (BL-9)

An aqueous latex (BL-9) containing core-shell polymer particles was obtained in the same manner as in production example B2-2 except that the shell monomer was changed to MMA 6 parts by weight and BA 7 parts by weight. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-9) was 0.21. Mu.m. The content of epoxy groups was 0mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 10; preparation of core-shell Polymer latex (BL-10)

An aqueous latex (BL-10) containing core-shell polymer particles was obtained in the same manner as in production example B2-2 except that the shell monomer was changed to 5 parts by weight of MMA, 6 parts by weight of BA and 2 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-10) was 0.21. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 11; preparation of core-shell Polymer latex (BL-11)

An aqueous latex (BL-11) containing core-shell polymer particles was obtained in the same manner as in production example B2-2 except that 13 parts by weight of MMA was changed to the shell monomer. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-11) was 0.21. Mu.m. The content of epoxy groups was 0mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 12; preparation of core-shell Polymer latex (BL-12)

An aqueous latex (BL-12) containing core-shell polymer particles was obtained in the same manner as in production examples B2-4 except that the shell monomer was changed to 4 parts by weight of MMA, 8 parts by weight of BA, 10 parts by weight of Butyl Methacrylate (BMA), and 4 parts by weight of GMA. The conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-12) was 0.22. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 13; preparation of core-shell Polymer latex (BL-13)

241 parts by weight (including 80 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-1) prepared in production example A1 and 71 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, and stirred at 60℃while nitrogen substitution was performed. After 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added, a mixture of a shell monomer (MMA 20 parts by weight) and 0.09 parts by weight of CHP was continuously added over 120 minutes. After completion of the addition, 0.04 parts by weight of CHP was added and stirring was continued for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (BL-13) containing core-shell polymer particles. The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-13) was 0.09. Mu.m. The content of epoxy groups was 0mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

Production examples B2 to 14; preparation of core-shell Polymer latex (BL-14)

145 parts by weight (including 48 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-2) prepared in production example A1 and 135 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, and stirred at 60℃while nitrogen substitution was performed. After adding 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.3 parts by weight of SFS, a mixture of shell monomers (MMA 8 parts by weight, BA 16 parts by weight, BMA 20 parts by weight, GMA 8 parts by weight), and CHP 0.24 parts by weight was continuously added over 240 minutes. After the completion of the addition, 0.04 parts by weight of CHP was added and the stirring was continued for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (BL-14) containing core-shell polymer particles. The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (BL-14) was 0.24. Mu.m. The content of epoxy groups was 1.1mmol/g relative to the total amount of the shell layers of the core-shell polymer particles.

B3. Preparation of Dispersion (M) of core-shell Polymer particles (B) dispersed in curable resin

Production example B3-1; preparation of the Dispersion (BM-1)

132g of the core-shell polymer latex (BL-1) obtained in production example B2-1 (corresponding to 40g of core-shell polymer particles) was introduced into a 1L mixing tank at 25℃with 132g of Methyl Ethyl Ketone (MEK) and stirred. After uniformly mixing, 200g of water was added at a feed rate of 80 g/min. After the completion of the supply, stirring was rapidly stopped to obtain a slurry liquid composed of a floatable aggregate and a part of an aqueous phase containing an organic solvent. Then, aggregates containing a part of the aqueous phase remained, and 360g of the aqueous phase was discharged from a discharge port in the lower part of the tank. To the obtained aggregate, MEK 90g was added and uniformly mixed to obtain a dispersion in which core-shell polymer particles were uniformly dispersed. To this dispersion, 60g of an epoxy resin (JER 828, liquid bisphenol A type epoxy resin, mitsubishi chemical Co., ltd.) was mixed as the component (A). MEK was removed from the mixture using a rotary evaporator. Thus, a dispersion (BM-1) in which core-shell polymer particles were dispersed in an epoxy resin was obtained.

Production examples B3-2 to 3-14; preparation of the dispersions (BM-2) to (BM-14)

In production example B3-1, dispersions (BM-2) to (BM-14) in which core-shell polymer particles are dispersed in an epoxy resin were obtained in the same manner as in production example B3-1, except that (BL-2) to (BL-14) obtained in production examples B2-2 to 2-14 were used as core-shell polymer latex instead of (BL-1).

Examples B1 to 17 and comparative examples B1 to 6

According to the formulations shown in tables 4 to 7, the respective components were measured and sufficiently mixed to obtain a first component and a second component of the two-component curable resin composition.

The viscosity, shear adhesion strength, dynamic cleavage resistance (impact peel adhesion resistance), thermal conductivity and flame retardancy (UL-94) of each of the two-component curable resin compositions in tables 4 to 7 were evaluated in the following manner.

< viscosity >

Using rheometer at shear rate 5s ^-1 The viscosities of the first component or the second component in tables 4 to 7 were measured at 25 ℃. The smaller the value of the viscosity, the more excellent the handleability.

< shear bond Strength >

Each of the compositions obtained by sufficiently mixing the first component and the second component in tables 4 to 6 was applied to 2 sheets of SPCC steel plate or aluminum plate (a-5052P) having a width of 25mm×length of 100mm×thickness of 1.6mm and bonded so that the adhesive layer had a width of 25mm×length of 12.5mm×thickness of 0.13mm, and cured at 23 ℃ for 7 days, to obtain a laminate.

The shear adhesion strength in MPa was measured under the measurement conditions that the measurement temperature was 23℃and the measurement speed was 1.3 mm/min.

Dynamic cleavage resistance (impact-resistant peel adhesion) >

Each composition obtained by thoroughly mixing the first component and the second component in tables 5 to 6 was applied to 2 SPCC steel plates, and the resultant was laminated so that the thickness of the adhesive layer was 0.25mm, and cured at 23 ℃ for 7 days to obtain a laminate. Using this laminate, dynamic cleavage resistance (impact peel adhesion) was measured at 23 ℃ in accordance with ISO 11343.

< Heat conductivity coefficient >)

The first component and the second component of Table 7 were mixed and then deaerated, and each of the compositions was poured between 2 glass plates sandwiching a spacer having a thickness of 3mm, and cured at 23℃for 7 days, to obtain a cured plate having a thickness of 3 mm. The cured plate was cut to obtain 2 disk-shaped samples having a diameter of 20 mm. The thermal conductivity of the cured product was measured by sandwiching a 4. Phi. Size sensor with 2 samples using a Hot Disk method thermal conductivity measuring apparatus TPA-501 (manufactured by Kyoto electronics Co., ltd.).

< flame retardance >)

The first component and the second component of Table 7 were mixed and then deaerated, and each of the compositions was poured between 2 glass plates sandwiching a spacer having a thickness of 3mm, and cured at 23℃for 7 days, to obtain a cured plate having a thickness of 3 mm. The cured plate was cut into a rectangle of 127mm by 12.7mm by 3mm thickness and evaluated according to the UL-94 20mm vertical burning test (V test). The test results were shown in the order of "V-0", "V-1" and "V-2" from those having good flame retardancy, and those having failed the UL-94V test were regarded as "non-conforming to the standard".

The following ingredients were used as the blending agents in tables 4 to 7.

Epoxy resin (A) >, and

a-1: JER828 (bisphenol A type epoxy resin, liquid at ordinary temperature, epoxy equivalent: 184-194 manufactured by Mitsubishi chemical Co., ltd.)

A-2: YED216M (alkyl diglycidyl ether, epoxy equivalent: 140-160, manufactured by Mitsubishi chemical Co., ltd.)

Dispersion (M) of polymer particles (B) dispersed in epoxy resin (A)

BM-1 to 14: the dispersions obtained in the above production examples B3-1 to 14

< aluminium hydroxide (C) >)

C-1: b303 (untreated aluminum hydroxide, manufactured by light metals Co., ltd., average particle diameter (Dp 50): 26 μm)

C-2: BE033 (untreated aluminum hydroxide, manufactured by Japanese light metals Co., ltd., average particle diameter (Dp 50): 3.2 μm)

Epoxy curing agent (D)

D-1:1, 3-bis (aminomethyl) cyclohexane (manufactured by FUJIFILM Wako Pure Chemical Co., ltd.)

D-2: jeffamine T-5000 (manufactured by Huntsman Co., ltd., glycerol poly (propylene oxide) triamine, molecular weight: about 5000, active hydrogen equivalent: 952 g/eq)

D-3: hypro ATBN 1300x16 (manufactured by Huntsman Co., ltd., amino terminated butadiene-acrylonitrile copolymer, molecular weight: about 3800, active hydrogen equivalent weight: 800-1000 g/eq)

Epoxy curing accelerator (E)

E-1: resorcinol (manufactured by FUJIFILM Wako Pure Chemical company)

Epoxy silane coupling agent (F) >)

F-1: DOWSIL Z-6040Silane (manufactured by Dow Toray Co., ltd.)

As is clear from table 4, the two-component curable resin compositions of examples B1 to 4, in which the first component contains the (a) component, the (B) component, and the (C) component, and the second component contains the (C) component, and the (D) component, have low viscosity and excellent handleability, and the resulting cured product has good shear adhesion.

The compositions of examples B1 to 4 and comparative examples B1 to 2 were different in the only component (B) added and were identical in the blend composition except for the component (B). The component (B) used in the compositions of examples B1 to 4 contained an alkyl (meth) acrylate having 1 to 4 carbon atoms as a main component (55 wt% or more) and an alkyl (meth) acrylate having 4 carbon atoms in an amount of 80 wt% or less as a monomer component constituting the shell layer. On the other hand, comparative example B1, in which the content of alkyl ester of carbon number 4 (meth) acrylic acid was 85 wt%, was very high in viscosity and poor in handleability, and therefore the shear adhesion strength was not measured. In addition, the composition of comparative example B2, in which the alkyl ester having 1 to 4 carbon atoms in (meth) acrylic acid was as small as 8% by weight and the shell layer comprising the other monomer component as the main component, showed a value that the viscosity of the first component was high and the shear adhesiveness of the obtained cured product was also low, as compared with examples B1 to 4.

As is clear from Table 5, the two-component curable resin compositions of examples B5 to 10 were low in viscosity and excellent in handleability as in examples B1 to 4 of Table 4.

The first component of examples B1 and 2 was the same, but the second component of example B2 reduced the addition amount of each of the compounding agents of the second component of example B1 to 0.75 times. Thus, the ratio of the number of moles of epoxy groups in component (A) to the number of moles of active hydrogen groups in component (D) in example B2 was a composition having an excess of epoxy, and the shear adhesion exhibited a very low value.

The compositions of examples B5 and 7 to 10 were different in the component (B) alone and were identical in the composition except for the component (B). (B) The composition of example B8, which contains a large amount of epoxy groups in the shell layer of the component, shows a low impact peel adhesion resistance. The composition of example B9, which does not contain an epoxy group in the shell layer of component (B), also shows a low impact peel adhesion resistance. The results indicate that the ratio of the number of moles of epoxy groups in the component (A)/the number of moles of active hydrogen groups in the component (D) is effective for shear adhesion strength, and the amount of epoxy groups in the shell layer of the component (B) is effective for impact peel adhesion resistance.

As is clear from Table 6, the two-component curable resin compositions of examples B11 to 14 have low viscosity and excellent handleability, and the cured products obtained have good shear adhesion and impact peel adhesion.

The compositions of examples B11 to 14 and comparative examples B3 to 5 were different in the only component (B) added and were all the same in the composition except for the component (B). The average particle diameter of the component (B) used in the compositions of examples B11 to 14 was 0.15 to 0.30. Mu.m, the weight ratio of the core layer to the shell layer was 65/35 to 92/8, and the monomer component constituting the shell layer was an alkyl ester of (meth) acrylic acid having 1 to 4 carbon atoms as the main component (55% by weight or more). On the other hand, the composition of comparative example B3, in which the alkyl ester of 1 to 4 carbon atoms was contained in an amount of as little as 8% by weight, the composition of comparative example B4, in which the average particle diameter of the component (B) was as small as 0.09. Mu.m, and the composition of comparative example B5, in which the core layer/shell layer weight ratio was 48/52, were each high in viscosity and poor in handleability. Further, since the composition of comparative example B5 shows a low value of impact peel adhesion, it is considered that the weight ratio of the core layer/shell layer of the component (B) is effective for impact peel adhesion. The compositions of example B12 and comparative example B4, in which the shell layer of component (B) does not contain an epoxy group, also show low impact peel adhesion. From the results, it is considered that the amount of the epoxy group in the shell layer of the component (B) is effective for the impact peel adhesion resistance.

As is clear from Table 7, the two-component curable resin compositions of examples B15 to 17, in which the first component contains the (A) component, the (B) component and the (C) component, and the second component contains the (C) component and the (D) component, have high thermal conductivity, excellent flame retardancy, low viscosity, and excellent handleability.

The compositions of examples B15 to 17 and comparative example B6 were different in the amount of only the component (C) added, and were identical in the composition except for the amount of the component (C). In comparative example B6 in which the total weight of the component (C) was small relative to the total weight of the curable resin composition, the heat conductivity was low, and the flame retardancy test of UL-94 was not satisfactory (does not meet the standard).

[ example C ]

Embodiment 2 will be described in further detail below with reference to example C, but the present invention is not limited to these example C.

(measurement of volume average particle diameter)

The method for measuring the average particle diameter of the polybutadiene rubber particles in the polybutadiene rubber latex described in production example C and the core-shell polymer particles in the core-shell polymer latex is the same as the method described in one of the above [ example A ] (measurement of volume average particle diameter). Therefore, the description of one item (measurement of volume average particle diameter) of the above [ example a ] is cited, and the description thereof is omitted here.

C1. Formation of a Nuclear layer

In example C, as the core layer, the "production example A1 by the above [ example a ] was used; preparation of polybutadiene rubber latex (R-2) R-2 obtained by the method described in "one item. Thus, reference is made to "manufacturing example A1" of the above [ example a ]; the preparation of polybutadiene rubber latex (R-2) is described in the item "A", and the description thereof is omitted here.

C2. Preparation of core-shell Polymer latex (formation of Shell)

Production example C2-1; preparation of core-shell Polymer latex (CL-1)

262 parts by weight (including 87 parts by weight of polybutadiene rubber particles) of the polybutadiene rubber latex (R-2) prepared in production example A1 and 57 parts by weight of deionized water were charged into a glass reactor having a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, and stirred at 60℃while nitrogen substitution was performed. After 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS were added, a mixture of 3 parts by weight of Methyl Methacrylate (MMA), 6 parts by weight of Styrene (ST), 2 parts by weight of Acrylonitrile (AN), 2 parts by weight of Glycidyl Methacrylate (GMA), and 0.04 parts by weight of Cumene Hydroperoxide (CHP) was continuously added over 120 minutes. After the completion of the addition, 0.04 parts by weight of CHP was added and the stirring was continued for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (CL-1) containing core-shell polymer particles (B). The polymerization conversion rate of the monomer component is more than 99%. The volume average particle diameter of the core-shell polymer particles (B) contained in the aqueous latex (CL-1) was 0.21. Mu.m.

C3. Preparation of Dispersion (M) of core-shell Polymer particles (B) dispersed in curable resin

Production example C3-1; preparation of the Dispersion (M-1)

132g of the core-shell polymer latex (CL-1) obtained in production example C2-1 (corresponding to 40g of core-shell polymer particles (B)) was introduced into a 1L mixing tank at 25℃with stirring. After uniformly mixing, 200g of water was added at a feed rate of 80 g/min. After the completion of the supply, stirring was rapidly stopped to obtain a slurry liquid composed of a floatable aggregate and a part of an aqueous phase containing an organic solvent. Then, aggregates containing a part of the aqueous phase remained, and 360g of the aqueous phase was discharged from a discharge port in the lower part of the tank. To the obtained aggregate, MEK 90g was added and uniformly mixed to obtain a dispersion in which the core-shell polymer particles (B) were uniformly dispersed. To this dispersion, 60g of an epoxy resin (A-1; manufactured by Mitsubishi chemical Co., ltd., JER/828: liquid bisphenol A type epoxy resin, epoxy equivalent: 184-194 g/eq) as a component (A) was mixed. MEK was removed from the mixture using a rotary evaporator. Thus, a dispersion (M-1) in which the core-shell polymer particles (B) were dispersed in the epoxy resin was obtained.

Production example C3-2; preparation of the Dispersion (M-2)

A dispersion (M-2) in which core-shell polymer particles (B) were dispersed in an epoxy resin was obtained in the same manner as in production example C3-1, except that 60g of an epoxy resin (A-2; manufactured by Hexion Co., ltd., EPON863: bisphenol F-type epoxy resin, epoxy equivalent: 165-174 g/eq) was used in place of 60g of the epoxy resin (A-1).

Examples C1 to 23 and comparative examples C1 to 7

The respective components were measured and sufficiently mixed according to the formulations shown in tables 8 to 12, to obtain a first component and a second component of the two-component curable resin composition. The two-component curable resin compositions obtained in examples C1 to 23 were curable resin compositions of embodiment 3 (two-component curable resin compositions).

For each two-component curable resin composition of table 8 or 9, the curing time was evaluated according to the following method.

< curing time >

The "bohlin cvo rheometer", manufactured by Malvern company, using PP25,at a shear rate of 5s at a plate gap of 0.2mm ^-1 The viscosity change at 50℃of each two-component curable resin composition obtained by sufficiently mixing the first component and the second component in Table 8 or 9 was measured. The viscosity was measured every 10 seconds, and the viscosity immediately after the first component and the second component were mixed was taken as the initial viscosity, and the time to reach a viscosity 10 times the initial viscosity was measured and taken as the curing time. The shorter the curing time, the more excellent the curability.

For each of the two-component curable resin compositions in tables 8 to 12, the shear adhesion strength was evaluated by the following method.

< shear bond Strength >

Each of the two-component curable resin compositions obtained by sufficiently mixing the first component and the second component in tables 8 to 12 was applied to a 2-piece aluminum plate (a-5052P) or a cold-rolled steel plate having a width of 25mm×a length of 100mm×a thickness of 1.6mm and bonded so that the applied two-component curable resin composition (adhesive layer) had a width of 25mm×a length of 12.5mm×a thickness of 0.25mm, and cured under conditions of 23 ℃ for 7 days, to obtain a laminate.

The shear adhesion strength in MPa was measured under the measurement conditions that the measurement temperature was 23℃and the measurement speed was 1.3 mm/min. The results are shown in tables 8 to 12.

For each of the two-component curable resin compositions in table 10, dynamic cleavage resistance (impact peel adhesion resistance) was evaluated by the following method.

Dynamic cleavage resistance (impact-resistant peel adhesion) >

Each composition obtained by thoroughly mixing the first component and the second component in table 10 was applied to 2 cold-rolled steel sheets, and the resultant was laminated so that the thickness of the adhesive layer was 0.25mm, and cured at 23 ℃ for 7 days to obtain a laminate. Using this laminate, dynamic cleavage resistance (impact peel adhesion) was measured at 23 ℃ in accordance with ISO 11343. The results are shown in Table 10.

The following ingredients were used as the compounding ingredients in tables 8 to 12.

Epoxy resin (A) >, and

a-1: JER828 (bisphenol A type epoxy resin, liquid at ordinary temperature, epoxy equivalent: 184-194 manufactured by Mitsubishi chemical Co., ltd.)

A-2: EPON863 (bisphenol F type epoxy resin, manufactured by Hexion Co., ltd., epoxy equivalent: 165-174)

Dispersion (M) of core-shell polymer particles (B) dispersed in epoxy resin (A)

CM-1-2: the dispersions obtained in the above production examples C3-1 to 2

< Compound (G) >)

Resorcinol (manufactured by FUJIFILM Wako Pure Chemical company)

Catechol (FUJIFILM Wako Pure Chemical company)

4-t-butylcatechol (manufactured by FUJIFILM Wako Pure Chemical Co., ltd.)

Methyl hydroquinone (Tokyo chemical Co., ltd.)

Tert-butylhydroquinone (Tokyo chemical Co., ltd.)

< Compound having phenolic hydroxyl group different from the component (G) >)

2, 5-Di-tert-butylhydroquinone (Tokyo Kabushiki Kaisha)

2,4, 6-tris (dimethylaminomethyl) phenol (Tokyo chemical Co., ltd.)

4-tert-butylphenol (Tokyo chemical Co., ltd.)

Phenol (FUJIFILM Wako Pure Chemical company)

4-methoxyphenol (manufactured by FUJIFILM Wako Pure Chemical Co., ltd.)

Epoxy curing agent (D)

D-1 (cycloaliphatic amine): 1, 3-bis (aminomethyl) cyclohexane (manufactured by FUJIFILM Wako Pure Chemical Co., ltd.)

D-2 (amine terminated polyether): ancamine 1922A (manufactured by Evonik Co., ltd., 3'- [ Oxybis (2, 1-ethylenedioxy) ] bis-1-propylamine (3, 3' - (Oxybis (2, 1-ethane-dioxy)) bis-1-popanamine), active hydrogen equivalent weight: 55 g/eq)

D-3 (amino terminated nitrile rubber): hypro ATBN 1300x16 (manufactured by Huntsman Co., ltd., amino terminated butadiene-acrylonitrile copolymer, molecular weight: about 3800, active hydrogen equivalent weight: 800-1000 g/eq)

D-4 (amidoamine): vegechem Green V140 (dimer acid, condensate of fatty acid and polyamine, active Hydrogen equivalent: 97g/eq, manufactured by Confucius of Daiki food industry Co., ltd.)

D-5 (amine terminated polyether): jeffamine T-5000 (manufactured by Huntsman Co., ltd., glycerol poly (propylene oxide) triamine, molecular weight: about 5000, active hydrogen equivalent: 952 g/eq)

< aluminium hydroxide (C) >)

C-1: b303 (untreated aluminum hydroxide, manufactured by light metals Co., ltd., average particle diameter (Dp 50): 26 μm)

C-2: BE033 (untreated aluminum hydroxide, manufactured by Japanese light metals Co., ltd., average particle diameter (Dp 50): 3.2 μm)

Epoxy silane coupling agent (F) >)

F-1: DOWSIL Z-6040Silane (3-glycidoxypropyl trimethoxysilane, manufactured by Dow Toray Co., ltd.)

F-2: KBM 603Silane (N-2- (aminoethyl) -3-aminopropyl trimethoxysilane, manufactured by Xinyue Silicone Co., ltd.)

< heavy calcium carbonate >)

WHITON SB (average particle size: 1.8 μm, manufactured by Bai Dangai Co., ltd.)

< carbon black >

MONARCH 280 (Cabot Co., ltd.)

< fumed silica >)

CAB-O-SIL TS-720 (fumed silica surface-treated with polydimethylsiloxane, manufactured by CABOT Co., ltd.),

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As is clear from Table 8, the two-component curable resin compositions of examples C1 to 12, in which the first component contains the (A) component to the (B) component and the second component contains the (G) component and the (D) component, have short curing time and excellent curability.

In particular, it was found that the two-component curable resin compositions of examples C1, 2, and 7 to 12 using the component (G) having no substituent other than a phenolic hydroxyl group on the aromatic ring had high shear adhesion strength and excellent adhesion of the obtained cured product.

It was also found that the two-component curable resin compositions of examples C9 to 10 containing an epoxy silane coupling agent as component (F) were particularly high in shear adhesion strength and excellent in adhesion.

On the other hand, as is clear from Table 9, the two-component curable resin compositions of comparative example C1 containing no component (G), comparative example C2 containing a compound having 2 phenolic hydroxyl groups and 2 tertiary alkyl groups in the ortho-position thereof, and comparative examples C3 to 6 containing a compound having 1 phenolic hydroxyl group were long in curing time and poor in curability.

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As is clear from Table 11, the two-component curable resin compositions of examples C14 to 19, in which the first component contained the (A) component to the (B) component and the second component contained the (G) component and the (D) component, exhibited good shear adhesion strength of the cured products.

The shear adhesion strength of the cured product obtained from the two-component curable resin composition of examples C15 to 17, in which the molar ratio was in the range of 1.1 to 1.6, was extremely high compared with the two-component curable resin composition of example C14, in which the molar ratio was 1.0, and the adhesion of the two-component curable resin composition, in which the molar ratio was 1.1 to 1.6, was particularly excellent.

It was also found that the two-component curable resin compositions of examples C18 to 19 containing the epoxy silane coupling agent as the component (F) were particularly high in shear adhesion strength and excellent in adhesion of the resulting cured product.

As is clear from table 12, the two-component curable resin compositions of examples C20 to 23, in which the first component contained the (a), the (B) and (G), and the second component contained the (G) and (D) or contained the (D), exhibited good shear adhesion strength of the cured product.

On the other hand, the two-component curable resin composition of comparative example C7, in which neither the first component nor the second component contained the (G) component, exhibited (i) a very long curing time and (ii) a very low shear adhesion strength, as compared with the two-component curable resin compositions of examples C20 to 23.

The components other than the component (G) (for example, the component (D), the component (E), the component (F), and the inorganic filler other than the component (E)) have substantially no influence on the curing time. Accordingly, the two-part type curable resin compositions of examples C13 to 23 exhibited a high degree of cure time to the same extent as in examples C1 or 2, with a high degree of cure time at least shorter than that of the two-part type curable resin compositions of comparative examples C1 to 7.

Industrial applicability

According to one embodiment of the present invention, a new curable resin composition that is more excellent than the conventional one can be provided as a two-component or multi-component epoxy resin composition. For example, according to embodiment 1, a two-component curable resin composition which can give a cured product exhibiting excellent thermal conductivity, flame retardancy, adhesive strength and impact peel adhesion resistance and which can be cured at room temperature or a low temperature close to room temperature can be provided. For example, according to embodiment 2, a two-component curable resin composition which can give a cured product exhibiting excellent thermal conductivity, flame retardancy and adhesive strength, has low viscosity and good handleability, and can be cured at room temperature or a low temperature close to room temperature can be provided. For example, according to embodiment 3, a two-component type or multi-component type curable resin composition excellent in quick curability can be provided. Therefore, the curable resin composition according to one embodiment of the present invention can be preferably used for applications such as adhesives for vehicles, structural adhesives for airplanes, adhesives for secondary batteries for EV battery cells and the like, adhesives for structural adhesives for wind power generation, paints, materials for lamination with glass fibers and/or carbon fibers to obtain composite materials, materials for printed wiring boards, solder resists, interlayer insulating films, build-up (build-up) materials, adhesives for FPCs, electrical insulating materials such as sealing materials for electronic parts such as semiconductors/LEDs, die-bonding materials, underfills, mounting materials for semiconductors (for example ACF, ACP, NCF, NCP and the like), sealing materials for display devices (for example liquid crystal panels and OLED displays and the like), and composite materials for repairing concrete, and the like, and particularly can be preferably used as adhesives for secondary batteries.

Claims (15)

1. A curable resin composition of two-component type,

the curable resin composition comprises a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D),

the curable resin composition further comprises a polymer particle (B) having a core-shell structure comprising a core layer and a shell layer,

the total weight of the aluminum hydroxide (C) is 55 to 85 wt% in 100 wt% of the total weight of the curable resin composition,

the aluminum hydroxide (C) has an average particle diameter of 11 μm or more and 200 μm or less.

2. The curable resin composition according to claim 1, wherein,

the polymer particles (B) have an average particle diameter of 0.15 μm or more and 0.30 μm or less,

the ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer/weight of the shell layer) in the polymer particles (B) is 65/35 to 92/8,

the shell layer of the polymer particle (B) is a copolymer obtained by polymerizing a monomer component containing 55wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100 wt%,

The monomer component contains 10 to 100wt% of an alkyl ester having 1 carbon atom (meth) acrylate and 0 to 80wt% of an alkyl ester having 4 carbon atom (meth) acrylate in 100 wt%.

3. The curable resin composition according to claim 1 or 2, wherein,

the epoxy curing agent (D) is at least 1 selected from aliphatic amine, alicyclic amine, amide amine, amino terminated polyether, amino terminated nitrile rubber, modified aliphatic amine, modified alicyclic amine, modified amide amine, modified amino terminated polyether and modified amino terminated nitrile rubber.

4. The curable resin composition according to claim 1 or 2, wherein,

the curable resin composition further comprises a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule,

in the compound (G), the number of tertiary alkyl groups located at the ortho position to the phenolic hydroxyl group is 0 or 1 in 1 molecule,

the epoxy curing agent (D) is at least 1 selected from aliphatic amine, alicyclic amine, amide amine, amino terminated polyether, amino terminated nitrile rubber, modified aliphatic amine, modified alicyclic amine, modified amide amine, modified amino terminated polyether and modified amino terminated nitrile rubber.

5. The curable resin composition according to any one of claim 1 to 4, wherein,

the ratio of the number of moles of the epoxy groups of the epoxy resin (a) to the number of moles of the active hydrogen groups of the epoxy curing agent (D) (the number of moles of the epoxy groups of the epoxy resin (a)/the number of moles of the active hydrogen groups of the epoxy curing agent (D)) is 0.5 to 1.5.

6. The curable resin composition according to any one of claims 1 to 5, wherein,

the polymer particles (B) have a diene rubber in the core layer, and the diene rubber is butadiene rubber and/or styrene-butadiene rubber.

7. The curable resin composition according to any one of claims 1 to 6, wherein,

the polymer particles (B) having the core-shell structure have epoxy groups in the shell layer.

8. The curable resin composition according to any one of claims 1 to 7, wherein,

the polymer particles (B) have epoxy groups in the shell layer, and the content of the epoxy groups in the shell layer is 0.1-2.0 mmol/g or less relative to the total amount of the shell layer.

9. The curable resin composition according to any one of claims 1 to 6, wherein,

The polymer particles (B) do not contain an epoxy group in the shell layer.

10. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 9.

11. An adhesive comprising the curable resin composition according to any one of claims 1 to 9.

12. The adhesive according to claim 11, wherein,

the adhesive is an adhesive for a secondary battery.

13. A laminate comprising 2 substrates and an adhesive layer obtained by curing the adhesive according to claim 12,

the adhesive layer bonds the 2 substrates together.

14. A curable resin composition is a two-component curable resin composition,

the curable resin composition comprises a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D),

the curable resin composition further comprises a polymer particle (B) having a core-shell structure comprising a core layer and a shell layer,

the total weight of the aluminum hydroxide (C) is 55 to 85 wt% in 100 wt% of the total weight of the curable resin composition,

the polymer particles (B) have an average particle diameter of 0.15 μm or more and 0.30 μm or less,

The ratio of the weight of the core layer to the weight of the shell layer (weight of the core layer/weight of the shell layer) in the polymer particles (B) is 65/35 to 92/8,

the shell layer of the polymer particle (B) is a copolymer obtained by polymerizing a monomer component containing 55wt% or more of an alkyl (meth) acrylate having 1 to 4 carbon atoms in 100wt%,

the monomer component contains 10 to 100wt% of an alkyl ester having 1 carbon atom (meth) acrylate and 0 to 80wt% of an alkyl ester having 4 carbon atom (meth) acrylate in 100 wt%.

15. A curable resin composition which is a two-component or multi-component curable resin composition,

the curable resin composition comprises a first component containing an epoxy resin (A) and a second component containing an epoxy curing agent (D),

the curable resin composition further comprises a polymer particle (B) having a core-shell structure comprising a core layer and a shell layer, and a compound (G) having (i) 1 aromatic ring and (ii) at least 2 phenolic hydroxyl groups in 1 molecule,

in the compound (G), the number of tertiary alkyl groups located at the ortho position to the phenolic hydroxyl group is 0 or 1 in 1 molecule,

The epoxy curing agent (D) is at least 1 selected from aliphatic amine, alicyclic amine, amide amine, amino terminated polyether, amino terminated nitrile rubber, modified aliphatic amine, modified alicyclic amine, modified amide amine, modified amino terminated polyether and modified amino terminated nitrile rubber.