WO2017170957A1 - Composition - Google Patents

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Publication number
WO2017170957A1
WO2017170957A1 PCT/JP2017/013452 JP2017013452W WO2017170957A1 WO 2017170957 A1 WO2017170957 A1 WO 2017170957A1 JP 2017013452 W JP2017013452 W JP 2017013452W WO 2017170957 A1 WO2017170957 A1 WO 2017170957A1
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WO
WIPO (PCT)
Prior art keywords
meth
component
mass
parts
acrylate
Prior art date
Application number
PCT/JP2017/013452
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French (fr)
Japanese (ja)
Inventor
麻希子 佐々木
剛介 中島
Original Assignee
デンカ株式会社
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Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to JP2018509481A priority Critical patent/JP6694057B2/en
Publication of WO2017170957A1 publication Critical patent/WO2017170957A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives

Definitions

  • the present invention relates to, for example, a composition.
  • room-temperature fast-curing adhesive composition is used as an adhesive that bonds at room temperature in a short time.
  • room-temperature fast-curing adhesive compositions include two-part fast-curing epoxy adhesive compositions, anaerobic adhesive compositions, instantaneous adhesive compositions, and second-generation acrylic adhesive compositions (SGA). )It has been known.
  • the two-part type fast-curing epoxy adhesive is one in which a main agent and a curing agent are measured, mixed, applied to an adherend, and cured by a reaction between the main agent and the curing agent.
  • the two-part type fast-curing epoxy adhesive is required to have higher peel strength and impact strength.
  • the anaerobic adhesive is cured by pressure-bonding the adhesive composition between adherends to block air.
  • the anaerobic adhesive composition is required to have a property of curing even if the part of the adhesive composition comes out of the adherend when it is pressure-bonded, even if the part of the adhesive composition comes into contact with air. .
  • a property of curing even when the clearance between adherends is large is required.
  • SGA is a two-component (meth) acrylic adhesive, but it does not require accurate metering of the two components, and even if metering or mixing is incomplete, it can be done for several minutes to several tens of minutes at room temperature just by contacting the two components. Excellent workability due to curing. Furthermore, since the peel strength and impact strength are high and the hardened portion is well cured, it is widely used from the electrical / electronic parts field to the civil engineering / architecture field and the transportation vehicle field.
  • a steel plate or an aluminum alloy is often subjected to a baking coating treatment.
  • the steel plate In this baking coating processing step, the steel plate is exposed to a high temperature of, for example, 220 ° C. for one hour. Therefore, the adhesion of the transportation vehicle parts that pass through the baking coating treatment process must have heat resistance that can withstand the treatment at such a high temperature.
  • SGA retains its adhesiveness even after high-temperature baking treatment when it is bonded to a steel sheet, but if it is bonded to an adherend with a high coefficient of thermal expansion such as an aluminum alloy, the adhesive strength may be reduced. Was demanded.
  • Patent Documents 1 to 4 are disclosed.
  • Patent Document 1 discloses that the elastomer (A) is 1 to 30% by mass, the hydroxyl group-containing acrylic acid derivative (B) is 40 to 99% by mass, and a (meth) acrylic polymerizable monomer (C) other than the above (B). Describes an adhesive composition containing 0 to 59% by mass of a polymerization initiator (D) and a reducing agent (E). However, the structure (1-3) of the present invention is not described. Patent Document 1 has no report on the effect of improving heat resistance.
  • Patent Document 2 contains resin fine particles (a) having a core-shell structure and a photocurable resin (b), has a viscosity at 25 ° C. of 100 Pa ⁇ s or less as measured using an E-type viscometer, and has a viscosity after prebaking. Describes a liquid crystal sealant having a viscosity of 100 Pa ⁇ s to 400 Pa ⁇ s. However, the structure (1-3) of the present invention is not described. In Patent Document 2, although heat treatment is performed at 90 to 130 ° C. for thickening and curing the adhesive composition, there is no report on heat resistance under high-temperature baking conditions such as 220 ° C. as in the present invention. .
  • Patent Document 3 has a static viscosity at 20 rpm of 110,000 mPa or less, a thixotropic coefficient obtained by dividing the static viscosity at 2 rpm by the static viscosity at 20 rpm is 1.7 or more, and (1) a polymerizable vinyl monomer is The curable resin composition containing is described. However, there is no description about (2-1) of the present invention.
  • Patent Document 4 is an acrylic adhesive composition comprising (1) a (meth) acrylic acid derivative monomer, (2) a polymerization initiator, (3) a reducing agent, and (4) a diene core-shell polymer.
  • the diene-based core-shell polymer is swellable in the (meth) acrylic acid derivative monomer, and the swelling degree in toluene at 25 ° C. is 9.5 or more.
  • An acrylic adhesive composition is described. However, there is no description about (2-1) of the present invention.
  • an object of the present invention is to provide a composition having heat resistance, for example.
  • the present invention is as follows.
  • composition according to ⁇ 1> wherein in the component (2-1), the core portion is a silicone / acrylic composite rubber and the shell portion is a vinyl polymer.
  • ⁇ 8> In 100 parts by mass of component (1), 10 to 85 parts by mass of component (1-1), 5 to 60 parts by mass of component (1-2), and 1 to 60 parts by mass of component (1-3) ⁇ 1> to ⁇ 7>.
  • composition according to ⁇ 1> to ⁇ 8> which contains an acidic phosphoric acid compound.
  • composition described in ⁇ 1> to ⁇ 10> is divided into a first agent and a second agent, the first agent contains at least (3) a polymerization initiator, and the second agent is at least (4) A two-pack composition containing a reducing agent.
  • the present invention has, for example, heat resistance.
  • (Meth) acrylate refers to, for example, a monomer having a (meth) acryloyl group.
  • Monofunctional (meth) acrylate refers to a monomer having one (meth) acryloyl group.
  • the polyfunctional (meth) acrylate refers to a monomer having two or more (meth) acryloyl groups.
  • the amount used is preferably the amount used relative to the total of the first agent and the second agent.
  • the total content of (1) (meth) acrylate and (2) elastomer is preferably 70 parts by mass or more, preferably 85 parts by mass or more, and 90 parts by mass or more in 100 parts by mass of the composition. Most preferably.
  • (1) (Meth) acrylate includes (1-1) monofunctional (meth) acrylate having an aromatic group, (1-2) monofunctional (meth) acrylate having a hydroxyl group, and (1-3) general formula ( The polyfunctional (meth) acrylate represented by A) is preferably contained.
  • the (1) (meth) acrylate may or may not contain (meth) acrylates other than the above (1-1), (1-2), and (1-3).
  • the monofunctional (meth) acrylate having an aromatic group makes the adhesive composition rigid and improves the solubility of the elastomer component.
  • (1-1) preferably excludes (1-2).
  • (1-1) is by definition different from polyfunctional (1-3).
  • (1-1) preferably has no hydroxyl group.
  • Examples of such a monomer include (meth) acrylate of formula (B), phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. In these, the (meth) acrylate of a formula (B) is preferable.
  • (meth) acrylate of the formula (B) benzyl (meth) acrylate, methylbenzyl (meth) acrylate, ethylbenzyl (meth) acrylate, propylbenzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) ) Acrylate and the like.
  • benzyl (meth) acrylate is preferred.
  • the amount of (1-1) used 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 in the total 100 parts by mass of (1).
  • the solubility of the elastomer component is improved, and workability and applicability are improved. If it is 85 parts by mass or less, the peel strength is improved.
  • a monofunctional (meth) acrylate having a hydroxyl group improves, for example, adhesion to an adherend.
  • (1-2) preferably excludes (1-1).
  • (1-2) is by definition different from polyfunctional (1-3).
  • (1-2) preferably has no aromatic ring.
  • Such monomers include hydroxyalkyl (meth) acrylate, glycerol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 4-hydroxycyclohexyl ( And meth) acrylate and 1,4-butanediol mono (meth) acrylate. Of these, hydroxyalkyl (meth) acrylate is preferred.
  • (meth) acrylates of formula (D) are preferred.
  • Formula (D) Z—O— (R 7 O) q —H (In the formula (D), Z represents a (meth) acryloyl group.
  • R 7 represents an alkylene group.
  • Q represents an integer of 1 to 10.
  • the alkylene group is preferably an alkylene group having 2 to 6 carbon atoms. 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 members selected from the group consisting of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable, and 2-hydroxypropyl (meth) acrylate is most preferable.
  • the amount of (1-2) 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 in 100 parts by mass of (1). If it is 5 parts by mass or more, the adhesion is improved. When it is 60 parts by mass or less, the solubility of the elastomer component is improved, workability and applicability are improved, and heat resistance is improved.
  • the monomer of the general formula (A) has the following structure.
  • a monomer represented by formula (A) has the following structure.
  • R 1 and R 1 ′ are preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an ethylene group having 2 carbon atoms.
  • R 2 and R 2 ′ are preferably a methyl group.
  • p and p ′ are preferably 0 to 8, more preferably 3 to 8, and most preferably 5.
  • Examples of such a monomer include 2,2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) Examples include propane and 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane. Of these, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane is preferred.
  • the amount of (1-3) used 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 in the total 100 parts by mass of (1). When it is 1 part by mass or more, the heat resistance is improved. When it is 60 parts by mass or less, the solubility of the elastomer component is improved, and workability and applicability are improved.
  • the elastomer contains, for example, (2-1) a silicone-modified acrylic core-shell (co) polymer.
  • the silicone-modified acrylic core-shell (co) polymer refers to a core-shell type elastomer having silicone-acrylic rubber.
  • Co polymer means a polymer and a copolymer.
  • the core-shell type for example, the core means the nucleus, the shell means the shell, and the material of the nucleus and the shell is different for one particle.
  • silicone / acrylic rubber is preferably the core part.
  • the silicone / acrylic rubber is preferably a silicone / acrylic composite rubber in which an alkyl (meth) acrylate rubber polymer is combined with a silicone rubber polymer in terms of mechanical properties.
  • the complexing can be carried out, for example, by adding an alkyl (meth) acrylate component to a polyorganosiloxane latex and polymerizing in the presence of a radical polymerization initiator.
  • the silicone-acrylic composite rubber refers to a rubber having a structure in which, for example, polyorganosiloxane and polyalkyl (meth) acrylate are intertwined so that they cannot be separated from each other.
  • the shell portion examples include homopolymers and copolymers. Of these, homopolymers are preferred.
  • the homopolymer is preferably a vinyl polymer such as polystyrene, (meth) acrylonitrile, (meth) acrylic acid alkyl ester and the like.
  • vinyl polymers (meth) acrylic acid alkyl ester polymers are preferred.
  • alkyl (meth) acrylates methyl (meth) acrylate is preferred.
  • Copolymers include styrene- (meth) acrylonitrile copolymer, styrene- (meth) methacrylic acid alkyl ester copolymer, acrylic acid-methacrylic acid copolymer, styrene- (meth) acrylonitrile- (meth) acrylic acid alkyl ester.
  • a copolymer etc. are mentioned.
  • styrene- (meth) acrylonitrile copolymers are preferred.
  • a shell part is obtained as follows, for example.
  • a vinyl monomer is added and polymerization is carried out to obtain a graft copolymer latex.
  • the obtained graft copolymer latex is coagulated and solidified to obtain a shell portion, which becomes a core-shell (co) polymer.
  • the silicone-modified acrylic core-shell polymer is preferably used in an amount of 5 to 40 parts by mass, more preferably 15 to 30 parts by mass with respect to 100 parts by mass in total of (1) and (2). If it is 5 parts by mass or more, high-temperature bake heat resistance is sufficient. If it is 40 parts by mass or less, the viscosity will not be high, and there will be no inconvenience in work.
  • the elastomer preferably contains an elastomer other than (2-2) and (2-1).
  • (2-2) is preferably not a core-shell (co) polymer. Not being a core-shell (co) polymer means having no core-shell structure.
  • (2-2) is preferably an elastomer soluble in (meth) acrylate.
  • the (2) elastomer may contain an elastomer other than the above (2-1) and (2-2), but preferably does not contain it.
  • Examples of (2-2) include (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer, and (meth) acrylonitrile-butadiene.
  • Examples include styrene-based thermoplastic elastomers such as copolymers, styrene-butadiene copolymers, chlorosulfonated polyethylene, and styrene-polybutadiene-styrene synthetic rubbers, as well as (butadiene) -modified polybutadienes and urethane elastomers. .
  • (meth) acrylonitrile-butadiene-methyl (meth) acrylate and acrylonitrile-butadiene copolymer are preferable, and (meth) acrylonitrile-butadiene copolymer is preferable. Is more preferable.
  • the amount of (2-2) used is preferably 5 to 30 parts by mass, more preferably 8 to 15 parts by mass with respect to 100 parts by mass in total of (1) and (2). If it is 5 parts by mass or more, the peel strength at low temperatures is improved. When it is 30 parts by mass or less, the adhesion is improved, the viscosity is not increased, and the handling property is improved.
  • the polymerization initiator is preferably an organic peroxide.
  • organic peroxides include cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. Can be mentioned. Among these, cumene hydroperoxide is preferable from the viewpoint of stability.
  • the polymerization initiator is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight in total of (1) and (2). Most preferred is 8-5 parts by weight.
  • the curing speed is increased.
  • the storage stability is improved, and when it is 10 parts by mass or less, the storage stability is further improved.
  • the reducing agent may be any known reducing agent that reacts with the polymerization initiator to generate radicals.
  • Representative reducing agents include, for example, tertiary amines, thiourea derivatives and transition metal salts.
  • Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, and N, N-dimethylparatoluidine.
  • Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea.
  • Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. Among these, transition metal salts are preferable in terms of reactivity. Of the transition metal salts, vanadyl acetylacetonate is preferred.
  • the amount of the reducing agent used is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (1) and (2). When it is 0.05 parts by mass or more, the curing speed is increased. When it is 15 parts by mass or less, the storage stability is improved.
  • the present invention preferably contains (5) an acidic phosphoric acid compound.
  • (5) is preferably an acidic phosphoric acid compound represented by the general formula (C).
  • component (5) examples include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate and bis (2- (meth) acryloyloxyethyl) phosphate. (5) is preferably contained in the second agent.
  • the use amount of (5) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, with respect to 100 parts by mass of (1) and (2).
  • it is 0.05 parts by mass or more, the curing speed is increased and the adhesiveness is improved. Adhesiveness will improve if it is 10 mass parts or less.
  • the present invention preferably contains (6) paraffins.
  • (6) in the composition of the present invention speeds up the curing of the part in contact with air.
  • paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, spermaceti, ceresin and candelilla wax. Of these, paraffin is preferred.
  • the amount of (6) used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (1) and (2).
  • the amount is 0.1 parts by mass or more, the portion in contact with air is hardened.
  • it is 5 parts by mass or less, the adhesive strength is improved.
  • an antioxidant or the like can be used.
  • the present invention can be used as a curable resin composition.
  • the present invention can be used as an adhesive composition.
  • it is preferably used as a two-component adhesive composition.
  • all the essential components of the adhesive composition of the present invention are not mixed during storage, the adhesive composition is divided into a first agent and a second agent, and at least a polymerization initiator is added to the first agent.
  • the two-part type is preferable in that it has excellent storage stability. In this case, it can be used as a two-component adhesive composition by applying both agents simultaneously or separately to contact and cure.
  • the adherend is joined by the adhesive composition of the present invention to produce a joined body.
  • the various materials of the adherend are not limited, such as paper, wood, ceramic, glass, ceramics, rubber, plastic, mortar, concrete, and metal, but when the adherend is metal, it exhibits excellent adhesion.
  • Silicone / acrylic core shell rubber (shell: (meth) methyl acrylate polymer): Silicone-modified acrylic core-shell polymer silicone / acrylic core-shell rubber (shell: styrene acrylonitrile copolymer) whose core is silicone acrylic rubber and whose shell is methyl methacrylate polymer:
  • the core part is a silicone-acrylic rubber, and the shell part is a styrene-acrylonitrile copolymer silicone-modified acrylic core-shell polymer
  • NBR acrylonitrile-butadiene copolymer
  • MBS methyl methacrylate-butadiene-styrene copolymer
  • Paraffins Paraffinic acid phosphate compound: Phosphate ester, acid phosphooxyethyl methacrylate (Structural formula below) (CH 2 ⁇ C (CH 3 ) —COOC 2 H 4 O) n P (O) (OH) 3-n n is 1 or 2.
  • Epoxy acrylate Use PE210 (miwon). In the epoxy acrylate, R 1 and R ′ 1 in the general formula (A) do not correspond to (1-3) because they have OH groups, and are polyfunctional (1-1) and (1-2) Not applicable.
  • Test piece an aluminum alloy A5052 plate subjected to a 100 ⁇ 25 ⁇ 2.0 mm wiping treatment was used.
  • JISK-6850 1999 under an environment of a temperature of 23 ° C. and a humidity of 50%, an adhesive mixed with the first agent and the second agent is applied to one side of one test piece, and the test pieces are immediately overlapped with each other. Pasted together. After that, it was cured at room temperature for 24 hours, and this was used as a sample for measuring the tensile shear strength, and the tensile shear strength (unit: MPa) was measured to obtain the initial tensile shear strength.
  • the sample for measuring tensile shear strength was baked at 220 ° C. for 1 hour, cooled to a temperature of 23 ° C., measured for tensile shear strength (unit: MPa), and baked. Of tensile shear strength. All the measurements were performed at a tensile speed of 10 mm / min in an environment at a temperature of 23 ° C.
  • the workability of the two-part acrylic adhesive composition was determined as follows based on the value of 20 rotational viscosity as measured by a B-type viscometer. ⁇ : Workability is very good (viscosity less than 100,000 mPa ⁇ s). (Triangle
  • the unit of the amount used of each substance is shown in parts by mass.
  • Examples 1 to 6, Comparative Examples 1 to 4 Two-component acrylic adhesive compositions were prepared with the compositions of Examples and Comparative Examples shown in Table 1, and the initial and post-baking treatments were measured for tensile shear strength, peel strength, and workability.
  • a silicone-modified acrylic core-shell (co) polymer high adhesive strength was exhibited even after baking.
  • a silicone-modified acrylic core-shell polymer whose shell part is a methyl (meth) acrylate polymer high adhesive strength was exhibited even after baking.
  • MBS methyl methacrylate-butadiene-styrene copolymer
  • an acrylic core-shell polymer were applied, the tensile shear strength and peel strength after baking were low.
  • a butadiene-based core-shell polymer was applied, the core-shell rubber did not disperse well in the adhesive.
  • epoxy acrylate was used, the adhesive strength after baking treatment was low.
  • a two-component adhesive composition having heat resistance is obtained. Since the obtained two-component adhesive composition can withstand a high temperature baking process, the industrial advantage is great.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Graft Or Block Polymers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polymerisation Methods In General (AREA)

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

組成物Composition
本発明は、例えば、組成物に関する。 The present invention relates to, for example, a composition.
省力化、省資源及び省エネルギーの点で、常温下、短時間で接着する接着剤として、常温速硬化型接着剤組成物が使用されている。従来、常温速硬化型接着剤組成物としては、二剤型速硬化エポキシ系接着剤組成物、嫌気性接着剤組成物、瞬間接着剤組成物及び第二世代のアクリル系接着剤組成物（ＳＧＡ）が知られている。 From the viewpoint of labor saving, resource saving, and energy saving, a room-temperature fast-curing adhesive composition is used as an adhesive that bonds at room temperature in a short time. Conventionally, room-temperature fast-curing adhesive compositions include two-part fast-curing epoxy adhesive compositions, anaerobic adhesive compositions, instantaneous adhesive compositions, and second-generation acrylic adhesive compositions (SGA). )It has been known.
二剤型速硬化エポキシ系接着剤は、主剤と硬化剤を計量、混合して被着体に塗布し、主剤と硬化剤の反応により硬化するものである。しかしながら、二剤型速硬化エポキシ系接着剤はより高い剥離強度と衝撃強度が要求されている。 The two-part type fast-curing epoxy adhesive is one in which a main agent and a curing agent are measured, mixed, applied to an adherend, and cured by a reaction between the main agent and the curing agent. However, the two-part type fast-curing epoxy adhesive is required to have higher peel strength and impact strength.
嫌気性接着剤は、被着体間において接着剤組成物を圧着して空気を遮断することにより硬化するものである。しかしながら、嫌気性接着剤組成物は、圧着する際に接着剤組成物の一部が被着体からハミ出した場合、ハミ出した部分が空気に接触しても硬化する性質が要求されている。又、被着体間のクリアランスが大きい場合にも硬化する性質が要求されている。 The anaerobic adhesive is cured by pressure-bonding the adhesive composition between adherends to block air. However, the anaerobic adhesive composition is required to have a property of curing even if the part of the adhesive composition comes out of the adherend when it is pressure-bonded, even if the part of the adhesive composition comes into contact with air. . In addition, a property of curing even when the clearance between adherends is large is required.
瞬間接着剤は通常シアノアクリレートを主成分とし、作業性に優れている。しかしながら、より高い剥離強度や衝撃強度が要求されている。 Instant adhesives usually have cyanoacrylate as the main component and are excellent in workability. However, higher peel strength and impact strength are required.
ＳＧＡは二剤型（メタ）アクリル系接着剤であるが、二剤の正確な計量を必要とせず、計量や混合が不完全でも二剤の接触だけで、常温で数分～数十分で硬化するため作業性に優れる。更に、剥離強度や衝撃強度が高く、ハミ出し部分の硬化も良好であるために、電気・電子部品分野から土木・建築分野、輸送車両分野に至るまで幅広く用いられている。 SGA is a two-component (meth) acrylic adhesive, but it does not require accurate metering of the two components, and even if metering or mixing is incomplete, it can be done for several minutes to several tens of minutes at room temperature just by contacting the two components. Excellent workability due to curing. Furthermore, since the peel strength and impact strength are high and the hardened portion is well cured, it is widely used from the electrical / electronic parts field to the civil engineering / architecture field and the transportation vehicle field.
輸送車両分野では、鋼板やアルミ合金に対して焼付塗装処理を施すことが多いが、この焼付塗装処理工程では、例えば２２０℃で１時間といった高温に曝される。そのため、焼付塗装処理工程を通る輸送車両部品の接着では、このような高温下での処理に耐えうる耐熱性をもたなければならない。 In the transportation vehicle field, a steel plate or an aluminum alloy is often subjected to a baking coating treatment. In this baking coating processing step, the steel plate is exposed to a high temperature of, for example, 220 ° C. for one hour. Therefore, the adhesion of the transportation vehicle parts that pass through the baking coating treatment process must have heat resistance that can withstand the treatment at such a high temperature.
ＳＧＡは、鋼板に対する接着では、高温焼付処理後も接着性を保持するが、アルミ合金等熱膨張率の大きい被着体に対する接着では高温焼付処理をすると、接着強度が低下することがあり、改良が求められていた。 SGA retains its adhesiveness even after high-temperature baking treatment when it is bonded to a steel sheet, but if it is bonded to an adherend with a high coefficient of thermal expansion such as an aluminum alloy, the adhesive strength may be reduced. Was demanded.
特許文献１～４が開示されている。 Patent Documents 1 to 4 are disclosed.
特許文献１は、エラストマー（Ａ）が１～３０質量％、水酸基含有アクリル酸誘導体（Ｂ）が４０～９９質量％、前記（Ｂ）以外の（メタ）アクリル系重合性単量体（Ｃ）が０～５９質量％、重合開始剤（Ｄ）及び還元剤（Ｅ）を含む接着剤組成物を記載している。しかしながら、本発明の（１－３）の構造について記載がない。特許文献１は、耐熱性の向上効果については報告がない。 Patent Document 1 discloses that the elastomer (A) is 1 to 30% by mass, the hydroxyl group-containing acrylic acid derivative (B) is 40 to 99% by mass, and a (meth) acrylic polymerizable monomer (C) other than the above (B). Describes an adhesive composition containing 0 to 59% by mass of a polymerization initiator (D) and a reducing agent (E). However, the structure (1-3) of the present invention is not described. Patent Document 1 has no report on the effect of improving heat resistance.
特許文献２は、コアシェル構造を有する樹脂微粒子（ａ）及び光硬化樹脂（ｂ）を含有し、Ｅ型粘度計を用いて測定した２５℃における粘度が１００Ｐａ・ｓ以下であり、プリベイク後の粘度が１００Ｐａ・ｓ以上４００Ｐａ・ｓ以下である液晶シール剤を記載している。しかしながら、本発明の（１－３）の構造について記載がない。特許文献２は、接着剤組成物の増粘及び硬化のために９０～１３０℃で加熱処理を行っているが、本発明のような２２０℃といった高温焼付条件下での耐熱性に関する報告はない。 Patent Document 2 contains resin fine particles (a) having a core-shell structure and a photocurable resin (b), has a viscosity at 25 ° C. of 100 Pa · s or less as measured using an E-type viscometer, and has a viscosity after prebaking. Describes a liquid crystal sealant having a viscosity of 100 Pa · s to 400 Pa · s. However, the structure (1-3) of the present invention is not described. In Patent Document 2, although heat treatment is performed at 90 to 130 ° C. for thickening and curing the adhesive composition, there is no report on heat resistance under high-temperature baking conditions such as 220 ° C. as in the present invention. .
特許文献３は、２０ｒｐｍでの静止粘度が１１万ｍＰａ以下であり、２ｒｐｍでの静止粘度を２０ｒｐｍでの静止粘度で割ったチクソトロピー係数が１．７以上であり、（１）重合性ビニルモノマーを含有してなる硬化性樹脂組成物を記載している。しかしながら、本発明の（２－１）について記載がない。 Patent Document 3 has a static viscosity at 20 rpm of 110,000 mPa or less, a thixotropic coefficient obtained by dividing the static viscosity at 2 rpm by the static viscosity at 20 rpm is 1.7 or more, and (1) a polymerizable vinyl monomer is The curable resin composition containing is described. However, there is no description about (2-1) of the present invention.
特許文献４は、（１）（メタ）アクリル酸誘導体モノマー、（２）重合開始剤、（３）還元剤、（４）ジエン系コアシェル重合体を含有してなるアクリル系接着剤組成物であって、前記ジエン系コアシェル重合体が、前記（メタ）アクリル酸誘導体モノマーに膨潤可能であり、且つ２５℃でのトルエン中での膨潤度が９．５以上であることを特徴とする二剤型アクリル系接着剤組成物を記載している。しかしながら、本発明の（２－１）について記載がない。 Patent Document 4 is an acrylic adhesive composition comprising (1) a (meth) acrylic acid derivative monomer, (2) a polymerization initiator, (3) a reducing agent, and (4) a diene core-shell polymer. The diene-based core-shell polymer is swellable in the (meth) acrylic acid derivative monomer, and the swelling degree in toluene at 25 ° C. is 9.5 or more. An acrylic adhesive composition is described. However, there is no description about (2-1) of the present invention.
特開２０１５－３０７４８号公報Japanese Patent Laid-Open No. 2015-30748 特開２０１０－２７７０７２号公報JP 2010-277072 A 特開２００２－３０８９４４号公報JP 2002-308944 A 特開２００５－１７９５４８号公報JP 2005-179548 A
本発明は、前記従来技術の状況に鑑みて、例えば、耐熱性を有する組成物を提供することを目的とする。 In view of the state of the prior art, an object of the present invention is to provide a composition having heat resistance, for example.
即ち、本発明は下記の通りである。 That is, the present invention is as follows.
＜１＞（１）下記（１－１）、（１－２）、及び（１－３）を含有する（メタ）アクリレート、
（１－１）芳香族基を有する単官能（メタ）アクリレート、
（１－２）水酸基を有する単官能（メタ）アクリレート、
（１－３）一般式（Ａ）
Figure JPOXMLDOC01-appb-C000002
 で示される多官能（メタ）アクリレート、
（２）下記（２－１）を少なくとも含有するエラストマー、
（２－１）シリコーン変性アクリル系コアシェル（共）重合体を含有するエラストマーを含有するエラストマー、
（３）重合開始剤、並びに
（４）還元剤、
を含有する組成物。 <1> (1) (meth) acrylate containing the following (1-1), (1-2), and (1-3),
(1-1) a monofunctional (meth) acrylate having an aromatic group,
(1-2) monofunctional (meth) acrylate having a hydroxyl group,
(1-3) General formula (A)
Figure JPOXMLDOC01-appb-C000002
 A polyfunctional (meth) acrylate represented by
(2) an elastomer containing at least the following (2-1):
(2-1) an elastomer containing an elastomer containing a silicone-modified acrylic core-shell (co) polymer,
(3) a polymerization initiator, and (4) a reducing agent,
A composition containing
＜２＞成分（２－１）において、コア部分がシリコーン・アクリル複合ゴムであり、シェル部分がビニル系重合体である＜１＞記載の組成物。 <2> The composition according to <1>, wherein in the component (2-1), the core portion is a silicone / acrylic composite rubber and the shell portion is a vinyl polymer.
＜３＞成分（２－１）のシェル部分が（メタ）アクリル酸アルキルエステルである＜１＞又は＜２＞記載の組成物。 <3> The composition according to <1> or <2>, wherein the shell portion of the component (2-1) is a (meth) acrylic acid alkyl ester.
＜４＞成分（２－１）の使用量が、成分（１）及び成分（２）の合計１００質量部に対して、５～４０質量部である＜１＞～＜３＞記載の組成物。 <4> The composition according to <1> to <3>, wherein the amount of the component (2-1) used is 5 to 40 parts by mass with respect to a total of 100 parts by mass of the component (1) and the component (2). .
＜５＞更に、成分（２）が
（２－２）成分（２－１）以外のエラストマー
を含有する＜１＞～＜４＞のうちの１項記載の組成物。 <5> The composition according to any one of <1> to <4>, wherein the component (2) further contains an elastomer other than the component (2-2) (2-1).
＜６＞成分（２－２）がコアシェル（共）重合体でない＜５＞記載の組成物。 <6> The composition according to <5>, wherein the component (2-2) is not a core-shell (co) polymer.
＜７＞成分（２－２）の使用量が、成分（１）及び成分（２）の合計１００質量部に対して、５～３０質量部である＜５＞又は＜６＞記載の組成物。 <7> The composition according to <5> or <6>, wherein the amount of component (2-2) used is 5 to 30 parts by mass with respect to 100 parts by mass in total of component (1) and component (2) .
＜８＞成分（１）１００質量部中、成分（１－１）１０～８５質量部、成分（１－２）５～６０質量部、成分（１－３）１～６０質量部である＜１＞～＜７＞記載の組成物。 <8> In 100 parts by mass of component (1), 10 to 85 parts by mass of component (1-1), 5 to 60 parts by mass of component (1-2), and 1 to 60 parts by mass of component (1-3) < 1> to <7>.
＜９＞更に、
（５）酸性リン酸化合物
を含有する＜１＞～＜８＞記載の組成物。 <9> Furthermore,
(5) The composition according to <1> to <8>, which contains an acidic phosphoric acid compound.
＜１０＞更に、
（６）パラフィン類
を含有する＜１＞～＜９＞のうちの１項記載の組成物。 <10> Furthermore,
(6) The composition according to one of <1> to <9>, which contains paraffins.
＜１１＞＜１＞～＜１０＞記載の組成物を含有する硬化性樹脂組成物。 <11> A curable resin composition containing the composition according to <1> to <10>.
＜１２＞＜１＞～＜１０＞のうちの１項記載の組成物を含有する接着剤組成物。 <12> An adhesive composition containing the composition according to one of <1> to <10>.
＜１３＞＜１＞～＜１０＞記載のうちの組成物を第一剤と第二剤に分け、第一剤が少なくとも（３）重合開始剤を含有し、第二剤が少なくとも（４）還元剤を含有する二剤型の組成物。 <13> The composition described in <1> to <10> is divided into a first agent and a second agent, the first agent contains at least (3) a polymerization initiator, and the second agent is at least (4) A two-pack composition containing a reducing agent.
＜１４＞＜１２＞記載の接着剤組成物により接合する接合体。 <14> A joined body joined by the adhesive composition according to <12>.
本発明は、例えば、耐熱性を有する。 The present invention has, for example, heat resistance.
以下、本発明を詳細に説明する。
（１）（メタ）アクリレートとは、例えば、（メタ）アクリロイル基を有するモノマーをいう。単官能（メタ）アクリレートとは、（メタ）アクリロイル基を１個有するモノマーをいう。多官能（メタ）アクリレートとは、（メタ）アクリロイル基を２個以上有するモノマーをいう。使用量は特記しない限り、第一剤と第二剤の合計に対する使用量が好ましい。（１）（メタ）アクリレートと（２）エラストマーの合計の含有量は、組成物１００質量部中、７０質量部以上であることが好ましく、８５質量部以上であることが好ましく、９０質量部以上であることが最も好ましい。 Hereinafter, the present invention will be described in detail.
(1) (Meth) acrylate refers to, for example, a monomer having a (meth) acryloyl group. Monofunctional (meth) acrylate refers to a monomer having one (meth) acryloyl group. The polyfunctional (meth) acrylate refers to a monomer having two or more (meth) acryloyl groups. Unless otherwise specified, the amount used is preferably the amount used relative to the total of the first agent and the second agent. The total content of (1) (meth) acrylate and (2) elastomer is preferably 70 parts by mass or more, preferably 85 parts by mass or more, and 90 parts by mass or more in 100 parts by mass of the composition. Most preferably.
（１）（メタ）アクリレートは、（１－１）芳香族基を有する単官能（メタ）アクリレート、（１－２）水酸基を有する単官能（メタ）アクリレート、及び（１－３）一般式（Ａ）で示される多官能（メタ）アクリレートを含有することが好ましい。なお（１）（メタ）アクリレートは、上記（１－１）、（１－２）、及び（１－３）以外の（メタ）アクリレートを含んでもよいし、あるいは含んでいなくともよい。 (1) (Meth) acrylate includes (1-1) monofunctional (meth) acrylate having an aromatic group, (1-2) monofunctional (meth) acrylate having a hydroxyl group, and (1-3) general formula ( The polyfunctional (meth) acrylate represented by A) is preferably contained. The (1) (meth) acrylate may or may not contain (meth) acrylates other than the above (1-1), (1-2), and (1-3).
（１－１）芳香族基を有する単官能（メタ）アクリレートは、例えば、接着剤組成物を剛直にするほか、エラストマー成分の溶解性を向上させる。 (1-1) The monofunctional (meth) acrylate having an aromatic group, for example, makes the adhesive composition rigid and improves the solubility of the elastomer component.
（１－１）は、（１－２）を除くことが好ましい。（１－１）は、多官能である（１－３）とは定義上異なる。（１－１）は、水酸基も有しないことが好ましい。このような単量体としては、式（Ｂ）の（メタ）アクリレート、フェノキシジエチレングリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート等が挙げられる。これらの中では、式（Ｂ）の（メタ）アクリレートが好ましい。 (1-1) preferably excludes (1-2). (1-1) is by definition different from polyfunctional (1-3). (1-1) preferably has no hydroxyl group. Examples of such a monomer include (meth) acrylate of formula (B), phenoxydiethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. In these, the (meth) acrylate of a formula (B) is preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
式（Ｂ）の（メタ）アクリレートとしては、ベンジル（メタ）アクリレート、メチルベンジル（メタ）アクリレート、エチルベンジル（メタ）アクリレート、プロピルベンジル（メタ）アクリレート、メトキシベンジル（メタ）アクリレート、クロロベンジル（メタ）アクリレート等が挙げられる。式（Ｂ）の（メタ）アクリレートの中では、ベンジル（メタ）アクリレートが好ましい。 As the (meth) acrylate of the formula (B), benzyl (meth) acrylate, methylbenzyl (meth) acrylate, ethylbenzyl (meth) acrylate, propylbenzyl (meth) acrylate, methoxybenzyl (meth) acrylate, chlorobenzyl (meth) ) Acrylate and the like. Of the (meth) acrylates of formula (B), benzyl (meth) acrylate is preferred.
（１－１）の使用量は、（１）の合計１００質量部中、１０～８５質量部が好ましく、２０～７０質量部がより好ましく、３５～６５質量部が最も好ましい。１０質量部以上だとエラストマー成分の溶解性が向上し、作業性や塗布性が向上する。８５質量部以下だと剥離強度が向上する。 The amount of (1-1) used 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 in the total 100 parts by mass of (1). When it is 10 parts by mass or more, the solubility of the elastomer component is improved, and workability and applicability are improved. If it is 85 parts by mass or less, the peel strength is improved.
（１－２）水酸基を有する単官能（メタ）アクリレートは、例えば、被着体との密着性を向上させる。 (1-2) A monofunctional (meth) acrylate having a hydroxyl group improves, for example, adhesion to an adherend.
（１－２）は、（１－１）を除くことが好ましい。（１－２）は、多官能である（１－３）とは定義上異なるものである。（１－２）は、芳香環を有しないことが好ましい。このような単量体としては、ヒドロキシアルキル（メタ）アクリレート、グリセロールモノ（メタ）アクリレート、１，６－へキサンジオールモノ（メタ）アクリレート、ネオペンチルグリコールモノ（メタ）アクリレート、４－ヒドロキシシクロヘキシル（メタ）アクリレート、１，４－ブタンジオールモノ（メタ）アクリレート等が挙げられる。これらの中では、ヒドロキシアルキル（メタ）アクリレートが好ましい。 (1-2) preferably excludes (1-1). (1-2) is by definition different from polyfunctional (1-3). (1-2) preferably has no aromatic ring. Such monomers include hydroxyalkyl (meth) acrylate, glycerol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, 4-hydroxycyclohexyl ( And meth) acrylate and 1,4-butanediol mono (meth) acrylate. Of these, hydroxyalkyl (meth) acrylate is preferred.
ヒドロキシアルキル（メタ）アクリレートの中では、式（Ｄ）の（メタ）アクリレートが好ましい。
式（Ｄ）　Ｚ－Ｏ－（Ｒ7Ｏ）q－Ｈ
（式（Ｄ）中、Ｚは（メタ）アクリロイル基を示す。Ｒ7はアルキレン基を示す。ｑは１～１０の整数を示す。）
アルキレン基は、炭素数２～６個のアルキレン基が好ましい。ｑは１であることが好ましい。 Of the hydroxyalkyl (meth) acrylates, (meth) acrylates of formula (D) are preferred.
Formula (D) Z—O— (R 7 O) q —H
(In the formula (D), Z represents a (meth) acryloyl group. R 7 represents an alkylene group. Q represents an integer of 1 to 10.)
The alkylene group is preferably an alkylene group having 2 to 6 carbon atoms. q is preferably 1.
式（Ｄ）の（メタ）アクリレートとしては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート等が挙げられる。これらの中では、２－ヒドロキシエチル（メタ）アクリレートと２－ヒドロキシプロピル（メタ）アクリレートからなる群の１種以上が好ましく、２－ヒドロキシプロピル（メタ）アクリレートが最も好ましい。 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 members selected from the group consisting of 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable, and 2-hydroxypropyl (meth) acrylate is most preferable.
（１－２）の使用量は、（１）の合計１００質量部中、５～６０質量部が好ましく、１０～５０質量部がより好ましく、１５～４０質量部が最も好ましい。５質量部以上だと接着性が向上する。６０質量部以下だとエラストマー成分の溶解性が向上し、作業性や塗布性が向上し、耐熱性が向上する。 The amount of (1-2) 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 in 100 parts by mass of (1). If it is 5 parts by mass or more, the adhesion is improved. When it is 60 parts by mass or less, the solubility of the elastomer component is improved, workability and applicability are improved, and heat resistance is improved.
（１－３）一般式（Ａ）の単量体は以下の構造をいう。
一般式（Ａ）で示される単量体。 (1-3) The monomer of the general formula (A) has the following structure.
A monomer represented by formula (A).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Ｒ1、Ｒ1’は炭素数２～６個のアルキレン基が好ましく、炭素数２個のエチレン基がより好ましい。Ｒ2、Ｒ2’はメチル基が好ましい。ｐ、ｐ’は０～８が好ましく、３～８がより好ましく、５が最も好ましい。 R 1 and R 1 ′ are preferably an alkylene group having 2 to 6 carbon atoms, and more preferably an ethylene group having 2 carbon atoms. R 2 and R 2 ′ are preferably a methyl group. p and p ′ are preferably 0 to 8, more preferably 3 to 8, and most preferably 5.
このような単量体としては、例えば、２，２－ビス（４－（メタ）アクリロキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシジエトキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシプロポキシフェニル）プロパン、２，２－ビス（４－（メタ）アクリロキシテトラエトキシフェニル）プロパン及び２，２－ビス（４－（メタ）アクリロキシポリエトキシフェニル）プロパン等が挙げられる。これらの中では、２，２－ビス（４－（メタ）アクリロキシポリエトキシフェニル）プロパンが好ましい。 Examples of such a monomer include 2,2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2- Bis (4- (meth) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) Examples include propane and 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane. Of these, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane is preferred.
（１－３）の使用量は、（１）の合計１００質量部中、１～６０質量部が好ましく、１０～４５質量部がより好ましく、１５～３０質量部が最も好ましい。１質量部以上だと耐熱性が向上する。６０質量部以下だとエラストマー成分の溶解性が向上し、作業性や塗布性が向上する。 The amount of (1-3) used 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 in the total 100 parts by mass of (1). When it is 1 part by mass or more, the heat resistance is improved. When it is 60 parts by mass or less, the solubility of the elastomer component is improved, and workability and applicability are improved.
（２）エラストマーは、例えば、（２－１）シリコーン変性アクリル系コアシェル（共）重合体を含有する。 (2) The elastomer contains, for example, (2-1) a silicone-modified acrylic core-shell (co) polymer.
（２－１）シリコーン変性アクリル系コアシェル（共）重合体とは、シリコーン・アクリルゴムを有するコアシェル型のエラストマーをいう。（共）重合体とは、重合体及び共重合体をいう。コアシェル型においては、例えば、コアは核を、シェルは殻をそれぞれ意味し、一つの粒子で核と殻の素材が異なる。 (2-1) The silicone-modified acrylic core-shell (co) polymer refers to a core-shell type elastomer having silicone-acrylic rubber. (Co) polymer means a polymer and a copolymer. In the core-shell type, for example, the core means the nucleus, the shell means the shell, and the material of the nucleus and the shell is different for one particle.
コアシェル型のエラストマーとしては、シリコーン・アクリルゴムがコア部分であることが好ましい。 As the core-shell type elastomer, silicone / acrylic rubber is preferably the core part.
シリコーン・アクリルゴムとしては、機械的特性の点で、シリコーンゴム重合体に、アルキル（メタ）アクリレートゴム重合体を複合化したシリコーン・アクリル複合ゴムが好ましい。複合化は、例えば、ポリオルガノシロキサンのラテックス中に、アルキル（メタ）アクリレート成分を添加し、ラジカル重合開始剤の存在下で重合することにより実施できる。シリコーン・アクリル複合ゴムとは、例えば、ポリオルガノシロキサンとポリアルキル（メタ）アクリレートとが互いに分離できないように絡み合った構造を有するゴムをいう。 The silicone / acrylic rubber is preferably a silicone / acrylic composite rubber in which an alkyl (meth) acrylate rubber polymer is combined with a silicone rubber polymer in terms of mechanical properties. The complexing can be carried out, for example, by adding an alkyl (meth) acrylate component to a polyorganosiloxane latex and polymerizing in the presence of a radical polymerization initiator. The silicone-acrylic composite rubber refers to a rubber having a structure in which, for example, polyorganosiloxane and polyalkyl (meth) acrylate are intertwined so that they cannot be separated from each other.
シェル部分としては、ホモポリマーやコポリマー等が挙げられる。これらの中では、ホモポリマーが好ましい。ホモポリマーとしては、ポリスチレン、（メタ）アクリロニトリル、（メタ）アクリル酸アルキルエステル等のビニル系重合体が好ましい。ビニル系重合体の中では、（メタ）アクリル酸アルキルエステル重合体が好ましい。（メタ）アクリル酸アルキルエステルの中では、（メタ）アクリル酸メチルが好ましい。コポリマーとしては、スチレン－（メタ）アクリロニトリル共重合体、スチレン－（メタ）メタクリル酸アルキルエステル共重合体、アクリル酸－メタクリル酸共重合体、スチレン－（メタ）アクリロニトリル－（メタ）アクリル酸アルキルエステル共重合体等が挙げられる。コポリマーの中では、スチレン－（メタ）アクリロニトリル共重合体が好ましい。 Examples of the shell portion include homopolymers and copolymers. Of these, homopolymers are preferred. The homopolymer is preferably a vinyl polymer such as polystyrene, (meth) acrylonitrile, (meth) acrylic acid alkyl ester and the like. Among vinyl polymers, (meth) acrylic acid alkyl ester polymers are preferred. Among alkyl (meth) acrylates, methyl (meth) acrylate is preferred. Copolymers include styrene- (meth) acrylonitrile copolymer, styrene- (meth) methacrylic acid alkyl ester copolymer, acrylic acid-methacrylic acid copolymer, styrene- (meth) acrylonitrile- (meth) acrylic acid alkyl ester. A copolymer etc. are mentioned. Of the copolymers, styrene- (meth) acrylonitrile copolymers are preferred.
シェル部分は、例えば、以下のようにして得られる。コア部分であるゴムラテックスの存在下に、ビニル系単量体を添加して、重合を行い、グラフト共重合体のラテックスを得る。得られたグラフト共重合体ラテックスを、凝析し、固化することにより、シェル部分が得られ、コアシェル（共）重合体となる。 A shell part is obtained as follows, for example. In the presence of the rubber latex as the core portion, a vinyl monomer is added and polymerization is carried out to obtain a graft copolymer latex. The obtained graft copolymer latex is coagulated and solidified to obtain a shell portion, which becomes a core-shell (co) polymer.
（２－１）シリコーン変性アクリル系コアシェル重合体の使用量は、（１）及び（２）の合計１００質量部に対して、５～４０質量部が好ましく、１５～３０質量部がより好ましい。５質量部以上だと高温焼付耐熱性が十分になる。４０質量部以下だと粘度が高くならず、作業上不都合が生じない。 (2-1) The silicone-modified acrylic core-shell polymer is preferably used in an amount of 5 to 40 parts by mass, more preferably 15 to 30 parts by mass with respect to 100 parts by mass in total of (1) and (2). If it is 5 parts by mass or more, high-temperature bake heat resistance is sufficient. If it is 40 parts by mass or less, the viscosity will not be high, and there will be no inconvenience in work.
（２）エラストマーは、（２－２）（２－１）以外のエラストマーを含有することが好ましい。（２－２）は、コアシェル（共）重合体でないことが好ましい。コアシェル（共）重合体でないとは、コアシェル構造を有しないことをいう。（２－２）は、（メタ）アクリレートに可溶なエラストマーが好ましい。なお（２）エラストマーは、上記（２－１）及び（２－２）以外のエラストマーを含んでもよいが、含んでいないことが好ましい。 (2) The elastomer preferably contains an elastomer other than (2-2) and (2-1). (2-2) is preferably not a core-shell (co) polymer. Not being a core-shell (co) polymer means having no core-shell structure. (2-2) is preferably an elastomer soluble in (meth) acrylate. The (2) elastomer may contain an elastomer other than the above (2-1) and (2-2), but preferably does not contain it.
（２－２）としては、例えば、（メタ）アクリロニトリル－ブタジエン－（メタ）アクリル酸共重合体、（メタ）アクリロニトリル－ブタジエン－メチル（メタ）アクリレート共重合体、並びに、（メタ）アクリロニトリル－ブタジエン共重合体、スチレン－ブタジエン共重合体、クロロスルホン化ポリエチレン、スチレン－ポリブタジエン－スチレン系合成ゴムといったスチレン系熱可塑性エラストマー、並びに末端を（メタ）アクリル変性したポリブタジエンや、ウレタン系エラストマー等が挙げられる。 Examples of (2-2) include (meth) acrylonitrile-butadiene- (meth) acrylic acid copolymer, (meth) acrylonitrile-butadiene-methyl (meth) acrylate copolymer, and (meth) acrylonitrile-butadiene. Examples include styrene-based thermoplastic elastomers such as copolymers, styrene-butadiene copolymers, chlorosulfonated polyethylene, and styrene-polybutadiene-styrene synthetic rubbers, as well as (butadiene) -modified polybutadienes and urethane elastomers. .
これらの中では、溶解性及び接着性の点で、（メタ）アクリロニトリル－ブタジエン－メチル（メタ）アクリレート及びアクリロニトリル－ブタジエン共重合体からなる１種以上が好ましく、（メタ）アクリロニトリル－ブタジエン共重合体がより好ましい。 Among these, from the viewpoint of solubility and adhesiveness, one or more of (meth) acrylonitrile-butadiene-methyl (meth) acrylate and acrylonitrile-butadiene copolymer are preferable, and (meth) acrylonitrile-butadiene copolymer is preferable. Is more preferable.
（２－２）の使用量は、（１）及び（２）の合計１００質量部に対して、５～３０質量部が好ましく、８～１５質量部がより好ましい。５質量部以上だと低温下での剥離強度が向上する。３０質量部以下だと接着性が向上し、粘度が上昇せず、ハンドリング性が良くなる。 The amount of (2-2) used is preferably 5 to 30 parts by mass, more preferably 8 to 15 parts by mass with respect to 100 parts by mass in total of (1) and (2). If it is 5 parts by mass or more, the peel strength at low temperatures is improved. When it is 30 parts by mass or less, the adhesion is improved, the viscosity is not increased, and the handling property is improved.
（３）重合開始剤としては、有機過酸化物が好ましい。有機過酸化物としては、例えば、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、ターシャリーブチルハイドロパーオキサイド、ジイソプロピルベンゼンジハイドロパーオキサイド、メチルエチルケトンパーオキサイド、ベンゾイルパーオキサイド及びターシャリーブチルパーオキシベンゾエート等が挙げられる。これらの中では、安定性の点で、クメンハイドロパーオキサイドが好ましい。 (3) The polymerization initiator is preferably an organic peroxide. Examples of organic peroxides include cumene hydroperoxide, paramentane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. Can be mentioned. Among these, cumene hydroperoxide is preferable from the viewpoint of stability.
（３）重合開始剤の使用量は、（１）及び（２）の合計１００質量部に対して、０．１～２０質量部が好ましく、０．５～１０質量部がより好ましく、０．８～５質量部が最も好ましい。０．５質量部以上だと硬化速度が早くなる。２０質量部以下だと貯蔵安定性が良くなり、１０質量部以下であるとさらに一層貯蔵安定性が良くなる。 (3) The polymerization initiator is preferably used in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight in total of (1) and (2). Most preferred is 8-5 parts by weight. When it is 0.5 parts by mass or more, the curing speed is increased. When it is 20 parts by mass or less, the storage stability is improved, and when it is 10 parts by mass or less, the storage stability is further improved.
（４）還元剤は、前記重合開始剤と反応し、ラジカルを発生する公知の還元剤であれば使用できる。代表的な還元剤としては例えば、第３級アミン、チオ尿素誘導体及び遷移金属塩等が挙げられる。 (4) The reducing agent may be any known reducing agent that reacts with the polymerization initiator to generate radicals. Representative reducing agents include, for example, tertiary amines, thiourea derivatives and transition metal salts.
第３級アミンとしては、トリエチルアミン、トリプロピルアミン、トリブチルアミン及びＮ，Ｎ－ジメチルパラトルイジン等が挙げられる。チオ尿素誘導体としては、２－メルカプトベンズイミダゾール、メチルチオ尿素、ジブチルチオ尿素、テトラメチルチオ尿素及びエチレンチオ尿素等が挙げられる。遷移金属塩としては、ナフテン酸コバルト、ナフテン酸銅及びバナジルアセチルアセトネート等が挙げられる。これらの中では、反応性の点で、遷移金属塩が好ましい。遷移金属塩の中では、バナジルアセチルアセトネートが好ましい。 Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, and N, N-dimethylparatoluidine. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. Among these, transition metal salts are preferable in terms of reactivity. Of the transition metal salts, vanadyl acetylacetonate is preferred.
（４）還元剤の使用量は（１）及び（２）の合計１００質量部に対して、０．０５～１５質量部が好ましく、０．１～５質量部がより好ましい。０．０５質量部以上だと硬化速度が早くなる。１５質量部以下だと貯蔵安定性が良くなる。 (4) The amount of the reducing agent used is preferably 0.05 to 15 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (1) and (2). When it is 0.05 parts by mass or more, the curing speed is increased. When it is 15 parts by mass or less, the storage stability is improved.
本発明は、（５）酸性リン酸化合物を含有することが好ましい。（５）としては、一般式（Ｃ）で示される酸性リン酸化合物が好ましい。 The present invention preferably contains (5) an acidic phosphoric acid compound. (5) is preferably an acidic phosphoric acid compound represented by the general formula (C).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（５）の成分としては例えば、アシッドホスホオキシエチル（メタ）アクリレート、アシッドホスホオキシプロピル（メタ）アクリレート及びビス（２－（メタ）アクリロイルオキシエチル）フォスフェート等が挙げられる。（５）は、第二剤に含有することが好ましい。 Examples of the component (5) include acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate and bis (2- (meth) acryloyloxyethyl) phosphate. (5) is preferably contained in the second agent.
（５）の使用量は、（１）及び（２）の合計１００質量に対して、０．０５～１０質量部が好ましく、０．１～７質量部がより好ましい。０．０５質量部以上だと硬化速度が早くなり、接着性が向上する。１０質量部以下だと接着性が向上する。 The use amount of (5) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, with respect to 100 parts by mass of (1) and (2). When it is 0.05 parts by mass or more, the curing speed is increased and the adhesiveness is improved. Adhesiveness will improve if it is 10 mass parts or less.
本発明は、（６）パラフィン類を含有することが好ましい。（６）は、本発明の組成物において、空気に接している部分の硬化を迅速にする。パラフィン類としては例えば、パラフィン、マイクロクリスタリンワックス、カルナバろう、蜜ろう、ラノリン、鯨ろう、セレシン及びカンデリラろう等が挙げられる。これらの中では、パラフィンが好ましい。 The present invention preferably contains (6) paraffins. (6) in the composition of the present invention speeds up the curing of the part in contact with air. Examples of paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, spermaceti, ceresin and candelilla wax. Of these, paraffin is preferred.
（６）の使用量は、（１）及び（２）の合計１００質量部に対して、０．１～５質量部が好ましい。０．１質量部以上だと空気に接している部分の硬化が良くなる。５質量部以下だと接着強度が向上する。 The amount of (6) used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass in total of (1) and (2). When the amount is 0.1 parts by mass or more, the portion in contact with air is hardened. When it is 5 parts by mass or less, the adhesive strength is improved.
更に、酸化防止剤等を使用することができる。 Further, an antioxidant or the like can be used.
本発明は、硬化性樹脂組成物として使用できる。本発明は、接着剤組成物として使用できる。本発明の実施態様として、二剤型の接着剤組成物として使用することが好ましい。二剤型については、本発明の接着剤組成物の必須成分全てを貯蔵中は混合せず、接着剤組成物を第一剤及び第二剤に分け、第一剤に少なくとも重合開始剤を、第二剤に少なくとも還元剤を別々に貯蔵する。二剤型は貯蔵安定性に優れる点で好ましい。この場合、両剤を同時に又は別々に塗布して接触、硬化することにより、二剤型の接着剤組成物として使用できる。 The present invention can be used as a curable resin composition. The present invention can be used as an adhesive composition. As an embodiment of the present invention, it is preferably used as a two-component adhesive composition. For the two-component type, all the essential components of the adhesive composition of the present invention are not mixed during storage, the adhesive composition is divided into a first agent and a second agent, and at least a polymerization initiator is added to the first agent. Store at least the reducing agent in the second agent separately. The two-part type is preferable in that it has excellent storage stability. In this case, it can be used as a two-component adhesive composition by applying both agents simultaneously or separately to contact and cure.
本発明の接着剤組成物により被着体を接合して接合体を作製する。被着体の各種材料については、紙、木材、セラミック、ガラス、陶磁器、ゴム、プラスチック、モルタル、コンクリート及び金属等制限はないが、被着体が金属等の場合、優れた接着性を示す。 The adherend is joined by the adhesive composition of the present invention to produce a joined body. The various materials of the adherend are not limited, such as paper, wood, ceramic, glass, ceramics, rubber, plastic, mortar, concrete, and metal, but when the adherend is metal, it exhibits excellent adhesion.
以下実験例により本発明を更に詳細に説明する。なお、各物質の使用量の単位は質量部で示す。 Hereinafter, the present invention will be described in more detail with reference to experimental examples. In addition, the unit of the usage-amount of each substance is shown by a mass part.
各物質として下記市販品を使用した。
シリコーン／アクリルコアシェルゴム（シェル：（メタ）アクリル酸メチルポリマー）：
コア部分はシリコーン・アクリルゴムであり、シェル部分はメタクリル酸メチルポリマーであるシリコーン変性アクリル系コアシェル重合体
シリコーン／アクリルコアシェルゴム（シェル：スチレンアクリロニトリル共重合体）：
コア部分はシリコーン・アクリルゴムであり、シェル部分はスチレン－アクリロニトリル共重合体であるシリコーン変性アクリル系コアシェル重合体
ＮＢＲ：アクリロニトリル－ブタジエン共重合体
ＭＢＳ：メタクリル酸メチルーブタジエンースチレン共重合体であるコアシェル重合体
ブタジエン系コアシェル重合体：ブタジエン系のコアシェル重合体
アクリル系コアシェル重合体：アクリル系のコアシェル重合体
２，２－ビス（４－メタクリロキシポリエトキシフェニル）プロパン：式（Ａ）において、ｐ＝ｐ’＝５のものを用いた。
パラフィン類：パラフィン
酸性リン酸化合物：リン酸エステル、アシッドホスホキシエチルメタクリレート（構造式は以下）
（ＣＨ2＝Ｃ（ＣＨ3）－ＣＯＯＣ2Ｈ4Ｏ）nＰ（Ｏ）（ＯＨ）3-n
ｎは１または２である。
エポキシアクリレート：ＰＥ２１０（ｍｉｗｏｎ社）を使用。エポキシアクリレートは、一般式（Ａ）のＲ1、Ｒ’1がＯＨ基を有するので、（１－３）に該当せず、かつ多官能であるので（１－１）及び（１－２）にも該当しない。 The following commercial products were used as each substance.
Silicone / acrylic core shell rubber (shell: (meth) methyl acrylate polymer):
Silicone-modified acrylic core-shell polymer silicone / acrylic core-shell rubber (shell: styrene acrylonitrile copolymer) whose core is silicone acrylic rubber and whose shell is methyl methacrylate polymer:
The core part is a silicone-acrylic rubber, and the shell part is a styrene-acrylonitrile copolymer silicone-modified acrylic core-shell polymer NBR: acrylonitrile-butadiene copolymer MBS: methyl methacrylate-butadiene-styrene copolymer Core-shell polymer Butadiene-based core-shell polymer: Butadiene-based core-shell polymer Acrylic core-shell polymer: Acrylic-based core-shell polymer 2,2-bis (4-methacryloxypolyethoxyphenyl) propane: In the formula (A), p = P '= 5 was used.
Paraffins: Paraffinic acid phosphate compound: Phosphate ester, acid phosphooxyethyl methacrylate (Structural formula below)
(CH 2 ═C (CH 3 ) —COOC 2 H 4 O) n P (O) (OH) 3-n
n is 1 or 2.
Epoxy acrylate: Use PE210 (miwon). In the epoxy acrylate, R 1 and R ′ 1 in the general formula (A) do not correspond to (1-3) because they have OH groups, and are polyfunctional (1-1) and (1-2) Not applicable.
各種物性については、次のようにして測定した。 Various physical properties were measured as follows.
〔引張剪断強度（引張剪断接着強さ）〕
試験片として１００×２５×２．０ｍｍのウエス拭き処理したアルミ合金Ａ５０５２板を用いた。温度２３℃、湿度５０％の環境下でＪＩＳＫ－６８５０：１９９９に従い、一枚の試験片の片面に第一剤と第二剤を混合した接着剤を塗布し、直ちに試験片同士を重ね合わせて貼り合わせた。こののち、室温で２４時間養生し、これを引張剪断強度測定用試料とし、引張剪断強度（単位：ＭＰａ）の測定を行い、初期の引張剪断強度とした。耐熱性の確認として、前記の引張剪断強度測定用試料に対して２２０℃で１時間焼付処理を施し、温度２３℃まで冷却し、引張剪断強度（単位：ＭＰａ）の測定を行い、焼付処理後の引張剪断強度とした。測定は何れも、温度２３℃の環境下、引張速度１０ｍｍ／分で行った。 [Tensile shear strength (tensile shear bond strength)]
As a test piece, an aluminum alloy A5052 plate subjected to a 100 × 25 × 2.0 mm wiping treatment was used. In accordance with JISK-6850: 1999 under an environment of a temperature of 23 ° C. and a humidity of 50%, an adhesive mixed with the first agent and the second agent is applied to one side of one test piece, and the test pieces are immediately overlapped with each other. Pasted together. After that, it was cured at room temperature for 24 hours, and this was used as a sample for measuring the tensile shear strength, and the tensile shear strength (unit: MPa) was measured to obtain the initial tensile shear strength. As confirmation of heat resistance, the sample for measuring tensile shear strength was baked at 220 ° C. for 1 hour, cooled to a temperature of 23 ° C., measured for tensile shear strength (unit: MPa), and baked. Of tensile shear strength. All the measurements were performed at a tensile speed of 10 mm / min in an environment at a temperature of 23 ° C.
〔剥離強度（剥離接着強さ）〕
試験片として２００×２５×１ｍｍのウエス拭き処理したＡ５０５２板を用いた。温度２３℃、湿度５０％の環境下でＪＩＳＫ－６８５４－３：１９９９に従い、一枚の試験片の片面に第一剤と第二剤を混合した接着剤を塗布し、直ちに試験片同士を重ね合わせて貼り合わせた。こののち、室温で２４時間養生し、これを剥離強度測定用試料とし、剥離強度（単位：ｋＮ／ｍ）の測定を行い、初期の剥離強度とした。耐熱性の確認として、前記の剥離強度測定用試料に対して２２０℃で１時間焼付処理を施し、温度２３℃まで冷却し、剥離強度（単位：ｋＮ／ｍ）の測定を行い、焼付処理後の剥離強度とした。測定は何れも、温度２３℃の環境下、引張速度５０ｍｍ／分で行った。 [Peel strength (peel strength)]
As a test piece, an A5052 plate subjected to 200 × 25 × 1 mm wiping treatment was used. In accordance with JISK-6854-3: 1999 under an environment of a temperature of 23 ° C. and a humidity of 50%, an adhesive mixed with the first agent and the second agent is applied to one side of one test piece, and the test pieces are immediately overlapped. I stuck together. Thereafter, the film was cured at room temperature for 24 hours, and this was used as a peel strength measurement sample, and the peel strength (unit: kN / m) was measured to obtain the initial peel strength. For confirmation of heat resistance, the sample for peel strength measurement was subjected to baking treatment at 220 ° C. for 1 hour, cooled to a temperature of 23 ° C., measured for peel strength (unit: kN / m), and after baking treatment The peel strength was determined. All the measurements were performed at a tensile speed of 50 mm / min in an environment at a temperature of 23 ° C.
〔作業性〕
二剤型アクリル系接着剤組成物の作業性は、Ｂ型粘度計による測定で２０回転粘度の値により次のように判定した。
○：作業性が大変よい（粘度１０００００ｍＰａ・ｓ未満）。
△：作業性がよい（粘度１０００００ｍＰａ・ｓ以上２０００００ｍＰａ・ｓ未満）。
以下実験例により本発明を更に詳細に説明する。各物質の使用量の単位は質量部で示す。 〔Workability〕
The workability of the two-part acrylic adhesive composition was determined as follows based on the value of 20 rotational viscosity as measured by a B-type viscometer.
○: Workability is very good (viscosity less than 100,000 mPa · s).
(Triangle | delta): Workability | operativity is good (viscosity 100000 mPa * s or more and less than 200000 mPa * s).
Hereinafter, the present invention will be described in more detail with reference to experimental examples. The unit of the amount used of each substance is shown in parts by mass.
（実施例１～６、比較例１～４）
表１に示す実施例や比較例の組成にて二剤型アクリル系接着剤組成物を作製し、初期と焼付処理後の引張剪断強度測定と剥離強度測定と作業性測定を行った。シリコーン変性アクリル系コアシェル（共）重合体を使用することにより、焼付処理後も高い接着強度を示した。シェル部分が（メタ）アクリル酸メチルポリマーであるシリコーン変性アクリル系コアシェル重合体を使用することにより、特に焼付処理後も高い接着強度を示した。メタクリル酸メチルーブタジエンースチレン共重合体（ＭＢＳ）とアクリル系のコアシェル重合体を適用した場合は、焼付処理後の引張剪断強度及び剥離強度は低かった。ブタジエン系のコアシェル重合体を適用した場合は、コアシェルゴムが接着剤中でうまく分散しなかった。エポキシアクリレートを使用した場合は、焼付処理後の接着強度が低かった。 (Examples 1 to 6, Comparative Examples 1 to 4)
Two-component acrylic adhesive compositions were prepared with the compositions of Examples and Comparative Examples shown in Table 1, and the initial and post-baking treatments were measured for tensile shear strength, peel strength, and workability. By using a silicone-modified acrylic core-shell (co) polymer, high adhesive strength was exhibited even after baking. By using a silicone-modified acrylic core-shell polymer whose shell part is a methyl (meth) acrylate polymer, high adhesive strength was exhibited even after baking. When a methyl methacrylate-butadiene-styrene copolymer (MBS) and an acrylic core-shell polymer were applied, the tensile shear strength and peel strength after baking were low. When a butadiene-based core-shell polymer was applied, the core-shell rubber did not disperse well in the adhesive. When epoxy acrylate was used, the adhesive strength after baking treatment was low.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
本発明により、例えば、耐熱性を有する二剤型接着剤組成物が得られる。得られた二剤型接着剤組成物は高温の焼付処理工程に耐えることができるので、産業上の有益性は大きい。 According to the present invention, for example, a two-component adhesive composition having heat resistance is obtained. Since the obtained two-component adhesive composition can withstand a high temperature baking process, the industrial advantage is great.

Claims (14)

  1. （１）下記（１－１）、（１－２）、及び（１－３）を含有する（メタ）アクリレート、
    （１－１）芳香族基を有する単官能（メタ）アクリレート、
    （１－２）水酸基を有する単官能（メタ）アクリレート、
    （１－３）一般式（Ａ）
    Figure JPOXMLDOC01-appb-C000001
     で示される多官能（メタ）アクリレート、
    （２）下記（２－１）を少なくとも含有するエラストマー、
    （２－１）シリコーン変性アクリル系コアシェル（共）重合体を含有するエラストマー、
    （３）重合開始剤、並びに
    （４）還元剤、
    を含有する組成物。     (1) a (meth) acrylate containing the following (1-1), (1-2), and (1-3),
    (1-1) a monofunctional (meth) acrylate having an aromatic group,
    (1-2) monofunctional (meth) acrylate having a hydroxyl group,
    (1-3) General formula (A)
    Figure JPOXMLDOC01-appb-C000001
     A polyfunctional (meth) acrylate represented by
    (2) an elastomer containing at least the following (2-1):
    (2-1) an elastomer containing a silicone-modified acrylic core-shell (co) polymer,
    (3) a polymerization initiator, and (4) a reducing agent,
    A composition containing
  2. 成分（２－１）において、コア部分がシリコーン・アクリル複合ゴムであり、シェル部分がビニル系重合体である請求項１記載の組成物。 2. The composition according to claim 1, wherein in component (2-1), the core portion is a silicone / acrylic composite rubber and the shell portion is a vinyl polymer.
  3. 成分（２－１）のシェル部分が（メタ）アクリル酸アルキルエステルである請求項１又は２記載の組成物。 The composition according to claim 1 or 2, wherein the shell portion of the component (2-1) is a (meth) acrylic acid alkyl ester.
  4. 成分（２－１）の使用量が、成分（１）及び成分（２）の合計１００質量部に対して、５～４０質量部である請求項１～３のうちの１項記載の組成物。 The composition according to any one of claims 1 to 3, wherein the amount of component (2-1) used is 5 to 40 parts by mass with respect to 100 parts by mass as a total of component (1) and component (2). .
  5. 更に、成分（２）が
    （２－２）成分（２－１）以外のエラストマー
    を含有する請求項１～４のうちの１項記載の組成物。     The composition according to any one of claims 1 to 4, wherein the component (2) further contains an elastomer other than the component (2-2) (2-1).
  6. 成分（２－２）がコアシェル（共）重合体でない請求項５記載の組成物。 The composition according to claim 5, wherein the component (2-2) is not a core-shell (co) polymer.
  7. 成分（２－２）の使用量が、成分（１）及び成分（２）の合計１００質量部に対して、５～３０質量部である請求項５又は６記載の組成物。 The composition according to claim 5 or 6, wherein the amount of the component (2-2) used is 5 to 30 parts by mass with respect to 100 parts by mass in total of the component (1) and the component (2).
  8. 成分（１）１００質量部中、成分（１－１）１０～８５質量部、成分（１－２）５～６０質量部、成分（１－３）１～６０質量部である請求項１～７のうちの１項記載の組成物。 Component (1) is 10 to 85 parts by mass, component (1-2) is 5 to 60 parts by mass, and component (1-3) is 1 to 60 parts by mass in 100 parts by mass of component (1). 8. A composition according to one of the seven.
  9. 更に、
    （５）酸性リン酸化合物
    を含有する請求項１～８のうちの１項記載の組成物。     Furthermore,
    (5) The composition according to any one of (1) to (8), which comprises an acidic phosphoric acid compound.
  10. 更に、
    （６）パラフィン類
    を含有する請求項１～９のうちの１項記載の組成物。     Furthermore,
    (6) The composition according to any one of (1) to (9), which contains paraffins.
  11. 請求項１～１０のうちの１項記載の組成物を含有する硬化性樹脂組成物。 A curable resin composition comprising the composition according to any one of claims 1 to 10.
  12. 請求項１～１０のうちの１項記載の組成物を含有する接着剤組成物。 An adhesive composition containing the composition according to any one of claims 1 to 10.
  13. 請求項１～１０のうちの１項記載の組成物を第一剤と第二剤に分け、第一剤が少なくとも（３）重合開始剤を含有し、第二剤が少なくとも（４）還元剤を含有する二剤型の組成物。 The composition according to any one of claims 1 to 10, wherein the composition is divided into a first agent and a second agent, the first agent contains at least (3) a polymerization initiator, and the second agent is at least (4) a reducing agent. A two-part composition comprising:
  14. 請求項１２記載の接着剤組成物により接合する接合体。 A joined body joined by the adhesive composition according to claim 12.
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US11742129B2 (en) 2018-12-17 2023-08-29 Nippon Steel Corporation Adhesively-laminated core, manufacturing method thereof, and electric motor
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