JP7547031B2 - Epoxy resin composition and adhesive - Google Patents

Description

The present invention relates to an epoxy resin composition and an adhesive containing the same.

Epoxy resins are widely used in civil engineering and construction materials, electrical and electronic materials, adhesives, etc., because their cured products have excellent dimensional stability, mechanical strength, electrical insulation properties, heat resistance, water resistance, chemical resistance, etc. However, the problem with cured epoxy resins is that they have low fracture toughness and are very brittle.

Patent Document 1 discloses a technology for improving the impact-resistant adhesive properties of epoxy resins by dispersing core-shell polymer particles having a core-shell structure in the epoxy resin.

Patent Document 2 describes a technique for increasing the toughness of an epoxy resin by blending an anhydride curing agent and a compound containing two active hydrogen atoms that can react with the epoxy resin, and discloses that the resin can be used for applications such as casting resin, laminating resin, molding compound, coating compound, or encapsulation systems for electric and electronic components.

Patent Document 3 discloses a method for molding fiber-reinforced thermoplastic resin by impregnating reinforcing fibers with a compound having two epoxy groups and a compound having two phenolic hydroxyl groups, and then allowing a polyaddition reaction to proceed. It is described that this method suppresses the generation of voids at the interface between the thermoplastic resin and the reinforcing fibers, and makes it possible to mold fiber-reinforced thermoplastic resin without the need for high temperature and high pressure.

International Publication No. 2015/053289 Japanese Patent Application Publication No. 6-49179 JP 2006-321897 A

Conventionally known epoxy resin compositions do not sufficiently improve impact peel adhesion, and there is a demand for epoxy resin compositions that can give cured products that exhibit superior impact peel adhesion.

In view of the above-mentioned current situation, the present invention aims to provide an epoxy resin composition that gives a cured product that exhibits excellent impact-resistant peel adhesion.

As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that by blending epoxy resin (A) with core-shell polymer particles (B), compound (C) having two functional groups in one molecule each having one active hydrogen that reacts with epoxy groups, and catalyst (D) that promotes the polyaddition reaction between components (A) and (C), and by blending component (C) in a specific amount or more, an epoxy resin composition can be obtained that gives a cured product that exhibits excellent impact-resistant peel adhesion.

That is, the present invention relates to an epoxy resin composition comprising an epoxy resin (A), core-shell polymer particles (B) having a core layer made of a diene rubber, a compound (C) having two functional groups in one molecule each having one active hydrogen that reacts with an epoxy group, a catalyst (D) that promotes a polyaddition reaction between the epoxy resin (A) and the compound (C), and an epoxy resin curing agent (E) as an optional component, in which the amount of the compound (C) is 20 parts by weight or more per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E). Preferably, the catalyst (D) is a phosphorus-based catalyst. Preferably, the compound (C) is a compound having two phenolic hydroxyl groups in one molecule. Preferably, the volume average particle diameter of the core-shell polymer particles (B) is 10 to 2000 nm. Preferably, the amount of the core-shell polymer particles (B) is 1 part by weight or more and 100 parts by weight or less per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E). Preferably, the amount of compound (C) is 70 parts by weight or less per 100 parts by weight of the total of epoxy resin (A) and epoxy resin curing agent (E). Preferably, the weight ratio of epoxy resin curing agent (E) to the total of epoxy resin (A) and epoxy resin curing agent (E) is 0% by weight or more and 20% by weight or less.
The present invention also relates to a cured product obtained by curing the epoxy resin composition. The present invention further relates to an adhesive containing the epoxy resin composition described above, and preferably the adhesive is a structural adhesive. The present invention also relates to a laminate comprising two substrates and an adhesive layer formed by curing the adhesive according to claim 9 or 10, which bonds the two substrates.

The present invention provides an epoxy resin composition that gives a cured product that exhibits excellent impact peel adhesion.

Embodiments of the present invention are described in detail below.

The present invention is an epoxy resin composition containing an epoxy resin (A), core-shell polymer particles (B) having a core layer composed of a diene rubber, a compound (C) having two functional groups in one molecule each having one active hydrogen that reacts with an epoxy group, a catalyst (D) that promotes the polyaddition reaction of the epoxy resin (A) and the compound (C), and, as an optional component, a curing agent for epoxy resins (E).

<Epoxy resin (A)>
The epoxy resin composition of the present invention contains an epoxy resin (A) as a curable resin. As the epoxy resin, various hard epoxy resins can be used, except for the rubber-modified epoxy resins and urethane-modified epoxy resins described below. For example, 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, novolac type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, hydrogenated bisphenol A (or F) type epoxy resins, fluorinated epoxy resins, flame-retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, various alicyclic epoxy resins, N,N-diglycidylaniline, N,N-diglycidyl amine type epoxy resins, novolac type epoxy resins, glycidyl ether type epoxy resins of bisphenol A propylene oxide adducts, hydrogenated bisphenol A (or F) type epoxy resins, fluorinated epoxy resins, flame-retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, p-oxybenzoic acid glycidyl ether ester type epoxy resins, m-aminophenol type epoxy resins, diaminodiphenylmethane type epoxy resins, various alicyclic epoxy resins, N,N-diglycidyl aniline, N,N-diglycidyl amine type epoxy resins ... Examples of the epoxy resin include glycidyl-o-toluidine, triglycidyl isocyanurate, divinylbenzene dioxide, resorcinol diglycidyl ether, polyalkylene glycol diglycidyl ether, glycol diglycidyl ether, diglycidyl ester of aliphatic polybasic acid, glycidyl ether of polyhydric aliphatic alcohol having two or more valences such as glycerin, epoxidized products of unsaturated polymers such as chelate-modified epoxy resins, hydantoin-type epoxy resins, petroleum resins, amino-containing glycidyl ether resins, and epoxy compounds obtained by addition reaction of the above-mentioned epoxy resins with bisphenol A (or F) or polybasic acids, but are not limited thereto, and generally used epoxy resins can be used. These epoxy resins may be used alone or in combination of two or more.

More specifically, the polyalkylene glycol diglycidyl ether includes polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc. More specifically, the glycol diglycidyl ether includes neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, etc. More specifically, the diglycidyl ester of the aliphatic polybasic acid includes dimer acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid diglycidyl ester, maleic acid diglycidyl ester, etc. More specifically, the glycidyl ether of the dihydric or higher polyhydric aliphatic alcohol includes trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil modified polyglycidyl ether, propoxylated glycerin triglycidyl ether, sorbitol polyglycidyl ether, etc. Examples of epoxy compounds obtained by addition reaction of polybasic acids and the like with epoxy resins include the addition reaction product of a dimer of tall oil fatty acid (dimer acid) and a bisphenol A type epoxy resin, as described in International Publication No. 2010-098950.

The polyalkylene glycol diglycidyl ether, the glycol diglycidyl ether, the diglycidyl ester of the aliphatic polybasic acid, and the glycidyl ether of the dihydric or higher polyhydric aliphatic alcohol are epoxy resins having a relatively low viscosity, and when used in combination with other epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, they function as reactive diluents, improving the balance between the viscosity of the composition and the physical properties of the cured product. The content of these epoxy resins functioning as reactive diluents in component (A) is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, and even more preferably 2 to 5% by weight.

The chelate-modified epoxy resin is a reaction product of an epoxy resin and a compound containing a chelate functional group (chelating ligand), and when the epoxy resin composition of the present invention to which the chelate functional group is added is used as a vehicle adhesive, the adhesiveness to the surface of a metal substrate contaminated with oily substances can be improved. The chelate functional group is a functional group of a compound having a plurality of coordination sites in the molecule capable of coordinating to a metal ion, and examples thereof include a phosphorus-containing acid group (e.g., -PO(OH) ₂ ), a carboxylic acid group (-CO ₂ H), a sulfur-containing acid group (e.g., -SO ₃ H), an amino group, and a hydroxyl group (particularly, hydroxyl groups adjacent to each other in an aromatic ring). Examples of the chelate ligand include ethylenediamine, bipyridine, ethylenediaminetetraacetic acid, phenanthroline, porphyrin, crown ether, and the like. Examples of commercially available chelate-modified epoxy resins include ADEKA Resin EP-49-10N manufactured by ADEKA. The amount of the chelate-modified epoxy resin used in component (A) is preferably 0.1 to 10% by weight, and more preferably 0.5 to 3% by weight.

Among these epoxy resins, those having at least two epoxy groups in one molecule are preferred because they have high curability, excellent flexibility after curing, and excellent impact peel resistance improvement effects due to the incorporation of core-shell polymer particles (B).

Among the above epoxy resins, bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferred because the resulting cured product has a high elastic modulus, excellent heat resistance and adhesiveness, and is relatively inexpensive, with bisphenol A type epoxy resins being particularly preferred.

Of the various epoxy resins, epoxy resins with an epoxy equivalent of less than 220 are preferred because the resulting cured product has a high elastic modulus and heat resistance, and epoxy equivalents of 90 or more and less than 210 are more preferred, and 150 or more and less than 200 are even more preferred.

In particular, bisphenol A type epoxy resins and bisphenol F type epoxy resins with an epoxy equivalent of less than 220 are preferred because they are liquid at room temperature and the resulting epoxy resin compositions are easy to handle.

Bisphenol A type epoxy resin or bisphenol F type epoxy resin with an epoxy equivalent of 220 or more but less than 5,000 is preferably added to component (A) in an amount of 40% by weight or less, more preferably 20% by weight or less, because the resulting cured product has excellent impact resistance.

<Core-shell polymer particles (B)>
The epoxy resin composition of the present invention contains core-shell polymer particles (B) including a core layer composed of a diene rubber and a shell layer. Due to the toughness improving effect of the (B) component, the resulting cured product has excellent toughness and impact peel adhesion. By using the (B) component in combination with the (C) component described below in addition to the (A) component, the impact peel adhesion of the cured product obtained from the epoxy resin composition can be greatly improved by the synergistic effect.

The core layer of component (B) is a diene rubber that has low affinity with epoxy resin (A), so there is no increase in viscosity over time due to swelling caused by component (A). In addition, because the core layer is a diene rubber, the impact peel adhesion strength of the cured product is higher than that of core-shell polymer particles with a core layer made of polysiloxane rubber or acrylic rubber.

From the perspective of balancing the ease of handling of the resulting epoxy resin composition with the toughness-improving effect of the resulting cured product, the amount of component (B) is preferably 1 to 100 parts by weight, more preferably 2 to 80 parts by weight, even more preferably 3 to 60 parts by weight, even more preferably 4 to 50 parts by weight, and particularly preferably 5 to 40 parts by weight, per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E) combined.

Component (B) may have an epoxy group. When component (B) contains an epoxy group, the content of the epoxy group in component (B) is preferably 0.01 to 0.8 mmol/g, more preferably 0.02 to 0.6 mmol/g, even more preferably 0.04 to 0.4 mmol/g, and particularly preferably 0.05 to 0.2 mmol/g, from the viewpoints of the impact peel adhesion of the obtained cured product, the storage stability of the composition, and the coatability of the epoxy resin composition to a substrate. However, component (B) may not have an epoxy group.

In addition, by setting the content of epoxy groups in component (B) while taking into consideration the amount of component (C) described below, it is possible to achieve better impact-resistant peel adhesion. For example, when the amount of component (C) is less than 50 parts by weight per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E), the content of epoxy groups in component (B) is preferably 0 to 0.1 mmol/g, more preferably 0.04 to 0.1 mmol/g. On the other hand, when the amount of component (C) is 50 parts by weight or more, the content of epoxy groups in component (B) is preferably 0.04 to 0.3 mmol/g, more preferably 0.1 to 0.2 mmol/g.

The particle size of the core-shell polymer particles is not particularly limited, but in consideration of industrial productivity, the volume average particle size (Mv) is preferably 10 to 2000 nm, more preferably 30 to 600 nm, even more preferably 50 to 400 nm, and particularly preferably 100 to 300 nm. The volume average particle size (Mv) of the polymer particles can be measured for the latex of the polymer particles using a Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).

It is preferable that component (B) has a half-value width in the particle size number distribution of 0.5 to 1 times the volume average particle size in the epoxy resin composition of the present invention, because the resulting epoxy resin composition has a low viscosity and is easy to handle.

From the viewpoint of easily achieving the above-mentioned specific particle size distribution, it is preferable that there are two or more maximum values in the number distribution of particle sizes of component (B), and from the viewpoint of the labor and cost during production, it is more preferable that there are two to three maximum values, and even more preferable that there are two maximum values. In particular, it is preferable that the composition contains 10 to 90% by weight of core-shell polymer particles having a volume average particle size of 10 nm or more and less than 150 nm, and 90 to 10% by weight of core-shell polymer particles having a volume average particle size of 150 nm or more and 2000 nm or less.

It is preferable that component (B) is dispersed in the epoxy resin composition in the form of primary particles. In the present invention, "the core-shell polymer particles are dispersed in the epoxy resin composition in the form of primary particles" (hereinafter also referred to as primary dispersion) means that the core-shell polymer particles are dispersed substantially independently (without contact) with each other, and the dispersion state can be confirmed, for example, by dissolving a part of the epoxy resin composition in a solvent such as methyl ethyl ketone and measuring the particle size with a particle size measuring device using laser light scattering.

The value of the volume average particle diameter (Mv)/number average particle diameter (Mn) measured by the particle diameter measurement is not particularly limited, but is preferably 3 or less, more preferably 2.5 or less, even more preferably 2 or less, and particularly preferably 1.5 or less. If the volume average particle diameter (Mv)/number average particle diameter (Mn) is 3 or less, it is considered that the (B) component is well dispersed, and the physical properties such as impact resistance and adhesion of the obtained cured product are good.

The volume average particle size (Mv)/number average particle size (Mn) can be measured using a Microtrack UPA (manufactured by Nikkiso Co., Ltd.) and calculated by dividing Mv by Mn.

Furthermore, the term "stable dispersion" of the core-shell polymer particles means a state in which the core-shell polymer particles are dispersed steadily under normal conditions for a long period of time without agglomeration, separation, or precipitation in the continuous layer. It is also preferable that the distribution of the core-shell polymer particles in the continuous layer does not change substantially, and that the "stable dispersion" can be maintained even if the composition is heated within a non-hazardous range to reduce the viscosity and stirred.

Component (B) may be used alone or in combination of two or more types.

The structure of the core-shell polymer particles is not particularly limited, but it is preferable that the particles have two or more layers. It is also possible for the particles to have a structure of three or more layers, which is composed of an intermediate layer that covers the core layer and a shell layer that further covers the intermediate layer.

Each layer will now be described in detail.
<Core layer>
The core layer is preferably an elastic core layer having rubber properties in order to increase the toughness of the cured product of the epoxy resin composition of the present invention. In order to have rubber properties, the elastic core layer preferably has a gel content of 60% by weight or more, more preferably 80% by weight or more, even more preferably 90% by weight or more, and particularly preferably 95% by weight or more. In addition, the gel content in this specification means the ratio of the insoluble content to the total amount of the insoluble content and the soluble content when 0.5 g of crumb obtained by solidification and drying is immersed in 100 g of toluene, left at 23° C. for 24 hours, and then the insoluble content and the soluble content are separated.

Examples of conjugated diene monomers constituting the diene rubber used in the core layer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, and 2-methyl-1,3-butadiene. These conjugated diene monomers may be used alone or in combination of two 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 even more preferably in the range of 90 to 100% by weight. If the content of the conjugated diene monomer is less than 50% by weight, the impact peel adhesion of the resulting cured product tends to decrease.

Examples of vinyl monomers copolymerizable with conjugated diene monomers include vinyl arenes such as styrene, α-methylstyrene, monochlorostyrene, and dichlorostyrene; vinyl carboxylic acids such as acrylic acid and methacrylic acid; vinyl cyanides such as acrylonitrile and methacrylonitrile; vinyl halides such as vinyl chloride, vinyl bromide, and chloroprene; vinyl acetate; alkenes such as ethylene, propylene, butylene, and isobutylene; and polyfunctional monomers such as diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene. These vinyl monomers may be used alone or in combination of two 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 of the core layer, more preferably in the range of 0 to 30% by weight, and even more preferably in the range of 0 to 10% by weight. If the content of the vinyl monomer copolymerizable with the conjugated diene monomer is more than 50% by weight, the impact peel adhesion of the resulting cured product tends to decrease.

Butadiene rubber using 1,3-butadiene or butadiene-styrene rubber, which is a copolymer of 1,3-butadiene and styrene, is preferred, with butadiene rubber being more preferred, because of its high toughness improving effect and impact peel adhesion improving effect, and its low affinity with the matrix resin means that the viscosity is unlikely to increase over time due to swelling of the core layer. Furthermore, butadiene-styrene rubber is more preferred, as it is possible to increase the transparency of the cured product obtained by adjusting the refractive index.

In the present invention, the glass transition temperature (hereinafter sometimes simply referred to as "Tg") of the core layer is preferably 0°C or lower, more preferably -20°C or lower, even more preferably -40°C or lower, and particularly preferably -60°C or lower, in order to increase the toughness of the resulting cured product.

The volume average particle diameter of the core layer is preferably 0.03 to 2 μm, and more preferably 0.05 to 1 μm. Within this range, stable production is possible, and the heat resistance and impact resistance of the cured product can be good. The volume average particle diameter can be measured using a Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).

The ratio of the core layer is preferably 40 to 97% by weight, more preferably 60 to 95% by weight, even more preferably 70 to 93% by weight, and particularly preferably 80 to 90% by weight, based on 100% by weight of the entire core-shell polymer particles. If the ratio of the core layer is less than 40% by weight, the toughness improving effect of the cured product may decrease. If the ratio of the core layer is more than 97% by weight, the core-shell polymer particles may be easily aggregated, and the epoxy resin composition may become highly viscous and difficult to handle.

The core layer is often a single-layer structure, but may be a multi-layer structure consisting of layers having rubber elasticity. In addition, when the core layer is a multi-layer structure, the polymer composition of each layer may be different within the range disclosed above.

<Middle Class>
In the present invention, an intermediate layer may be formed as necessary. In particular, the following rubber surface cross-linked layer may be formed as the intermediate layer. From the viewpoint of the effect of improving the toughness and the impact peel adhesion of the obtained cured product, it is preferable not to contain an intermediate layer, and in particular not to contain the following rubber surface cross-linked layer.

When an intermediate layer is present, the ratio 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, even more preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight.

The rubber surface cross-linked layer is made of an intermediate layer polymer obtained by polymerizing a rubber surface cross-linked layer component consisting of 30 to 100% by weight of a polyfunctional monomer having two or more radically polymerizable double bonds in one molecule and 0 to 70% by weight of other vinyl monomers, and has the effect of reducing the viscosity of the epoxy resin composition of the present invention and improving the dispersibility of the core-shell polymer particles (B) in the (A) component. It also has the effect of increasing the cross-link density of the core layer and the grafting efficiency of the shell layer.

Specific examples of the polyfunctional monomer do not include conjugated diene monomers such as butadiene, and include allyl alkyl (meth)acrylates such as allyl (meth)acrylate and allyl alkyl (meth)acrylate; allyloxyalkyl (meth)acrylates; polyfunctional (meth)acrylates having two 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, and divinylbenzene; and preferably allyl methacrylate and triallyl isocyanurate. In the present invention, (meth)acrylate means acrylate and/or methacrylate.

<Shell layer>
The shell layer present on the outermost side of the core-shell polymer particle is formed by polymerizing a monomer for forming the shell layer, and is made of a shell polymer that plays a role in improving the compatibility between the core-shell polymer particle (B) and the component (A) and enabling the core-shell polymer particle (B) to be dispersed in the form of primary particles in the epoxy resin composition of the present invention or in the cured product thereof.

Such a shell polymer is preferably grafted to the core layer and/or intermediate layer. Hereinafter, when the term "grafted to the core layer" is used, it also includes the case where an intermediate layer is formed on the core layer, in which case the shell polymer is grafted to the intermediate layer. More precisely, it is preferable that the monomer component used to form the shell layer is graft polymerized to the core polymer forming the core layer (when an intermediate layer is formed, the core polymer also includes the intermediate layer polymer forming the intermediate layer. The same applies below) so that the shell polymer and the core polymer are substantially chemically bonded (when an intermediate layer is formed, it is also preferable that the shell polymer and the intermediate layer polymer are chemically bonded). That is, the shell polymer is preferably formed by graft polymerizing the monomer for forming the shell layer in the presence of the core polymer, and in this way, the shell polymer is graft polymerized to the core polymer and covers a part or the whole of the core polymer. This polymerization operation can be carried out by adding the monomer for forming the shell polymer layer to the latex of the core polymer prepared in an aqueous polymer latex state and polymerizing it.

As the monomer for forming the shell layer, from the viewpoint of compatibility and dispersibility in the epoxy resin composition of component (B), for example, aromatic vinyl monomers, vinyl cyan monomers, and (meth)acrylate monomers are preferred, and (meth)acrylate monomers are more preferred. These monomers for forming the shell layer may be used alone or in appropriate combination.

The total amount of aromatic vinyl monomer, vinyl cyan monomer, and (meth)acrylate monomer is preferably 10 to 99.5% by weight, more preferably 50 to 99% by weight, even more preferably 65 to 98% by weight, particularly preferably 67 to 80% by weight, and most preferably 67 to 85% by weight, based on 100% by weight of the monomers for forming the shell layer.

In order to maintain a good dispersion state of component (B) without agglomeration in the cured product or epoxy resin composition, and from the viewpoint of chemically bonding with component (A), it is preferable that the monomer for forming the shell layer contains a reactive group-containing monomer containing one or more selected from the group consisting of epoxy groups, oxetane groups, hydroxyl groups, amino groups, imide groups, carboxylic acid groups, carboxylic anhydride groups, cyclic esters, cyclic amides, benzoxazine groups, and cyanate ester groups, and in particular, a monomer having an epoxy group.

From the viewpoint of impact peel adhesion and storage stability, the monomer having an epoxy group is preferably contained in an amount of 0.5 to 90% by weight, more preferably 1 to 50% by weight, even 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 the shell layer.

The monomer having an epoxy group is preferably used to form the shell layer, and more preferably used only in the shell layer.

In addition, the use of a polyfunctional monomer having two or more radically polymerizable double bonds as the monomer for forming the shell layer is preferable because it prevents swelling of the core-shell polymer particles in the epoxy resin composition and also tends to reduce the viscosity of the epoxy resin composition and improve its handleability. On the other hand, from the viewpoint of improving the toughness and impact peel adhesion of the resulting cured product, it is preferable not to use a polyfunctional monomer having two or more radically polymerizable double bonds as the monomer for forming the shell layer.

The polyfunctional monomer 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 the shell layer.

Specific examples of the aromatic vinyl monomer include vinylbenzenes such as styrene, α-methylstyrene, p-methylstyrene, and divinylbenzene.

Specific examples of the vinyl cyan monomer include acrylonitrile and methacrylonitrile.

Specific examples of the (meth)acrylate monomer include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; and (meth)acrylic acid hydroxyalkyl esters.

Specific examples of the (meth)acrylic acid hydroxyalkyl ester include hydroxy linear alkyl (meth)acrylates (particularly hydroxy linear C1-6 alkyl (meth)acrylates) such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; caprolactone-modified hydroxy (meth)acrylates; hydroxy branched alkyl (meth)acrylates such as α-(hydroxymethyl)methyl acrylate and α-(hydroxymethyl)ethyl acrylate; and hydroxyl group-containing (meth)acrylates such as mono(meth)acrylates of polyester diols (particularly saturated polyester diols) obtained from divalent carboxylic acids (such as phthalic acid) and dihydric alcohols (such as propylene glycol).

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 two or more radically polymerizable double bonds include the same monomers as the polyfunctional monomers described above, with allyl methacrylate and triallyl isocyanurate being preferred.

In the present invention, it is preferable to use a shell layer that is a polymer of a shell layer-forming monomer (total 100% by weight) that is a combination of, for example, 0 to 50% by weight (preferably 1 to 50% by weight, more preferably 2 to 48% by weight) of an aromatic vinyl monomer (particularly styrene), 0 to 50% by weight (preferably 0 to 30% by weight, more preferably 10 to 25% by weight) of a vinyl cyan monomer (particularly acrylonitrile), 0 to 100% by weight (preferably 0 to 90% by weight, more preferably 20 to 85% by weight) of a (meth)acrylate monomer (particularly methyl methacrylate), and 0.5 to 50% by weight (preferably 1 to 30% by weight, more preferably 2 to 20% by weight) of a monomer having an epoxy group (particularly glycidyl methacrylate). This allows the desired toughness improvement effect and mechanical properties to be achieved in a well-balanced manner. In particular, it is preferable to include glycidyl methacrylate as a constituent component, as this is believed to improve the interfacial adhesion with the (A) component.

These monomer components may be used alone or in combination of two or more. The shell layer may be formed by including other monomer components in addition to the above monomer components.

The graft ratio of the shell layer is preferably 70% or more (more preferably 80% or more, and even more preferably 90% or more). If the graft ratio is less than 70%, the viscosity of the liquid resin composition may increase. In this specification, the graft ratio is calculated as follows.

First, the aqueous latex containing the core-shell polymer particles is coagulated and dehydrated, and finally dried to obtain a powder of the core-shell polymer particles. Next, 2 g of the powder of the core-shell polymer particles is immersed in 100 g of methyl ethyl ketone (MEK) at 23°C for 24 hours, after which the MEK soluble matter is separated from the MEK insoluble matter, and the methanol insoluble matter is further separated from the MEK soluble matter. The graft ratio is then calculated by determining the ratio of the MEK insoluble matter to the total amount of the MEK insoluble matter and the methanol insoluble matter.

<Method for producing core-shell polymer particles>
(Method of Manufacturing Core Layer)
The core layer constituting the core-shell polymer particles used in the present invention can be produced by, for example, emulsion polymerization, suspension polymerization, microsuspension polymerization, etc., and the method described in, for example, WO 2005/028546 can be used.

(Method of forming shell layer and intermediate layer)
The intermediate layer can be formed by polymerizing the intermediate layer-forming monomer by known radical polymerization. When the rubber elastic body constituting the core layer is obtained as an emulsion, the intermediate layer-forming monomer is preferably polymerized by an emulsion polymerization method.

The shell layer can be formed by polymerizing the monomer for forming the shell layer by known radical polymerization. When the core layer or the polymer particle precursor formed by coating the core layer with the intermediate layer is obtained as an emulsion, it is preferable to polymerize the monomer for forming the shell layer by emulsion polymerization, and it can be produced, for example, according to the method described in WO 2005/028546.

Examples of emulsifiers (dispersants) that can be used in emulsion polymerization include anionic emulsifiers (dispersants) such as alkyl or aryl sulfonic acids, such as dioctyl sulfosuccinic acid and dodecylbenzenesulfonic acid, alkyl or aryl ether sulfonic acids, alkyl or aryl sulfuric acids, such as dodecyl sulfate, alkyl or aryl ether sulfate, alkyl or aryl substituted phosphoric acids, alkyl or aryl ether substituted phosphoric acids, N-alkyl or aryl sarcosinic acids, such as dodecyl sarcosinic acid, alkyl or aryl carboxylic acids, such as oleic acid and stearic acid, alkyl or aryl ether carboxylic acids, and various other acids, as well as alkali metal or ammonium salts of these acids; nonionic emulsifiers (dispersants), such as alkyl or aryl substituted polyethylene glycol; and dispersants such as polyvinyl alcohol, alkyl substituted cellulose, polyvinylpyrrolidone, and polyacrylic acid derivatives. These emulsifiers (dispersants) may be used alone or in combination of two or more.

As long as it does not impair the dispersion stability of the aqueous latex of the polymer particles, it is preferable to use a small amount of emulsifier (dispersant). In addition, the higher the water solubility of the emulsifier (dispersant), the more preferable it is. High water solubility makes it easier to wash off the emulsifier (dispersant) with water, and makes it easier to prevent adverse effects on the final cured product.

When the emulsion polymerization method is used, known initiators, such as 2,2'-azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, and ammonium persulfate, can be used as thermal decomposition initiators.

Redox initiators can also be used that use organic peroxides such as t-butyl peroxyisopropyl carbonate, paramenthane hydroperoxide, cumene hydroperoxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and t-hexyl peroxide; inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate, in combination with reducing agents such as sodium formaldehyde sulfoxylate and glucose, and transition metal salts such as iron (II) sulfate, as required, chelating agents such as disodium ethylenediaminetetraacetate, and phosphorus-containing compounds such as sodium pyrophosphate, as required.

When a redox type initiator system is used, polymerization can be carried out even at a low temperature where the peroxide does not substantially decompose thermally, and the polymerization temperature can be set in a wide range, which is preferable. Among them, it is preferable to use an organic peroxide such as cumene hydroperoxide, dicumyl peroxide, or t-butyl hydroperoxide as a redox type initiator. The amount of the initiator used, and the amount of the reducing agent, transition metal salt, chelating agent, etc. used when a redox type initiator is used, can be used within a known range. In addition, when polymerizing a monomer having two or more radically polymerizable double bonds, a known chain transfer agent can be used within a known range. A surfactant can be additionally used, which is also within a known range.

Conditions for polymerization, such as polymerization temperature, pressure, and deoxidation, that are within the publicly known ranges can be applied. Furthermore, polymerization of the intermediate layer forming monomer may be carried out in one stage or in two or more stages. For example, in addition to a method of adding the intermediate layer forming monomer to the emulsion of the rubber elastomer that constitutes the elastic core layer all at once or a method of adding them continuously, a method of adding the emulsion of the rubber elastomer that constitutes the elastic core layer to a reactor that has already been charged with the intermediate layer forming monomer and then carrying out polymerization can be employed.

<Compound (C) Having Two Functional Groups Each Having One Active Hydrogen Reactive with an Epoxy Group in One Molecule>
The compound (C) having two functional groups in one molecule, each of which has one active hydrogen that reacts with an epoxy group, undergoes a polyaddition reaction with the epoxy resin (A) to form a linear polymer, which can improve the impact peel adhesion of the cured product formed from the epoxy resin composition of the present invention.

The functional group having one active hydrogen that reacts with an epoxy group is not particularly limited, but examples thereof include a phenolic hydroxyl group, a secondary amino group, a thiol group, and a carboxyl group. Among these, a phenolic hydroxyl group is preferred from the viewpoint of reactivity with an epoxy group. In other words, a compound having two phenolic hydroxyl groups in one molecule is preferred as compound (C).

Compounds having two phenolic hydroxyl groups per molecule are not particularly limited, but examples include mononuclear aromatic dihydroxy compounds having one benzene ring, such as catechol, resorcin, hydroquinone, methylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; bisphenols such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 1,1-bis(4-hydroxyphenyl)ethane (bisphenol AD), bis(hydroxyphenyl)methane (bisphenol F), bisphenol fluorene, and biscresol fluorene; compounds having condensed rings, such as dihydroxynaphthalene; and bifunctional phenol compounds having an allyl group, such as diallyl resorcin, diallyl bisphenol A, and triallyl dihydroxybiphenyl. Only one type of compound (C) may be used, or two or more types may be combined.

Regarding the amount of compound (C), in order to obtain the effect of improving impact peel adhesion by adding compound (C), the amount of compound (C) per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E) is preferably 20 parts by weight or more. More preferably, it is 25 parts by weight or more, even more preferably 30 parts by weight or more, and even more preferably 40 parts by weight or more.

On the other hand, if the amount of compound (C) is too large, the fluidity of the epoxy resin composition decreases, and the applicability to the substrate tends to decrease. From this viewpoint, the amount of compound (C) per 100 parts by weight of the total of epoxy resin (A) and epoxy resin curing agent (E) is preferably 70 parts by weight or less. More preferably, it is 65 parts by weight or less, even more preferably 60 parts by weight or less, and even more preferably 55 parts by weight or less.

<Catalyst (D)>
The catalyst (D) is a catalyst that promotes the polyaddition reaction of the epoxy resin (A) and the compound (C). When the catalyst (D) is mixed with the epoxy resin (A) and the compound (C) and a polyaddition reaction is caused by heating or the like, a linear polymer that does not have a crosslinked structure is mainly formed. As such a catalyst, a catalyst that promotes the reaction between an epoxy group and a functional group having an active hydrogen that reacts with the epoxy group can be used. Specific examples of the catalyst include, but are not limited to, phosphorus-based catalysts; tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol incorporated in a poly(p-vinylphenol) matrix, triethylenediamine, and N,N-dimethylpiperidine; and imidazoles such as 1,2-alkylenebenzimidazole (TBZ), 2-aryl-4,5-diphenylimidazole (NPZ), C1-C12 alkyleneimidazole, N-arylimidazole, 2-methylimidazole, 2-ethyl-2-methylimidazole, N-butylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, and addition products of epoxy resins and imidazole. As the catalyst (D), only one type may be used, or two or more types may be used in combination. As the catalyst (D), a phosphorus-based catalyst is preferred because it is less likely to cause side reactions and is more likely to be effective in improving impact peel adhesion.

Examples of the phosphorus catalyst include phosphine catalysts such as dicyclohexylphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, cyclohexyldiphenylphosphine, triphenylphosphine, triphenylphosphine-triphenylborane complex, and tri(m-tolyl)phosphine-triphenylborane complex. Of these, tri(o-tolyl)phosphine and tri(m-tolyl)phosphine-triphenylborane complex are preferred.

The amount of catalyst (D) to be used can be set as appropriate, but from the viewpoint of curability and stability of the epoxy resin composition, it is preferable that the amount of catalyst (D) to be used per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E) combined is 0.1 to 10 parts by weight. It is more preferable that the amount is 0.3 to 6 parts by weight, and even more preferable that the amount is 0.5 to 5 parts by weight.

<Epoxy resin curing agent (E)>
The epoxy resin curing agent (E) is a component that forms a three-dimensional crosslinked structure in the cured product by reacting with the epoxy resin (A), and can enhance the curability of the epoxy resin composition. However, the epoxy resin curing agent (E) is an optional component, and the epoxy resin composition of the present invention may or may not contain the epoxy resin curing agent (E).

When the epoxy resin composition of the present invention is used as a one-component epoxy resin composition, it is preferable to select component (E) so that the epoxy resin composition cures rapidly when heated to a temperature of 80°C or higher, preferably 140°C or higher. Conversely, it is preferable to select component (E) and component (F) described below so that the composition cures very slowly, if at all, at room temperature (about 22°C) or at temperatures up to at least 50°C.

As component (E), a component that becomes active when heated (sometimes referred to as a latent epoxy curing agent) can be used. As such a latent epoxy curing agent, an N-containing curing agent such as a specific amine-based curing agent (including an imine-based curing agent) can be used. Examples of such amine-based curing agents include boron trichloride/amine complex, boron trifluoride/amine complex, dicyandiamide, melamine, diallylmelamine, guanamine (e.g., acetoguanamine and benzoguanamine), aminotriazole (e.g., 3-amino-1,2,4-triazole), hydrazide (e.g., adipic acid dihydrazide, stearic acid dihydrazide, isophthalic acid dihydrazide, semicarbazide), cyanoacetamide, and aromatic polyamine (e.g., metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc.). Among these, dicyandiamide, isophthalic acid dihydrazide, adipic acid dihydrazide, and 4,4'-diaminodiphenyl sulfone are preferred, with dicyandiamide being particularly preferred.

Among the curing agents (E), latent epoxy curing agents are preferred because they can make the epoxy resin composition of the present invention into a one-component composition.

On the other hand, when the epoxy resin composition of the present invention is used as a two-component or multi-component composition, amine-based curing agents (including imine-based curing agents) and mercaptan-based curing agents (sometimes called room temperature curing curing agents) other than those mentioned above can be used as component (E) that is active at relatively low temperatures around room temperature.

Examples of components (E) that are active at such relatively low temperatures include chain aliphatic polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, and hexamethylenediamine; N-aminoethylpiperazine, bis(4-amino-3-methylcyclohexyl)methane, menthenediamine, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (spiroacetaldiamine), and norbornanediamine. Examples of such amines include cyclic aliphatic polyamines such as cycloaliphatic polyamines, tricyclodecanediamine, and 1,3-bisaminomethylcyclohexane; aliphatic aromatic amines such as metaxylenediamine; polyamine epoxy resin adducts, which are the reaction products of epoxy resins and excess polyamines; ketimines, which are the dehydration reaction products of polyamines and ketones such as methyl ethyl ketone and isobutyl methyl ketone; polyamidoamines produced by condensation of a dimer (dimer acid) of tall oil fatty acid and a polyamine; amidoamines produced by condensation of tall oil fatty acid and a polyamine; and polymercaptans.

Amine-terminated polyethers that contain a polyether backbone and have an average of 1 to 4 (preferably 1.5 to 3) amino and/or imino groups per molecule can also be used as component (E). Commercially available amine-terminated polyethers include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, and Jeffamine T-5000 manufactured by Huntsman.

Furthermore, amine-terminated rubbers that contain a conjugated diene polymer backbone and have an average of 1 to 4 (more preferably 1.5 to 3) amino and/or imino groups per molecule can also be used as component (E). Here, the backbone of the rubber is preferably a polybutadiene homopolymer or copolymer, more preferably a polybutadiene/acrylonitrile copolymer, and particularly preferably a polybutadiene/acrylonitrile copolymer with an acrylonitrile monomer content of 5 to 40% by weight (more preferably 10 to 35% by weight, and even more preferably 15 to 30% by weight). Commercially available amine-terminated rubbers include Hypro 1300X16 ATBN manufactured by CVC Corporation.

Among the above amine-based curing agents that are active at relatively low temperatures around room temperature, polyamidoamines, amine-terminated polyethers, and amine-terminated rubbers are preferred, and it is particularly preferred to use polyamidoamines, amine-terminated polyethers, and amine-terminated rubbers in combination.

Acid anhydrides and phenols can also be used as component (E). Acid anhydrides and phenols require higher temperatures than amine-based curing agents, but they have a long pot life and the cured product has a good balance of physical properties such as electrical properties, chemical properties, and mechanical properties. Examples of acid anhydrides include polysebacic polyanhydride, polyazelaic polyanhydride, succinic anhydride, citraconic anhydride, itaconic anhydride, alkenyl-substituted succinic anhydride, dodecenylsuccinic anhydride, maleic anhydride, tricarballylic anhydride, nadic anhydride, methylnadic anhydride, linoleic acid adduct with maleic anhydride, 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 chlorendic anhydride, as well as maleic anhydride-grafted polybutadiene. Examples of phenols include phenol novolac, bisphenol A novolac, and cresol novolac.

Component (E) may be used alone or in combination of two or more types.

By blending the epoxy resin curing agent (E), a three-dimensional crosslinked structure can be formed in the cured product, but if the blending amount of the (E) component is too large, it becomes difficult to obtain the effect of improving the impact peel adhesion by adding the compound (C). Therefore, the blending amount of the epoxy resin curing agent (E) is preferably an amount such that the weight ratio of the epoxy resin curing agent (E) to the total of the epoxy resin (A) and the epoxy resin curing agent (E) is 20% by weight or less. More preferably, it is 10% by weight or less, and even more preferably, it is 5% by weight or less. There is no particular limit to the blending amount of the (E) component, and it may be 0, but when blended, in order to obtain the effect of blending the (E) component, it is preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and even more preferably 1% by weight or more.

<Curing Accelerator (F)>
The epoxy resin composition of the present invention may contain a curing accelerator (F) together with the epoxy resin curing agent (E). The component (F) is a catalyst for promoting the reaction between the epoxy group and the epoxide reactive group in the curing agent or other component of the adhesive, and can form a three-dimensional crosslinked structure when used together with the epoxy resin curing agent (E). This can accelerate the curing reaction between the epoxy resin (A) and the epoxy resin curing agent (E).

Examples of the (F) component include ureas such as p-chlorophenyl-N,N-dimethylurea (trade name: Monoron), 3-phenyl-1,1-dimethylurea (trade name: Phenuron), 3,4-dichlorophenyl-N,N-dimethylurea (trade name: Diuron), N-(3-chloro-4-methylphenyl)-N',N'-dimethylurea (trade name: Chlortoluron), and 1,1-dimethylphenylurea (trade name: Dyhard); 6-caprolactam, etc. The (F) component may be used alone or in combination of two or more kinds. The (F) component may be encapsulated, or may be a latent type that becomes active only when the temperature is increased.

When component (F) is added, the amount of component (F) added is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, even more preferably 0.5 to 3 parts by weight, and particularly preferably 0.8 to 2 parts by weight, per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E) combined, from the viewpoints of improving the curing property and storage stability.

<Reaction retarder>
The epoxy resin composition of the present invention may contain a reaction retarder. By incorporating this, the progress of the curing reaction can be delayed when the epoxy resin composition is applied, and the applicability of the epoxy resin composition to a substrate can be improved. As such a reaction retarder, trialkyl borates such as tri-n-butyl borate, tri-n-octyl borate, and tri-n-dodecyl borate, and triaryl borates such as triphenyl borate can be used. These may be used alone or in combination of two or more. Among these, tri-n-octyl borate is preferred because it is liquid at room temperature and therefore has excellent miscibility, and has a high effect of retarding reactions at 80° C. or less.

When a reaction retarder is added, the amount of reaction retarder added is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the epoxy resin (A) and the epoxy resin curing agent (E) combined.

<Reinforcement agent>
In the present invention, a rubber-modified epoxy resin, a urethane-modified epoxy resin, or a blocked urethane may be used as a reinforcing agent, if necessary, for the purpose of further improving performance such as toughness, impact resistance, shear adhesion, and peel adhesion. The reinforcing agents may be used alone or in combination of two or more kinds.

<Rubber-modified epoxy resin>
The rubber-modified epoxy resin is a reaction product obtained by reacting rubber with an epoxy group-containing compound, and has an average of 1.1 or more epoxy groups per molecule, preferably 2 or more. Examples of the rubber include rubber-based polymers such as acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), hydrogenated nitrile rubber (HNBR), ethylene propylene rubber (EPDM), acrylic rubber (ACM), butyl rubber (IIR), butadiene rubber, polyoxyalkylene such as polypropylene oxide, polyethylene oxide, and polytetramethylene oxide. The rubber-based polymer is preferably one having a reactive group such as an amino group, a hydroxyl group, or a carboxyl group at its terminal. The product obtained by reacting these rubber-based polymers with an epoxy resin at an appropriate mixing ratio by a known method is the rubber-modified epoxy resin used in the present invention. Among these, acrylonitrile-butadiene rubber modified epoxy resins and polyoxyalkylene modified epoxy resins are preferred from the viewpoint of adhesiveness and impact peel adhesion of the resulting epoxy resin composition, and acrylonitrile-butadiene rubber modified epoxy resins are more preferred. Note that acrylonitrile-butadiene rubber modified epoxy resins can be obtained, for example, by reacting carboxyl-terminated NBR (CTBN) with bisphenol A type 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 viewpoint of the adhesiveness and impact peel adhesion of the resulting epoxy resin composition. From the viewpoint of the workability of the resulting epoxy resin composition, 20 to 30% by weight is particularly preferable.

In addition, for example, the rubber-modified epoxy resin also includes an addition reaction product (hereinafter also referred to as "adduct") between an amino-terminated polyoxyalkylene and an epoxy resin. The adduct can be easily produced by a known method, for example, as described in U.S. Pat. No. 5,084,532 and U.S. Pat. No. 6,015,865. The epoxy resin used in producing the adduct can be, for example, the specific examples of component (A) exemplified in the present invention, but bisphenol A type epoxy resin or bisphenol F type epoxy resin is preferable, and bisphenol A type epoxy resin is more preferable. The commercially available amino-terminated polyoxyalkylene used in producing the adduct can be, for example, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-5000, etc., manufactured by Huntsman.

The average number of epoxide reactive end groups per molecule in the rubber is preferably 1.5 to 2.5, more preferably 1.8 to 2.2. The number average molecular weight of the rubber, measured by GPC in terms of polystyrene, is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, and particularly preferably 3,000 to 6,000.

There is no particular restriction on the method of producing the rubber-modified epoxy resin. For example, the rubber-modified epoxy resin can be produced by reacting the rubber with an epoxy group-containing compound in a large amount of the epoxy group-containing compound. Specifically, it is preferable to produce the rubber-modified epoxy resin by reacting two or more equivalents of the epoxy group-containing compound per equivalent of the epoxy reactive terminal group in the rubber. It is more preferable to react a sufficient amount of the epoxy group-containing compound so that the resulting product is a mixture of an adduct of the rubber and the epoxy group-containing compound and a free epoxy group-containing compound. For example, the rubber-modified epoxy resin is produced by heating to a temperature of 100 to 250°C in the presence of a catalyst such as phenyldimethylurea or triphenylphosphine. There is no particular restriction on the epoxy group-containing compound used in producing the rubber-modified epoxy resin, but bisphenol A type epoxy resin or bisphenol F type epoxy resin is preferred, and bisphenol A type epoxy resin is more preferred. In the present invention, when an excessive amount of the epoxy group-containing compound is used in producing the rubber-modified epoxy resin, the unreacted epoxy group-containing compound remaining after the reaction is not included in the rubber-modified epoxy resin of the present invention.

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

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

The number average molecular weight of the rubber-modified epoxy resin, as calculated using polystyrene standards and measured by GPC, is preferably 1,500 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. 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, and particularly preferably 1.5 to 2.5.

The amount of rubber-modified epoxy resin used is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, even more preferably 5 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight, per 100 parts by weight of component (A).

The rubber-modified epoxy resins can be used alone or in combination of two or more types.

<Urethane-modified epoxy resin>
The urethane-modified epoxy resin is a reaction product having an average of 1.1 or more, preferably 2 or more, epoxy groups per molecule, obtained by reacting a compound containing an epoxy group and a group reactive with an isocyanate group with a urethane prepolymer containing an isocyanate group. 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, as calculated using polystyrene standards and measured by GPC, is preferably 1,500 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. 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, and particularly preferably 1.5 to 2.5.

The amount of urethane-modified epoxy resin used is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, even more preferably 5 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight, per 100 parts by weight of component (A).

The urethane-modified epoxy resins can be used alone or in combination of two or more.

<Blocked urethane>
The blocked urethane is an elastomer type compound containing a urethane group and/or a urea group, and a compound having an isocyanate group at its terminal, in which all or a part of the terminal isocyanate groups are capped with various blocking agents having active hydrogen groups. In particular, a compound in which all of the terminal isocyanate groups are capped with a blocking agent is preferred. Such a compound can be obtained, for example, by reacting an organic polymer having an active hydrogen-containing group at its terminal with an excess of a polyisocyanate compound to form a polymer (urethane prepolymer) having a urethane group and/or a urea group in the main chain and an isocyanate group at its terminal, and then, simultaneously, by capping all or a part of the isocyanate groups with a blocking agent having an active hydrogen group.

The blocked urethane may be, for example, a compound represented by the following general formula (1):
A-(NR ² -C(=O)-X) _a (1)
(In the formula, a ^R2 's are each independently a hydrocarbon group having 1 to 20 carbon atoms. a represents the average number of capped isocyanate groups per molecule, and is preferably 1.1 or more, more preferably 1.5 to 8, even more preferably 1.7 to 6, and particularly preferably 2 to 4. X is a residue obtained by removing an active hydrogen atom from the blocking agent. A is a residue obtained by removing a terminal isocyanate group from an isocyanate-terminated prepolymer.)

The number average molecular weight of the blocked urethane, as calculated using polystyrene standards and measured by GPC, is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. 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, and particularly preferably 1.5 to 2.5.

(C-1 Organic polymer having active hydrogen-containing group at the terminal)
Examples of the main chain skeleton constituting the organic polymer having an active hydrogen-containing group at the terminal include polyether-based polymers, polyacrylic-based polymers, polyester-based polymers, polydiene-based polymers, saturated hydrocarbon-based polymers (polyolefins), and polythioether-based polymers.

(Active hydrogen group)
Examples of the active hydrogen-containing group constituting the organic polymer having an active hydrogen-containing group at the end include a hydroxyl group, an amino group, an imino group, and a thiol group. Among these, from the viewpoint of availability, a hydroxyl group, an amino group, and an imino group are preferred, and from the viewpoint of ease of handling (viscosity) of the resulting blocked urethane, a hydroxyl group is more preferred.

Examples of organic polymers having active hydrogen-containing groups at the terminal include polyether polymers (polyether polyols) having hydroxyl groups at the terminals, polyether polymers (polyether amines) having amino groups and/or imino groups at the terminals, polyacrylic polyols, polyester polyols, diene polymers (polydiene polyols) having hydroxyl groups at the terminals, saturated hydrocarbon polymers (polyolefin polyols) having hydroxyl groups at the terminals, polythiol compounds, polyamine compounds, etc. Among these, polyether polyols, polyether amines, and polyacrylic polyols are preferred because they have excellent compatibility with component (A), the glass transition temperature of the organic polymer is relatively low, and the resulting cured product has excellent impact resistance at low temperatures. In particular, polyether polyols and polyether amines are more preferred because the resulting organic polymer has a low viscosity and good workability, and polyether polyols are particularly preferred.

The organic polymer having an active hydrogen-containing group at the end, which is used in preparing the urethane prepolymer, which is the precursor of the blocked urethane, may be used alone or in combination of two or more kinds.

The number average molecular weight of the organic polymer having an active hydrogen-containing group at its terminal is preferably 800 to 7000, more preferably 1500 to 5000, and particularly preferably 2000 to 4000, in terms of polystyrene equivalent molecular weight measured by GPC.

(Polyether Polymer)
The polyether polymer essentially has the general formula (2):
-R ¹ -O- (2)
(wherein R ¹ is a linear or branched alkylene group having 1 to 14 carbon atoms), and R ¹ in general formula (2) is preferably a linear or branched alkylene group having 1 to 14 carbon atoms, more preferably 2 to 4 carbon atoms. Specific examples of the repeating unit represented by general formula (2) are:
-CH ₂ O-, -CH 2 CH ₂ O-, -CH ₂ CH(CH ₃ )O-, -CH ₂ CH(C ₂ H ₅ )O-, -CH ₂ C(CH ₃ ) _{2 O-} , -CH ₂ CH ₂ CH ₂ CH ₂ O-
The main chain skeleton of the polyether polymer may be composed of only one type of repeating unit, or may be composed of two or more types of repeating units. In particular, those composed of a polymer mainly composed of polypropylene glycol having 50% by weight or more of propylene oxide repeating units are preferred from the viewpoint of T-peel adhesive strength. Also, polytetramethylene glycol (PTMG) obtained by ring-opening polymerization of tetrahydrofuran is preferred from the viewpoint of dynamic splitting resistance.

When used in combination with component (B), the ratio of component (B) to blocked urethane is preferably 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 1.

(Polyether polyol)
The polyether polyol is a polyether polymer having a hydroxyl group at its terminal, and the polyether amine is a polyether polymer having an amino group or an imino group at its terminal.

(Polyacrylic polyol)
The polyacrylic polyol may be a polyol having a (meth)acrylic acid alkyl ester (co)polymer skeleton and having a hydroxyl group in the molecule. In particular, a polyacrylic polyol obtained by copolymerizing a hydroxyl group-containing (meth)acrylic acid alkyl ester monomer such as 2-hydroxyethyl methacrylate is preferred.

The polyester polyols include polymers obtained by polycondensing polybasic acids such as maleic acid, fumaric acid, adipic acid, and phthalic acid, and their acid anhydrides, and polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and neopentyl glycol, in the presence of an esterification catalyst at a temperature range of 150 to 270°C. Other examples include ring-opening polymers such as ε-caprolactone and valerolactone, and active hydrogen compounds having two or more active hydrogens, such as polycarbonate diol and castor oil.

(Polydiene polyol)
Examples of the polydiene polyol include polybutadiene polyol, polyisoprene polyol, and polychloroprene polyol, with polybutadiene polyol being particularly preferred.

(Polyolefin polyol)
Examples of the polyolefin polyol include polyisobutylene polyol and hydrogenated polybutadiene polyol.

(C-2 Polyisocyanate)
Specific examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene (tolylene) diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, and aliphatic polyisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated toluene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Among these, aliphatic polyisocyanates are preferred from the viewpoint of heat resistance, and isophorone diisocyanate and hexamethylene diisocyanate are more preferred from the viewpoint of availability.

(C-3 Blocking Agent)
Examples of the blocking agent include primary amine-based blocking agents, secondary amine-based blocking agents, oxime-based blocking agents, lactam-based blocking agents, active methylene-based blocking agents, alcohol-based blocking agents, mercaptan-based blocking agents, amide-based blocking agents, imide-based blocking agents, heterocyclic aromatic compound-based blocking agents, hydroxy-functional (meth)acrylate-based blocking agents, and phenol-based blocking agents. Among these, oxime-based blocking agents, lactam-based blocking agents, hydroxy-functional (meth)acrylate-based blocking agents, and phenol-based blocking agents are preferred, hydroxy-functional (meth)acrylate-based blocking agents and phenol-based blocking agents are more preferred, and phenol-based blocking agents are even more preferred.

(Primary amine blocking agent)
Examples of the primary amine blocking agent include butylamine, isopropylamine, dodecylamine, cyclohexylamine, aniline, and benzylamine. Examples of the secondary amine blocking agent include dibutylamine, diisopropylamine, dicyclohexylamine, diphenylamine, dibenzylamine, morpholine, and piperidine. Examples of the oxime blocking agent include formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, diacetylmonoxime, and cyclohexaneoxime. Examples of the lactam blocking agent include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-butyrolactam. Examples of the active methylene blocking agent include ethyl acetoacetate and acetylacetone. Examples of the alcohol-based blocking agent include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, cyclohexanol, 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate. Examples of the mercaptan-based blocking agent include butyl mercaptan, hexyl mercaptan, decyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, and ethylthiophenol. Examples of the amide-based blocking agent include acetate amide and benzamide. Examples of the imide-based blocking agent include succinimide and maleimide. Examples of the heterocyclic aromatic compound-based blocking agent include imidazoles such as imidazole and 2-ethylimidazole; pyrroles such as pyrrole, 2-methylpyrrole, and 3-methylpyrrole; pyridines such as pyridine, 2-methylpyridine, and 4-methylpyridine; and diazabicycloalkenes such as diazabicycloundecene and diazabicyclononene.

(Hydroxy-functional (meth)acrylate blocking agents)
The hydroxy-functional (meth)acrylate-based blocking agent is a (meth)acrylate having one or more hydroxyl groups. Specific examples of the hydroxy-functional (meth)acrylate-based blocking agent include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate.

(Phenol-based blocking agent)
The phenolic blocking agent contains at least one phenolic hydroxyl group, i.e., a hydroxyl group directly bonded to a carbon atom of an aromatic ring. The phenolic compound may have two or more phenolic hydroxyl groups, but preferably contains only one phenolic hydroxyl group. The phenolic compound may contain other substituents, but these substituents are preferably those that do not react with isocyanate groups under the conditions of the capping reaction, and are preferably alkenyl or allyl groups. Other substituents include alkyl groups such as linear, branched or cycloalkyl; aromatic groups (e.g., phenyl, alkyl-substituted phenyl, alkenyl-substituted phenyl, etc.); aryl-substituted alkyl groups; and phenol-substituted alkyl groups. Specific examples of phenol-based blocking agents include phenol, cresol, xylenol, chlorophenol, ethylphenol, allylphenol (particularly o-allylphenol), resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and 2,2'-diallyl-bisphenol A.

The blocking agent is preferably bonded to the end of the polymer chain of the urethane prepolymer in such a manner that the end to which it is bonded no longer has a reactive group.
The blocking agents may be used alone or in combination of two or more kinds.

The blocked urethane may contain residues of a crosslinking agent, residues of a chain extender, or both.

(Crosslinking Agent)
The crosslinking agent preferably has a molecular weight of 750 or less, more preferably 50 to 500, and is a polyol or polyamine compound having at least three hydroxyl, amino and/or imino groups per molecule. The crosslinking agent is useful for imparting branching to the blocked urethane and increasing the functionality of the blocked urethane (i.e., the number of capped isocyanate groups per molecule).

(Chain extender)
The molecular weight of the chain extender is preferably 750 or less, more preferably 50 to 500, and is a polyol or polyamine compound having two hydroxyl groups, amino groups and/or imino groups per molecule. Chain extenders are useful for increasing the molecular weight of the blocked urethane without increasing the functionality.

Specific examples of the crosslinking agent and chain extender include trimethylolpropane, glycerin, trimethylolethane, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, sucrose, sorbitol, pentaerythritol, ethylenediamine, triethanolamine, monoethanolamine, diethanolamine, piperazine, and aminoethylpiperazine. In addition, compounds having two or more phenolic hydroxyl groups, such as resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1,1-bis(4-hydroxylphenyl)-1-phenylethane), bisphenol F, bisphenol K, bisphenol M, tetramethylbiphenol, and 2,2'-diallyl-bisphenol A, are also included.

(Amount of blocked urethane)
The amount of blocked urethane is preferably 1 to 50 parts by weight, more preferably 10 to 40 parts by weight, and particularly preferably 10 to 35 parts by weight, based on 100 parts by weight of the epoxy resin (A). If the amount is less than 1 part by weight, the modifying effects such as toughness, impact resistance, and adhesiveness may be insufficient, whereas if the amount is more than 50 parts by weight, the elastic modulus of the obtained cured product may be low.

<Inorganic filler>
The epoxy resin composition of the present invention may contain an inorganic filler. As the inorganic filler, for example, silicic acid and/or silicate may be used, and specific examples thereof include dry silica, wet silica, aluminum silicate, magnesium silicate, calcium silicate, wollastonite, talc, etc.

The dry silica is also called fumed silica, and includes hydrophilic fumed silica with no surface treatment, and hydrophobic fumed silica produced by chemically treating the silanol group portion of hydrophilic fumed silica with silane or siloxane. From the viewpoint of dispersibility in component (A), hydrophobic fumed silica is preferred.

Other inorganic fillers include reinforcing fillers such as dolomite and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, titanium oxide, ferric oxide, fine aluminum powder, zinc oxide, activated zinc oxide, etc.

It is preferable that the inorganic filler is surface-treated with a surface treatment agent. The surface treatment improves the dispersibility of the inorganic filler in the composition, thereby improving various physical properties of the resulting cured product.

The amount of inorganic filler used is preferably 1 to 100 parts by weight, more preferably 2 to 70 parts by weight, even more preferably 5 to 40 parts by weight, and particularly preferably 7 to 20 parts by weight, per 100 parts by weight of component (A).

The inorganic fillers may be used alone or in combination of two or more types.

<Calcium oxide>
The epoxy resin composition of the present invention may contain calcium oxide.

Calcium oxide reacts with the moisture in the epoxy resin composition to remove it, solving various problems with physical properties caused by the presence of moisture. For example, it acts as an air bubble inhibitor to prevent a decrease in adhesive strength caused by moisture removal.

Calcium oxide can be surface-treated with a surface treatment agent. The surface treatment improves the dispersibility of calcium oxide in the composition. As a result, the physical properties of the resulting cured product, such as adhesive strength, are improved compared to when calcium oxide that has not been surface-treated is used. In particular, the T-peel adhesion and impact-resistant peel adhesion are significantly improved. The surface treatment agent is not particularly limited, but fatty acids are preferred.

The amount of calcium oxide used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, even more preferably 0.5 to 3 parts by weight, and particularly preferably 1 to 2 parts by weight, per 100 parts by weight of component (A). If it is less than 0.1 part by weight, the moisture removing effect may be insufficient, and if it is more than 10 parts by weight, the strength of the obtained cured product may be reduced.
The calcium oxide may be used alone or in combination of two or more kinds.

<Radical curing resin>
The epoxy resin composition of the present invention may contain a radical curable resin having two or more double bonds in the molecule, if necessary. In addition, if necessary, a low molecular weight compound having at least one double bond in the molecule and a molecular weight of less than 300 may be added. The low molecular weight compound has a function of adjusting the viscosity, the physical properties of the cured product, and the curing speed when used in combination with the radical curable resin, and functions as a so-called reactive diluent for the radical curable resin. Furthermore, a radical polymerization initiator may be added to the epoxy resin composition of the present invention. Here, the radical polymerization initiator is preferably a latent type that is activated when the temperature is increased (preferably, about 50°C to about 150°C).

The radical curable resin may be an unsaturated polyester resin, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, polyether (meth)acrylate, acrylated (meth)acrylate, or the like. These may be used alone or in combination. Specific examples of the radical curable resin include the compounds described in International Publication No. 2014-115778. Specific examples of the low molecular weight compound and the radical polymerization initiator include the compounds described in International Publication No. 2014-115778.

As described in International Publication No. 2010-019539, if the radical polymerization initiator is activated at a temperature different from the curing temperature of the epoxy resin, the epoxy resin composition can be partially cured by selective polymerization of the radical curable resin. This partial curing can increase the viscosity of the composition after application and improve wash-off resistance. In addition, in a water shower process in a production line for vehicles, etc., the uncured adhesive composition may be partially dissolved, scattered, or deformed by the shower water pressure during the water shower process, which may adversely affect the corrosion resistance of the steel plate in the applied portion or reduce the rigidity of the steel plate, and the "resistance to washing off" refers to the resistance to this problem. In addition, this partial curing can provide a function of temporarily fixing (temporarily adhering) the substrates together until the composition is completely cured. In this case, the free radical initiator is preferably activated by heating to 80°C to 130°C, more preferably 100°C to 120°C.

<Monoepoxide>
The epoxy resin composition of the present invention may optionally contain a monoepoxide, which may function as a reactive diluent. Specific examples of monoepoxides include aliphatic glycidyl ethers such as butyl glycidyl ether, or aromatic glycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, ethers consisting of an alkyl group having 8 to 10 carbon atoms and a glycidyl group, such as 2-ethylhexyl glycidyl ether, ethers consisting of a phenyl group having 6 to 12 carbon atoms and a glycidyl group which may be substituted by an alkyl group having 2 to 8 carbon atoms, such as p-tert-butylphenyl glycidyl ether, and ethers consisting 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 versatic acid glycidyl ester, neodecanoic acid glycidyl ester, and lauric acid glycidyl ester; and p-t-butylbenzoic acid glycidyl ester.

When a monoepoxide is used, the amount used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and particularly preferably 1 to 5 parts by weight, per 100 parts by weight of component (A). If the amount is less than 0.1 part by weight, the viscosity-lowering effect may not be sufficient, and if the amount is more than 20 parts by weight, physical properties such as adhesiveness may decrease.

<Photopolymerization initiator>
In addition, when the epoxy resin composition of the present invention is photocured, a photopolymerization initiator may be added. Examples of such photopolymerization initiators include onium salts such as aromatic sulfonium salts and aromatic iodonium salts with anions such as hexafluoroantimonate, hexafluorophosphate, and tetraphenylborate, and photocationic polymerization initiators (photoacid generators) such as aromatic diazonium salts and metallocene salts. These photopolymerization initiators may be used alone or in combination of two or more.

<Other ingredients>
In the present invention, other blending components can be used as necessary. Examples of other blending components include expanding agents such as azo-type chemical foaming agents and thermally expandable microballoons, fiber pulp such as aramid pulp, colorants such as pigments and dyes, extender pigments, ultraviolet absorbers, antioxidants, stabilizers (gelling inhibitors), plasticizers, leveling agents, defoamers, silane coupling agents, antistatic agents, flame retardants, lubricants, viscosity reducers, low-shrinkage agents, organic fillers, thermoplastic resins, desiccants, dispersants, etc.

<Method for producing epoxy resin composition>
The epoxy resin composition of the present invention is a curable resin composition containing component (A) which is a curable resin, and core-shell polymer particles (B), and is preferably a composition in which the core-shell polymer particles (B) are dispersed in the state of primary particles.

Various methods can be used to obtain a composition in which the core-shell polymer particles (B) are dispersed in the form of primary particles. Examples of such methods include a method in which the core-shell polymer particles obtained in an aqueous latex state are brought into contact with component (A) and then unnecessary components such as water are removed, and a method in which the core-shell polymer particles are first extracted into an organic solvent and then mixed with component (A), and then the organic solvent is removed. However, it is preferable to use the method described in WO 2005/028546. The specific production method preferably includes the following steps in order: a first step of mixing an aqueous latex containing the core-shell polymer particles (B) (more specifically, a reaction mixture obtained after the production of the core-shell polymer particles by emulsion polymerization) with an organic solvent having a solubility in water of 5% by weight or more and 40% by weight or less at 20°C, and then mixing with an excess of water to aggregate the polymer particles; a second step of separating and recovering the aggregated core-shell polymer particles (B) from the liquid phase, and then mixing with an organic solvent again to obtain an organic solvent solution of the core-shell polymer particles (B); and a third step of mixing the organic solvent solution with the (A) component, and then distilling off the organic solvent.

It is preferable that component (A) is liquid at 23°C, since this facilitates the third step. "Liquid at 23°C" means that the softening point is 23°C or lower, and the component is fluid at 23°C.

The composition obtained through the above process, in which the core-shell polymer particles (B) are dispersed in the form of primary particles in the component (A), can be mixed with additional components (A), (C), (D), (E), and other components as necessary to obtain the epoxy resin composition of the present invention in which the core-shell polymer particles (B) are dispersed in the form of primary particles.

On the other hand, the powdered core-shell polymer particles (B) obtained by solidifying by a method such as salting out and then drying can be redispersed in component (A) using a dispersing machine with high mechanical shear force, such as a triple paint roll, roll mill, or kneader. In this case, component (A) and component (B) can be efficiently dispersed by applying mechanical shear force at high temperature to component (B). The temperature during dispersion is preferably 50 to 200°C, more preferably 70 to 170°C, even more preferably 80 to 150°C, and particularly preferably 90 to 120°C.

The epoxy resin composition of the present invention can be used as a one-liquid type epoxy resin composition that is prepared by mixing all the ingredients in advance, storing in a sealed state, applying, and curing by heating or irradiating light. It can also be prepared as a two-liquid or multi-liquid type epoxy resin composition consisting of an A liquid containing the main component (A) and further containing the component (B) and, if necessary, the component (C), and a separately prepared B liquid containing the component (D) or (E) and further containing the component (B) and/or the component (C) if necessary, and the A liquid and the B liquid are mixed before use. The curable composition of the present invention is particularly useful when used as a one-liquid type epoxy resin composition because of its excellent storage stability.

Component (B) and component (C) may be contained in at least one of liquid A and liquid B, respectively. For example, they may be contained only in liquid A, only in liquid B, or both in liquid A and liquid B.

<Cured Product>
The present invention includes a cured product obtained by curing the epoxy resin composition of the present invention. In the case of an epoxy resin composition in which the core-shell polymer particles are dispersed in the state of primary particles, a cured product in which the core-shell polymer particles are uniformly dispersed can be easily obtained by curing the epoxy resin composition. In addition, since the core-shell polymer particles are not easily swollen and the viscosity of the epoxy resin composition is low, the cured product can be obtained with good workability.

<Application method>
The epoxy resin composition of the present invention can be applied to a substrate by any method. According to a preferred embodiment of the present invention, it can be applied at a low temperature, such as room temperature, and can also be applied after heating as necessary. The epoxy resin composition of the present invention has excellent storage stability and is therefore particularly useful in a method of application after heating.

The epoxy resin composition of the present invention can be extruded onto a substrate in the form of a bead, monofilament, or swirl using a coating robot, or can be applied mechanically using a caulking gun or other manual means. The composition can also be applied to a substrate using a jet spray method or streaming method. The epoxy resin composition of the present invention is applied to one or both substrates, and the substrates are brought into contact with each other so that the composition is disposed between the two substrates to be joined, and the composition is cured in this state, thereby joining the two substrates. The viscosity of the epoxy resin composition is not particularly limited, and is preferably about 150 to 600 Pa·s at 45°C in the extrusion bead method, about 100 Pa·s at 45°C in the swirl coating method, and about 20 to 400 Pa·s at 45°C in the high-volume coating method using a high-speed flow device.

When the epoxy resin composition of the present invention is used as a vehicle adhesive, increasing the viscosity of the composition is effective in improving the "resistance to washing off," and the epoxy resin composition of the present invention is preferable because it has high thixotropy and is prone to becoming highly viscous. A highly viscous composition can be adjusted to a coatable viscosity by heating.

In order to improve the "resistance to washing off," it is preferable to incorporate a polymeric compound having a crystalline melting point near the application temperature of the composition into the curable composition of the present invention, as described in International Publication No. 2005-118734. The composition has a low viscosity at the application temperature (easy application), and a high viscosity at the temperature of the water shower washing process, improving the "resistance to washing off." Examples of the polymeric compound having a crystalline melting point near the application temperature include various polyester resins such as crystalline or semi-crystalline polyester polyols.

Another method for improving the "resistance to washing off" is to make the epoxy resin composition a two-liquid type and add a small amount of a room temperature curing agent (room temperature curing agent) such as an amine-based curing agent having an amino group or an imino group as the curing agent used, as described in International Publication No. 2006-093949. By using two or more types of curing agents with significantly different curing temperatures, partial curing begins immediately after the composition is applied, and the composition becomes highly viscous by the time of the water shower washing process, improving the "resistance to washing off".

<Adhesive>
When the epoxy resin composition of the present invention is used as an adhesive to bond various substrates, it is possible to bond substrates such as wood, metal, plastic, and glass. It is preferable to bond automobile parts, and more preferable to bond automobile frames to each other or to bond an automobile frame to another automobile part. Examples of substrates include various plastic substrates such as steel materials such as cold-rolled steel and hot-dip galvanized steel, aluminum materials such as aluminum and coated aluminum, general-purpose plastics, engineering plastics, and composite materials such as CFRP and GFRP.

The epoxy resin composition of the present invention has excellent adhesive properties. Therefore, a laminate obtained by bonding a plurality of members including an aluminum substrate, sandwiching the epoxy resin composition of the present invention between the members, and then curing the epoxy resin composition to obtain the laminate is preferable because it shows high adhesive strength.

The epoxy resin composition of the present invention has excellent toughness and is therefore suitable for bonding different substrates with different linear expansion coefficients.

The epoxy resin composition of the present invention can also be used to bond aerospace components, particularly exterior metal components.

<Curing temperature>
The curing temperature of the epoxy resin composition of the present invention is not particularly limited, but when used as a one-component epoxy resin composition, it is preferably 50° C. to 250° C., more preferably 80° C. to 220° C., even more preferably 100° C. to 200° C., and particularly preferably 130° C. to 180° C. When used as a two-component epoxy resin composition, it is not particularly limited, but it is preferably 0° C. to 150° C., more preferably 10° C. to 100° C., even more preferably 15° C. to 80° C., and particularly preferably 20° C. to 60° C.

When the epoxy resin composition of the present invention is used as an automotive adhesive, it is preferable to apply the adhesive to an automotive component, then apply a coating, and bake and cure the coating while curing the adhesive at the same time, from the viewpoint of shortening and simplifying the process.

<Applications>
From the viewpoint of handling, the epoxy resin composition of the present invention is preferably a one-liquid type epoxy resin composition.

The epoxy resin composition of the present invention is preferably used for applications such as structural adhesives for vehicles and aircraft, adhesives such as structural adhesives for wind power generation, paints, lamination materials with glass fibers, materials for printed wiring boards, solder resists, interlayer insulating films, build-up materials, adhesives for FPCs, electrical insulating materials such as sealants for electronic components such as semiconductors and LEDs, die bond materials, underfills, semiconductor mounting materials such as ACF, ACP, NCF, and NCP, and sealants for display and lighting devices such as liquid crystal panels, OLED lighting, and OLED displays. It is particularly useful as a structural adhesive for vehicles.

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

(Measurement of Volume Average Particle Size)
The average particle size of each of the polybutadiene rubber particles in the polybutadiene rubber latex and the core-shell polymer particles in the core-shell polymer latex described in the Production Examples was measured by the following method. The volume average particle size (Mv) of the particles dispersed in the aqueous latex was measured using a Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.). The measurement sample was diluted with deionized water. The measurement was performed by inputting the refractive index of water and the refractive index of each polymer particle, adjusting the sample concentration so that the measurement time was 600 seconds and the signal level was within the range of 0.6 to 0.8.

1. Formation of Core Layer Production Example 1: Preparation of Polybutadiene Rubber Latex (R-2) 200 parts by weight of water, 0.03 parts by weight of tripotassium phosphate, 0.002 parts by weight of disodium ethylenediaminetetraacetate (EDTA), 0.001 parts by weight of ferrous sulfate heptahydrate (FE) , and 1.55 parts by weight of sodium dodecylbenzenesulfonate (SDBS) were charged into a pressure-resistant polymerization reactor, and the mixture was thoroughly substituted with nitrogen while stirring to remove oxygen, after which 100 parts by weight of butadiene (Bd) was charged into the system and the temperature was raised to 45°C. 0.03 parts by weight of paramenthane hydroperoxide (PHP) was charged, followed by 0.10 parts by weight of sodium formaldehyde sulfoxylate (SFS) to initiate polymerization. 0.025 parts by weight of paramenthane hydroperoxide (PHP) was charged at 3, 5, and 7 hours after the start of polymerization, respectively. Further, 0.0006 parts by weight of EDTA and 0.003 parts by weight of ferrous sulfate heptahydrate were added at 4, 6, and 8 hours after the start of polymerization. At 15 hours after the polymerization, the remaining monomers were removed by volatilization under reduced pressure to terminate the polymerization, thereby obtaining a polybutadiene rubber latex (R-1) mainly composed of polybutadiene rubber. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 80 nm.

21 parts by weight of polybutadiene rubber latex (R-1) (including 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 ferrous sulfate heptahydrate were added to a pressure-resistant polymerization reactor, and the mixture was thoroughly purged with nitrogen while stirring to remove oxygen. Then, 93 parts by weight of Bd was added to the system, and the temperature was raised to 45°C. 0.02 parts by weight of PHP was added, followed by 0.10 parts by weight of SFS to initiate polymerization. 0.025 parts by weight of PHP, 0.0006 parts by weight of EDTA, and 0.003 parts by weight of ferrous sulfate heptahydrate were added every 3 hours until the 24th hour after the start of polymerization. After 30 hours of polymerization, the polymerization was terminated by removing the residual monomers under reduced pressure and volatilizing, to obtain a polybutadiene rubber latex (R-2) mainly composed of polybutadiene rubber. The volume average particle diameter of the polybutadiene rubber particles contained in the obtained latex was 200 nm.

2. Preparation of Core-Shell Polymer Latex (Formation of Shell Layer)
Preparation Example 2-1: Preparation of Core-Shell Polymer Latex (L-1) In a glass reactor equipped with a thermometer, a stirrer, a reflux condenser, a nitrogen inlet, and a monomer addition device, 262 parts by weight of the polybutadiene rubber latex (R-2) prepared in Preparation Example 1 (containing 87 parts by weight of polybutadiene rubber particles) and 57 parts by weight of deionized water were charged and stirred at 60° C. while performing nitrogen substitution. After adding 0.004 parts by weight of EDTA, 0.001 parts by weight of FE, and 0.2 parts by weight of SFS, a mixture of shell monomers (6 parts by weight of styrene (ST), 2 parts by weight of acrylonitrile (AN), 5 parts by weight of methyl methacrylate (MMA)) and 0.04 parts by weight of cumene hydroperoxide (CHP) was continuously added over 120 minutes. After the addition was completed, 0.04 parts by weight of CHP was added, and the mixture was further stirred for 2 hours to complete the polymerization, thereby obtaining an aqueous latex (L-1) containing core-shell polymer particles. The polymerization conversion rate of the monomer components was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (L-1) was 0.21 μm. The epoxy group content of the core-shell polymer particles was 0 mmol/g.

Production Example 2-2: Preparation of Core-Shell Polymer Latex (L-2) Except for changing the shell monomer to 6 parts by weight of styrene (ST), 2 parts by weight of acrylonitrile (AN), 4 parts by weight of methyl methacrylate (MMA), and 1 part by weight of glycidyl methacrylate (GMA), the same procedure as in Production Example 2-1 was followed to obtain an aqueous latex (L-2) containing core-shell polymer particles. The conversion rate of the monomer components was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (L-2) was 0.21 μm. The epoxy group content of the core-shell polymer particles was 0.07 mmol/g.

Production Example 2-3: Preparation of Core-Shell Polymer Latex (L-3) Except for changing the shell monomer to 6 parts by weight of styrene (ST), 2 parts by weight of acrylonitrile (AN), 3 parts by weight of methyl methacrylate (MMA), and 2 parts by weight of glycidyl methacrylate (GMA), the same procedure as in Production Example 2-1 was followed to obtain an aqueous latex (L-3) containing core-shell polymer particles. The conversion rate of the monomer components was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (L-3) was 0.20 μm. The epoxy group content of the core-shell polymer particles was 0.14 mmol/g.

Production Example 2-4: Preparation of Core-Shell Polymer Latex (L-4) Except for changing the shell monomer to 1 part by weight of styrene (ST), 2 parts by weight of acrylonitrile (AN), 2 parts by weight of methyl methacrylate (MMA), and 8 parts by weight of glycidyl methacrylate (GMA), the same procedure as in Production Example 2-1 was followed to obtain an aqueous latex (L-4) containing core-shell polymer particles. The conversion rate of the monomer components was 99% or more. The volume average particle diameter of the core-shell polymer particles contained in the aqueous latex (L-4) was 0.21 μm. The epoxy group content of the core-shell polymer particles was 0.56 mmol/g.

3. Preparation of Dispersion (M) in which Core-Shell Polymer Particles (B) are Dispersed in a Curable Resin Production Example 3-1; Preparation of Dispersion (M-1) 132 g of methyl ethyl ketone (MEK) was introduced into a 1 L mixing tank at 25 ° C., and 132 g of the core-shell polymer latex (L-1) obtained in Production Example 2-1 (corresponding to 40 g of core-shell polymer particles) was added while stirring. After uniform mixing, 200 g of water was added at a feed rate of 80 g / min. After the end of the supply, the stirring was promptly stopped, and a slurry liquid consisting of floating aggregates and an aqueous phase containing a part of an organic solvent was obtained. Next, 360 g of the aqueous phase was discharged from the discharge port at the bottom of the tank, leaving the aggregates containing a part of the aqueous phase. 90 g of MEK was added to the obtained aggregates and mixed uniformly, and a dispersion in which the core-shell polymer particles were uniformly dispersed was obtained. 60 g of epoxy resin (Mitsubishi Chemical Corporation, JER828: liquid bisphenol A type epoxy resin) which is component (A) was mixed with this dispersion. MEK was removed from this mixture using a rotary evaporator. In this way, a dispersion (M-1) in which core-shell polymer particles were dispersed in the epoxy resin was obtained.

Production Example 3-2; Preparation of Dispersion (M-2) A dispersion (M-2) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 3-1, except that (L-2) obtained in Production Example 2-2 was used instead of (L-1) as the core-shell polymer latex in Production Example 3-1.

Production Example 3-3; Preparation of Dispersion (M-3) A dispersion (M-3) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 3-1, except that (L-3) obtained in Production Example 2-3 was used instead of (L-1) as the core-shell polymer latex in Production Example 3-1.

Production Example 3-4; Preparation of Dispersion (M-4) A dispersion (M-4) in which core-shell polymer particles were dispersed in an epoxy resin was obtained in the same manner as in Production Example 3-1, except that (L-4) obtained in Production Example 2-4 was used instead of (L-1) as the core-shell polymer latex in Production Example 3-1.

(Examples 1 to 9, Comparative Examples 1 to 10)
Using the dispersions (M-1) to (M-4) in which the core-shell polymer particles (B) were dispersed in the epoxy resin (A) obtained in Production Examples 3-1 to 3-4, each component was weighed out to obtain the formulation shown in Table 1 or 2, and mixed thoroughly to obtain an epoxy resin composition. In each of the Examples and Comparative Examples, the amounts of the (A) and (B) components shown in Table 1 or 2 were satisfied by adding the dispersions (M-1) to (M-4) and separately adding the epoxy resin (A). In other words, the amount of the (A) component in Table 1 or 2 is the total amount of the amount of the epoxy resin contained in the dispersion (M) in which the core-shell polymer particles (B) were dispersed, and the amount of the epoxy resin added separately.

Each epoxy resin composition in Table 1 or 2 was evaluated for dynamic splitting resistance and workability (applicability) using the following methods. The results are shown in Table 1 or 2.

<Dynamic splitting resistance (impact peel adhesion)>
The epoxy resin composition was applied to two SPCC steel plates, 20 mm wide, 90 mm long and 0.8 mm thick, and the plates were overlapped so that the adhesive layer thickness was 0.25 mm, cured at 170°C for 30 minutes, and the dynamic splitting resistance at 23°C was measured in accordance with ISO 11343. When the end point of the splitting could not be determined in the measurement chart (time-force curve), the measured value was recorded as 0. The test results are shown in Tables 1 and 2.

<Workability (applicability)>
The epoxy resin composition was placed on a steel plate and left at a predetermined temperature (room temperature or 50°C) for 10 minutes. Thereafter, the workability (applicability) was evaluated based on the fluidity of the epoxy resin composition when it was spread with a metal spatula. If the epoxy resin composition spreads easily, it was rated as "A", if the epoxy resin composition was semi-solid and could be spread by applying force, it was rated as "B", and if the epoxy resin composition was solid and could not be spread, it was rated as "C". The test results are shown in Tables 1 and 2.

The components shown in Tables 1 and 2 are as follows.
<Epoxy resin (A)>
A-1: JER828 (manufactured by Mitsubishi Chemical, bisphenol A type epoxy resin that is liquid at room temperature, epoxy equivalent: 184-194)
<Core-shell polymer particles (B)>
L-1 to L-4: Core-shell polymer particles in the core-shell polymer latexes (L-1) to (L-4) obtained in Production Examples 2-1 to 2-4 <Compound (C) having two functional groups each having one active hydrogen atom reactive with an epoxy group in the molecule>
C-1: Bisphenol A (Tokyo Chemical Industry Co., Ltd.)
<Catalyst (D) for promoting the polyaddition reaction of epoxy resin (A) and compound (C) having two functional groups each having one active hydrogen atom reactive with an epoxy group in the molecule>
D-1: Tri(o-tolyl)phosphine (Tokyo Chemical Industry Co., Ltd.)
<Epoxy resin curing agent (E)>
E-1: Dyhard 100S (manufactured by AlzChem, dicyandiamide)
<Curing accelerator>
Dyhard UR300 (manufactured by AlzChem, 1,1-dimethyl-3-phenylurea)
<Reaction retarder>
Tri-n-octyl borate (Tokyo Chemical Industry Co., Ltd.)
<Fumed Silica>
CAB-O-SIL TS-720 (manufactured by CABOT, fumed silica surface-treated with polydimethylsiloxane)
<Calcium carbonate>
Whiten SB (manufactured by Shiraishi Calcium, surface-untreated heavy calcium carbonate, average particle size: 1.8 μm, specific surface area: 1.2 m ² /g)
<Calcium oxide>
CML#31 (Omi Chemical Industry Co., Ltd., calcium oxide surface-treated with fatty acid)

From Table 1, it can be seen that the epoxy resin compositions of Examples 1 to 9, which contain components (A), (B), and (D), and further contain 20 parts by weight or more of component (C) per 100 parts by weight of the total of components (A) and (E), have high dynamic splitting resistance values, i.e., excellent impact-resistant peel adhesion.

All of the epoxy resin compositions of Examples 1 to 9 spread easily at 50°C and had good workability (applicability). Among them, the epoxy resin compositions of Examples 1 to 4 had good fluidity even at room temperature and also had good workability (applicability) at room temperature.

It can be seen from Table 2 that all of the epoxy resin compositions of Comparative Examples 1 to 10 exhibited lower dynamic splitting resistance than those of Examples 1 to 9. Comparative Examples 1 and 2 contain a small amount of component (C), Comparative Example 3 does not contain components (B) and (C), Comparative Examples 4 to 6 do not contain component (B), and Comparative Examples 7 to 10 do not contain component (C).

Claims (10)

Epoxy resin (A),
Core-shell polymer particles (B) having a core layer composed of a diene rubber;
a compound (C) having two functional groups each having one active hydrogen reactive with an epoxy group in one molecule , the compound (C) being capable of forming a linear polymer by a polyaddition reaction with the epoxy resin (A) ;
The composition contains a catalyst (D) for promoting a polyaddition reaction between an epoxy resin (A) and a compound (C), and an epoxy resin curing agent (E) as an optional component (excluding those corresponding to the compound (C)) ,
the compound (C) is blended in an amount of 20 parts by weight or more per 100 parts by weight of the total of the epoxy resin (A) and the epoxy resin curing agent (E);
the catalyst (D) is one or more phosphorus-based catalysts selected from the group consisting of dicyclohexylphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, cyclohexyldiphenylphosphine, triphenylphosphine, triphenylphosphine-triphenylborane complex, and tri(m-tolyl)phosphine-triphenylborane complex;
An epoxy resin composition comprising 0.1 to 10 parts by weight of a catalyst (D) based on 100 parts by weight of the total of an epoxy resin (A) and an epoxy resin curing agent (E). The epoxy resin composition according to claim 1, wherein compound (C) is a compound having two phenolic hydroxyl groups in one molecule. The epoxy resin composition according to claim 1 or 2, wherein the volume average particle diameter of the core-shell polymer particles (B) is 10 to 2000 nm. The epoxy resin composition according to any one of claims 1 to 3, in which the amount of the core-shell polymer particles (B) is 1 part by weight or more and 100 parts by weight or less per 100 parts by weight of the total of the epoxy resin (A) and the epoxy resin curing agent (E). The epoxy resin composition according to any one of claims 1 to 4, in which the amount of compound (C) is 70 parts by weight or less per 100 parts by weight of the total of epoxy resin (A) and epoxy resin curing agent (E). The epoxy resin composition according to any one of claims 1 to 5, wherein the weight ratio of the epoxy resin curing agent (E) to the total of the epoxy resin (A) and the epoxy resin curing agent (E) is 0% by weight or more and 20% by weight or less. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 6. An adhesive comprising the epoxy resin composition according to any one of claims 1 to 6. The adhesive of claim 8, wherein the adhesive is a structural adhesive. A laminate comprising two substrates and an adhesive layer formed by curing the adhesive according to claim 8 or 9, which bonds the two substrates.