2-component adhesive composition

Abstract

The purpose of the present invention is to provide a two-component adhesive composition with which it is possible to bond a low-surface-energy resin such as polyethylene (PE), polypropylene (PP), or polytetrafluoroethylene (PTFE) in a well-balanced manner using a single adhesive agent. This adhesive composition contains the following components (A)-(D). (A) Radical polymerizable compound. (B) (B-1) polymer comprising at least one repeating unit derived from a polymerizable compound represented by formula (I), or (B-2) polymer comprising at least one repeating unit derived from a polymerizable compound represented by formula (I) and at least one repeating unit derived from another radical polymerizable compound. (C) Polymerization initiator. (D) Reducing agent.

Description

[Technical Field]

[0001] The present invention relates to a two-component adhesive composition. This application claims priority to Japanese Patent Application No. 2020-067496, filed on April 3, 2020, the contents of which are incorporated herein by reference. [Background technology]

[0002] There is a need for an effective single-component adhesive that can provide a balanced bond to a variety of plastic resins, including low-surface-energy resin substrates such as polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyacetal (POM), nylon 6 (PA6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polydimethylsilicone (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). Low-surface-energy plastics are notoriously difficult to bond.

[0003] Adhesion of these poorly adhesive substrates often requires surface treatments such as flame treatment, Itro treatment, corona discharge, plasma treatment, oxidation with ozone or oxidizing acid, and sputter etching. While the surface of the poorly adhesive substrate may be coated with a primer containing a high surface energy material, such surface treatments may be necessary to ensure adequate adhesion of the primer. Thus, adhesion of poorly adhesive substrates often requires complex and expensive treatments, and even such treatments may not provide sufficient adhesive strength.

[0004] On the other hand, two-component acrylic adhesives, known as second-generation acrylic adhesive compositions (SGA), do not require precise measurement of the two components; even if the measurement or mixing is incomplete, they cure at room temperature in just a few minutes to a few tens of minutes upon contact, making them easy to work with. They also have high peel strength and impact strength, and cure well even in overhanging areas, making them widely used in fields ranging from electrical and electronic components to civil engineering and construction. Recently, SGAs with reduced odors have also become available, making them suitable for use in places with insufficient ventilation.

[0005] However, it was difficult for conventional two-component acrylic adhesives (SGA) to bond a wide range of plastic resins with low to high surface energy using only one adhesive agent.

[0006] For example, Patent Document 1 discloses a two-component acrylic adhesive (SGA) that uses an alkylborane complex as an initiator. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent Publication No. 2019-143063 Summary of the Invention [Problem to be solved by the invention]

[0008] Acrylic adhesives containing a polymerization initiator system based on an organoboron amine complex, such as that disclosed in Patent Document 1, have problems such as being unable to bond PA6 or POM, being unable to bond large areas due to their short usable life, and having to be stored refrigerated. The present invention aims to provide a two-component adhesive composition that can provide well-balanced adhesion with a single component 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). [Means for solving the problem]

[0009] The present invention includes the following aspects. (1) An adhesive composition containing the following components (A) to (D): (A) Radical polymerizable compound (B) (B-1) A polymer comprising at least one repeating unit derived from a polymerizable compound represented by formula (I), or (B-2) A polymer comprising at least one repeating unit derived from the polymerizable compound represented by formula (I) and at least one repeating unit derived from another radically polymerizable compound. [ka] (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 a polymerizable functional group. (C) Polymerization initiator (D) Reducing agent (2) The adhesive composition according to (1), wherein the polymerization initiator is cumene hydroperoxide. (3) The adhesive composition according to (1) or (2), wherein the reducing agent is at least one selected from the group consisting of vanadyl acetylacetonate, cobalt octoate, cobalt naphthenate, and ethylenethiourea. (4) The adhesive composition according to any one of (1) to (3), further comprising polybutadiene. (5) An adhesive composition according to any one of (1) to (4), which comprises a mixture of a first part containing at least component (C) and a second part containing at least component (D). (6) A molded article obtained by applying the adhesive composition according to any one of (1) to (5) onto a plastic substrate and providing a cured layer on or between the substrates. [Effects of the Invention]

[0010] The present invention can provide a two-component adhesive composition that can provide well-balanced adhesion with a single agent to a variety of plastic resins, including 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). DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail.

[0012] The adhesive composition of the present invention contains at least the following components (A) to (D). However, before use as an adhesive, the adhesive composition of the present invention is formed by mixing the two parts together immediately before or at the time of application to a substrate. That is, the adhesive composition of the present invention comprises a mixture of a first part containing at least component (C) and a second part containing at least component (D). <Component (A) Radical Polymerizable Compound> The radical polymerizable compound (1) used in the present invention refers to a compound having at least one radically polymerizable group in the molecule. The radical polymerizable compound has a chemical form of a monomer, oligomer, or polymer that is liquid or solid at room temperature and normal pressure. Examples of such radical polymerizable compounds include: Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc., and salts, esters, acid amides, or acid anhydrides thereof; (Meth)acrylonitrile; styrenes such as styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, and pt-butoxycarbonylstyrene; Other vinyl compounds such as vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, and vinyl 2-ethylhexanoate; olefinic compounds such as ethylene, propylene, and butadiene; Examples of such compounds include oligomers and polymers thereof. Of the above radically polymerizable components, (meth)acrylic acids are preferred.

[0013] The (meth)acrylic acids refer to “acrylic acids” or “methacrylic acids.” The (meth)acrylic acids of the present invention include monofunctional or polyfunctional (meth)acrylic acids, (meth)acrylates ((meth)acrylic acid esters), (meth)acrylamides, (meth)acrylonitriles, and oligomers and polymers thereof.

[0014] Among the (meth)acrylic acids, (meth)acrylates are preferred, and monofunctional (meth)acrylates having one (meth)acryloyl group are more preferred. Of the monofunctional (meth)acrylates, at least one selected from the group consisting of alkyl (meth)acrylates, alicyclic acrylates, (meth)acrylates having an ether skeleton, (meth)acrylates having a cyclic ether skeleton, and (meth)acrylates having an aromatic group are preferred.

[0015] Examples of monofunctional (meth)acrylates are shown below. Examples of alkyl (meth)acrylates 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, etc. One or more of these can be used.

[0016] The alicyclic (meth)acrylate is preferably a (meth)acrylate having an alicyclic hydrocarbon group. Examples of the (meth)acrylate having an alicyclic hydrocarbon group include cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, and methoxylated cyclodecatriene (meth)acrylate. One or more of these can be used.

[0017] Examples of (meth)acrylates having an ether skeleton include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and diethylene glycol monomethyl ether (meth)acrylate, and at least one of these can be used.

[0018] Examples of (meth)acrylates having a cyclic ether skeleton include glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3-ethyl-3-oxetanylmethyl (meth)acrylate, (2-methyl-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, cyclic trimethylolpropane formal (meth)acrylate, γ-butyrolactone (meth)acrylate, dioxolane (meth)acrylate, oxetane (meth)acrylate, etc. One or more of these can be used.

[0019] Examples of (meth)acrylates having an aromatic group include phenyl (meth)acrylate, benzyl (meth)acrylate, methylbenzyl (meth)acrylate, ethylbenzyl (meth)acrylate, propylbenzyl (meth)acrylate, methoxybenzyl (meth)acrylate, phenoxyethyl (meth)acrylate, chlorobenzyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, etc. One or more of these can be used.

[0020] Examples of polyfunctional (meth)acrylates are shown below. The polyfunctional (meth)acrylate is a compound having two or more (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, 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- Examples of suitable (meth)acrylates include bifunctional (meth)acrylates such as (meth)acryloxytetraethoxyphenyl)propane and 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane; and trifunctional or higher functional (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. At least one of these can be used.

[0021] 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. One or more of these can be used.

[0022] Examples of (meth)acrylamides include methyl(meth)acrylamide, dimethyl(meth)acrylamide, ethyl(meth)acrylamide, hydroxyethyl(meth)acrylamide, diethyl(meth)acrylamide, n-propyl(meth)acrylamide, dipropyl(meth)acrylamide, diisopropyl(meth)acrylamide, isopropylacrylamide, n-butyl(meth)acrylamide, i-butyl(meth)acrylamide, n-hexyl(meth)acrylamide, 2-ethylhexyl(meth)acrylamide, decyl(meth)acrylamide, lauryl(meth)acrylamide, stearyl(meth)acrylamide, cyclohexyl(meth)acrylamide, trityl(meth)acrylamide, 4-t-butylcyclohexylacrylamide, dimethylaminopropyl(meth)acrylamide, 4-acryloylmorpholine, 4-methacryloylmorpholine, [3-(acryloylamino)propyl]trimethylaminium chloride, and [3-(methacryloylamino)propyl]trimethylaminium chloride. One or more of these can be used.

[0023] <Component (B): Polymer Having 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), component (2) used in the present invention, is a polymer comprising at least one repeating unit derived from the polymerizable compound represented by formula (I) below, or a polymer comprising at least one of the repeating units and at least one repeating unit derived from another radically polymerizable compound: [ka] Specifically, the polymer of component (2) used in the present invention includes the following polymers: i) a homopolymer consisting of only one type of repeating unit derived from the polymerizable compound represented by formula (I); ii) A copolymer consisting of two or more kinds of repeating units derived from the polymerizable compound represented by formula (I), iii) A copolymer comprising one repeating unit derived from the polymerizable compound represented by formula (I) and at least one repeating unit derived from another radically polymerizable compound. iv) A copolymer consisting of two or more repeating units derived from the polymerizable compound represented by formula (I) and at least one repeating unit derived from another radically polymerizable compound. Of the above polymers, the copolymers ii) to iv) may be those in which the repeating units are arranged randomly, alternately, or in blocks. Furthermore, in the case of the copolymer of the present invention, the molecular chain may be a straight chain or a branched chain. 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).

[0024] The number average molecular weight of the polymer of the present invention is not limited as long as it is within a range that allows application onto a substrate, and examples thereof include copolymers having number average molecular weights within ranges such as 1,000 to 1,000,000, 5,000 to 500,000, 10,000 to 150,000, 10,000 to 200,000, and 20,000 to 100,000. The molecular weight distribution (PDI) of the polymer according to the present invention, expressed as the ratio of weight average molecular weight to 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.

[0025] (Polymerizable compound represented by formula (I)) [ka]

[0026] During the ceremony, X 1 , X 2each independently represents a C7 to C20 alkyl group or a C7 to C20 alkoxy group.

[0027] X 1 and X 2 As the C7 to C20 alkyl group in the formula (I), both straight-chain and branched-chain alkyl groups can be preferably used. Examples of straight-chain alkyl groups include n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl groups. 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-4-methylpentyl group. Examples include a methylpentyl group, a 1-ethyl-1-methylpentyl group, a 1,1-dimethylhexyl group, a 3,3-dimethylhexyl group, a 4,4-dimethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 6-methylheptyl group, a 1,3,5-trimethylhexyl group, a 1,1,3-trimethylhexyl group, a 1-butyl-1-methylheptyl group, a 1-methylheptyl group, and a 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 alkyl 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 3-ethyl-4-methylpentyloxy group. Examples thereof 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.

[0028] In the formula, n represents 0 or 1.

[0029] 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-C3 alkylene group in the formula include methylene, ethylene, and propane-1,3-diyl.

[0030] 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 acceptable and has the effects of the present invention. Examples of the organic group include C1 to C6 alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, and n-hexyl, C6 to C10 aryl groups such as phenyl and naphthyl, C1 to C6 alkoxy groups such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, s-butoxy, i-butoxy, and t-butoxy, and C1 to C6 haloalkyl groups such as chloromethyl, chloroethyl, trifluoromethyl, 1,2-dichloro-n-propyl, 1-fluoro-n-butyl, and perfluoro-n-pentyl. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and an iodo group.

[0031] In the formula, m1 and m2 each independently represent an integer of 0 to 4.

[0032] 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.

[0033] The compounds represented by the above formula (I) include 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).

[0034] 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.

[0035] (Other radical polymerizable compounds) "Other radical polymerizable compounds" are radical polymerizable compounds other than the compound represented by formula (I), and may be appropriately selected depending on the desired physical properties such as melting point, viscosity, or refractive index. They are not particularly limited, and examples thereof include (meth)acrylic acids, (meth)acrylonitrile, styrenes, vinyl compounds, olefin compounds, unsaturated carboxylic acid anhydrides, etc., and one or more of these can be used. Specific examples include the same compounds as those exemplified for component (1) radical polymerizable compounds. In particular, the "other radically polymerizable compounds" are preferably (meth)acrylates, (meth)acrylic acids such as (meth)acrylamides, unsaturated dicarboxylic acid anhydrides, and styrenes, and the (meth)acrylates are preferably unsubstituted or optionally substituted C1 to C18 alkyl (meth)acrylates. The alkyl moiety of the alkyl(meth)acrylate may be linear, branched, or cyclic (alicyclic), and is preferably a linear or branched alkyl group. In the case of a linear or branched alkyl(meth)acrylate, the alkyl moiety is preferably a C1 to C12 group.

[0036] Examples of the substituent of the "optionally substituted C1-C18 alkyl (meth)acrylate" include, but are not limited to, an aliphatic hydrocarbon group, a polar group, an aromatic hydrocarbon group, a heteroaromatic group, and a substituted amino group. Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl and ethyl groups, alkenyl groups such as vinyl and allyl groups, and alkynyl groups such as ethynyl groups. Examples of the polar group include a hydroxyl group, an amino group, and a tetrahydrofurfuryl group. The aromatic hydrocarbon group is an aromatic hydrocarbon group containing one or more rings, such as a phenyl group or 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. Examples of the substituted amino group include a methylamino group, an ethylamino group, a phenylamino group, a dimethylamino group, and a methylethylamino group.

[0037] Specific examples of the "unsubstituted or optionally substituted C1 to C18 alkyl (meth)acrylate" 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, and stearyl (meth)acrylate. acrylate, cyclohexyl (meth)acrylate, trityl (meth)acrylate, 4-t-butylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminopropyl (meth)acrylate, (2-acryloyloxyethyl)trimethylaminium chloride, (2-methacryloyloxyethyl)trimethylaminium chloride, (2-acryloyloxyethyl)dimethylbenzylaminium chloride, (2-methacryloyloxyethyl)dimethylbenzylaminium chloride, and the like.

[0038] Examples of (meth)acrylamides include methyl(meth)acrylamide, dimethyl(meth)acrylamide, ethyl(meth)acrylamide, hydroxyethyl(meth)acrylamide, diethyl(meth)acrylamide, n-propyl(meth)acrylamide, dipropyl(meth)acrylamide, diisopropyl(meth)acrylamide, isopropylacrylamide, and n-butyl(meth)acrylamide. Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, citraconic anhydride, and itaconic anhydride. Examples of styrenes include styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, and pt-butoxycarbonylstyrene.

[0039] (Composition ratio of repeating units) In the polymer used in the present invention, the content of the repeating units derived from the polymerizable compound represented by formula (I) and the repeating units derived from other radical polymerizable compounds is not particularly limited. The molar ratio of the repeating units derived from the polymerizable compound represented by formula (I) to the repeating units derived from other radical polymerizable compounds can be selected from the range of 100:0 to 50:50, 99.5:0.5 to 60:40, 99:1 to 70:30, 98:2 to 75:25, 95:5 to 80:20, etc.

[0040] (Combination ratio of components (A) and (B)) The blending ratio of component (A) and component (B) is not particularly limited, but is preferably 0.1 to 80 parts by mass, more preferably 1 to 50 parts by mass, and most preferably 1 to 30 parts by mass, per 100 parts by mass of (A).

[0041] (Method for producing compounds represented by formula (I) and formula (II)) The polymerizable compounds used in the present invention, which are represented by formula (I) and formula (II), can be synthesized by the methods in the Examples or other known methods. For example, when Y in formula (I) is an acryloyl group or a methacryloyl 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; and inorganic bases such as hydroxides of alkali metals or alkaline earth metals, and carbonates 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. The reaction temperature is -50°C to 200°C.

[0042] (Polymerization method) The polymer used in the present invention can be any polymer obtained by polymerizing at least one polymerizable compound represented by formula (I) or formula (II), or by polymerizing such a compound with another polymerizable compound. The polymerization reaction is not particularly limited and may be any known method for synthesizing polyacrylates, etc., such as radical polymerization, anionic polymerization, cationic polymerization, ring-opening polymerization, and coordination polymerization. Examples are shown in the Examples. For example, when radically polymerizing a compound of formula (I) or (II) in which Y is an acryloyl group or a methacryloyl group with a (meth)acrylate, the polymerizable compound of formula (I) or formula (II) and the (meth)acrylate are heated or irradiated with light in a solvent in the presence of a radical polymerization initiator to carry out the polymerization reaction. The polymerization solvent is not particularly limited as long as it is a solvent that does not participate in the polymerization reaction and is compatible with the polymer, and specific examples include non-polar or low-polarity solvents such as ether compounds such as diethyl ether, tetrahydrofuran (THF), dioxane, and trioxane, ester compounds such as ethyl acetate, ketone compounds such as methyl ethyl ketone and cyclohexanone, and aliphatic, aromatic, or alicyclic hydrocarbon compounds such as hexane and toluene. These solvents can be used alone or as a mixed solvent of two or more. 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.

[0043] <Component (C) Polymerization initiator> The polymerization initiator is preferably a thermal radical polymerization initiator. The thermal radical polymerization initiator is preferably an organic peroxide. Examples of the organic peroxide include cumene hydroperoxide, paramenthane hydroperoxide, tertiary butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, and tertiary butyl peroxybenzoate. Among these, cumene hydroperoxide is preferred in terms of stability.

[0044] The amount of the polymerization initiator used is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, and most preferably 0.8 to 5 parts by mass, per 100 parts by mass of (A). When the amount is 0.1 part by mass or more, the curing rate increases. When the amount is 20 parts by mass or less, the storage stability improves.

[0045] <Component (D) Reducing Agent> Any reducing agent can be used as long as it reacts with the polymerization initiator to generate radicals.

[0046] Examples of reducing agents include tertiary amines, thiourea derivatives, and transition metal salts. Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of transition metal salts include cobalt octoate, cobalt naphthenate, copper naphthenate, and vanadyl acetylacetonate. Among these, transition metal salts are preferred in terms of reactivity. Among transition metal salts, vanadyl acetylacetonate is preferred.

[0047] 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, per 100 parts by mass of (A). When the amount is 0.05 parts by mass or more, the curing rate increases. When the amount is 15 parts by mass or less, the storage stability improves.

[0048] <Optional ingredients> The adhesive composition of the present invention may contain an appropriate amount of additives, such as adhesion aids such as silane coupling agents, thickeners, elastomers, core-shell polymers, reactive diluents, non-reactive diluents or solvents, vinyl aromatic compounds, paraffins, non-reactive colorants, fillers, antioxidants, light stabilizers, phosphates, plasticizers, tackifiers such as tackifiers, storage stabilizers such as BHT, dyes, pigments, flame retardants, sensitizers, heavy metal deactivators, ion trapping agents, emulsifiers, water dispersion stabilizers, antifoaming agents, release agents, leveling agents, rheology control agents, surfactants, etc., within the scope of the present invention.

[0049] 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, and 3-methacryloxypropyldimethylmonomethoxysilane; Examples of suitable silanes include (meth)acryloyl group-containing silane coupling agents such as silane, 3-methacryloxypropyldimethylmonoethoxysilane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropylmethyldipropyloxysilane, 3-acryloxypropyldimethylmonopropyloxysilane, 3-acryloxypropyldimethylmonomethoxysilane, 3-acryloxypropyldimethylmonoethoxysilane, 3-acryloxypropyldimethylmonopropyloxysilane, and γ-methacryloxypropyltrimethoxysilane; amino group-containing silane coupling agents such as N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; and γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc. These may be used alone or in combination of two or more.

[0050] An effective thickener is polybutyl methacrylate having a molecular weight of about 10,000 to about 40,000. The use of a thickener can increase the viscosity of the adhesive to a syrup-like consistency that provides excellent application properties. Such thickeners can generally be used in an amount of about 50% by weight or less based on the total weight of the adhesive.

[0051] Elastomers can be used in the adhesive composition. Elastomeric materials can improve the fracture toughness of the cured adhesive. For example, this can be beneficial when bonding rigid, high-yield strength materials (e.g., metal substrates that do not mechanically absorb energy as easily as materials such as flexible polymeric substrates). Such additives can generally be used in amounts of up to about 50% by weight based on the total weight of the adhesive.

[0052] The elastomer used in the present adhesive composition is preferably a polymeric substance that has rubber-like elasticity at room temperature, and is preferably one that can be dissolved or dispersed in a polymerizable vinyl monomer.

[0053] Examples of such elastomers include polybutadiene, (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer, (meth)acrylonitrile-butadiene-methyl(meth)acrylate copolymer, methyl(meth)acrylate-butadiene-styrene copolymer (MBS), (meth)acrylonitrile-butadiene rubber (NBR), butadiene (co)polymers such as styrene-butadiene, 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.

[0054] Core-shell polymers can also be used to improve the spreadability and flow properties of the adhesive. Improved spreadability and flow properties can be evidenced by a reduction in undesirable stringing that remains when the adhesive is dispensed from a syringe-type applicator or sagging after the adhesive is applied to a vertical surface. The core-shell polymer can generally be added in an amount of 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.

[0055] A reactive diluent may be added. Suitable reactive diluents include 1,4-dioxo-2-butene functional compounds and aziridine compounds.

[0056] Vinyl aromatic compounds may also be added to increase the working life of the adhesive without substantially affecting the rate of polymerization, cure time, and desired properties of the cured adhesive.

[0057] Useful vinyl aromatic compounds include, for example, α-methylstyrene group-containing oligomers prepared by reacting 3-isopropenyl-α,α-dimethylbenzyl isocyanate with mono- or polyfunctional reactive hydrogen compounds, preferably mono- or polyfunctional amines, alcohols, or combinations thereof. Particularly preferred monofunctional or polyfunctional amines include amine-terminated polyethers commercially available under the trade name JEFFAMINE, available from Huntsman PetroChemical Corp., Houston, Texas, such as JEFFAMINE ED600 (a diamine-terminated polyether having a nominal molecular weight of 600), JEFFAMINE D400 (a diamine-terminated polyether having a nominal molecular weight of 400), JEFFAMINE D2000 (a diamine-terminated polyether having a nominal molecular weight of 2000), JEFFAMINE T3000 (a triamine-terminated polyether having a nominal molecular weight of 3000), and JEFFAMINE M2005 (a monoamine-terminated polyether having a nominal molecular weight of 2000). Suitable alcohol-containing compounds include, for example, polypropylene glycol, polycaprolactone triol, and diethylene glycol. The vinyl aromatic compound can generally be added in an amount of about 1% by weight or more, about 2% by weight or more, or about 5% by weight or more, about 30% by weight or less, about 20% by weight or less, or about 10% by weight or less, based on the total weight of the adhesive.

[0058] 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 cured adhesive.

[0059] The adhesive composition of the present invention can contain various paraffins to rapidly cure the portions exposed to air. Examples of paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, spermaceti, ceresin, and candelilla wax. Among these, paraffin is preferred. The melting point of the paraffins is preferably 40 to 100°C.

[0060] The amount of paraffins used is preferably 0.1 to 5 parts by mass per 100 parts by mass of the (1) polymerizable vinyl monomer. If it is 0.1 part by mass or more, the curing of the part in contact with air will be improved, and if it is 5 parts by mass or less, the adhesive strength will not decrease.

[0061] Furthermore, various antioxidants including polymerization inhibitors can be used to improve storage stability, 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.

[0062] The amount of antioxidant used is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of (1) polymerizable vinyl monomer. When it is 0.001 part by mass or more, it is effective, and when it is 3 parts by mass or less, adhesiveness is improved.

[0063] Of the optional components listed above, the addition of an antioxidant and a light stabilizer is preferred to improve the weather resistance of the adhesive composition. Commercially available antioxidants and light stabilizers can be used. 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 ... 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 (registered trademark) AO-330, ADK STAB (registered trademark) PEP-4C, ADK STAB (registered trademark) PEP-8, ADK STAB (registered trademark) PEP-24G, ADK STAB (registered trademark) PEP-36, ADK STAB (registered trademark) HP-10, ADK STAB (registered trademark) 2112, ADK STAB (registered trademark) 260, ADK STAB (registered trademark) 522A, ADK STAB (registered trademark) 329K, ADK STAB (registered trademark) 1500, Examples of such antioxidants include ADK STAB® C, ADK STAB® 135A, and ADK 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 Ciba 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, per 100 parts by mass of component (B).

[0064] Furthermore, in this embodiment, it is preferable to use phosphate salts to improve adhesion and increase the curing rate.

[0065] Among the phosphates, in terms of adhesiveness and curing speed, examples include acid phosphooxyethyl (meth)acrylate, acid phosphooxypropyl (meth)acrylate, and bis(2-(meth)acryloyloxyethyl)phosphate, etc. Among these, in terms of adhesiveness and curing speed, acid phosphooxyethyl (meth)acrylate is preferred.

[0066] The amount of phosphate used is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, per 100 parts by mass of (1) polymerizable vinyl monomer. When the amount is 0.05 part by mass or more, the curing speed increases and adhesion, particularly to aluminum, improves, while when the amount is 10 parts by mass or less, adhesion improves.

[0067] <Use form of adhesive composition> 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 using complicated surface treatment techniques such as flame treatment, Itro treatment, corona discharge, and primer treatment. In the present disclosure, "low surface energy plastics" include 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-modified products of these materials, and polymer blends of these materials with elastomers such as ethylene-propylene rubber (EPM) and ethylene-propylene-diene rubber (EPDM). In this disclosure, "high surface energy plastics" include polyvinyl chloride (PVC), polycarbonate (PC), and polymethyl methacrylate (PMMA). The two-component adhesive of the present disclosure can be advantageously used on substrates containing modified elastomers and polymer blends of elastomers that are prone to oxygen absorption. Suitable substrates containing modified elastomers and polymer blends of elastomers include olefin-based elastomer substrates including elastomer-based modified 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 and polypropylene, particularly polypropylene-based elastomer substrates including elastomer-based modified 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.

[0068] The adhesive composition of the present invention is preferably used as a two-part adhesive composition. In the two-part type, all of the essential components of the adhesive composition of this embodiment are not mixed during storage, but the adhesive composition is divided into a first part and a second part, and at least the polymerization initiator (component (C)) is stored in the first part, and at least the reducing agent (component (D)) is stored in the second part separately. Specifically, the first agent can be a composition containing components (A), (B), and (C), and the second agent can be a composition containing components (A), (B), and (D). Alternatively, the first agent can be a composition containing (A) and (C), and the second agent can be a composition containing components (B) and (D), or the first agent can be a composition containing (A), (B), and (C), and the second agent can be only (D). Optional components may be added to each agent as needed. The two-component type is preferred because it has excellent storage stability. In this case, the two components can be applied simultaneously or separately, brought into contact, and cured to form a two-component adhesive composition.

[0069] The adhesive composition of the present invention does not require accurate measurement of the two components, and cures at room temperature even with incomplete measurement or mixing, or even with only contact between the two components. UV light is not required for curing the adhesive composition of the present invention. The adhesive composition of the present invention has excellent workability.

[0070] <Molded body> The molded article of the present invention is obtained by applying the adhesive composition described above to a plastic substrate and then providing a layer of the cured adhesive composition directly on or between the substrates. [Example]

[0071] The number average molecular weights of the polymers obtained in the examples were measured using the following apparatus and conditions. [Device] Sample injection device: Waters 2695 Alliance Separation column: Shodex KF-G, 805L, 804L, 804L Detector: Waters 2414 Differential Refractive Index (RI) Detector, 2998 Photodiode Array (PDA) Detector Column oven: Waters column oven [conditions] Column oven temperature: 40°C RI detector temperature: 40℃ Mobile phase: tetrahydrofuran Flow rate: 1.0mL / min Standard injection volume: 200μL PDA detector extracted wavelength: 254.0 nm Quantitative calculation: Standard polymethyl methacrylate equivalent

[0072] (Synthesis Example 1) Synthesis of N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide (DOPAA) [ka] A 1-L four-neck flask was charged with bis[4-(1,1,3,3-tetramethylbutyl)phenyl]amine (50.00 g, 0.127 mol), N,N-dimethylaniline (46.17 g, 0.381 mol), and 477 mL of ultra-dehydrated dichloromethane, and stirred until homogeneous. The reaction solution was then cooled to below 0°C in an ice / ethanol bath, and acrylic acid chloride (22.99 g, 0.254 mol) was slowly added dropwise and stirred for 30 minutes. The reaction solution was then warmed to room temperature and reacted for 24 hours. After completion of the reaction, the solvent was removed using an evaporator, and the crude product was dissolved in 250 mL of ethyl acetate. The mixture was then washed with 1N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, and brine. The organic layer was dehydrated over magnesium sulfate, and the filtrate was evaporated using an evaporator. The obtained crude product was purified by recrystallization from 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.

[0073] (Synthesis Example 2) Preparation of adhesive polymer 1 (DOPAA / EA=90 / 10) A 300 mL four-neck flask was charged with 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45 g of toluene. The mixture was degassed by reducing the pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.10 g of AIBN was then added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried in a vacuum dryer at 60°C under reduced pressure. Yield: 28.19 g, Mn = 17,379, Mw / Mn = 2.08

[0074] (Synthesis Example 3) Preparation of adhesive polymer 2 (DOPAA / EA=90 / 10) A 300 mL four-neck flask was charged with 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 40.62 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 27.82 g, Mn = 26,399, Mw / Mn = 2.20

[0075] (Synthesis Example 4) Preparation of adhesive polymer 3 (DOPAA / EA=90 / 10) A 300 mL four-neck flask was charged with 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 36.69 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 29.01 g, Mn = 29,109, Mw / Mn = 2.10

[0076] (Synthesis Example 5) Preparation of adhesive polymer 4 (DOPAA / EA=90 / 10) A 300 mL four-neck flask was charged with 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 33.18 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 28.87 g, Mn = 31,641, Mw / Mn = 2.20

[0077] (Synthesis Example 6) Preparation of Adhesive Polymer 5 (DOPAA / EA=90 / 10) A 300 mL four-neck flask was charged with 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 30.02 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 27.31 g, Mn = 34,687, Mw / Mn = 2.38

[0078] (Synthesis Example 7) Preparation of adhesive polymer 6 (DOPAA / EA=90 / 10) A 300 mL four-neck flask was charged with 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 20.02 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 28.11 g, Mn = 36,941, Mw / Mn = 2.94

[0079] (Synthesis Example 8) Preparation of adhesive polymer 7 (DOPAA / EA=85 / 15) A 300 mL four-neck flask was charged with 25.52 g of DOPAA, 4.50 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45.03 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 29.33 g, Mn = 21,484, Mw / Mn = 2.11

[0080] (Synthesis Example 9) Preparation of adhesive polymer 8 (DOPAA / EA=80 / 20) A 300 mL four-neck flask was charged with 24.02 g of DOPAA, 6.00 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45.03 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring were stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 28.13 g, Mn = 24,577, Mw / Mn = 1.98

[0081] (Synthesis Example 10) Preparation of Adhesive Polymer 9 (DOPAA / EA=70 / 30) A 300 mL four-neck flask was charged with 21.01 g of DOPAA, 9.00 g of ethyl acrylate (EA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45.03 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 28.83 g, Mn = 19,320, Mw / Mn = 2.18

[0082] (Synthesis Example 11) Preparation of adhesive polymer 10 (DOPAA / MA=90 / 10) A 300 mL four-neck flask was charged with 18.10 g of DOPAA, 2.00 g of methyl acrylate (MA: Tokyo Chemical Industry Co., Ltd.), and 0.14 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 30 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.07 g of AIBN was then added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 16.23 g, Mn = 13,360, Mw / Mn = 1.84

[0083] (Synthesis Example 12) Preparation of adhesive polymer 11 (DOPAA / nBA=90 / 10) A 300 mL four-neck flask was charged with 18.09 g of DOPAA, 2.10 g of n-butyl acrylate (nBA: Tokyo Chemical Industry Co., Ltd.), and 0.18 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 30 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.09 g of AIBN was then added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 17.93 g, Mn = 15,615, Mw / Mn = 1.71

[0084] (Synthesis Example 13) Preparation of adhesive polymer 12 (DOPAA / iBA=90 / 10) A 300 mL four-neck flask was charged with 18.09 g of DOPAA, 2.10 g of i-butyl acrylate (iBA: Tokyo Chemical Industry Co., Ltd.), and 0.18 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 30 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. 0.09 g of AIBN was then added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring were stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 18.03 g, Mn = 16,271, Mw / Mn = 1.88

[0085] (Synthesis Example 14) Preparation of adhesive polymer 13 (DOPAA / THFA=90 / 10) A 300 mL four-neck flask was charged with 26.97 g of N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide (DOPAA), 2.99 g of tetrahydrofurfuryl acrylate (THFA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure in a vacuum dryer at 60°C. Yield: 27.23 g, Mn=13,901, Mw / Mn=2.21

[0086] (Synthesis Example 15) Preparation of adhesive polymer 14 (DOPAA / HEA=90 / 10) A 300 mL four-neck flask was charged with 27.10 g of DOPAA, 3.03 g of 2-hydroxyethyl acrylate (HEA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 27.15 g, Mn = 22,703, Mw / Mn = 2.29

[0087] (Synthesis Example 16) Preparation of adhesive polymer 15 (DOPAA / EHA=90 / 10) A 300 mL four-neck flask was charged with 27.03 g of DOPAA, 3.02 g of 2-ethylhexyl acrylate (EHA: Tokyo Chemical Industry Co., Ltd.), and 0.20 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 45 g of toluene. The mixture was degassed under 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 the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 26.90 g, Mn = 12,588, Mw / Mn = 1.80

[0088] (Synthesis Example 17) Preparation of adhesive polymer 16 (DOPAA / styrene = 90 / 10) A 300 mL four-neck flask was charged with 30.00 g of DOPAA, 3.33 g of styrene (Tokyo Kasei), and 0.20 g of AIBN (Tokyo Kasei), and dissolved in 50 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring were stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 31.60 g, Mn = 22,408, Mw / Mn = 2.36

[0089] (Synthesis Example 18) Preparation of adhesive polymer 17 (DOPAA / DEAA=90 / 10) A 300 mL four-neck flask was charged with 30.00 g of DOPAA, 3.33 g of N,N-diethylacrylamide (DEAA: Tokyo Kasei), and 0.19 g of AIBN (Tokyo Kasei), and dissolved in 50 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 30.00 g, Mn = 25,377, Mw / Mn = 2.08

[0090] (Synthesis Example 19) Preparation of Adhesive Polymer 18 (DOPAA / Maleic Anhydride = 90 / 10) A 300 mL four-neck flask was charged with 20.00 g of DOPAA, 2.22 g of maleic anhydride (Tokyo Kasei), and 0.14 g of AIBN (Tokyo Kasei), and dissolved in 22.2 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring was stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 20.07 g, Mn = 28,576, Mw / Mn = 1.78

[0091] (Synthesis Example 20) Preparation of adhesive polymer 19 (DOPAA / iBMA=90 / 10) A 300 mL four-neck flask was charged with 20.00 g of DOPAA, 2.22 g of isobutyl methacrylate (iBMA: Tokyo Kasei), and 0.13 g of AIBN (Tokyo Kasei), and dissolved in 22.2 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring were stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 21.11 g, Mn = 26,758, Mw / Mn = 2.33

[0092] (Synthesis Example 21) Preparation of adhesive polymer 20 (DOPAA / EHMA=90 / 10) A 300 mL four-neck flask was charged with 20.00 g of DOPAA, 2.22 g of 2-ethylhexyl methacrylate (EHMA: Tokyo Chemical Industry Co., Ltd.), and 0.12 g of AIBN (Tokyo Chemical Industry Co., Ltd.), and dissolved in 22.2 g of toluene. The mixture was degassed under reduced pressure, and heated and stirred at 65°C for 6 hours in a nitrogen atmosphere. Then, 0.10 g of AIBN was added, and the mixture was stirred at 80°C for 5 hours. Heating and stirring were stopped, and the reaction solution was sampled and analyzed by gel permeation chromatography. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The resulting precipitate was filtered and dried under reduced pressure at 60°C in a vacuum dryer. Yield: 21.38 g, Mn = 35,929, Mw / Mn = 1.90

[0093] (Synthesis Example 22) Preparation of Adhesive Polymer 21 (Poly{N,N-bis(4-(1,1,3,3-tetramethylbutyl)phenyl)acrylamide} (PDOPAA)) A 500 mL four-neck flask was charged with 100.0 g of DOPAA, 150.0 g of toluene, and 0.322 g of AIBN and heated to 30°C under a nitrogen atmosphere. After confirming that the system was homogeneous, the mixture was stirred with a magnetic stirrer and degassed under reduced pressure three times using a diaphragm pump. After degassing, the mixture was heated to 65°C and stirred for 24 hours. The flask was then returned to room temperature, and reprecipitation was carried out using 1600 mL of methanol. The mixture was then vacuum dried at 120°C for 2 hours to obtain a white powder. Yield: 96.00 g, Mn = 14,315, Mw / Mn = 1.89

[0094] (Preparation of Adhesive Composition) The components shown in Tables 1 to 11 were mixed and stirred to obtain adhesive compositions. (2) The composition using cumene hydroperoxide was used as the first part, and (3) the composition using vanadyl acetylacetonate was used as the second part. Equal amounts of the first and second parts were mixed and stirred to obtain adhesive compositions.

[0095] The amount of each compounded substance is shown in parts by mass in Tables 1 to 11. Details of each compounded substance are as follows. EHMA: 2-ethylhexyl methacrylate, commercially available MMA: Methyl methacrylate, commercially available EMA: Ethyl methacrylate, commercially available nBMA: n-butyl methacrylate, commercially available iBMA: i-butyl methacrylate, commercially available CHMA: Cyclohexyl methacrylate, commercially available IBOMA: Isobornyl methacrylate, commercially available LMA: Lauryl methacrylate, commercially available BzMA: benzyl methacrylate, commercially available THFMA: tetrahydrofurfuryl methacrylate, commercially available Cumene hydroperoxide: commercially available Vanadyl acetylacetonate: commercially available Cobalt octoate: commercially available Cobalt naphthenate: commercially available Ethylenethiourea: commercially available NBR: Acrylonitrile-butadiene rubber, commercially available SBR: styrene-butadiene rubber, commercially available Bis-GMA: 2,2-bis[4(-hydroxy-3-methacryloyloxypropoxy)phenyl]propane, commercially available TE-2000: Nippon Soda Co., Ltd., urethane methacrylate-terminated polybutadiene TEAI-1000: Nippon Soda Co., Ltd., urethane acrylate-terminated polybutadiene

[0096] (Tensile shear strength (tensile shear adhesive strength)) The following test pieces were used: Examples 1 to 40 and Comparative Examples 1 to 4: Polypropylene (PP) Example 41: High Density Polyethylene (HDPE) Example 42: Low Density Polyethylene (LDPE) Example 43: Cycloolefin polymer (COP) Example 44: Cycloolefin copolymer (COC) Example 45: Polymethylpentene (PMP) Examples 46-61: Polytetrafluoroethylene (PTFE) Example 47: Polydimethylsilicone (PDMS) Example 48: Polycarbonate (PC) Example 49: Polystyrene (PS) Example 50: Polymethyl methacrylate (PMMA) Example 51: Polyethylene terephthalate (PET) Example 52: Rigid Polyvinyl Chloride (PVC) Example 53: Nylon 6 (PA6) Example 54: Polyacetal (POM) Example 55: Polyetheretherketone (PEEK) Example 56: Liquid Crystal Polyester (LCP) Example 57: Polyphenylene sulfide (PPS) Example 58: Modified Polyphenylene Ether (m-PPE) Example 59: Polybutylene terephthalate (PBT) Example 60: Acrylonitrile-Butadiene-Styrene (ABS) All adherend substrates measured 100 x 25 x 2.0 mm. The adherends were wiped with a rag before use. According to JIS K-6850, an adhesive composition consisting of a mixture of the first and second parts was applied to one side of one test piece at a temperature of 23°C and humidity of 50%, and the test pieces were immediately bonded together. The thickness of the adhesive layer was 0.1 mm. After aging for 24 hours at room temperature, this was used as a sample for measuring tensile shear strength, and the tensile shear strength (unit: MPa) was measured and recorded as the tensile shear strength. The measurement was performed at a temperature of 23°C and a pulling speed of 10 mm / min.

[0097] [Table 1]

[0098] [Table 2]

[0099] [Table 3]

[0100] [Table 4]

[0101] [Table 5]

[0102] [Table 6]

[0103] [Table 7]

[0104] [Table 8]

[0105] [Table 9]

[0106] [Table 10]

[0107] [Table 11]

[0108] These test results show that the adhesive composition of the present invention has excellent adhesion to a variety of plastic resins, including 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). 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.

Claims

1. Contains the following components (A) to (D): A two-component adhesive composition comprising a first part containing at least component (C) and a second part containing at least component (D). (A) Radical polymerizable compound (B) (B-1) A polymer comprising at least one repeating unit derived from a polymerizable compound represented by formula (I), or (B-2) A polymer comprising at least one repeating unit derived from the polymerizable compound represented by formula (I) and at least one repeating unit derived from another radically polymerizable compound. 【Chemical 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. (C) Polymerization initiator (D) Reducing agent

2. 2. The two-component adhesive composition according to claim 1, wherein the polymerization initiator is cumene hydroperoxide.

3. 3. The two-component adhesive composition according to claim 1, wherein the reducing agent is at least one selected from the group consisting of vanadyl acetylacetonate, cobalt octoate, cobalt naphthenate, and ethylenethiourea.

4. The two-component adhesive composition according to any one of claims 1 to 3, further comprising polybutadiene.

5. A molded article, which is obtained by applying the two-component adhesive composition according to any one of claims 1 to 4 onto a plastic substrate and providing a cured layer on or between the substrates.

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