WO2020262423A1 - Adhesive composition - Google Patents

Abstract

The present invention addresses the problem of providing an adhesive composition which exhibits excellent bondability and adhesion to various plastics such as a polypropylene resin, a polyethylene resin and a cycloolefin resin.　An adhesive composition according to the present invention contains a copolymer that has a repeating unit derived from a polymerizable compound represented by formula (I) and a repeating unit derived from a (meth)acrylic acid ester. (In the formula, X¹ represents a C7-C20 alkyl group or a C7-C20 alkoxy group; X² represents a C7-C20 alkyl group, a C7-C20 alkoxy group or the like; n represents 0 or 1; each of Z¹ and Z² independently represents a single bond or a C1-C3 alkylene group; each R independently represents a halogeno group or an organic group; each of m1 and m2 independently represents an integer of from 0 to 4; and Y represents a polymerizable functional group.)

Description

Adhesive composition

The present invention relates to a novel adhesive composition, particularly an adhesive composition having excellent adhesiveness and adhesion to a plastic base material, and an adhesive composition that can be used as a coating agent or an adhesive. The present application claims priority to Japanese Patent Application No. 2019-120067 filed on June 27, 2019, the contents of which are incorporated herein by reference.

Patent Document 1 describes that an adhesive composition using a polymer of N, N-diphenylacrylamide is a coating agent having excellent adhesiveness and adhesion to a cycloolefin resin. In the document, as the alkyl group which is a substituent of the phenyl group of the above N, N-diphenylacrylamide, only a C1 to C6 alkyl group, specifically a methyl group is disclosed, and a long chain alkyl of C7 or more is disclosed. The group is not disclosed.

WO2018 / 070079 Pamphlet

However, since these adhesive compositions did not have sufficient adhesiveness to polyethylene and polypropylene, it was necessary to devise ways to improve the adhesiveness in order to use them as these base materials. Further, in the homopolymer in which the phenyl group of N, N-diphenylacrylamide is substituted with a long-chain alkyl group of C7 or more, the solubility in the (meth) acrylic acid ester monomer is low and the peel peeling strength is low, so that the homopolymer has adhesiveness. In preparing the composition, it was necessary to improve this.

As a result of diligent studies to achieve the above problems, the present inventors have added a repeating unit derived from a polymerizable compound in which N, N-diphenylacrylamide is substituted with a C7 to C20 alkyl chain or the like, and a (meth) acrylic acid ester. By making a copolymer having a repeating unit derived from it, it has excellent adhesiveness and adhesion to various plastics including polyethylene and polypropylene resins, and also has excellent solubility in (meth) acrylic acid ester monomers, etc., and peel peeling strength. It was found that the above was improved, and the present invention was completed.

That is, the present invention relates to the following invention.
(1) Equation (I)

(During the ceremony,
X ¹ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.
X ² represents an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.
n represents 0 or 1 and represents
Z ¹ and Z ² independently represent a single bond or a C1-C3 alkylene group.
Each R independently represents a halogeno group or an organic group.
m1 and m2 independently represent an integer of 0 to 4, respectively.
Y represents a polymerizable functional group. )
Repeating unit derived from a polymerizable compound represented by, and
An adhesive composition containing a copolymer having repeating units derived from a (meth) acrylic acid ester.
(2) The adhesive composition according to (1), wherein Y is an acryloyl group or a methacryloyl group in the formula (I).
(3) The polymerizable compound represented by the formula (I) is the formula (II).

(During the ceremony,
X ¹⁰ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.
X ²⁰ represents a hydrogen atom, an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.
Z ¹ and Z ² independently represent a single bond or a C1-C3 alkylene group.
Each R independently represents a halogeno group or an organic group.
m1 and m2 independently represent an integer of 0 to 4, respectively.
Y represents a polymerizable functional group)
The adhesive composition according to (1) or (2), which is a compound represented by.
(4) The adhesive composition according to any one of (1) to (3), wherein the alkyl group of C7 to C20 and the alkoxy group of C7 to C20 are branched chains.
(5) The above-mentioned (1) to (4), wherein the (meth) acrylic acid ester is an unsubstituted or optionally having a substituent (meth) acrylic acid C1 to C18 alkyl ester. Adhesive composition.
(6) The adhesive composition according to any one of (1) to (5), wherein the (meth) acrylic acid ester is a linear or branched alkyl ester of (meth) acrylic acid.
(7) The adhesive composition according to any one of (1) to (6), further containing a monofunctional or polyfunctional (meth) acrylic acid ester monomer.
(8) The adhesive composition according to any one of (1) to (7), wherein the adhesive composition is an adhesive composition for a plastic base material.
(9) The adhesive composition according to (8), wherein the plastic base material is a polyolefin base material.
(10) The adhesive composition according to (8), wherein the plastic base material is a polypropylene base material or a polyethylene base material.
(11) The adhesive composition according to (8), wherein the adhesive composition is a coating agent.
(12) The adhesive composition according to (11), wherein the coating agent is a primer.
(13) The adhesive composition according to (8), wherein the adhesive composition is an adhesive.
(14) Equation (I)

(During the ceremony,
X ¹ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.
X ² represents an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.
n represents 0 or 1 and represents
Z ¹ and Z ² independently represent a single bond or a C1-C3 alkylene group.
Each R independently represents a halogeno group or an organic group.
m1 and m2 independently represent an integer of 0 to 4, respectively.
Y represents a polymerizable functional group. )
A copolymer having a repeating unit derived from a polymerizable compound represented by and a repeating unit derived from a (meth) acrylic acid ester.

By using the adhesive composition of the present invention, it is possible to form a coating film having excellent adhesiveness and adhesion to a plastic base material, particularly a polyolefin base material such as polycycloolefin, polyethylene and polypropylene. Conventionally, there has been no adhesive composition that can be widely used for these various plastic substrates, but the adhesive composition of the present invention can do so. Functional films that could not be directly formed in the past can be laminated via the coating film of the present invention, and further, plastic substrates containing these can be adhered to each other via the coating film.
Since it is not necessary to modify the surface by UV ozone treatment or the like, the initial characteristics of the plastic base material can be maintained. In addition, since it is highly soluble in solvents and resins, it is easy to prepare various adhesive compositions. In addition, it is highly soluble in various (meth) acrylic acid ester monomers and the like, and the peel peeling strength is also improved, which is advantageous for producing an adhesive composition.
It can also be used as an adhesive.

1. 1. Adhesive composition [copolymer]
The adhesive composition of the present invention contains a copolymer having a repeating unit derived from a polymerizable compound represented by the formula (I) and a repeating unit derived from a (meth) acrylic acid ester.
In the present invention, "(meth) acrylic acid ester" means "acrylic acid ester" and / or "methacrylic acid ester", and "(meth) acrylamide" means "acrylamide" and / or "methacrylamide".

(Polymerizable compound represented by the formula (I))

In the formula, X ¹ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20, and X ² represents an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.

As the alkyl group of C7 to C20 in X ¹ and X ² , a linear group or a branched chain group can be preferably used.
As linear ones, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecylic group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group. Groups, n-eikosyl groups and the like can be mentioned.
The branched chains 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 Group, 3-ethyl-3-methylpentyl group, 3-ethyl-4-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- Examples thereof include a methyl heptyl group, a 1-methyl heptyl group, a 1-methyl-1-octylundecyl group and the like.
In X ¹ and ^{X 2,} the alkoxy group of C7 ~ C20, also a straight-chain, some are branched chain, can be preferably used.
As linear ones, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n -Hexadecyloxy group, n-octadecyloxy group, n-eicosyloxy group and the like can be mentioned.
The branched chains include 1,1,2,2-tetramethylpropyloxy group, 1,1,3-trimethylbutyloxy group, 1-ethylpentyloxy group, 1,1,3,3-tetramethylbutyl. Oxy 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, 1-ethyl-1-methylpentyloxy group, 1,1-dimethylhexyl Oxy group, 3,3-dimethylhexyloxy group, 4,4-dimethylhexyloxy group, 2-ethylhexyloxy group, 3-ethylhexyloxy group, 6-methylheptyloxy group, 1,3,5-trimethylhexyloxy Groups, 1,1,3-trimethylhexyloxy group, 1-butyl-1-methylheptyloxy group, 1-methylheptyloxy group, 1-methyl-1-octylundecyloxy group and the like can be mentioned.
Examples of the halogeno group in X ² include a fluoro group, a chloro group, a bromo group, an iod group and the like.
The organic group in X ² is not particularly limited as long as it is chemically acceptable and has the effect of the present invention. Organic groups include 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. C1-6 alkyl groups such as C1-6 alkyl groups, C6-10 aryl groups such as phenyl groups and naphthyl groups, methoxy groups, ethoxy groups, n-propoxy groups, i-propoxy groups, n-butoxy groups, s-butoxy groups, i. -C1-6 alkoxy groups such as butoxy group and t-butoxy group, chloromethyl group, chloroethyl group, trifluoromethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, per Examples thereof include C1 to 6 haloalkyl groups such as a fluoro-n-pentyl group.

In the formula, n represents 0 or 1.

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

In the formula, R represents a halogeno group or an organic group.
The halogeno group and an organic group include the same ones the halogeno group and an organic group of X ^2.

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

In the formula, Y represents a polymerizable functional group. The polymerizable functional group includes acryloyl group, methacryloyl group, vinyloxycarbonyl group, prop-1-ene-2-yloxycarbonyl group, allyloxycarbonyl group, vinyl group, allyl group and other polymerizable carbon-carbons. Examples include a group having a double bond.
In the present invention, Y is preferably an acryloyl group or a methacryloyl group.

The above formula (I) includes a compound represented by the following formula (II).

In the formula, Y, Z ¹ , Z ² , R, m1, and m2 are the same as those described in the formula (I).

In the formula, X ¹⁰ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20, and X ²⁰ is a hydrogen atom, an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group. For both X ¹⁰ and X ²⁰ , an alkyl group of C7 to C20 or an alkoxy group of C7 to C20 is preferable.
C7 ~ C20 alkyl group in X ¹⁰ and ^{X 20} may include the same as the C7 ~ C20 alkyl group in ^X 1, ^{X 2} in formula (I).
Alkoxy groups X ¹⁰ and ^{X 20} in the C7 ~ C20 may be mentioned the same ones as the alkoxy group of C7 ~ C20 in ^X 1, ^{X 2} in formula (I).
Examples of the halogeno group and the organic group in X ²⁰ can be the same as the halogeno group and the organic group in X ² .

Among the polymerizable compounds represented by the formula (I) or the formula (II) used in the present invention, N, N-bis (4- (1,1,3,3-tetramethylbutyl) phenyl) is preferable. Acrylamide, N, N-bis (4- (1,1,3,3-tetramethylbutyl) phenyl) methacrylicamide, N-phenyl-N- (4- (2,4,4-trimethylpentane-2-yl) ) Phenyl) acrylamide, N-Phenyl-N- (4- (2,4,4-trimethylpentan-2-yl) phenyl) Methacrylate, N, N-bis (4-octylphenyl) acrylamide, N, N- Examples thereof include bis (4-octylphenyl) methacrylicamide, N- (4-octylphenyl) -N-phenylacrylamide, and N- (4-octylphenyl) -N-phenylmethacrylicamide.

((Meta) acrylic acid ester)
The repeating unit derived from the (meth) acrylic acid ester means a repeating unit derived from one or more (meth) acrylic acid esters.
As a repeating unit derived from (meth) acrylic acid ester,
The (meth) acrylic acid ester is preferably a C1-C18 alkyl (meth) acrylic acid ester which may have a substituent or a substituent.
The alkyl moiety of the alkyl (meth) acrylic acid ester may be linear, branched or cyclic (alicyclic).
Specific examples of these alkyl groups include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group and n-. Direct C1 to C20 such as pentyl group, n-hexyl group, n-nonyl group, i-nonyl group, n-decyl group, lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group, etc. Chain or branched alkyl group; C3 to C8 cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.

Examples of the substituent which may be substituted with 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 an alkyl group such as a methyl group and an ethyl group, an alkenyl group such as a vinyl group and an allyl group, and an alkynyl group such as an ethynyl group.
Examples of the polar group include a hydroxyl group, an amino group, and a tetrahydrofuryl group.
Aromatic groups are aromatic hydrocarbon groups containing one or more rings. For example, a phenyl group, a naphthyl group and the like can be mentioned.
A heteroaromatic group is an aromatic group having at least one O, S, or N as a heteroatom. For example, a pyridinyl group, a thienyl group, a frill group, a benzimidazolyl group and the like can be mentioned.

Specific examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, hydroxyethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, and 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 (Meta) acrylate, trityl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (2-acryloyloxyethyl) trimethylaminium chloride, Examples thereof include (2-methacryloyloxyethyl) trimethylaminium chloride, (2-acryloyloxyethyl) dimethylbenzylaminium chloride, and (2-methacryloyloxyethyl) dimethylbenzylaminium chloride.

(Composition of repeating unit)
In the copolymer used in the present invention, the content of the repeating unit derived from the polymerizable compound represented by the formula (I) and the repeating unit derived from the (meth) acrylic acid ester is not particularly limited.
The repeating unit derived from the polymerizable compound represented by the formula (I) and the repeating unit derived from the (meth) acrylic acid ester may be in the mass ratio of 99: 1 to 1:99, which is preferable. Is 99: 1 to 30:70, more preferably 99: 1 to 50:50.

The copolymer used in the present invention is not particularly limited as long as it has a repeating unit derived from a polymerizable compound represented by the formula (I) and a repeating unit derived from a polymerizable compound derived from (meth) acrylic acid ester. And may have repeating units derived from other polymerizable compounds.

(Other polymerizable compounds)
The polymerizable compound represented by the formula (I) and the polymerizable compound other than the (meth) acrylic acid ester may be appropriately selected according to the desired physical properties such as melting point, viscosity or refractive index, and are particularly limited. Although not a compound, specific examples include the following.

Vinyl compounds such as styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ether, acrolein, and divinylbenzene;
Olefin compounds such as ethylene, propylene and butadiene.

The copolymer contained in the adhesive composition of the present invention has a repeating unit derived from a polymerizable compound represented by the formula (I) and a repeating unit derived from a (meth) acrylic acid ester randomly arranged, alternating with each other. It may be arranged or block-arranged.

In 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 formed by branching at one point (star type) and a branched chain formed by branching at a plurality of points (graft type).

(Production method of compounds represented by formulas (I) and (II))
The polymerizable compounds used in the present invention, formulas (I) and (II), can be synthesized by the methods of Examples or other known methods.
For example, when Y of the formula (I) is an acrylic group or a methacrylic group, it can be produced by the following method.
Equation (I')

(In the formula, X ¹ , X ² , n, Z ¹ , Z ² , R, m1, m2 are the same as the definitions in the formula (I).) Secondary amine and (meth) acrylic represented by the formula (I). A (meth) acrylic acid halide such as acid chloride is reacted 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, and ether solvents such as tetrahydrofuran (THF), 1,2-dimethoxyethane, diethyl ether and methyl cellsolve. Aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene and benzonitrile, saturated hydrocarbons such as pentane, hexane, octane and cyclohexane, halogens such as dichloromethane, chloroform, carbon tetrachloride and 1,2-dichloroethane. Dimethylformamide and the like can be mentioned, and one or more of these mixed solvents can be used.
Examples of the base include aliphatic amines such as triethylamine and tributylamine, aromatic amines such as pyridine, N-ethylpyridine, N, N-dimethylaniline, N, N-dimethylaminopyridine, sodium ethylate, and sodium methylate. Organic bases such as metal alkoxides and alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, sodium hydrogencarbonate, etc. Alternatively, an inorganic base such as an alkali earth metal hydroxide, an alkali metal or an alkaline earth metal carbonate can be used.
The reaction temperature is −50 ° C. to 200 ° C.

(Copolymerization method)
The copolymer used in the present invention can be used without particular limitation as long as it is obtained by polymerizing a polymerizable compound represented by the formula (I) and a (meth) acrylic acid ester. The polymerization reaction is not particularly limited, and may be a known method for synthesizing polyacrylate or the like, and examples thereof include radical polymerization, anionic polymerization, cationic polymerization, ring-opening polymerization, and coordination polymerization. An example is shown in the examples.
For example, in the case of radical polymerization of a compound in which Y of the formula (I) is an acrylic group or a methacrylic group and a compound of (meth) acrylic acid ester, the polymerizable compound represented by the formula (I) or the formula (II) is used. A polymerization reaction is carried out by heating or irradiating a compound of (meth) acrylic acid ester in a solvent in the presence of a radical polymerization initiator.
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 specifically, ether compounds such as diethyl ether, tetrahydrofuran (THF), dioxane, and trioxane and the like. To exemplify ester compounds such as ethyl acetate, ketone compounds such as methyl ethyl ketone and cyclohexanone, and non-polar solvents or low polar solvents such as aliphatic, aromatic or alicyclic hydrocarbon compounds such as hexane and toluene. Can be done. These solvents can be used alone or as a mixed solvent of two or more kinds.
Examples of the radical polymerization initiator include azobisisobutyronitrile (hereinafter sometimes referred to as AIBN), azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis-2-amidinopropane / hydrochloride, and the like. Examples thereof include potassium peroxobisulfate, ammonium peroxobisulfate, t-butylhydroperoxide, di-t-butylcumenhydroperoxide peroxide, acetyl peroxide, benzoyl peroxide, and lauroyl peroxide.

The molecular weight of the polymer used in the adhesive composition of the present invention is not limited as long as it can be applied onto the substrate, and is, for example, 1,000 to 1,000,000, 5,000 to 500, Copolymers having a number average molecular weight in the range of 000, 10,000 to 150,000, 10,000 to 200,000, 20,000 to 100,000 and the like can be mentioned.
The molecular weight distribution (PDI) of the polymer according to the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 4. In terms of the ratio of weight average molecular weight / number average molecular weight (Mw / Mn). 0, most preferably 1.0 to 3.0.
The weight average molecular weight and the 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 polymethylmethacrylate used as a standard.

[Other ingredients]
In the adhesive composition of the present invention, various components can be added depending on the intended purpose as long as the effects of the present invention are not impaired. Such components include binder resins, polymerization initiators, solvents, dehydrators, flame retardants, heat stabilizers, antioxidants, slip agents, antistatic agents, UV absorbers, colorants and mold release agents, and organics. Examples thereof include a condensate of a silane compound and a metal compound. These can be used in combination of two or more.

(Binder resin)
Examples of the binder resin contained in the adhesive composition of the present invention include (meth) acrylic resin, melamine resin, urethane resin, epoxy resin, silicone resin, polyester resin, polyamic acid resin, and polyimide resin. A resin, a styrene maleic acid-based resin, a styrene anhydride-based maleic acid-based resin, or the like can be used.

In the adhesive composition of the present invention, a curable resin such as an ionizing radiation curable resin or a thermosetting resin can also be used as the binder resin. Here, the "ionizing radiation curable resin" refers to a resin that is cured by irradiation with any of ionizing radiation including all electromagnetic waves such as infrared rays, visible rays, ultraviolet rays, X-rays, and electron beams.

The ionizing radiation curable resin and the heat-curable resin are not particularly limited, but monomers, prepolymers, oligomers, polymers and the like having a vinyl group, a (meth) acryloyl group, an epoxy group, or an oxetanyl group can be used. .. Of these, it is preferable to use a polyfunctional resin. In the present invention, "(meth) acryloyl group" means "acryloyl group" and / or "methacryloyl group".

Specifically, as the ionizing radiation curable resin or the thermosetting resin, a monofunctional or polyfunctional (meth) acrylic acid ester monomer, a (meth) acrylic acid ester oligomer, or the like can be used. Among them, it is preferable to contain a polyfunctional (meth) acrylic acid ester having two or more polymerizable unsaturated groups.

The monofunctional (meth) acrylic acid ester monomer is a monomer having one (meth) acrylic acid ester group in the molecule, for example, tricyclodecane acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate and the like. Can be mentioned.

The polyfunctional (meth) acrylic acid ester monomer is a monomer having two or more (meth) acrylic acid ester groups in the molecule, preferably 2 to 6, for example, tricyclodecanedimethylol diacrylate, neo. Pentyl glycol diacrylate, neopentyl glycol diacrylate hydroxypivalate, dioxane glycol diacrylate, trimethyl propantriacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylol propanetetraacrylate, bisphenol A type polyethoxylate diacrylate, Examples thereof include dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.

Further, examples of the (meth) acrylic acid ester oligomer include an epoxy acrylate oligomer, a polyester polyacrylate oligomer, and a urethane acrylate oligomer.

These monofunctional or polyfunctional (meth) acrylic acid ester monomers or oligomers can be used alone or in combination of two or more.
As the binder resin, a monofunctional or polyfunctional (meth) acrylic acid ester monomer is preferable.

When an ionizing radiation curable resin or a thermosetting resin is used as the binder resin, the adhesive composition of the present invention contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator.

Examples of the photopolymerization initiator that can be used in the present invention include 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone [DaroCure®-2959: manufactured by Merck]; α-hydroxy. -Α, α'-Dimethylacetophenone [DaroCure (registered trademark) -1173: manufactured by Merck]; methoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone [Irgacure (registered trademark) -651] and other acetphenone-based initiators Agents; benzoin ether-based initiators such as benzoin ethyl ether and benzoin isopropyl ether; other examples include halogenated ketones, acylphosphinoxides, and acylphosphonates.

Thermal polymerization initiators that can be used in the present invention include azo-based initiators and peroxide-based initiators.

Examples of the azo-based initiator include azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), and 2,2'-azobis {2-methyl-N- [1,1-. Bis (hydroxymethyl) ethyl] propionamide}, 2, 2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2, 2'-azobis [2- (hydroxymethyl) propionitrile ], 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobisisobutyrate dimethyl, 2,2 '-Azobis [2- (2-imidazolin-2-yl) propane], 2,2'-Azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} Etc. can be exemplified. Of these, azobisisobutyronitrile is preferable from the viewpoint of cost and versatility.

Examples of the peroxide-based initiator include benzoyl peroxide, isobutyryl peroxide, cumylperoxyoctate, and the like. As the peroxide-based initiator, a peroxide-based initiator having a short thermal polymerization time and being stable as a reactive composition before polymerization can be appropriately selected.

The amount of the polymerization initiator used in the adhesive composition of the present invention is preferably 0.01 to 20% by weight, more preferably 0.1 to 10% by weight, based on the total amount of the curable resin. preferable.

(solvent)
The adhesive composition of the present invention may further contain a solvent. The solvent is not particularly limited, but for example, an inorganic solvent such as water or an organic solvent can be used, and these solvents may be used alone or in combination of two or more.

(Organic solvent)
The adhesive composition of the present invention may contain an organic solvent. Typical organic solvents that can be used include ether-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ketone-based, and organic halide-based solvents.
Diethyl ether, dipropyl ether, dibutyl ether, diamil ether as ether-based organic solvents; ethyl acetate, propyl acetate, butyl acetate, amyl acetate, heptyl acetate, ethyl butyrate, isoamyl isovari as ester-based organic solvents. Rate; Normal hexane, normal heptane, cyclohexane as aliphatic hydrocarbon-based organic solvents; toluene, xylene as aromatic organic solvents; methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone as ketone-based organic solvents; organic halogen Examples of the compound-based organic solvent include trichloroethane, trichloroethylene; and the like. Furthermore, relatively inactive organic solvents such as propylene glycol monomethyl ether and propylene glycol monoethyl ether can also be used.
Among them, considering that the present invention is often used in an open system in a natural environment, volatile ester-based esters such as propyl acetate, butyl acetate, isoamyl acetate, heptyl acetate, ethyl butyrate and isoamyl isovalylate. Organic solvent is preferred.

(Dehydrating agent)
Examples of the dehydrating agent include methyl orthoformate, methyl orthoacetate, tetraethoxysilane and the like.

(Flame retardants)
As the flame retardant, a brominated flame retardant usually used for a thermoplastic resin is preferable, and an inorganic flame retardant may be used in combination. Examples of the brominated flame retardant include an aliphatic type, an aromatic type, a phenol type, an epoxy type, a bisphenol type, and a biphenyl type. Examples of the inorganic flame retardant include antimony trioxide, tin oxide, molybdenum oxide, and zinc borate.

(Heat stabilizer)
Examples of the heat stabilizer include phosphorus-based heat stabilizers such as phosphite ester and phosphoric acid ester.
Examples of the phosphite ester include triphenylphosphite, trisnonylphenylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, trinonylphosphite, tridecylphosphite, and trioctylphosphite. , Trioctadecylphosphite, distearylpentaerythritol diphosphite, tricyclohexylphosphite, monobutyldiphenylphosphite, monooctyldiphenylphosphite, distearylpentaerythritol diphosphite, bis (2,4-di-tert-butyl) Phosphite) pentaerythritol phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, etc. Examples of phosphite triester, diester, monoester and the like.
Examples of the phosphate ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and tetrakis (2,4-di-). tert-Butylphenyl) -4,4-diphenylene phosphonite and the like.

(Antioxidant)
Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, a phosphite-based antioxidant, and a thiourea-based antioxidant.

(Slip agent)
Examples of the slipper include higher fatty acids, ester waxes, polyethylene waxes, metal soaps and the like.

(Antistatic agent)
Examples of the antistatic agent include fatty acid amines, fatty acid alcohols, fatty acid esters, fatty acid amides, and sulfonic acid compounds.

(UV absorber)
Examples of the ultraviolet absorber include benzotriazole compounds such as salicylic acid derivative compounds, benzophenone compounds and benzotriazole derivatives, and cyanoacrylate compounds.

(Colorant)
Examples of the colorant include organic pigments, inorganic pigments, dyes, and brighteners. Examples of organic pigments include phthalocyanine-based, benzimidazolone-based, azo-based, azomethine-azo-based, azomethine-based, anthracinone-based, perinone-perylene-based, indigo-thioindigo-based, dioxazine-based, quinacridone-based, isoindoline-based, and iso Examples thereof include indoline-based pigments and carbon black pigments, and examples of the inorganic pigments include extender pigments, titanium oxide-based pigments, iron oxide-based pigments, spinnel pigments and the like. More specifically, insoluble azo pigments such as toluidin red, toluidin maroon, hanza ero, benzine ero, pyrazolone red, soluble azo pigments such as litol red, heliobordeaux, pigment scarlet, permanent red 2B, phthalocyanine blue, phthalocyanine green and the like. Phthalocyanin, quinacridone red, quinacridone magenta, etc., perylene red, perylene carlet, etc., isoindolinone ero, isoindolinone orange, etc., isoindolinone, pyranthrone red, pyranthron orange, etc. , Thioindigo-based, condensed azo-based, benzimidazolone-based, quinophthalone yellow, nickel azoero, perinone orange, anthron orange, dianthraquinonyl red, dioxazine violet and other conventionally known pigments can be used. As the dye, for example, conventionally known dyes such as direct dyes, basic dyes, cationic dyes, acidic dyes, medium dyes, acidic medium dyes, sulfide dyes, naphthol dyes, disperse dyes, and reactive dyes can be used. Examples of the glittering agent include aluminum paste, mica, and flaky iron oxide.

(Release agent)
Examples of the release agent include at least one compound selected from an aliphatic carboxylic acid, an ester of an aliphatic carboxylic acid and an alcohol, an aliphatic hydrocarbon compound having a number average molecular weight of 200 to 15,000, and a polysiloxane-based silicone oil. Can be done.
Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acids. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Specific examples of aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, caproic acid, lauric acid, araquinic acid, bechenic acid, lignoseric acid, cerotic acid, melissic acid, tetrariacontanoic acid, montanic acid, and adipic acid. , Azelaic acid and the like.
As the aliphatic carboxylic acid in the ester of the aliphatic carboxylic acid and the alcohol, the same one as the above-mentioned aliphatic carboxylic acid can be used. Examples of the alcohol that reacts with the aliphatic carboxylic acid to form an ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. Here, the aliphatic term also contains an alicyclic compound. Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. And so on. These ester compounds of the aliphatic carboxylic acid and the alcohol may contain the aliphatic carboxylic acid and / or the alcohol as impurities, or may be a mixture of a plurality of compounds.

Specific examples of esters of aliphatic carboxylic acid and alcohol include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, and glycerin monosteer. Examples thereof include rate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.
Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon also includes an alicyclic hydrocarbon. Moreover, these hydrocarbon compounds may be partially oxidized.
Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, phenyl methyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone. These may be used alone or in combination of two or more.

(Condensate of organic silane compound)
The adhesive composition of the present invention can contain a condensate of an organic silane compound for the purpose of mineralizing the surface of the coating film. As a result, a glass-like hard coat layer can be laminated on the surface of the plastic base material.

The condensate of the organic silane compound can be produced by using a known silanol condensation method for the organic silane compound represented by the formula (A).
(R ⁴ ) _n Si (R ³ ) _4-n (A)

In the formula, R ⁴ represents an alkyl group of C1 to C30 which may be substituted with an epoxy group, a glycidyloxy group or a (meth) acryloxy group, an alkenyl group of C2 to C8, or an aryl group of C6 to C10. R ³ represents a hydroxyl group or a hydrolyzable group. n represents 1 or 2.

The alkyl group of R ⁴ C1 ~ at C30, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, s- butyl, t- butyl group, n- pentyl group, isopentyl Group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, isononyl group, decyl group, lauryl group, tridecyl group , Myristyl group, pentadecyl group, palmityl group, heptadecyl group, stearyl group and the like.
Examples of the alkenyl group of C2 to C8 include a vinyl group, an allyl group, a 1-propenyl group and the like.
Examples of the aryl group of C6 to C10 include a phenyl group and a naphthyl group.

The hydrolyzable group of R ³ is a group that can be hydrolyzed to form a silanol group by heating at 25 ° C. to 100 ° C. under non-catalytic conditions or in the presence of excess water, or siloxane condensation. It means a group capable of forming a substance, and specific examples thereof include an alkoxy group, an acyloxy group, a halogeno group, an isocyanate group and the like, and an alkoxy group of C1 to C4 or an acyloxy group of C1 to C6 is preferable. ..

Here, examples of the alkoxy group C1 to C4 include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a t-butoxy group and the like, and an acyloxy group of C1 to C6. Means an acyloxy group having 1 to 6 carbon atoms other than the carbonyl group, and examples of the acyloxy group of C1 to C6 include an acetyloxy group and a benzoyloxy group. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, an iod group and the like.

Specific examples of the organic silane compound represented by the formula (A) include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltriisopropoxysilane, and allyltrimethoxysilane, 3. -Butenyltrimethoxysilane, divinyldichlorosilane, divinyldiacetoxysilane, divinyldimethoxysilane, diallyldimethoxysilane, di3-butenyldimethoxysilane, vinylmethyldimethoxysilane, vinylethyldiethoxysilane, methyltri (meth) acryloxisilane , Methyltris [2- (meth) acryloxiethoxy] silane, methyltriglycidyloxysilane, methyltris (3-methyl-3-oxetanmethoxy) silane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxy Silane, ethyltrimethoxysilane, ethyltriisopropoxysilane, ethyltri (n-butoxy) silane, n-butyltrimethoxysilane, dimethyldichlorosilane, dimethyldiacetoxysilane, dimethyldimethoxysilane, di-n-butyldimethoxysilane, 2 -Cyclopropenyltrimethoxysilane, 2-cyclopentenyltrimethoxysilane, trifluoromethyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, pentafluorophenyltrimethoxysilane, 4-oxacyclohexyltrimethoxysilane, 2- (3) , 4-Epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxy-n-propylmethyldiethoxysilane, 3-glycidyloxy-n-propyltrimethoxysilane, 3-glycidyloxy-n-propyltriethoxysilane, 3-methacryloxy-n -Propylmethyldimethoxysilane, 3-methacryloxy-n-propyltrimethoxysilane, 3-methacryloxy-n-propylmethyldiethoxysilane, 3-methacryloxy-n-propyltriethoxysilane, 3-acryloxy-n-propyltrimethoxysilane And so on.

Specific examples of the known silanol condensation method include a method using a silanol condensation catalyst. The silanol condensation catalyst is not particularly limited as long as it hydrolyzes a hydrolyzable group in the compound represented by the formula (A) and condenses silanol to form a siloxane bond, and is an organic metal or an organic acid metal salt. , Metal hydroxides, acids, bases, metal complexes, hydrolysates thereof, condensates thereof and the like. The silanol condensation catalyst can be used alone or in combination of two or more.

Specific examples of the organic metal include alkyl metal compounds such as tetramethyltitanium and tetrapropylzirconium; and metal alcoholates such as tetraisopropoxytitanium and tetrabutoxyzirconium.

The organic acid metal salt is a compound composed of a metal ion and a salt obtained from the organic acid, and examples of the organic acid include carboxylic acids such as acetic acid, oxalic acid, tartaric acid and benzoic acid; and sulfur-containing organic substances such as sulfonic acid and sulfic acid. Examples thereof include organic compounds exhibiting acidity such as acids; phenol compounds; enol compounds; oxime compounds; imide compounds; aromatic sulfonamides; Specific examples thereof include carboxylic acid metal salts, sulfonic acid metal salts, and phenol metal salts.

Metal hydroxide is a metal compound having hydroxide ions as anions.

The metal complex is preferably a metal complex having a hydroxyl group or a hydrolyzable group, and more preferably a metal complex having two or more hydroxyl groups or a hydrolyzable group. In addition, having 2 or more hydroxyl groups or hydrolyzable groups means that the total of hydrolyzable groups and hydroxyl groups is 2 or more. Examples of the hydrolyzable group include an alkoxy group, an acyloxy group, a halogen group and an isocyanate group, and C1 to C4 alkoxy groups and C1 to C4 acyloxy groups are preferable.

The metal complex is preferably a β-ketocarbonyl compound, a β-ketoester compound, and an α-hydroxyester compound, and specifically, methyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n acetoacetate. -Β-ketoesters such as butyl, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane- Β-diketones such as 2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4-dione; hydroxycarboxylic acids such as glycolic acid and lactic acid coordinated to metal elements. Examples include compounds.

The metal elements in these organic metals, organic acid metal salts, metal hydroxides, and metal complexes include titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), germanium (Ge), and indium. Examples thereof include (In), tin (Sn), tantalum (Ta), zinc (Zn), tungsten (W), lead (Pb), and among these, titanium (Ti), zirconium (Zr), and aluminum (Al). , Tin (Sn) is preferable, and titanium (Ti) is particularly preferable. These may be used alone or in combination of two or more.

Examples of the acid include organic acid and mineral acid, examples of the organic acid include acetic acid, formic acid, oxalic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid and methanesulfonic acid, and examples of the mineral acid include hydrochloric acid and nitric acid. , Carbonate, boric acid, borohydrochloric acid and the like.
Here, a photoacid generator that generates an acid by light irradiation, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like are also included in the acid.

Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidylpropyltrimethoxysilane; organic amines, carboxylic acid neutralized salts of organic amines, and quaternary ammonium salts.

The compounding ratio of the silanol condensation catalyst is 1:99 to 99: 1, preferably 1:99 to 50:50 with respect to the mass of the organic silane compound.

(Metal compounds, etc.)
A metal compound can be added to the adhesive composition of the present invention for the purpose of increasing the refractive index and hardness of the coating film. Examples of the metal compound include the above-mentioned organic silane compound, an organic metal exemplified as a ziranol condensation catalyst, an organic acid metal salt, a metal hydroxide, and a metal complex. Examples of other metal compounds include metal oxides. Specific examples thereof include metal oxide particles of silicon dioxide, titanium oxide, aluminum oxide, chromium oxide, manganese oxide, iron oxide, zirconia oxide (zirconia), and cobalt oxide. Zirconium oxide is particularly preferable.
Examples of the shape of the particles include spherical, porous powder, scaly, fibrous and the like, but the porous powder is more preferable.
Further, as the metal oxide particles of the present invention, colloidal metal oxide particles can also be used. Specific examples thereof include colloidal silica and colloidal zirconium, and examples thereof include water-dispersed colloidal metal oxide particles and organic solvent-dispersed colloidal metal oxide particles such as methanol and isopropanol.

In addition to the above, other additives such as various surfactants, silane coupling agents other than the above, titanium coupling agents, dyes, dispersants, thickeners, leveling agents, etc. are added to the adhesive composition of the present invention. If necessary, additive components such as a sensitizer, a rust preventive, and a preservative can be added.

The copolymer of the present invention has excellent solubility. The adhesive composition of the present invention is also excellent in molding processability.

[Preparation of adhesive composition]
In the adhesive composition of the present invention, in addition to the copolymer of the present invention, the polymerizable compound, the condensate of the organic silane compound, the photopolymerization initiator, the metal compound and the like are usually mixed in an organic solvent, if necessary. Is prepared. The solid content in the adhesive composition of the present invention is preferably 1 to 90% by mass, more preferably 5 to 60% by mass.

2. 2. Molded article The molded article of the present invention is obtained by applying the adhesive composition on a plastic base material and directly providing a film (coating film) obtained by curing the adhesive composition on the base material. is there.

〔Base material〕
As the base material to which the adhesive composition of the present invention can be used, a plastic base material is preferable, and specifically, a cycloolefin resin such as a cycloolefin polymer or a cycloolefin copolymer; polyethylene, polypropylene, polyisoprene, polybutadiene, polymethyl. Examples thereof include polyolefin resins such as penten; polycarbonate resins; polyisocyanate resins; polyimide resins; polyester resins; acrylic resins; methacrylic resins; epoxy resins; polyethylene terephthalate resins; aromatic polyether ketone resins.
In particular, polyethylene resin and polypropylene resin are preferably used.

[Formation of coating film]
In the adhesive composition of the present invention, since the copolymer of the present invention adheres firmly to the surface of the substrate, a coating film can be formed only by applying the adhesive composition and then heating and drying it. When the adhesive composition further contains a polymerizable compound, it is preferable to carry out an ultraviolet irradiation treatment using a photopolymerization initiator in combination or a heat treatment using a thermal polymerization initiator in combination.
Since it is not necessary to modify the surface of the base material by UV ozone treatment or the like, the initial characteristics of the plastic base material can be maintained.

As a coating method of the adhesive composition, a known coating method can be used, and a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, etc. An inkjet method and the like can be mentioned. The thickness of the coating film formed is not particularly limited, and is about 0.1 to 200 μm.

The heat-drying treatment of the coating film is preferably carried out at 40 to 200 ° C. for about 0.5 to 120 minutes, and more preferably at 60 to 120 ° C. for about 1 to 60 minutes.
The irradiation of ultraviolet rays can be carried out using a known device such as a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or an excimer lamp.
The heat treatment can be performed continuously with the drying treatment.

[Lamination of functional membranes]
Since the coating film of the present invention has very good adhesion to a plastic substrate, the coating film of the present invention can be used as a primer layer. As a result, a functional film that could not be directly formed on a plastic base material can be laminated via the coating film of the present invention. A plurality of layers can be laminated, and the coating agent of the present invention can be further applied onto the plurality of layers and further laminated.

Examples of the functional film include a conductive film, an antireflection film, a gas barrier film, a hard coat film, a water repellent film, a hydrophilic film and the like.
Examples of the conductive film include tin-doped indium oxide film (ITO film), fluorine-doped tin oxide film (FTO film), antimony-doped zinc oxide film, and indium-doped zinc oxide film. Can be mentioned.
The gas barrier film is not particularly limited as long as it has gas barrier properties such as oxygen and water vapor, but is preferably a thin film of an inorganic compound, and in particular, titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, and the like. Thin films of metal oxides, metal nitrides, metal carbides or composites thereof having a metal element selected from the group consisting of tungsten and lead are preferable.

The thickness of these functional films is usually 10 to 300 nm, preferably 10 to 200 nm, and more preferably 10 to 100 nm.

The method for forming a conductive film, a gas barrier film, etc. made of an inorganic compound on the coating film of the present invention can be formed by a known method, such as a sputtering method, a vacuum vapor deposition method, an ion plating method, etc. It can be carried out by a physical method of the above, a chemical method such as a spray method, a dip method, a thermal CVD method, or a plasma CVD method.

For example, according to a sputtering method or the like, a film made of silicon oxide can be formed by using a silicon compound sintered in the presence of oxygen gas as a target, and a film made of silicon oxide can be formed as a target in the presence of oxygen. A film can also be formed by reactive sputtering in. Further, according to the plasma CVD method, silane gas can be supplied together with oxygen gas and nitrogen gas into a chamber in which plasma is generated and reacted to form a film made of silicon nitride on a substrate. .. Further, according to the thermal CVD method or the like, a film made of silicon oxide can be formed by using an organic solvent solution or the like containing a silicon compound as an evaporator.

In the present invention, it is particularly preferable to form a functional film by a sputtering method, a vacuum vapor deposition method, an ion plating method or a plasma CVD method. Further, when forming the functional film, the surface of the coating film of the present invention may be subjected to plasma treatment or UV ozone treatment in advance, if necessary.

The coating film of the present invention can also be used as an adhesive layer used when adhering plastic substrates to each other or between a plastic substrate and another molded sheet.
The molded sheet is a plastic sheet made of a material such as polyvinyl chloride resin, cellulose resin, polyethylene resin, polystyrene resin, ABS resin, polyamide resin, polyester resin, polyurethane resin, cycloolefin resin; polarizing plate, phase difference. Optical films such as films and antireflection films; metal foils such as aluminum, copper and silicon; and the like can be mentioned.

Examples are shown below, but the technical scope of the present invention is not limited to these examples.

The measurement of the number average molecular weight of the polymer obtained in the examples was carried out under the following equipment and conditions.
[apparatus]
Sample Injection Device: Waters 2695 Alliance Separation Column: Shodex KF-G, 805L, 804L
Detector: Waters 2414 Differential Refractometer (RI) Detector
2998 Photodiode Array (PDA) Detector Column Oven: Waters Column Oven [Conditions]
Column oven temperature: 40 ° C
RI detector temperature: 40 ° C
Mobile phase: tetrahydrofuran Flow rate: 1.0 mL / min
Standard injection volume: 200 μL
PDA detector extract wave: 254.0 nm
Quantitative calculation: Standard polymethyl methacrylate conversion

≪Polymer production≫
(Synthesis Example 1) Preparation of Adhesive Polymer A (DOCAA / THFA = 90/10) N, N-bis (4- (1,1,3,3-tetramethylbutyl) phenyl in a 300 mL four-necked flask ) Acrylamide (DOPAA) 26.97 g, tetrahydrofurfuryl acrylate (THFA: Tokyo Chemicals) 2.99 g, and AIBN (Tokyo Chemicals) 0.20 g were charged and dissolved in toluene 45 g. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 27.23g, Mn = 13,900, Mw / Mn = 2.21

(Synthesis Example 2) Preparation of Adhesive Polymer B (DOCAA / HEA = 90/10) 27.10 g of DOPAA, 3.03 g of 2-hydroxyethyl acrylate (HEA: Tokyo Chemicals) in a 300 mL four-necked flask, 0.20 g of AIBN (Tokyo Chemicals) was charged and dissolved in 45 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 27.15g, Mn = 22,700, Mw / Mn = 2.29

(Synthesis Example 3) Preparation of Adhesive Polymer C (DOCAA / MA = 90/10) 18.10 g of DOPAA, 2.00 g of methyl acrylate (MA: Tokyo Chemicals), AIBN (Tokyo) in a 300 mL four-necked flask. Chemical product) 0.14 g was charged and dissolved in 30 g of toluene. A depressurization operation was performed to degas, and the mixture was heated and stirred at 65 ° C. for 6 hours in a nitrogen atmosphere. Then, 0.07 g of AIBN was added, and the mixture was stirred at 80 ° C. for 5 hours. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 16.23g, Mn = 13,400, Mw / Mn = 1.84

(Synthetic Example 4) Preparation of Adhesive Polymer D (DOCAA / EA = 90/10) 26.98 g of DOPAA, 3.04 g of ethyl acrylate (EA: Tokyo Chemicals), AIBN (Tokyo) in a 300 mL four-necked flask. (Chemical product) 0.20 g was charged and dissolved in 45 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 28.19g, Mn = 17,400, Mw / Mn = 2.08

(Synthesis Example 5) Preparation of Adhesive Polymer E (DOPAA / nBA = 90/10) 18.09 g of DOPAA, n-butyl acrylate (nBA: Tokyo Chemicals) 2.10 g, AIBN in a 300 mL four-necked flask. (Tokyo Chemicals) 0.18 g was charged and dissolved in 30 g of toluene. A depressurization operation was performed to degas, and the mixture was heated and stirred at 65 ° C. for 6 hours in a nitrogen atmosphere. Then, 0.09 g of AIBN was added, and the mixture was stirred at 80 ° C. for 5 hours. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 17.93g, Mn = 15,600, Mw / Mn = 1.71

(Synthesis Example 6) Preparation of Adhesive Polymer F (DOPAA / EHA = 90/10) 27.03 g of DOPAA, 3.02 g of 2-ethylhexyl acrylate (EHA: Tokyo Chemicals), AIBN in a 300 mL four-necked flask. (Tokyo Chemicals) 0.20 g was charged and dissolved in 45 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 26.90g, Mn = 12,600, Mw / Mn = 1.80

(Synthetic Example 7) Preparation of Adhesive Polymer H (DOPAA / EA = 85/15) 25.52 g of DOPAA, 4.50 g of ethyl acrylate (EA: Tokyo Chemicals), AIBN (Tokyo) in a 300 mL four-necked flask. (Chemical product) 0.20 g was charged and dissolved in 45.03 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 29.33g, Mn = 21,500, Mw / Mn = 2.11.

(Synthesis Example 8) Preparation of Adhesive Polymer I (DOCAA / EA = 80/20) In a 300 mL four-necked flask, 24.02 g of DOPAA, 6.00 g of ethyl acrylate (EA: Tokyo Chemicals), AIBN (Tokyo). (Chemical product) 0.20 g was charged and dissolved in 45.03 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 28.13g, Mn = 24,600, Mw / Mn = 1.98

(Synthesis Example 9) Preparation of Adhesive Polymer J (DOPAA / EA = 70/30) 21.01 g of DOPAA, 9.01 g of ethyl acrylate (EA: Tokyo Chemicals), AIBN (Tokyo) in a 300 mL four-necked flask. (Chemical product) 0.20 g was charged and dissolved in 45.03 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 28.83g, Mn = 19,300, Mw / Mn = 2.18

(Synthesis Example 10) Preparation of Adhesive Polymer K (DOPAA / iBA = 90/10) 18.09 g of DOPAA, i-butyl acrylate (iBA: Tokyo Chemicals) 2.10 g, AIBN in a 300 mL four-necked flask. (Tokyo Chemicals) 0.18 g was charged and dissolved in 30 g of toluene. A depressurization operation was performed to degas, and the mixture was heated and stirred at 65 ° C. for 6 hours in a nitrogen atmosphere. Then, 0.09 g of AIBN was added, and the mixture was stirred at 80 ° C. for 5 hours. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 18.03g, Mn = 16,300, Mw / Mn = 1.88

(Synthesis Example 11) Preparation of Adhesive Polymer L (DOPAA / iBMA = 90/10) 20.00 g of DOPAA, 2.22 g of isobutyl methacrylate (iBMA: Tokyo Chemicals), AIBN (Tokyo) in a 300 mL four-necked flask. Chemical product) 0.13 g was charged and dissolved in 22.2 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 21.11g, Mn = 26,800, Mw / Mn = 2.33

(Synthesis Example 12) Preparation of Adhesive Polymer M (DOPAA / EHMA = 90/10) 20.00 g of DOPAA, 2.22 g of 2-ethylhexyl methacrylate (EHMA: Tokyo Chemicals), AIBN in a 300 mL four-necked flask. (Tokyo Chemicals) 0.12 g was charged and dissolved in 22.2 g of toluene. A depressurization operation was performed to degas, and the mixture was 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. The heating and stirring were stopped, the reaction solution was sampled, and gel permeation chromatography measurement was performed. The reaction solution was added dropwise to 800 mL of methanol to form a powder. The obtained precipitate was filtered off and dried in a vacuum dryer at 60 ° C. under reduced pressure. Yield 21.38 g, Mn = 35,900, Mw / Mn = 1.90

(Synthetic Comparative Example 1) Preparation of Adhesive Polymer G (Poly {N, N-Bis (4- (1,1,3,3-Tetramethylbutyl) Phenyl) Acrylamide} (PDOPAA)) 500 mL Four-necked Flask 100.0 g of DOPAA, 150.0 g of toluene and 0.322 g of AIBN were charged in the mixture, and the mixture was heated to 30 ° C. in a nitrogen atmosphere. After confirming that the inside of the system became uniform, decompression and degassing was performed three times with a diaphragm pump while stirring with a magnetic stirrer. After degassing, the mixture was heated to 65 ° C. and stirred for 24 hours. Then, the flask was returned to room temperature, reprecipitated with 1600 mL of methanol, and vacuum dried at 120 ° C. for 2 hours to obtain a white powder. Yield 96.00g, Mn = 14,300, Mw / Mn = 1.89

≪Solubility test for acrylic acid ester monomer≫
(Test method)
The solubility of each polymer in each acrylic ester monomer was examined. Polymers A to M and acrylic acid ester monomers were charged in a sample bottle containing a stirrer so as to have a weight ratio of 30:70, and the mixture was stirred at room temperature for 2 hours. After dissolving by stirring at room temperature for 2 hours, ○. After melting by heating at 60 ° C for 2 hours, Δ. Insoluble was judged by x. The judgment was made visually. The results are shown in Tables 1 and 2. The reagents used are shown below.
Methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (nBA), i-butyl acrylate (iBA), t-butyl acrylate (tBA), cyclohexyl acrylate (CHA), isobornyl acrylate (IBOA), 2-Ethylhexyl acrylate (EHA), tetrahydrofurfuryl acrylate (THFA).

(result)

　

≪Compatibility test with urethane acrylate≫
(Test method)
The compatibility of each polymer with the bifunctional urethane acrylate was investigated. Each polymer and urethane acrylate were charged in a sample bottle in a weight ratio of 30:70 to prepare a 30 wt% toluene solution. Toluene was removed at 120 ° C., and compatibility was visually confirmed. Judgment: Insoluble is ○, insoluble is ×. The results are shown in Table 2. The reagents used are shown below.
Art resin UN-9200A (manufactured by Negami Kogyo, polycarbonate skeleton, M _w 15,000),
Art resin UN-6305 (manufactured by Negami Kogyo, polyether skeleton, M _w 27,000),
Nisso-PB TEAI-1000 (manufactured by Nippon Soda, polybutadiene skeleton, M _n 2,000).

(result)

 

≪Tension shear peeling test≫
(Preparation of adhesive composition)
Add 1.35 g of IBOA, 1.35 g of EHA, 0.3 g of adhesive polymer (AM) and diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide (UV polymerization initiator) to the sample bottle and completely dissolve. Stirred at room temperature. By the above operation, transparent adhesive compositions (A-1 to M-1) were obtained. For comparison, a composition containing no adhesive polymer (Comparison-1) was also prepared and tested.
(Subject)
The adherends used are described below.
・ Polypropylene (hereinafter abbreviated as PP)
Sold by Standard Test Piece, manufactured by Hitachi Kasei, PP-N-BN, 2.0 mm x 25 mm x 100 mm, polycarbonate (hereinafter abbreviated as PC)
Sold by Standard Test Piece, Carbo Glass Polish Clear, 2.0 mm x 25 mm x 100 mm
(Preparation of test piece)
The PP substrate and the PC substrate were bonded together with an adhesive composition. Using a UV irradiation device (belt conveyor type UV irradiation device UB044 equipped with a high-pressure mercury lamp as a light source manufactured by Eye Graphics Co., Ltd.), UV irradiation from the PC substrate side in a nitrogen atmosphere (cumulative irradiation amount 2000 mJ / cm) By performing ² ), an adhesion test piece was obtained.
(Test method)
Equipment: Shimadzu AGS-J desktop precision universal testing machine equipped with 5 kN load cell and 1 kN tensile test jig, temperature condition: at room temperature, speed: 100 mm / min, distance between jigs: 120 mm

(result)
The average value of 2 to 3 measurements is shown in Table 3.

≪180 ° peel peeling test≫
(Adhesive composition)
A-1 to M-1 and Comparison-1 were used.
(Subject)
The adherends used are described below.
・ Polypropylene (hereinafter abbreviated as PP)
Sold by Standard Test Piece, manufactured by Hitachi Kasei, PP-N-BN, 2.0 mm x 25 mm x 100 mm
・ Polyethylene terephthalate (hereinafter abbreviated as PET)
Made by TOYOBO, Cosmo Shine A4300, 0.1 mm x 25 mm x 210 mm
(Preparation of test piece)
The PP substrate and the PET film were bonded together with an adhesive composition. Using a UV irradiation device (belt conveyor type UV irradiation device UB044 equipped with a high-pressure mercury lamp as a light source manufactured by Eye Graphics Co., Ltd.), UV irradiation from the PET substrate side in a nitrogen atmosphere (cumulative irradiation amount 2000 mJ / cm) By performing ² ), an adhesion test piece was obtained.
(Test method)
Equipment: Shimadzu AGS-J desktop precision universal testing machine equipped with 5 kN load cell and 1 kN tensile test jig, temperature condition: at room temperature, speed: 100 mm / min, distance between jigs: 110 mm

(result)
The average value of the three measurements is shown in Table 4.

From this test result, it can be seen that the compound of the present invention has excellent solubility in various solvents and resins.

From the test results, the adhesive composition of the present invention has excellent adhesiveness to polyethylene and polypropylene, has high solubility (compatibility) with various solvents, (meth) acrylic acid ester monomers, etc., and also has peel peel strength. You can see that it improves.
The adhesive composition of the present invention can be adhered to a wider range of substrates and can take a wider variety of composition forms.

Claims (14)

1. Equation (I)
   

   

   (During the ceremony,
   X ¹ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.
   X ² represents an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.
   n represents 0 or 1 and represents
   Z ¹ and Z ² independently represent a single bond or a C1-C3 alkylene group.
   Each R independently represents a halogeno group or an organic group.
   m1 and m2 independently represent an integer of 0 to 4, respectively.
   Y represents a polymerizable functional group. )
   An adhesive composition containing a copolymer having a repeating unit derived from a polymerizable compound represented by and a repeating unit derived from a (meth) acrylic acid ester.
2. The adhesive composition according to claim 1, wherein in the formula (I), Y is an acryloyl group or a methacryloyl group.
3. The polymerizable compound represented by the formula (I) is the formula (II).
   

   

   (During the ceremony,
   X ¹⁰ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.
   X ²⁰ represents a hydrogen atom, an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.
   Z ¹ and Z ² independently represent a single bond or a C1-C3 alkylene group.
   Each R independently represents a halogeno group or an organic group.
   m1 and m2 independently represent an integer of 0 to 4, respectively.
   Y represents a polymerizable functional group)
   The adhesive composition according to claim 1 or 2, which is a compound represented by.
4. The adhesive composition according to any one of claims 1 to 3, wherein the alkyl group of C7 to C20 and the alkoxy group of C7 to C20 are branched chains.
5. The adhesive composition according to any one of claims 1 to 4, wherein the (meth) acrylic acid ester is an unsubstituted or optionally having a substituent (meth) acrylic acid C1 to C18 alkyl ester. Stuff.
6. The adhesive composition according to any one of claims 1 to 5, wherein the (meth) acrylic acid ester is a linear or branched alkyl ester of (meth) acrylic acid.
7. The adhesive composition according to any one of claims 1 to 6, further comprising a monofunctional or polyfunctional (meth) acrylic acid ester monomer.
8. The adhesive composition according to any one of claims 1 to 7, wherein the adhesive composition is an adhesive composition for a plastic base material.
9. The adhesive composition according to claim 8, wherein the plastic base material is a polyolefin base material.
10. The adhesive composition according to claim 8, wherein the plastic base material is a polypropylene base material or a polyethylene base material.
11. The adhesive composition according to claim 8, wherein the adhesive composition is a coating agent.
12. The adhesive composition according to claim 11, wherein the coating agent is a primer.
13. The adhesive composition according to claim 8, wherein the adhesive composition is an adhesive.
14. Equation (I)
    

    

    (In the formula, X ¹ represents an alkyl group of C7 to C20 or an alkoxy group of C7 to C20.
    X ² represents an alkyl group of C7 to C20, an alkoxy group of C7 to C20, a halogeno group or an organic group.
    n represents 0 or 1 and represents
    Z ¹ and Z ² independently represent a single bond or a C1-C3 alkylene group.
    Each R independently represents a halogeno group or an organic group.
    m1 and m2 independently represent an integer of 0 to 4, respectively.
    Y represents a polymerizable functional group. )
    A copolymer having a repeating unit derived from a polymerizable compound represented by and a repeating unit derived from a (meth) acrylic acid ester.