TW201809023A - Composition - Google Patents

Abstract

A composition having heat resistance is provided. The composition comprises (1) (meth)acrylates comprising (1-1) a monofunctional (meth)acrylate having an aromatic group, (1-2) a monofunctional (meth)acrylate having a hydroxy group, and (1-3) a polyfunctional (meth)acrylate represented by general formula (A), (2) elastomers including (2-1) an elastomer which comprises a silicone-modified acrylic core/shell (co)polymer, (3) a polymerization initiator, and (4) a reducing agent. Formula (A) (In the formula, Z and Z' may be the same or different and each represent a (meth)acryloyl group; R1 and R1' may be the same or different and each represent an alkylene group; R2 and R2' may be the same or different and each represent a hydrogen atom or a C1-4 alkyl group; and p and p' may be the same or different and each represent an integer of 0-8.).

Description

Composition

The present invention relates to, for example, a composition.

In terms of labor saving, resource saving, and energy saving, a normal temperature quick-curing type adhesive composition is used as an adhesive agent to be adhered in a short time at normal temperature. Conventionally, the room temperature quick-curing adhesive composition is known as a two-part quick-curing epoxy-based adhesive composition, an anaerobic adhesive composition, an instant adhesive composition, and a second-generation acrylic adhesive composition ( SGA).

The two-component type quick-curing epoxy-based adhesive agent measures and mixes the main agent and the hardener, applies it to the adherend, and hardens by the reaction between the main agent and the hardener. However, two-component quick-curing epoxy-based adhesives have higher requirements for peel strength and impact strength.

Anaerobic adhesives are those in which the adhesive composition is pressed between the adherends to block air and thereby harden. However, the anaerobic adhesive composition requires the following properties: When a part of the adhesive composition oozes out of the adherend during compression, it can harden even if the oozed part contacts the air. In addition, it is required to have a property that it can harden even when the gap between the adherends is large.

The instant adhesive usually has a cyanoacrylate as a main component and is excellent in workability. But the indirect adhesive has higher requirements for peel strength and impact strength.

SGA is a two-component (meth) acrylic adhesive, but it is not necessary to accurately measure the two components. Even if the measurement or mixing is not complete, the two components can be hardened at room temperature for several minutes to tens of minutes, so the workability is excellent. . What's more, due to the high peel strength and impact strength, and the hardening of the exudate is also good, it is widely used in the fields of electrical and electronic parts, civil engineering, and transportation vehicles.

In the field of transportation vehicles, baking coating treatment is often applied to steel plates or aluminum alloys. However, the baking coating processing step is exposed to a high temperature of 220 ° C. for 1 hour, for example. Therefore, it is necessary to have the heat resistance to withstand such a high temperature during the bonding of the transportation vehicle parts after the baking coating process step.

SGA can maintain its adhesiveness even after high-temperature baking treatment in the bonding of steel plates. However, if high-temperature baking treatment is performed in the bonding of adherends with large thermal expansion rates such as aluminum alloys, the bonding strength will decrease. Therefore, there is a need for improvement.

Related SGA inventions have been disclosed in Patent Documents 1 to 4.

Patent Document 1 describes an adhesive composition containing (A) 1 to 30% by mass of an elastomer, (B) 40 to 99% by mass of a hydroxyacrylic acid derivative, and (C) (meth) acrylic acid other than the above (B) 0 to 59% by mass of the polymerizable monomer, (D) a polymerization initiator and (E) a reducing agent. However, the structure of the component (1-3) of the present invention is not described. Patent Document 1 does not mention the effect of improving heat resistance.

Patent Document 2 describes a liquid crystal sealant containing (a) resin fine particles and (b) a light-hardening resin having a core-shell structure, and the viscosity at 25 ° C measured using an E-type viscometer is 100 Pa. s below, and the viscosity after pre-baking is 100Pa. 400Pa above s. s or less. However, the structure of the component (1-3) of the present invention is not described. In Patent Document 2, heat treatment is performed at 90 to 130 ° C. in order to thicken and harden the adhesive composition, but does not mention heat resistance under the high-temperature baking conditions of 220 ° C. as in the present invention.

Patent Document 3 describes that the curable resin composition containing (1) a polymerizable vinyl monomer has a static viscosity at 20 rpm of 110,000 mPa or less, and a shake viscosity coefficient obtained by dividing the static viscosity at 2 rpm by the static viscosity at 20 rpm. It is 1.7 or more. However, the component (2-1) of the present invention is not described.

Patent Document 4 describes a two-component acrylic adhesive composition containing (1) a (meth) acrylic acid derivative monomer, (2) a polymerization initiator, (3) a reducing agent, and (4) a diene core. In the case of the shell polymer, the diene-based core-shell polymer can swell in the (meth) acrylic acid derivative monomer, and the swelling degree in toluene at 25 ° C is 9.5 or more. However, the component (2-1) of the present invention is not described.

[Prior technical literature]

Patent Document 1: Japanese Patent Application Laid-Open No. 2015-30748.

Patent Document 2: Japanese Patent Application Laid-Open No. 2010-277072.

Patent Document 3: Japanese Patent Application Laid-Open No. 2002-308944.

Patent Document 4: Japanese Patent Application Laid-Open No. 2005-179548.

The present invention has been made in view of the foregoing state of the art, and an object thereof is to provide, for example, a composition having heat resistance.

That is, the present invention is as described below.

<1> A composition comprising: component (1): (meth) acrylate containing the following component (1-1), component (1-2), and component (1-3); component (2) : An elastomer containing at least the following component (2-1); component (3): a polymerization initiator; and component (4): a reducing agent.

Among them, component (1-1) is a monofunctional (meth) acrylate having an aromatic group; component (1-2) is a monofunctional (meth) acrylate having a hydroxyl group; component (1-3) is A polyfunctional (meth) acrylate represented by formula (A);

In the formula, Z and Z 'represent (meth) acrylfluorenyl groups, Z and Z' may be the same or different, R ₁ and R ₁ ′ are alkylene groups, and R ₁ and R ₁ ′ may be the same or different R ₂ and R ₂ ′ represent hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₂ ′ may be the same or different, p and p ′ represent integers from 0 to 8 and p and p ′ may be the same Or different.

Ingredient (2-1) is an elastomer containing a polysiloxane modified acrylic core-shell (co) polymer.

<2> The composition according to <1>, wherein the core portion of the component (2-1) is a polysiloxane-acrylic composite rubber, and the shell portion is a vinyl-based polymer.

<3> The composition according to <1> or <2>, wherein the shell portion of the component (2-1) is an alkyl (meth) acrylate.

<4> The composition according to <1> to <3>, wherein the used amount of the component (2-1) is 5 to 40 parts by mass based on 100 parts by mass of the total of the ingredients (1) and (2).

<5> The composition according to any one of <1> to <4>, wherein the component (2) further contains a component (2-2): an elastomer other than the component (2-1).

<6> The composition according to <5>, wherein the component (2-2) is a non-core-shell (co) polymer.

<7> The composition according to <5> or <6>, wherein the used amount of the component (2-2) is 5 to 30 parts by mass relative to 100 parts by mass of the total of the ingredients (1) and (2).

<8> The composition according to <1> to <7>, wherein the component (1) is 100 to 85 parts by mass, the component (1-1) is 10 to 85 parts by mass, and the component (1-2) is 5 to 60 The parts by mass and component (1-3) are 1 to 60 parts by mass.

<9> The composition according to <1> to <8>, further comprising a component (5): an acidic phosphoric acid compound.

<10> The composition according to any one of <1> to <9>, further comprising a component (6): a paraffin.

<11> A curable resin composition containing the composition according to <1> to <10>.

<12> An adhesive composition containing the composition according to any one of <1> to <10>.

<13> A two-dose composition, which divides the composition described in <1> to <10> into a first agent and a second agent. The first agent contains at least a polymerization initiator of component (3). The second agent contains at least a reducing agent of component (4).

<14> A bonded body which is bonded with the adhesive composition according to <12>.

The present invention has, for example, heat resistance.

The present invention is explained in detail below.

The (meth) acrylate of the component (1) means, for example, a monomer having a (meth) acrylfluorenyl group. The monofunctional (meth) acrylate refers to a monomer having one (meth) acrylfluorenyl group. The polyfunctional (meth) acrylate means a monomer having two or more (meth) acrylfluorenyl groups. Unless otherwise stated, the amount used is preferably the total amount of the first agent and the second agent. The total content of the (meth) acrylate of the component (1) and the elastomer of the component (2) is preferably 70 parts by mass or more, more preferably 85 parts by mass or more, and most preferably 90 parts by mass of the composition More than mass parts.

The (meth) acrylate of component (1) preferably contains: component (1-1): a monofunctional (meth) acrylate having an aromatic group; component (1-2): a monofunctional (meth) acrylate having a hydroxyl group (Meth) acrylate; and component (1-3): a polyfunctional (meth) acrylate represented by the general formula (A). However, the (meth) acrylate of the component (1) may or may not contain the (meth) acrylate other than the said component (1-1), the component (1-2), and the component (1-3).

The monofunctional (meth) acrylate having an aromatic group in the component (1-1) can, for example, make the adhesive composition more rigid and improve the solubility of the elastomer component.

The component (1-1) is preferably one excluding the component (1-2). The component (1-1) is different from the polyfunctional component (1-3) in definition. Component (1-1) preferably has no hydroxyl group. Examples of such monomers include (meth) acrylates of formula (B), phenoxydiethylene glycol (meth) acrylates, and phenoxyethyl (meth) acrylates. Among these, a (meth) acrylate of the formula (B) is preferred.

In the formula (B), Z represents a (meth) acrylfluorenyl group, and R ₃ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.

Examples of the (meth) acrylate of the formula (B) include benzyl (meth) acrylate, methyl benzyl (meth) acrylate, ethyl benzyl (meth) acrylate, and propyl benzyl (meth) acrylate , Methoxybenzyl (meth) acrylate, chlorobenzyl (meth) acrylate, and the like. Among the (meth) acrylates of the formula (B), benzyl (meth) acrylate is preferred.

The used amount of the component (1-1) is preferably 10 to 85 parts by mass, more preferably 20 to 70 parts by mass, and most preferably 35 to 65 parts by mass, out of 100 parts by mass of the total amount of the ingredient (1). When the content is 10 parts by mass or more, the solubility of the elastomer component is improved, and workability and coatability are improved. When the amount is 85 parts by mass or less, the peel strength is improved.

The monofunctional (meth) acrylate having a hydroxyl group in the component (1-2) can improve adhesion to an adherend, for example.

The component (1-2) is preferably one excluding the component (1-1). Ingredient (1-2) is different from polyfunctional ingredient (1-3) in definition. It is more preferable that the component (1-2) does not have an aromatic ring. Examples of such monomers include hydroxyalkyl (meth) acrylate, glycerol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and the like. Among these, hydroxyalkyl (meth) acrylate is preferable.

Among the hydroxyalkyl (meth) acrylates, a (meth) acrylate of the formula (D) is preferred.

Formula (D) ZO- (R ₇ O) _q -H

In the formula (D), Z represents a (meth) acrylfluorenyl group, R ₇ represents an alkylene group, and q represents an integer of 1 to 10.

The alkylene group is preferably an alkylene group having 2 to 6 carbon atoms, and q is preferably 1.

Examples of the (meth) acrylate of the formula (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like. Among these, one or more groups of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred, and 2-hydroxypropyl (meth) acrylate is most preferred.

The amount of the component (1-2) to be used is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and most preferably 15 to 40 parts by mass of the total 100 parts by mass of the ingredient (1). When it is 5 parts by mass or more, the adhesiveness is improved. When the content is 60 parts by mass or less, the solubility of the elastomer component is improved, and workability, coatability, and heat resistance are improved.

The monomer of the general formula (A) in the component (1-3) has the following structure.

The monomer represented by the general formula (A) is as follows.

In the formula, Z and Z 'represent (meth) acrylfluorenyl groups, Z and Z' may be the same or different, R ₁ and R ₁ ′ are alkylene groups, and R ₁ and R ₁ ′ may be the same or different R ₂ and R ₂ ′ represent hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₂ ′ may be the same or different, p and p ′ represent integers from 0 to 8 and p and p ′ may be the same Or different.

R ₁ and R ₁ ′ are preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an alkylene group having 2 carbon atoms. R ₂ and R ₂ ′ are preferably methyl. p and p 'are preferably 0 to 8, more preferably 3 to 8, and most preferably 5.

Such monomers may be, for example, 2,2-bis (4- (meth) propenyloxyphenyl) propane, 2,2-bis (4- (meth) propenyloxyethoxyphenyl) propane , 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, etc. . Among these, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane is preferred.

The used amount of the component (1-3) is preferably 1 to 60 parts by mass, more preferably 10 to 45 parts by mass, and most preferably 15 to 30 parts by mass, out of 100 parts by mass of the total amount of the ingredient (1). When 1 mass part or more is used, heat resistance improves. When the content is 60 parts by mass or less, the solubility of the elastomer component is improved, and workability and coatability are improved.

The elastomer of the component (2) is, for example, a polysiloxane modified acrylic core-shell (co) polymer containing the component (2-1).

The polysiloxane modified acrylic core-shell (co) polymer of the component (2-1) refers to a core-shell type elastomer having a polysiloxane-acrylic rubber. (Co) polymer refers to polymers and copolymers. In the core-shell type, for example, a core represents a core and a shell represents a shell. The core and the shell materials in a particle are different.

The core-shell type elastomer is preferably a polysiloxane-acrylic rubber with a core portion.

From the viewpoint of mechanical properties, the polysiloxane-acrylic rubber is preferably a polysiloxane-acrylic composite rubber obtained by compounding an alkyl (meth) acrylate rubber polymer with a polysiloxane polymer. Compounding can be performed, for example, by adding an alkyl (meth) acrylate component to a polyorganosiloxane emulsion and polymerizing in the presence of a radical polymerization initiator. The polysiloxane-acrylic composite rubber refers to, for example, a rubber having a structure in which a polyorganosiloxane and a poly (meth) acrylate cannot be separated from each other.

Examples of the shell portion include a homopolymer and a copolymer. Among these, a homopolymer is preferred. The homopolymer is preferably a vinyl-based polymer such as polystyrene, (meth) acrylonitrile, or (meth) acrylic acid alkyl ester. Among vinyl-based polymers, alkyl (meth) acrylate polymers are preferred. Among alkyl (meth) acrylates, methyl (meth) acrylate is preferred. Examples of the copolymer include a styrene- (meth) acrylonitrile copolymer, a styrene- (meth) alkyl methacrylate copolymer, an acrylic acid-methacrylic acid copolymer, and a styrene- (meth) acrylonitrile- ( (Meth) alkyl acrylate copolymers and the like. Among the copolymers, a styrene- (meth) acrylonitrile copolymer is preferred.

The shell portion can be obtained, for example, in the following manner. A vinyl-based monomer is added in the presence of the rubber latex in the core portion to polymerize to obtain a latex of a graft copolymer. The obtained graft copolymer latex is subjected to coagulation and curing, thereby obtaining a shell portion, thereby becoming a core-shell (co) polymer.

The amount of the polysiloxane modified acrylic core-shell polymer of the component (2-1) is preferably 5 to 40 parts by mass, more preferably 15 to 100 parts by mass of the total of the ingredients (1) and (2). ~ 30 parts by mass. 5 mass parts or more has sufficient high-temperature baking heat resistance. When the content is less than 40 parts by mass, the viscosity does not increase, and there is no work defect.

The elastomer of the component (2) is preferably an elastomer containing the component (2-2) and the component (2-1). The component (2-2) is preferably a non-core-shell (co) polymer. A non-core-shell (co) polymer means that it does not have a core-shell structure. The component (2-2) is preferably an (meth) acrylate-soluble elastomer. Moreover, the elastomer of the component (2) may contain elastomers other than the said component (2-1) and the component (2-2), Preferably it does not contain.

The component (2-2) includes, for example, a (meth) acrylonitrile-butadiene- (meth) acrylic copolymer, a (meth) acrylonitrile-butadiene- (meth) acrylate copolymer, and (Meth) acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, chlorinated polyethylene, styrene-polybutadiene-styrene synthetic rubber, and other styrene-based thermoplastic elastomers, and The terminal is modified into (meth) acrylic polybutadiene, urethane-based elastomer, and the like.

Among these, from the viewpoints of solubility and adhesiveness, preferred among these are (meth) acrylonitrile-butadiene- (meth) acrylate and (meth) acrylonitrile-butadiene copolymers. One or more, more preferably a (meth) acrylonitrile-butadiene copolymer.

The used amount of the component (2-2) is preferably 5 to 30 parts by mass, and more preferably 8 to 15 parts by mass with respect to 100 parts by mass of the total of the ingredients (1) and (2). When it is 5 parts by mass or more, the peel strength at low temperature is improved. When the content is 30 parts by mass or less, the adhesiveness is improved, the viscosity is not increased, and the handleability is improved.

The polymerization initiator of the component (3) is preferably an organic peroxide. Examples of the organic peroxide include cumene hydroperoxide, p-menthane hydroperoxide, third butyl hydroperoxide, diisopropylbenzene dihydroperoxide, and methyl ethyl ketone peroxide. , Benzamyl peroxide and third butyl peroxybenzoate. From the viewpoint of stability, cumene hydroperoxide is preferred among these.

The amount of the polymerization initiator of the component (3) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 0.8 to 100 parts by mass of the total of the ingredients (1) and (2). ~ 5 parts by mass. When it is 0.5 part by mass or more, the hardening speed is increased. Storage stability is better at 20 parts by mass or less, and storage stability is better at 10 parts by mass or less.

The reducing agent of component (4) can be used if it is a well-known reducing agent which can react with the said polymerization initiator and generate | occur | produce a radical. Typical reducing agents include tertiary amines, thiourea derivatives, and transition metal salts.

Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, and N, N-dimethyl-p-toluidine. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylthiourea. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadylacetone. Among these, from the viewpoint of reactivity, transition metal salts are preferred. Among the transition metal salts, vanadylacetoneacetate is preferred.

The used amount of the reducing agent of the component (4) is preferably from 0.05 to 15 parts by mass, more preferably from 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the ingredients (1) and (2). When it is 0.05 parts by mass or more, the hardening speed is increased. When it is 15 parts by mass or less, storage stability is better.

The present invention preferably contains the component (5): an acidic phosphoric acid compound. The component (5) is preferably an acidic phosphoric acid compound represented by the general formula (C).

In the formula, R ₄ represents CH ₂ = CR ₅ CO (OR ₆ ) _m -group (but R ₅ represents hydrogen or methyl group, R ₆ represents -C ₂ H _4- , -C ₃ H _6- , -CH ₂ CH (CH ₃ )-, -C ₄ H _8- , -C ₆ H _12- , or ; M represents an integer from 1 to 10), n represents an integer of 1 or 2.

The component of the component (5) may be, for example, (meth) acrylic acid dioxyphosphoryloxyethyl, (meth) acrylic acid dioxyphosphoryloxypropyl, or bis (2- (meth) acrylic acid) Ethyl) phosphate and the like. Ingredient (5) is preferably contained in the second agent.

The used amount of the component (5) is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 7 parts by mass with respect to the total mass of the ingredients (1) and (2). When it is 0.05 parts by mass or more, the curing speed is increased, and the adhesiveness is improved. When it is 10 parts by mass or less, the adhesiveness is improved.

The present invention preferably contains the component (6): paraffin. The component (6) accelerates the hardening of the air-contacting portion of the composition of the present invention. Examples of the paraffin wax include paraffin wax, microcrystalline wax, palm wax, beeswax, lanolin, whale wax, ceresin wax, and candela wax. Among these, paraffin is preferred.

The used amount of the component (6) is preferably 0.1 to 5 parts by mass based on 100 parts by mass of the total of the ingredients (1) and (2). When it is 0.1 parts by mass or more, the hardening of the air-contacted portion becomes good. When the content is 5 parts by mass or less, the bonding strength increases.

Furthermore, antioxidants and the like can be used in the present invention.

The present invention can be used as a curable resin composition, and the present invention can also be used as an adhesive composition. Embodiments of the present invention are preferably used as a two-dose type adhesive composition. Regarding the two-dose form, all necessary components of the adhesive composition of the present invention are not mixed during storage, and the adhesive composition is divided into a first agent and a second agent. Contains at least reducing agents and stores them separately. The two-dose form is preferable because of its excellent storage stability. In this case, a two-component type adhesive composition can be used by applying and curing the two components simultaneously or separately.

The adherend is bonded using the adhesive composition of the present invention to produce a bonded body. Various materials of the adherend may be paper, wood, ceramics, glass, ceramics, rubber, plastic, mortar, concrete, and metal, etc., but there is no limitation, but the adherend exhibits excellent adhesion when it is metal.

[Example]

The present invention is explained in more detail by the following experimental examples. The unit of the amount of each substance used is expressed in parts by mass.

For each substance, the following commercially available products were used.

Polysiloxane-acrylic core-shell rubber (shell: (meth) methyl methacrylate polymer): Polysiloxane-acrylic rubber at the core and polysiloxane modified by methyl methacrylate at the shell Acrylic core-shell polymer.

Polysiloxane-acrylic core-shell rubber (shell: styrene-acrylonitrile copolymer): The core part is polysiloxane-acrylic rubber, and the shell part is polysiloxane modified acrylic core. Shell polymer.

NBR: acrylonitrile-butadiene copolymer.

MBS: Core-shell polymer of methyl methacrylate-butadiene-styrene copolymer.

Butadiene-based core-shell polymers: Butadiene-based core-shell polymers.

Acrylic core-shell polymer: acrylic core-shell polymer.

2,2-bis (4-Methacryloxypolyethoxyphenyl) propane: Use p = p '= 5 in formula (A).

Paraffin: Paraffin.

Acidic phosphoric acid compounds: phosphoric acid esters, acidic dioxyphosphoryloxyethyl methacrylate (the structural formula is shown below).

(CH ₂ = C (CH ₃ ) -COOC ₂ H ₄ O) _n P (O) (OH) _3-n

n is 1 or 2.

Epoxy acrylate: PE210 (manufactured by Miwon) was used. Acrylic epoxy esters have an OH group because R ₁ and R ₁ ′ have an OH group, so they are not the component (1-3), and they are not the component (1-1) and the component (1- because of their multifunctionality. 2).

Various physical properties were measured by the following methods.

[Tensile shear strength (tensile shear strength)]

The test piece was a 100 × 25 × 2.0 mm aluminum alloy A5052 plate which was wiped with a wiping cloth. Under the environment of a temperature of 23 ° C and a humidity of 50%, the first agent and the second agent mixed adhesive were coated on one side of a test piece according to JISK-6850: 1999 standard, and the test pieces were immediately overlapped and adhered to each other. Then, it was hardened at room temperature for 24 hours, and was used as a sample for measuring tensile shear strength, and then the tensile shear strength (unit: MPa) was measured and used as the initial tensile shear strength. To confirm the heat resistance, the sample for measuring tensile shear strength was subjected to a baking treatment at 220 ° C for 1 hour, and cooled to a temperature of 23 ° C to measure the tensile shear strength (unit: MPa) as a baking test. Tensile shear strength after baking treatment. The measurement was performed under the conditions of a temperature of 23 ° C and a tensile speed of 10 mm / min.

[Peel Strength (Peel Adhesion)]

The test piece was a 200 × 25 × 1 mm A5052 board which was wiped with a wiping cloth. Under the environment of a temperature of 23 ° C. and a humidity of 50%, one side of a test piece was coated with the first agent and the second agent mixed adhesive in accordance with JISK-6854-3: 1999 standard, and the test pieces were immediately overlapped and adhered to each other. Thereafter, it was cured at room temperature for 24 hours to be used as a sample for measuring peel strength, and then the peel strength (unit: kN / m) was measured and used as the initial peel strength. To confirm the heat resistance, the sample for peel strength measurement was subjected to a baking treatment at 220 ° C. for 1 hour, and cooled to a temperature of 23 ° C. to measure the peel strength (unit: kN / m). Peel strength. The measurement was performed under the conditions of a temperature of 23 ° C and a stretching speed of 50 mm / min.

[Workability]

The workability of the two-component acrylic adhesive composition was determined based on a 20-rotation viscosity measured by a B-type viscometer, and was determined in the following manner.

○: Very good workability (viscosity less than 100,000 mPa · s).

△: Good workability (viscosity of 100,000 mPa.s or more and less than 200,000 mPa.s).

The present invention is explained in more detail by the following experimental examples. The unit of the amount of each substance used is expressed in parts by mass.

[Examples 1 to 6, Comparative Examples 1 to 4]

A two-component acrylic adhesive composition was prepared with the composition of the examples or comparative examples shown in Table 1, and tensile shear strength measurement, peel strength measurement, and workability measurement were performed at the initial stage and after the baking process. By using a polysiloxane modified acrylic core-shell (co) polymer, high adhesion strength can be exhibited even after baking treatment. As the shell portion, a polysiloxane modified acrylic core-shell polymer using methyl (meth) acrylate polymer is used, and thus, a high adhesion strength can be exhibited especially after baking treatment. When methyl methacrylate-butadiene-styrene copolymer (MBS) and acrylic core-shell polymer are used, the tensile shear strength and peel strength after baking treatment are low. When a butadiene-based core-shell polymer is used, the core-shell rubber cannot be smoothly dispersed in the adhesive. When acrylic acrylate is used, the adhesive strength after baking is low.

[Industrial availability]

According to the present invention, for example, a two-dose type adhesive composition having heat resistance can be obtained. The obtained two-component adhesive composition can withstand high-temperature baking treatment steps, and thus has high industrial applicability.

Claims (14)

A composition comprising: component (1): (meth) acrylate containing the following component (1-1), component (1-2), component, and (1-3); component (2): containing at least Elastomer of the following component (2-1); component (3): polymerization initiator; and component (4): reducing agent; wherein this component (1-1) is a monofunctional (formaldehyde) having an aromatic group Group) acrylate; the component (1-2) is a monofunctional (meth) acrylate having a hydroxyl group; the component (1-3) is a polyfunctional (meth) acrylate represented by the general formula (A); In the formula, Z and Z 'represent (meth) acrylfluorenyl groups, Z and Z' may be the same or different, R ₁ and R ₁ ′ are alkylene groups, and R ₁ and R ₁ ′ may be the same or different R ₂ and R ₂ ′ represent hydrogen or an alkyl group having 1 to 4 carbon atoms, R ₂ and R ₂ ′ may be the same or different, p and p ′ represent integers from 0 to 8 and p and p ′ may be the same Or different; the component (2-1) is an elastomer containing a polysiloxane modified acrylic core-shell (co) polymer. The composition according to item 1 of the scope of patent application, wherein the core portion of the component (2-1) is a polysiloxane-acrylic composite rubber, and the shell portion is a vinyl-based polymer. The composition according to item 1 or item 2 of the scope of patent application, wherein the shell portion of the component (2-1) is an alkyl (meth) acrylate. The composition according to item 1 or item 2 of the scope of patent application, wherein the amount of the component (2-1) is 5 to 40 with respect to 100 parts by mass of the total of the component (1) and the component (2) Parts by mass. The composition according to item 1 or item 2 of the scope of patent application, wherein the component (2) further contains component (2-2): an elastomer other than component (2-1). The composition according to item 5 of the scope of patent application, wherein the component (2-2) is a non-core-shell (co) polymer. The composition according to item 5 of the scope of patent application, wherein the amount of the component (2-2) used is 5 to 30 parts by mass relative to 100 parts by mass of the total of the ingredient (1) and the ingredient (2). The composition according to item 1 or item 2 of the scope of patent application, wherein the component (1-1) is 10 to 85 parts by mass and the component (1-2) is 5 to 60 parts by mass, and the component (1-3) is 1 to 60 parts by mass. The composition according to item 1 or item 2 of the scope of patent application, further comprising component (5): an acidic phosphoric acid compound. The composition according to item 1 or item 2 of the scope of patent application, further comprising ingredient (6): paraffin. A curable resin composition containing the composition according to any one of claims 1 to 10 of the scope of patent application. An adhesive composition containing the composition according to any one of claims 1 to 10 of the scope of patent application. A two-dose composition is divided into a first agent and a second agent according to any one of the items 1 to 10 of the scope of patent application, and the first agent contains at least the component (3) Polymerization initiator, the second agent contains at least the reducing agent of the component (4). A bonded body is bonded with an adhesive composition as described in claim 12 of the scope of patent application.