Adhesive composition

Abstract

The present invention addresses the problem of providing an adhesive composition which exhibits excellent adhesiveness and adhesion to various plastics such as polypropylene, polyethylene, and cycloolefin resin. The adhesive composition of the present invention contains the following components (A) to (C). (A) A radically polymerizable compound; (B) a polymer having a weight average molecular weight of 35,000-110,000 and having a repeating unit derived from a polymerizable compound represented by formula (I) (in which X1 and X2 each independently represent a C7-C20 alkyl group or a C7-C20 alkoxy group, n represents 0 or 1, Z1 and Z2 each independently represent a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogeno group, m1 and m2 each independently represent any integer of 0-4, and Y represents a polymerizable functional group); and (C) a radical polymerization initiator

Description

[Technical field]

[0001] The present invention relates to an adhesive composition. This application claims priority to Japanese Patent Application No. 2020-067404, filed on April 3, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] Conventionally, radical curing adhesives whose main component is (meth)acrylate can be cured by a variety of methods, including light curing, heat curing, anaerobic curing, and two-liquid mixing curing, and are used in a wide range of fields, including the automotive and transportation equipment sectors, electrical and electronic parts, aircraft, building materials, sporting goods, civil engineering, packaging, and medicine. However, conventional radical curing adhesives have difficulty in providing a balanced bond to a variety of plastic resins, such as low surface energy resin substrates, such as polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyacetal (POM), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polydimethyl silicone (PDMS), polyether ether ketone (PEEK), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), cycloolefin polymer (COP), cycloolefin copolymer (COC), polymethylpentene (PMP), and liquid crystal polyester (LCP), as well as high surface energy resin substrates, such as polyvinyl chloride (PVC), polycarbonate (PC), and polymethyl methacrylate (PMMA), using a single agent.

[0003] For example, Patent Document 1 discloses an active energy ray-curable adhesive composition for plastic films or sheets, which contains a predetermined amount of a urethane (meth)acrylate, an ethylenically unsaturated group-containing compound having a hydroxyl group in the molecule, an ethylenically unsaturated group-containing compound having a homopolymer glass transition temperature of 50°C or higher, and an ethylenically unsaturated group-containing compound having a homopolymer glass transition temperature of 20°C or lower. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-009339 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, with the active energy ray-curable adhesive composition for plastic films or sheets disclosed in Patent Document 1, it was difficult to bond various plastics in a balanced manner.

[0006] The present invention has been made in view of the above circumstances, and has an object to provide an adhesive composition having excellent adhesive strength to various poorly adhesive materials. [Means for solving the problem]

[0007] The present invention is as follows. (1) An adhesive composition comprising the following (A) to (C): (A) Radical polymerizable compound (B) Formula (I) [ka] (In the formula, X 1 , X 2 each independently represents an alkyl group having 7 to 20 carbon atoms or an alkoxy group having 7 to 20 carbon atoms; n represents 0 or 1; Z 1 , Z 2 each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogeno group, each m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group. A polymer having a weight average molecular weight of 35,000 to 110,000, which has a repeating unit derived from a polymerizable compound represented by the following formula: (C) Radical polymerization initiator (2) The adhesive composition according to (1), wherein in formula (I), Y is an acryloyl group or a methacryloyl group. (3) The adhesive composition according to (1) or (2), wherein the polymer having a repeating unit derived from the polymerizable compound represented by formula (I) is a copolymer having a repeating unit derived from the polymerizable compound represented by formula (I) and a repeating unit derived from a (meth)acrylic acid ester. (4) The adhesive composition according to any one of (1) to (3), which is an adhesive composition for use on plastic substrates. (5) (C) The adhesive composition according to any one of (1) to (4), wherein the radical polymerization initiator is a photopolymerization initiator. (6) (C) The adhesive composition according to any one of (1) to (4), wherein the radical polymerization initiator is an organic peroxide. (7) The adhesive composition according to (5), which is a coating agent. (8) The adhesive composition according to (7), wherein the coating agent is a primer. (9) The adhesive composition according to (5) or (6), which is an adhesive. (10) A molded article, comprising an adhesive composition according to any one of (1) to (9) coated on a plastic substrate, and a cured layer provided on or between the substrates. Effect of the Invention

[0008] The present invention can provide an adhesive composition that has excellent adhesion to various poorly adhesive materials such as polyethylene terephthalate, polyethylene, polypropylene, modified polyphenylene ether, polyphenylene sulfide, and cycloolefin polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] This embodiment will be described in detail below.

[0010] <Component (A)> Radical polymerizable compound The radical polymerizable compound is not particularly limited, but may be a monomer having a group having an unsaturated double bond such as a vinyl group, an allyl group, or a (meth)acryloyl group, or an oligomer or polymer thereof. In the present invention, the term "(meth)acryloyl group" means an "acryloyl group" and / or a "methacryloyl group".

[0011] As the radically polymerizable compound, preferably, monofunctional or polyfunctional (meth)acrylate, (meth)acrylamide, or oligomers thereof can be used.

[0012] Examples of the monofunctional (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isononyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, methoxylated cyclodecatriene (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, and glycol monomethyl ether (meth)acrylate. Examples of the acrylates include sidyl (meth)acrylate, furfuryl (meth)acrylate, epoxy (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, (2-methyl-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropaneformal (meth)acrylate, γ-butyrolactone (meth)acrylate, dioxolane (meth)acrylate, oxetane (meth)acrylate, (meth)acryloylmorpholine, phenyl (meth)acrylate, benzyl (meth)acrylate, methylbenzyl (meth)acrylate, ethylbenzyl (meth)acrylate, propylbenzyl (meth)acrylate, methoxybenzyl (meth)acrylate, phenoxyethyl (meth)acrylate, chlorobenzyl (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate.

[0013] The polyfunctional (meth)acrylate monomer is a monomer having two or more, preferably 2 to 6, (meth)acrylate groups in the molecule, and examples thereof include neopentyl glycol di(meth)acrylate, stearic acid modified pentaerythritol di(meth)acrylate, dicyclopentenyl diacrylate, di(meth)acryloyl isocyanurate, alkylene oxide modified bisphenol di(meth)acrylate, dioxane glycol di(meth)acrylate, 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)acryloxypropionyl)propane, and the like. bifunctional (meth)acrylates such as 2,2-bis(4-(meth)acryloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, etc.; and trifunctional or higher (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(acryloyloxyethyl)isocyanurate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol pentaacrylate, and dipentaerythritol hexa(meth)acrylate.

[0014] Examples of the (meth)acrylate oligomer include urethane (meth)acrylates with a polybutadiene skeleton, urethane (meth)acrylates with a hydrogenated polybutadiene skeleton, urethane (meth)acrylates with a polycarbonate skeleton, urethane (meth)acrylates with a polyether skeleton, urethane (meth)acrylates with a polyester skeleton, urethane (meth)acrylates with a castor oil skeleton, isoprene-based (meth)acrylates, hydrogenated isoprene-based (meth)acrylates, and epoxy (meth)acrylate oligomers.

[0015] These monofunctional or polyfunctional (meth)acrylate monomers or (meth)acrylate oligomers can be used alone or in combination of two or more kinds.

[0016] Examples of the (meth)acrylamide include dimethyl(meth)acrylamide, diethyl(meth)acrylamide, and isopropyl(meth)acrylamide. The radical polymerizable compound other than the above-mentioned (meth)acrylate and (meth)acrylamide may be appropriately selected depending on the desired physical properties such as melting point, viscosity, or refractive index, and is not particularly limited. Specific examples include the following:

[0017] Vinyl compounds such as styrene, maleic anhydride, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ether, acrolein, and divinylbenzene; olefin compounds such as ethylene, propylene, and butadiene.

[0018] <Component (B)> A polymer having a repeating unit derived from a polymerizable compound represented by formula (I) The component (B) is a compound represented by the formula (I) [ka] (In the formula, X 1 , X 2 each independently represents an alkyl group having 7 to 20 carbon atoms or an alkoxy group having 7 to 20 carbon atoms; n represents 0 or 1; Z 1 , Z 2 each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogeno group, each m1 and m2 independently represents an integer of 0 to 4, and Y represents a polymerizable functional group. The polymer has a weight average molecular weight of 35,000 to 110,000.

[0019] The polymer having a repeating unit derived from the polymerizable compound represented by formula (I) refers to a polymer having one or more types of repeating units derived from the polymerizable compound represented by formula (I). The polymer having a repeating unit derived from the polymerizable compound represented by formula (I) may further have a repeating unit derived from a (meth)acrylic acid ester as a repeating unit derived from a radically polymerizable compound other than formula (I).

[0020] In the case of a copolymer consisting of two or more kinds of repeating units derived from the polymerizable compound represented by formula (I) or a copolymer consisting of a repeating unit derived from the polymerizable compound represented by formula (I) and a repeating unit derived from a (meth)acrylic acid ester, the repeating units may be arranged randomly, alternately, or in a block fashion.

[0021] The copolymer may have a linear or branched molecular chain, and examples of the branched chain include a branched chain branched at one point (star type) and a branched chain branched at multiple points (graft type).

[0022] (Polymerizable compound represented by formula (I)) In formula (I), X 1 , X 2 each independently represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.

[0023] X 1 and X 2 As the C7 to C20 alkyl group, both straight chain and branched chain ones can be preferably used. Examples of linear alkyl groups include an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, and an n-eicosyl group. Examples of branched chain alkyl groups include 1,1,2,2-tetramethylpropyl group, 1,1,3-trimethylbutyl group, 1-ethylpentyl group, 1,1,3,3-tetramethylbutyl group, 2,2,3,3-tetramethylbutyl group, 1,2,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 2,2,4-trimethylpentyl group, 1-ethyl-4-methylpentyl group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-methylpentyl group, and 3-ethyl-5-methylpentyl group. Examples of such alkyl groups include methylpentyl group, 1-ethyl-1-methylpentyl group, 1,1-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 6-methylheptyl group, 1,3,5-trimethylhexyl group, 1,1,3-trimethylhexyl group, 1-butyl-1-methylheptyl group, 1-methylheptyl group, and 1-methyl-1-octylundecyl group. X 1 and X 2 As the C7 to C20 alkoxy group in the formula (I), both straight-chain and branched-chain alkoxy groups can be preferably used. Examples of linear alkoxy groups include n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-dodecyloxy, n-tridecyloxy, n-tetradecyloxy, n-hexadecyloxy, n-octadecyloxy, and n-eicosyloxy groups. Examples of branched chain alkyl groups include 1,1,2,2-tetramethylpropyloxy group, 1,1,3-trimethylbutyloxy group, 1-ethylpentyloxy group, 1,1,3,3-tetramethylbutyloxy group, 2,2,3,3-tetramethylbutyloxy group, 1,2,4-trimethylpentyloxy group, 2,4,4-trimethylpentyloxy group, 2,2,4-trimethylpentyloxy group, 1-ethyl-4-methylpentyloxy group, 3-ethyl-3-methylpentyloxy group, 3-ethyl-4-methylpentyloxy group, and 5-ethyl-6-methylpentyloxy group. Examples of the aryloxy group include an ethylhexyloxy group, a 1-ethyl-1-methylpentyloxy group, a 1,1-dimethylhexyloxy group, a 3,3-dimethylhexyloxy group, a 4,4-dimethylhexyloxy group, a 2-ethylhexyloxy group, a 3-ethylhexyloxy group, a 6-methylheptyloxy group, a 1,3,5-trimethylhexyloxy group, a 1,1,3-trimethylhexyloxy group, a 1-butyl-1-methylheptyloxy group, a 1-methylheptyloxy group, and a 1-methyl-1-octylundecyloxy group.

[0024] In the formula, n represents 0 or 1.

[0025] In the formula, Z 1 , Z 2 each independently represents a single bond or a C1-C3 alkylene group. Z 1 , Z 2 Examples of the C1 to C3 alkylene group in the formula include methylene, ethylene, and propane-1,3-diyl.

[0026] In the formula, R represents an organic group or a halogeno group. The organic group is not particularly limited as long as it is chemically permissible and has the effect of the present invention. Examples of the organic group include C1-C6 alkyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, and n-hexyl group, C6-C10 aryl groups such as phenyl group and naphthyl group, C1-C6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, and t-butoxy group, and C1-C6 haloalkyl groups such as chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, and perfluoro-n-pentyl group. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0027] In the formula, m1 and m2 each independently represent an integer of 0 to 4.

[0028] In the formula, Y represents a polymerizable functional group, such as a group having a polymerizable carbon-carbon double bond, including a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a vinyloxycarbonyl group, a prop-1-en-2-yloxycarbonyl group, and an allyloxycarbonyl group. In the present invention, Y is preferably an acryloyl group or a methacryloyl group.

[0029] The above formula (I) includes compounds represented by the following formula (II). [ka] In the formula, Y, Z 1 , Z 2 , X 1 , X 2 , R, m1, and m2 are the same as those described in formula (I).

[0030] Of the polymerizable compounds represented by formula (I) or formula (II) used in the present invention, preferred are N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide, N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)methacrylamide, N-phenyl-N-(4-(2,4,4-trimethylpentan-2-yl)phenyl)acrylamide, N-phenyl-N-(4-(2,4,4-trimethylpentan-2-yl)phenyl)methacrylamide, N,N-bis(4-octylphenyl)acrylamide, N,N-bis(4-octylphenyl)methacrylamide, N-(4-octylphenyl)-N-phenylacrylamide, and N-(4-octylphenyl)-N-phenylmethacrylamide.

[0031] ((Meth)acrylic acid ester) The (meth)acrylic acid ester is preferably an unsubstituted or optionally substituted C1 to C18 alkyl (meth)acrylic acid ester. The alkyl moiety of the alkyl (meth)acrylate ester may be any of linear, branched, and cyclic (alicyclic), and is preferably a linear or branched alkyl group. In the case of a linear or branched alkyl (meth)acrylate ester, the alkyl moiety is preferably C1 to C12.

[0032] Examples of the substituent that may be substituted on the (meth)acrylic acid ester include, but are not limited to, an aliphatic group, a polar group, an aromatic group, and a heteroaromatic group. Examples of the aliphatic group include alkyl groups such as a methyl group and an ethyl group, alkenyl groups such as a vinyl group and an allyl group, and alkynyl groups such as an ethynyl group. Examples of the polar group include a hydroxyl group, an amino group, and a tetrahydrofurfuryl group. Examples of the aromatic group include an aromatic hydrocarbon group containing one or more rings, such as a phenyl group and a naphthyl group. The heteroaromatic group is an aromatic group having one or more heteroatoms, such as O, S, or N. Examples include a pyridinyl group, a thienyl group, a furyl group, and a benzimidazolyl group.

[0033] Specific examples of the (meth)acrylic acid ester include methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, trityl (meth)acrylate, and the like. Examples of the methacryloyloxyethyl acrylate include 2-acryloyloxyethyl dimethyl benzyl aminium chloride, 4-t-butyl cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (2-acryloyloxyethyl) trimethyl aminium chloride, (2-methacryloyloxyethyl) trimethyl aminium chloride, (2-acryloyloxyethyl) dimethyl benzyl aminium chloride, and (2-methacryloyloxyethyl) dimethyl benzyl aminium chloride.

[0034] (Repeating unit composition ratio) When the component (B) used in the present invention has a repeating unit derived from the polymerizable compound represented by formula (I) and a repeating unit derived from a (meth)acrylic acid ester, that is, when it is a copolymer consisting of a repeating unit derived from the polymerizable compound represented by formula (I) and a repeating unit derived from a (meth)acrylic acid ester, the content of the repeating unit derived from the polymerizable compound represented by formula (I) and the repeating unit derived from a (meth)acrylic acid ester in the copolymer is not particularly limited. The repeating unit derived from the polymerizable compound represented by formula (I) and the repeating unit derived from the (meth)acrylic acid ester can be selected in a molar ratio range of 99.5:0.5 to 60:40, 99:1 to 70:30, 98:2 to 75:25, 95:5 to 80:20, 20:80 to :5:95, 40:60 to 0.5:99.5, etc.

[0035] The component (B) used in the present invention can be any polymer consisting only of a repeating unit derived from the polymerizable compound represented by formula (I) or a copolymer having a repeating unit derived from the polymerizable compound represented by formula (I) and a repeating unit derived from a (meth)acrylic acid ester, without any particular limitation, and may also have a repeating unit derived from another radically polymerizable compound.

[0036] (Other radical polymerizable compounds) The repeating units derived from other radical polymerizable compounds refer to repeating units derived from one or more radical polymerizable compounds other than the repeating units derived from the polymerizable compound represented by formula (I) and the repeating units derived from a (meth)acrylic acid ester. The polymerizable compound represented by formula (I) and the polymerizable compound other than the (meth)acrylic acid ester may be appropriately selected depending on the desired physical properties such as melting point, viscosity, or refractive index, and is not particularly limited. Specific examples include the following.

[0037] Vinyl compounds such as (meth)acrylamide, styrene, maleic anhydride, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ether, acrolein, and divinylbenzene; olefin compounds such as ethylene, propylene, and butadiene.

[0038] (Method for producing compounds represented by formula (I) and formula (II)) The polymerizable compounds of formula (I) and formula (II) used in the present invention can be synthesized by the methods in the Examples or other known methods. For example, when Y in formula (I) is an acryl group or a methacryl group, it can be produced by the following method. Formula (I') [ka] (In the formula, X 1 , X 2 , n, Z 1 , Z 2 , R, m1, and m2 are defined as in formula (I). A secondary amine represented by the formula (I) is reacted with a (meth)acrylic acid halide such as (meth)acrylic acid chloride in a solvent in the presence of a base. Examples of the solvent include amide solvents such as N,N-dimethylformamide (DMF) and N,N-dimethylacetamide; ether solvents such as tetrahydrofuran (THF), 1,2-dimethoxyethane, diethyl ether, and methyl cellosolve; aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, and benzonitrile; saturated hydrocarbons such as pentane, hexane, octane, and cyclohexane; and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and 1,2-dichloroethane. One or a mixture of two or more of these solvents can be used. Examples of the base that can be used include organic bases such as aliphatic amines such as triethylamine and tributylamine; aromatic amines such as pyridine, N-ethylpyridine, N,N-dimethylaniline, and N,N-dimethylaminopyridine; and metal alkoxides such as sodium ethylate and sodium methylate. In addition, inorganic bases such as hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, and sodium hydrogencarbonate, and carbonates of alkali metals or alkaline earth metals can be used. The reaction temperature is -50°C to 200°C.

[0039] (Polymerization method) The polymer used in the present invention can be any polymerizable compound represented by formula (I) alone, or a polymerizable compound represented by formula (I) and a (meth)acrylic acid ester polymerized together. The polymerization reaction is not particularly limited, and may be a known method for synthesizing polyacrylates, etc., such as radical polymerization, anionic polymerization, cationic polymerization, ring-opening polymerization, and coordination polymerization. An example is shown in the Examples. For example, when a compound in which Y of formula (I) is an acrylic group or a methacrylic group is radically polymerized with a (meth)acrylic acid ester compound, the polymerizable compound represented by formula (I) or formula (II) and the (meth)acrylic acid ester compound are heated or irradiated with light in a solvent in the presence of a radical polymerization initiator to carry out a polymerization reaction. The polymerization solvent is not particularly limited as long as it is a solvent that is not involved in the polymerization reaction and is compatible with the polymer, and specific examples thereof include non-polar solvents or low polar solvents such as ether compounds such as diethyl ether, tetrahydrofuran (THF), dioxane, trioxane, etc., ester compounds such as ethyl acetate, ketone compounds such as methyl ethyl ketone, cyclohexanone, etc., and aliphatic, aromatic, or alicyclic hydrocarbon compounds such as hexane, toluene, etc. These solvents can be used alone or as a mixed solvent of two or more kinds. Examples of the radical polymerization initiator include azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane hydrochloride, potassium peroxodisulfate, ammonium peroxodisulfate, t-butyl hydroperoxide, di-t-butylcumene hydroperoxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide.

[0040] The molecular weight of the polymer used in the adhesive composition of the present invention is, in terms of weight average molecular weight, 35,000 to 110,000, and preferably 55,000 to 80,000. The molecular weight distribution (PDI) of the polymer according to the present invention, expressed as the ratio of weight average molecular weight / number average molecular weight (Mw / Mn), is preferably 1.0 to 5.0, more preferably 1.0 to 4.0, and most preferably 1.0 to 3.0. The weight average molecular weight and number average molecular weight are values ​​obtained by converting data measured by gel permeation chromatography (GPC) using THF as a solvent, based on the molecular weight of polymethyl methacrylate used as a standard.

[0041] In this specification, the term "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).

[0042] [GPC measurement equipment] Tosoh Corporation EcoSEC HLC-8320GPC [GPC measurement results] GPC column: TSK gel SuperMultipore HZ-M Flow rate: 0.35ml / min Injection amount: 40μm Column temperature: 40℃ System temperature: 40℃ Eluent: Tetrahydrofuran

[0043] (Mixing ratio of component (A) and component (B)) The blending ratio of the (A) component and the (B) component is not particularly limited, but the blending ratio of the (B) component is preferably 0.1 to 80 parts by mass, more preferably 1 to 50 parts by mass, and particularly preferably 1 to 30 parts by mass, per 100 parts by mass of the (A) component.

[0044] <Component (C)> Radical polymerization initiator Examples of the component (C) that can be used in the present invention include a photoradical polymerization initiator or an organic peroxide. The curing form of the adhesive composition of the present invention can be selected from photocuring, heat curing, and redox curing by selecting the component (C) of the present invention. For example, if one wishes to impart "photocurability" to the adhesive composition, one should select a photoradical initiator, and if one wishes to impart "curing by heat or redox reaction," one should select an organic peroxide.

[0045] The amount of the (C) component is not particularly limited, but it is preferable that 0.01 to 10 parts by mass of the (C) component be added per 100 parts by mass of the (A) component. When the (C) component is 0.01 part by mass or more, the curing property is excellent, and when the (C) component is less than 10 parts by mass, the storage property of the adhesive composition is good. More preferably, 0.04 to 8 parts by mass are added, and even more preferably, 0.06 to 6 parts by mass are added.

[0046] The photoradical initiator, which is the component (C) used in the present invention, is not limited as long as it is a compound that generates radicals by irradiation with active energy rays. Examples of the component (C) include acetophenone-based photoradical initiators, benzoin-based photoradical initiators, benzophenone-based photoradical initiators, thioxanthone-based photoradical initiators, acylphosphine oxide-based photoradical initiators, and titanocene-based photoradical initiators, and among these, acetophenone-based photoradical initiators and acylphosphine oxide-based photoradical initiators are preferred from the viewpoint of excellent photocurability. These may be used alone or in combination of two or more.

[0047] Examples of the acetophenone-based photoradical initiator include, but are not limited to, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone oligomer. Commercially available products include IRGACURE (registered trademark) 184 and DAROCUR (registered trademark) 1173 (manufactured by BASF).

[0048] Examples of the acylphosphine oxide-based photoradical initiator include, but are not limited to, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like.

[0049] The organic peroxide, which is the component (C) used in the present invention, is a compound that generates radical species when heated to 50° C. or higher or when subjected to a redox reaction. The use of a redox reaction is preferred because it allows radical species to be generated at room temperature. The component (C) is not particularly limited, and examples thereof include ketone peroxide compounds such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, and acetylacetone peroxide; peroxyketal compounds such as 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, and 2,2-bis(t-butylperoxy)butane; t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexahydroperoxide, and the like. hydroperoxide compounds such as di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3; diacyl peroxide compounds such as acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide;Peroxydicarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, bis-(4-t-butylcyclohexyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, and diallyl peroxydicarbonate; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, cumyl peroxyneodecanoate, and t-butyl-2-ethylperoxyhexanoate. Examples of the organic peroxide include peroxyester compounds such as t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, di-t-butyl peroxy isophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxy maleic acid, t-butyl peroxy isopropyl carbonate, cumyl peroxy octoate, t-hexyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy neohexanoate, t-hexyl peroxy neohexanoate, and cumyl peroxy neohexanoate; and acetylcyclohexylsulfonyl peroxide and t-butyl peroxy allyl carbonate. These organic peroxides may be used alone or in combination. Among these, from the viewpoint of curability, dialkyl peroxide compounds, peroxy dicarbonate compounds, and peroxy ester compounds are preferably used. In addition, examples of organic peroxides suitable for redox reactions include dialkyl peroxide compounds.

[0050] When an organic peroxide is used as the (C) component, a curing accelerator can be added to accelerate the redox reaction. Such a curing accelerator is not particularly limited, but preferably, saccharin (o-benzoixulfimide), hydrazine compounds, amine compounds, mercaptan compounds, metal organic compounds, etc. are used. The above curing accelerators may be used alone or in combination. It is more preferable to use them in combination because the curing acceleration effect is good.

[0051] Examples of the hydrazine compounds include 1-acetyl-2-phenylhydrazine, 1-acetyl-2(p-tolyl)hydrazine, 1-benzoyl-2-phenylhydrazine, 1-(1',1',1'-trifluoro)acetyl-2-phenylhydrazine, 1,5-diphenyl-carbohydrazine, 1-formyl-2-phenylhydrazine, 1-acetyl-2-(p-bromophenyl)hydrazine, 1-acetyl-2-(p-nitrophenyl)hydrazine, 1-acetyl-2-(2'-phenylethylhydrazine), ethyl carbazate, p-nitrophenylhydrazine, and p-trisulfonylhydrazide.

[0052] Examples of the amine compound include heterocyclic secondary amines such as 2-ethylhexylamine, 1,2,3,4-tetrahydroquinone, and 1,2,3,4-tetrahydroquinaldine; heterocyclic tertiary amines such as quinoline, methylquinoline, quinaldine, and quinoxalinephenazine; aromatic tertiary amines such as N,N-dimethyl-para-toluidine, N,N-dimethyl-anisidine, and N,N-dimethylaniline; and azole compounds such as 1,2,4-triazole, oxazole, oxadiazole, thiadiazole, benzotriazole, hydroxybenzotriazole, benzoxazole, 1,2,3-benzothiadiazole, and 3-mercaptobenzotriazole.

[0053] Examples of the mercaptan compound include n-dodecyl mercaptan, ethyl mercaptan, butyl mercaptan, tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, and pentaerythritol tetrakis thioglycolate.

[0054] Examples of the metal organic compound include iron pentadione, cobalt pentadione, cobalt neodecanoate, copper pentadione, copper propylenediamine, copper ethylenediamine, copper neodecanoate, iron naphthate, nickel naphthate, cobalt naphthate, copper naphthate, copper octate, iron hexoate, iron propionate, and vanadium acetylacetonate.

[0055] The adhesive composition of the present invention can be used as a one-liquid composition, but can also be used as a two-liquid composition. When making a two-liquid composition, it is preferable to include the radical polymerization initiator (C) in one liquid and the metal organic compound in the other liquid. By separating the radical polymerization initiator (C) and the metal organic compound into separate liquids in this way, unnecessary reactions during storage can be suppressed and storage stability can be improved. When using the composition, the two liquids can be mixed, or can be applied separately and then contacted and cured. Here, the components other than the radical polymerization initiator and metal organic compound (C) can be divided at any ratio and included in either liquid.

[0056] <Optional ingredients> In the present invention, additives such as adhesion aids such as silane coupling agents, thickeners, elastomers, core-shell polymers, reactive diluents, non-reactive diluents or solvents, antioxidants, light stabilizers, fillers, tackifiers such as tackifiers, vinyl aromatic compounds, paraffins, non-reactive colorants, phosphates, rubber-like polymer particles, storage stabilizers such as BHT, plasticizers, dyes, pigments, flame retardants, sensitizers, heavy metal deactivators, ion trapping agents, emulsifiers, water dispersion stabilizers, defoamers, release agents, leveling agents, waxes, rheology control agents, surfactants, etc. may be blended in appropriate amounts within the scope of the present invention without impairing the object of the present invention.

[0057] Examples of the silane coupling agent include glycidyl group-containing silane coupling agents such as 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldipropyloxysilane, 3-glycidoxypropyldimethylmonomethoxysilane, 3-glycidoxypropyldimethylmonoethoxysilane, 3-glycidoxypropyldimethylmonopropyloxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropylmethyldiethoxysilane; vinyl group-containing silane coupling agents such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyldimethylmonomethoxysilane, and 3-glycidoxypropyldimethylmonomethoxysilane; Examples of the silane include silane, 3-methacryloxypropyl dimethyl monoethoxysilane, 3-acryloxypropyl methyl dipropyloxysilane, 3-acryloxypropyl methyl dimethoxysilane, 3-acryloxypropyl methyl diethoxysilane, 3-acryloxypropyl methyl dipropyloxysilane, 3-acryloxypropyl dimethyl monopropyloxysilane, 3-acryloxypropyl dimethyl monomethoxysilane, 3-acryloxypropyl dimethyl monoethoxysilane, 3-acryloxypropyl dimethyl monopropyloxysilane, γ-methacryloxypropyl trimethoxysilane and other (meth)acryl group-containing silane coupling agents, N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane and other amino group-containing silane coupling agents, γ-mercaptopropyl trimethoxysilane, γ-chloropropyl trimethoxysilane, etc. These may be used alone or in combination of two or more.

[0058] As the thickener, polybutyl methacrylate having a molecular weight of about 10,000 to about 40,000 is effective. By using the thickener, the viscosity of the adhesive composition can be increased to a syrup-like consistency with excellent applicability. Such a thickener can generally be used in an amount of about 50% by mass or less based on the total mass of the adhesive composition.

[0059] The adhesive composition of the present invention can use an elastomer. The elastomeric material can improve the fracture toughness of the adhesive composition cured product. For example, it can be beneficial when bonding rigid high yield strength materials (e.g., metal substrates that do not mechanically absorb energy as easily as other materials, such as flexible polymeric substrates). Such additives can generally be used in an amount of about 50% by weight or less based on the total weight of the adhesive composition.

[0060] The elastomer used in the adhesive composition of the present invention is preferably a polymeric substance having rubber-like elasticity at room temperature, and is preferably soluble or dispersible in a polymerizable vinyl monomer.

[0061] Examples of such elastomers include butadiene (co)polymers such as polybutadiene, (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer, (meth)acrylonitrile-butadiene-methyl (meth)acrylate copolymer, methyl (meth)acrylate-butadiene-styrene copolymer (MBS), styrene-butadiene, (meth)acrylonitrile-butadiene rubber (NBR), as well as various synthetic rubbers such as linear polyurethane, natural rubber, various thermoplastic elastomers, etc. One or more of these elastomers may be used as long as there is no problem with compatibility.

[0062] The core-shell polymer can also be used to improve the spreadability and flowability of the adhesive composition. Improved spreadability and flowability can be confirmed by a reduction in undesirable stringing that remains when the adhesive composition is dispensed from a syringe-type applicator or sagging after the adhesive composition is applied to a vertical surface. The core-shell polymer can be added in an amount of generally about 5% by weight or more, about 10% by weight or more, or about 20% by weight or more, about 50% by weight or less, about 40% by weight or less, or about 30% by weight or less, based on the total weight of the adhesive composition.

[0063] A reactive diluent may be added. Suitable reactive diluents include 1,4-dioxo-2-butene functional compounds and aziridine compounds.

[0064] These include non-reactive diluents or solvents (e.g., acetone, methyl ethyl ketone, ethyl acetate, N-methyl caprolactam, etc.), non-reactive colorants, fillers (e.g., carbon black, polyethylene, hollow glass / ceramic beads, silica, titanium dioxide, solid glass / ceramic microspheres, silica alumina ceramic microspheres, electrically and / or thermally conductive particles, antistatic compounds, chalk, etc.) Various optional additives can be added in amounts that do not substantially decrease the rate of polymerization of the monomers or the desired properties of the adhesive cured product.

[0065] Furthermore, for the purpose of improving storage stability, various antioxidants including polymerization inhibitors can be used, such as hydroquinone, hydroquinone monomethyl ether, 2,6-ditertiarybutyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tertiarybutylphenol), triphenyl phosphite, phenothiazine, and N-isopropyl-N'-phenyl-p-phenylenediamine.

[0066] The amount of the antioxidant used is preferably 0.001 to 3 parts by mass, and more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the radical polymerizable compound (A). When it is 0.001 part by mass or more, it is effective, and when it is 3 parts by mass or less, the adhesiveness is improved.

[0067] Of the optional components described above, the addition of an antioxidant and a light stabilizer is preferred in order to improve the weather resistance of the adhesive composition. Commercially available products can be used as the antioxidant and light stabilizer. For example, Sumilizer (registered trademark) BHT, Sumilizer (registered trademark) S, Sumilizer (registered trademark) BP-76, Sumilizer (registered trademark) MDP-S, Sumilizer (registered trademark) GM, Sumilizer (registered trademark) BBM-S, Sumilizer (registered trademark) WX-R, Sumilizer (registered trademark) NW, Sumilizer (registered trademark) BP-179, Sumilizer (registered trademark) BP-101, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GA-101 ... Miraizer (registered trademark) TNP, Sumilizer (registered trademark) TPP-R, Sumilizer (registered trademark) P-16 (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB (registered trademark) AO-20, ADK STAB (registered trademark) AO-30, ADK STAB (registered trademark) AO-40, ADK STAB (registered trademark) AO-50, ADK STAB (registered trademark) AO-60, ADK STAB (registered trademark) AO-70, ADK STAB (registered trademark) AO-80, ADK STAB ADK STAB(R) AO-330, ADK STAB(R) PEP-4C, ADK STAB(R) PEP-8, ADK STAB(R) PEP-24G, ADK STAB(R) PEP-36, ADK STAB(R) HP-10, ADK STAB(R) 2112, ADK STAB(R) 260, ADK STAB(R) 522A, ADK STAB(R) 329K, ADK STAB(R) 1500, Examples of such antioxidants include Adeka STAB C, Adeka STAB 135A, Adeka STAB 3010 (manufactured by Asahi Denka Kogyo Co., Ltd.), TINUVIN 770, TINUVIN 765, TINUVIN 144, TINUVIN 622, TINUVIN 111, TINUVIN 123, and TINUVIN 292 (manufactured by Chiba Specialty Chemicals Co., Ltd. (BASF)). The amount of these antioxidants and light stabilizers to be added is not particularly limited, but is preferably 0.001 to 10 parts by mass, and more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of component (A).

[0068] <Substrates to which the adhesive composition can be applied> The adhesive composition of the present invention is particularly useful for bonding low surface energy plastic or polymer substrates, which are difficult to bond to, without the use of complicated surface treatment techniques such as flame treatment, Itro treatment, corona discharge, primer treatment, etc. In the present disclosure, the term "low surface energy plastic" refers to olefin-based materials such as polyethylene (PE), polypropylene (PP), cycloolefin polymer (COP), and cycloolefin copolymer (COC), polyacetal (POM), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polydimethyl silicone (PDMS), polyether ether ketone (PEEK), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), polymethylpentene (PMP), liquid crystal polyester (LCP), acrylonitrile-butadiene-styrene (ABS), and fluorinated polymers such as polytetrafluoroethylene (PTFE), as well as elastomer modifications of these materials, and polymer blends of these materials with elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM). In the present disclosure, the "high surface energy plastic" includes polyvinyl chloride (PVC), polycarbonate (PC), and polymethyl methacrylate (PMMA). The two-component adhesive of the present disclosure can be advantageously used for substrates containing elastomer modified bodies and polymer blends of elastomers that are prone to adsorb oxygen. Suitable substrates containing elastomer modified bodies and polymer blends of elastomers include olefin-based elastomer substrates including elastomer modified bodies of polyolefins such as polyethylene and polypropylene, or polymer blends of elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM) with polyethylene, polypropylene, etc., in particular polypropylene-based elastomer substrates including elastomer modified bodies of polypropylene and polymer blends of elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM) with polypropylene.However, the invention is not limited to this extent and the compositions may be used to bond any thermoplastic resin as well as wood, ceramic, concrete and primed metal, fiber reinforced plastics.

[0069] <Manufacturing method> The adhesive composition of the present invention can be produced by a conventionally known method. For example, it can be produced by blending the predetermined amounts of components (A) to (C) and mixing them using a mixing means such as a mixer at a temperature of preferably 10 to 70° C. for preferably 0.1 to 5 hours. It is also preferable to produce the composition in a light-shielded environment.

[0070] <Application method> The adhesive composition of the present invention can be applied to an adherend by known methods for sealants or adhesives. For example, methods such as dispensing using an automatic coater, spraying, inkjet, screen printing, gravure printing, dipping, and spin coating can be used. From the viewpoint of coatability, the adhesive composition of the present invention is preferably liquid at 25°C. The term "liquid at 25°C" refers to a composition that exhibits a viscosity of 0.01 to 1000 Pa·s measured at 25°C using a cone-plate viscometer.

[0071] <Curing method and cured product> The curing form of the adhesive composition of the present invention can be selected to be photocurable, heat curable, or redox curable by selecting the component (C) of the present invention. For example, if one wishes to impart "photocurability" to the adhesive composition, one may select a photoradical initiator, and if one wishes to impart "heat curing or curing by redox reaction", one may select an organic peroxide.

[0072] Regarding the curing conditions when the adhesive composition of the present invention is given photocurability, the light source when the adhesive composition of the present invention is cured by irradiating it with light such as ultraviolet light or visible light is not particularly limited, and examples thereof include a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a black light lamp, a microwave excited mercury lamp, a metal halide lamp, a sodium lamp, a halogen lamp, a xenon lamp, an LED, a fluorescent lamp, sunlight, an electron beam irradiation device, etc. The amount of irradiation of light is 500 mJ / cm from the viewpoint of the properties of the cured product. 2 More preferably, it is 1000 mJ / cm or more. 2 There is no particular upper limit, but for example, 10,000 mJ / cm 2 The following is the result.

[0073] In addition, the curing conditions when the adhesive composition of the present invention is given heat curing properties are not particularly limited, but are preferably, for example, a temperature of 45°C or more and less than 200°C, more preferably 50°C or more and less than 150°C. The curing time is not particularly limited, but in the case of a temperature of 45°C or more and less than 200°C, it is preferably 3 minutes or more and less than 5 hours, more preferably 10 minutes or more and less than 3 hours. A cured product obtained by curing the adhesive composition of the present invention is also a part of the embodiment of the present invention. A bonded body bonded with the adhesive composition of the present invention is also a part of the embodiment of the present invention.

[0074] <Molded body> The molded article of the present invention is obtained by applying the above adhesive composition onto a plastic substrate, followed by curing to form a layer directly on or between substrates.

[0075] <Application> Specific applications of the adhesive composition of the present invention include, in the automotive and transportation fields, adhesion of automotive switch parts, headlamps, engine internal parts, electrical components, drive engines, brake oil tanks, front hoods, fenders, body panels such as doors, windows, etc.; in the flat panel displays, adhesion of liquid crystal displays, organic electroluminescence, light emitting diode displays, field emission displays, etc.; in the recording field, adhesion of video discs, CDs, DVDs, MDs, pickup lenses, hard disk peripherals (spindle motor members, magnetic head actuator members, etc.), Blu-ray discs, etc.; in the electronic materials field, adhesion of electronic components, electric circuits, electric contacts, semiconductor elements, etc., sealing materials, die bonding agents, conductive adhesives, anisotropic conductive adhesives, interlayer adhesives for multilayer boards including build-up boards, solder resists, etc.; in the battery field, adhesives for lithium batteries, manganese batteries, alkaline batteries, nickel-based batteries, fuel cells, silicon-based solar cells, dye-sensitized solar cells, organic solar cells, etc.; in the optical component field, adhesives for optical switch peripherals in optical communication systems, optical fiber materials for optical connector peripherals, optical passive components, optical circuit components, and adhesives for optoelectronic integrated circuits, etc.; in the optical equipment field, adhesives for camera modules, still camera lens materials, finder prisms, target prisms, finder covers, light receiving sensors, photographic lenses, projection TV projection lenses, etc.; in the infrastructure field, adhesives, lining agents, sealing, casting, molding, coating materials, etc. for gas pipes, water pipes, etc.

[0076] Resins used in the automobile and transportation fields include, for example, PP (polypropylene), PE (polyethylene), polyurethane, ABS, phenolic resin, CFRP (carbon fiber reinforced plastic), and GFRP (glass fiber reinforced plastic). In particular, CFRP (carbon fiber reinforced plastic) and GFRP (glass fiber reinforced plastic) are used for the car body. The frame of the electrolyte membrane of the fuel cell is made of a material that is difficult to bond, such as PP or PEN. The bonding points of the camera module include between the image sensor such as CMOS or CCD and the substrate, between the cut filter and the substrate, between the substrate and the housing, between the housing and the cut filter, and between the housing and the lens unit. The materials of the housing and the lens unit are made of a material that is difficult to bond, such as LCP (liquid crystal polymer), PPS (polyphenylene sulfide), and polycarbonate. EXAMPLES

[0077] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, the operations were carried out under the conditions of room temperature (25°C) and relative humidity of 40 to 50% RH.

[0078] (Synthesis Example 1) Synthesis of N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide (DOPAA) [ka] In a nitrogen-purged 1L four-neck flask, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]amine (50.00g, 0.127mol), N,N-dimethylaniline (46.17g, 0.381mol), and 477mL of ultra-dehydrated dichloromethane were charged and stirred until uniformly dissolved. Next, the reaction solution was cooled to below 0°C in an ice / ethanol bath, and acrylic acid chloride (22.99g, 0.254mol) was slowly added dropwise and stirred for 30 minutes. Then, the reaction solution was warmed to room temperature and reacted for 24 hours. After the reaction was completed, the solvent was distilled off with an evaporator, and the crude product was dissolved in 250mL of ethyl acetate. Then, it was washed with 1N hydrochloric acid aqueous solution, saturated sodium bicarbonate water, and saline. The organic layer was dehydrated with magnesium sulfate, and the filtrate was then distilled off with an evaporator. The obtained crude product was purified by recrystallization with hexane to obtain N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide (38.67 g, yield 68%). The results of mass spectrometry are shown below. High Resolution ESI-TOF-MS m / z Calcd. for [C 31 H 45 NO([M+Na] + )]: 470.3393 found 470.3317.

[0079] (Synthesis Example 2) Preparation of adhesive polymer 1 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.20 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 45 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was dropped into 800 mL of methanol to powderize it. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 28.19 g, Mw = 36,148, Mw / Mn = 2.08

[0080] (Synthesis Example 3) Preparation of adhesive polymer 2 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.17 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 45 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction liquid was sampled and subjected to gel permeation chromatography measurement. The reaction liquid was dropped into 800 mL of methanol to powderize it. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 26.33 g, Mw = 46,229, Mw / Mn = 2.07

[0081] (Synthesis Example 4) Preparation of adhesive polymer 3 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.15 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 45 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.08 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction liquid was sampled and subjected to gel permeation chromatography measurement. The reaction liquid was dropped into 800 mL of methanol to powderize it. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 25.98 g, Mw = 53,810, Mw / Mn = 2.11

[0082] (Synthesis Example 5) Preparation of adhesive polymer 4 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.20 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 40.62 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction liquid was sampled and subjected to gel permeation chromatography measurement. The reaction liquid was dropped into 800 mL of methanol to powderize it. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 27.82 g, Mw = 58,078, Mw / Mn = 2.20

[0083] (Synthesis Example 6) Preparation of adhesive polymer 5 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.20 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 36.69 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was powdered by dropping it into 800 mL of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 29.01 g, Mw = 61,128, Mw / Mn = 2.10

[0084] (Synthesis Example 7) Preparation of adhesive polymer 6 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.20 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 33.18 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was powdered by dropping it into 800 mL of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 28.87 g, Mw = 69,610, Mw / Mn = 2.20

[0085] (Synthesis Example 8) Preparation of adhesive polymer 7 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.20 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 30.02 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was powdered by dropping it into 800 mL of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 27.31 g, Mw = 82,555, Mw / Mn = 2.38

[0086] (Synthesis Example 9) Preparation of adhesive polymer 8 (DOPAA / EA=90 / 10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Kasei Co., Ltd.), and 0.20 g of AIBN (Tokyo Kasei Co., Ltd.) were charged into a 300 mL four-neck flask and dissolved in 20.02 g of toluene. The mixture was degassed by applying a reduced pressure and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added and stirred at 80°C for 5 hours. Heating and stirring were stopped and the reaction solution was sampled and subjected to gel permeation chromatography measurement. The reaction solution was powdered by dropping it into 800 mL of methanol. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield 28.11 g, Mw = 108,606, Mw / Mn = 2.94

[0087] (Preparation of Adhesive Composition) The components shown in Tables 1 to 4 were mixed with stirring at 25° C. in a light-shielded environment to obtain adhesive compositions.

[0088] The amount of each compounded substance is shown in parts by mass in Tables 1 to 4. Details of each compounded substance are as follows. IBOX: Isobornyl acrylate, commercially available EHA: 2-ethylhexyl acrylate, commercially available TPO: Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, commercially available

[0089] The test methods used in the examples in Tables 1 to 4 are as follows.

[0090] (adherent) ·First adherend The following materials were used: high density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyacetal (POM), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polydimethyl silicone (PDMS), polyether ether ketone (PEEK), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), polymethylpentene (PMP), liquid crystal polyester (LCP), acrylonitrile-butadiene-styrene (ABS), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), and polystyrene (PS). All substrates were 2.0 mm thick x 25 mm x 100 mm in size. All substrates were commercially available. ·Second adherend A polycarbonate (PC) substrate measuring 2.0 mm thick x 25 mm x 100 mm was used. A commercially available product was used as the substrate.

[0091] (Preparation of test specimens) Each photocurable adhesive composition was applied to the first adherend to a thickness of 100 μm.

[0092] Next, the second adherend, PC (polycarbonate), was attached to the surface to create an adhesive area of ​​25 mm x 25 mm, and then the total light intensity was 2000 mJ / m 2 The mixture was cured by exposure to ultraviolet light to prepare test specimens.

[0093] (Tensile shear strength (tensile shear adhesive strength)) The tensile shear strength (unit: MPa) was measured and taken as the tensile shear strength. The measurement was performed in an environment at a temperature of 23° C. and at a tensile speed of 100 mm / min.

[0094] [Table 1]

[0095] [Table 2]

[0096] [Table 3]

[0097] [Table 4]

[0098] From these test results, it can be seen that the adhesive composition of the present invention has excellent adhesion to various plastic resins such as low surface energy resin substrates, e.g., polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyacetal (POM), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polydimethyl silicone (PDMS), polyether ether ketone (PEEK), modified polyphenylene ether (PPE), polyphenylene sulfide (PPS), cycloolefin polymer (COP), cycloolefin copolymer (COC), polymethylpentene (PMP), and liquid crystal polyester (LCP), as well as high surface energy resin substrates, e.g., polyvinyl chloride (PVC), polycarbonate (PC), and polymethyl methacrylate (PMMA). The adhesive composition of the present invention is capable of adhering to a wider range of substrates and can take a wider variety of composition forms. In addition, when a polymer having a repeating unit derived from the compound represented by formula (I) of the present invention is not used, or when other polymers are used, excellent adhesion to the various plastic resins described above cannot be obtained.

Claims

1. An adhesive composition comprising the following (A) to (C): (A) Radically polymerizable compound (B) Formula (I) 【Chemistry 1】 (In the formula, X １ , X ２ each independently represents a C7 to C20 alkyl group or a C7 to C20 alkoxy group, n represents 0 or 1, Z １ , Z ２ each independently represents a single bond or a C1-C3 alkylene group, each R independently represents an organic group or a halogeno group, each m1 and m2 independently represents an integer of 0 to 4, and Y represents an acryloyl group or a methacryloyl group. A repeating unit derived from a polymerizable compound represented by the formula: A copolymer having a weight average molecular weight of 35,000 to 110,000, which has a repeating unit derived from a (meth)acrylic acid ester. (C) Radical polymerization initiator

2. 2. The adhesive composition according to claim 1, which is an adhesive composition for use on plastic substrates.

3. 3. The adhesive composition according to claim 1 or 2, wherein the radical polymerization initiator (C) is a photopolymerization initiator.

4. 4. The adhesive composition according to claim 1, wherein the radical polymerization initiator (C) is an organic peroxide.

5. 4. The adhesive composition according to claim 3, which is a coating agent.

6. 6. The adhesive composition according to claim 5, wherein the coating agent is a primer.

7. 5. The adhesive composition according to claim 3, which is an adhesive.

8. A molded article comprising a plastic substrate coated with the adhesive composition according to any one of claims 1 to 7, and a cured layer formed on or between the substrates.

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