JP2006299257A - Adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition from which a heat-, weather- and oil-resistant adhesive is obtained. <P>SOLUTION: The adhesive composition contains component (A) and component (B). (A): A vinyl polymer having not less than two groups expressed by (A) general formula (1): -OC(O)C(R<SP>a</SP>)=CH<SB>2</SB>(wherein, R<SP>a</SP>is a hydrogen atom or a 1-20C organic group) in the molecule and not less than one group out of the groups expressed by general formula (1) at the molecular terminal. (B): A redox initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to an adhesive composition containing a vinyl polymer having a (meth) acryloyl group at a molecular terminal as an essential component, and more particularly to an elastic adhesive composition having good adhesion durability.

In recent years, reactive acrylic adhesives have been widely used because of their adhesiveness, durability, and ease of handling. Above all, it develops adhesive strength in a relatively short time at room temperature, has little shrinkage when cured, has good oil surface adhesion, flexibility, peel resistance, impact resistance, solvent resistance, and range of adherends Therefore, a room temperature reaction type acrylic adhesive (second generation type adhesive, hereinafter referred to as SGA) using a redox reaction has been widely used (see Non-Patent Document 1).
However, SGA can be bonded at room temperature, has high adhesive strength, and exhibits good adhesion to a wide range of adherends. On the other hand, SGA has weather resistance when used outdoors and in high-temperature and high-humidity environments due to the effects of the elastomer contained. In some cases, heat resistance during use is inferior to some epoxy resins.
"Structural adhesive", edited by Koichi Nakamura, published by CMC Co., Ltd., May 21, 1984, page 179

The objective of this invention is providing the adhesive composition which can give the adhesive agent excellent in heat resistance, a weather resistance, and oil resistance.

As a result of intensive studies to solve the above problems, the above problems can be solved by an adhesive composition containing a vinyl polymer having a (meth) acryloyl group at the molecular end and a redox initiator. The headline, the present invention has been reached.

That is, the present invention relates to the following adhesive composition.
(1) (A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) a redox initiator,
An adhesive composition comprising:
(2) The adhesive composition according to (1), wherein the vinyl monomer constituting the main chain of the component (A) is a (meth) acrylic monomer.
(3) The adhesive composition according to (1) or (2), wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer.
(4) Any of (1) to (3), wherein the vinyl monomer constituting the main chain of component (A) contains at least one selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. The adhesive composition described in 1.
(5) The adhesive composition according to any one of (1) to (4), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

(6) The adhesive composition according to (5), wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group.
(7) The adhesive composition according to any one of (1) to (6), wherein the component (B) is a combination of an inorganic peroxide initiator and an inorganic reducing agent.
(8) The adhesive composition according to any one of (1) to (6), wherein the component (B) is a combination of an organic peroxide and a tertiary amine, or a combination of an organic peroxide and a transition metal. object.
(9) The adhesive composition according to any one of (1) to (8), which further comprises (C) a vinyl monomer in addition to the components (A) and (B).
(10) The adhesive composition according to (9), wherein the component (C) is a (meth) acrylic monomer.

(11) The adhesive composition according to any one of (1) to (10), further comprising (D) a compound having a SO ₂ Cl group.
(12) The adhesive composition according to (11), wherein the component (D) is a polymer having a SO ₂ Cl group.
(13) The adhesive composition according to (12), wherein the component (D) is an elastomer.
(14) The adhesive composition according to any one of (1) to (13), further comprising (E) a polymer that dissolves the components (A) to (D).
(15) The adhesive composition according to any one of (1) to (14), further comprising (F) an adhesion-imparting resin.
(16) The component (A) is
To the vinyl polymer having a halogen group at the end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The adhesive composition according to any one of (1) to (15), which is produced by reacting a compound represented by the formula:

(17) A vinyl polymer having a halogen group at the terminal is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The adhesive composition according to (16), which has a group represented by:
(18) The component (A) is
To the vinyl polymer having a hydroxyl group at the end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The adhesive composition according to any one of (1) to (15), which is produced by reacting a compound represented by the formula:
(19) The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(2) Residual isocyanate group and general formula (5):
HO-R'- OC (O) C (R ^a ) = CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The adhesive composition according to any one of (1) to (15), which is produced by reacting with a compound represented by the formula:
(20) The adhesive composition according to any one of (1) to (19), wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer.
(21) The adhesive composition according to (20), wherein the living radical polymerization is atom transfer radical polymerization.

(22) The adhesive composition according to (21), wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron.
(23) The adhesive composition according to (22), wherein the transition metal complex is a copper complex.
(24) The adhesive composition according to any one of (1) to (19), wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent.
(25) The adhesive composition according to any one of (1) to (24), wherein the number average molecular weight of the component (A) is 3000 or more.
(26) Any of (1) to (25), wherein the vinyl polymer of the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of less than 1.8. An adhesive composition according to claim 1.

Below, the adhesive composition of this invention is described.
The adhesive composition of the present invention is a composition comprising the following components (A) and (B).
(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) Redox initiator.

<< (A) component >>
The component (A) is represented by the general formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
Is a vinyl polymer having 2 or more groups per molecule, and having 1 or more groups represented by the general formula (1) at the molecular terminals.

The number of groups ((meth) acryloyl group) represented by the general formula (1) in the component (A) is 2 or more per molecule, and 1 or more at the molecular end. Two per molecule are preferred.
Since the side reaction may actually occur when the component (A) is produced, the average number of the (meth) acryloyl group in the produced vinyl polymer mixture is less than 2. May be. In the present invention, when the average value of the number of (meth) acryloyl groups in the actually produced vinyl polymer mixture is 1.1 or more, this mixture is referred to as component (A). That is, the component (A) includes a mixture of vinyl polymers containing a vinyl polymer having two or more (meth) acryloyl groups per molecule and one or more at the molecular end.
From the viewpoint of crosslinking, the average value of the number of the (meth) acryloyl group is preferably 1.5 or more per molecule.
Furthermore, one or more of the (meth) acryloyl group is present at the molecular end, but the position of the other (meth) acryloyl group is not particularly limited. From the viewpoint that the distance between cross-linking points can be increased, a form close to the other molecular end is preferable, and a form close to the other molecular end is particularly preferable.

R ^a in the (meth) acryloyl group represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. And the like.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.
Preferred examples of R ^a include, for example, —H, —CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), —C ₆ H ₅ , — CH ₂ OH, —CN and the like can be mentioned, and preferably —H, —CH ₃ .

(A) There is no limitation in particular as a vinyl-type monomer which comprises the principal chain of a component, A various thing can be used. Examples include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, N-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylic Acid toluyl, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic 3-methoxybutyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ -(Methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, (meth) acrylic acid 2- Perfluoroethyl ethyl, (meth) acrylic acid 2-perfluoroethyl-2-perfluorobutyl ethyl, (meth) acrylic acid 2-perfluoroethyl, (meth) acrylic acid perfluoromethyl, (meth) acrylic acid diper Fluoromethylmethyl, (meth) acrylic acid 2-perf (Meth) such as fluoromethyl-2-perfluoroethylethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Acrylic monomers; aromatic vinyl monomers such as styrene, vinyl toluene, α-methyl styrene, chlorostyrene, styrene sulfonic acid and their salts; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, vinylidene fluoride; vinyl Silicon-containing vinyl monomers such as trimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; Maleimide monomers such as reimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile Amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene, isoprene, etc. And conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, and allyl alcohol. These may be used alone or in combination.

Of these, aromatic vinyl monomers and (meth) acrylic monomers are preferred from the viewpoint of physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and more preferred are butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Further, from the viewpoint of oil resistance and the like, the vinyl monomer constituting the main chain particularly preferably contains at least one selected from butyl acrylate, ethyl acrylate and 2-methoxyethyl acrylate. Most preferably, it comprises at least two selected from ethyl acid and 2-methoxyethyl acrylate.

In the present invention, these preferable monomers may be copolymerized with the other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

The molecular weight distribution of the component (A) [the ratio of the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) to the number average molecular weight (Mn) (Mw / Mn)] is not particularly limited, but preferably Is less than 1.8, more preferably 1.7 or less, even more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less.
In the GPC measurement in the present invention, usually, chloroform or tetrahydrofuran is used as a mobile phase, a polystyrene gel column is used, and the molecular weight value is obtained in terms of polystyrene.

The lower limit of the number average molecular weight of the component (A) is preferably 500, more preferably 3000, and the upper limit is preferably 100,000, more preferably 40000. If the molecular weight is less than 500, the original characteristics of the vinyl polymer tend to be hardly expressed, and if it exceeds 100,000, handling tends to be difficult.

<Production method of component (A)>
(A) There is no limitation in particular about the manufacturing method of a component.
The vinyl polymer is generally produced by anionic polymerization or radical polymerization, but radical polymerization is preferred because of the versatility of the monomer or ease of control. Among radical polymerizations, it is preferably produced by living radical polymerization or radical polymerization using a chain transfer agent, and the former is particularly preferable.

The radical polymerization method used for the production of the component (A) is a method in which a monomer having a specific functional group and a vinyl monomer are simply copolymerized using an azo compound, a peroxide or the like as a polymerization initiator. Can be classified into “radical polymerization method” and “controlled radical polymerization method” in which a specific functional group can be introduced at a controlled position such as a terminal.

The “general radical polymerization method” is a simple method. However, in this method, a monomer having a specific functional group is introduced into the polymer only in a probabilistic manner, so an attempt is made to obtain a polymer having a high functionalization rate. In such a case, it is necessary to use this monomer in a considerably large amount. On the contrary, if the monomer is used in a small amount, there is a problem that the proportion of the polymer in which this specific functional group is not introduced increases. Moreover, since it is free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

The “controlled radical polymerization method” further includes a “chain transfer agent method” in which a vinyl polymer having a functional group at a terminal is obtained by polymerization using a chain transfer agent having a specific functional group, and a polymerization growth terminal. Can be classified as a “living radical polymerization method” in which a polymer having a molecular weight almost as designed can be obtained by growing without causing a termination reaction or the like.

In the “chain transfer agent method”, a polymer having a high functionalization rate can be obtained, but a chain transfer agent having a considerably large amount of a specific functional group with respect to the initiator is required. There is an economic problem. Further, like the above-mentioned “general radical polymerization method”, there is also a problem that only a polymer having a wide molecular weight distribution and high viscosity can be obtained because of free radical polymerization.

Unlike these polymerization methods, the “living radical polymerization method” is a radical polymerization that is difficult to control because the polymerization rate is high and a termination reaction due to coupling between radicals is likely to occur. It is difficult to obtain a polymer having a narrow molecular weight distribution (Mw / Mn is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
Therefore, in the “living radical polymerization method”, a polymer having a narrow molecular weight distribution and a low viscosity can be obtained, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.

Living polymerisation means, in a narrow sense, polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization in which is grown while in equilibrium. The definition in the present invention is also the latter.

The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in Journal of the American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules, 1994, Vol. 27, page 7228, using radical scavengers such as nitroxide compounds, organic halides and the like as initiators and transition metal complexes as catalysts. Atom transfer radical polymerization (ATRP) etc. are mentioned.

Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned “living radical polymerization method”. In addition to the characteristics of "", it has a halogen which is relatively advantageous for functional group conversion reaction at the end, and has a great degree of freedom in designing initiators and catalysts. Therefore, production of vinyl polymers having specific functional groups The method is more preferable.

Examples of the atom transfer radical polymerization method include, for example, Matyjazewski et al., Journal of the American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules. 1995, 28, 7901, Science 1996, 272, 866, WO 96/30421 pamphlet, WO 97/18247 pamphlet or Sawamoto et al., Macromolecules 1995, 28, The method described in page 1721 etc. is mentioned.

In the present invention, there is no particular restriction as to which of these methods is used, but basically, a controlled radical polymerization method is used, and a living radical polymerization method is preferred from the viewpoint of ease of control, and particularly an atom transfer radical. A polymerization method is preferred.

First, one of the controlled radical polymerization methods, a polymerization method using a chain transfer agent will be described.
The radical polymerization using a chain transfer agent (telomer) is not particularly limited, but the following two methods are exemplified as a method for obtaining a vinyl polymer having a terminal structure suitable for the present invention.
JP-A-4-132706 discloses a method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent, JP-A-61-271306, JP-A-2594402, This is a method for obtaining a hydroxyl-terminated polymer by using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent as disclosed in JP-A-54-47782.

Next, the living radical polymerization method will be described.
First, a method using a radical scavenger (capping agent) such as a nitroxide compound will be described.
In this polymerization method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but are cyclic such as 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical. Nitroxy free radicals from hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.

Specific examples of the nitroxy free radical compound include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl- 1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, Examples include 1,1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds.
Although the combined ratio of both is not particularly limited, 0.1 to 10 mol of the radical initiator is appropriate for 1 mol of the radical capping agent.

As the radical generator, various compounds can be used, but a peroxide capable of generating a radical under polymerization temperature conditions is preferable.
The peroxide is not particularly limited, but diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis Examples include peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctoate, and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable.
Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.

As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, the following alkoxyamine compound may be used as an initiator. I do not care.

When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as described above, a polymer having a functional group at the terminal can be obtained. When this is used in the present invention, a polymer having a functional group at the terminal can be obtained.

There are no particular limitations on the polymerization conditions such as the monomer, solvent, and polymerization temperature used in the polymerization using a radical scavenger such as the nitroxide compound, but it may be the same as that used for the atom transfer radical polymerization described below.

Next, an atom transfer radical polymerization method that is more preferable as the living radical polymerization method used in the present invention will be described.
In this atom transfer radical polymerization method, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having halogen at the α-position or a compound having halogen at the benzyl-position), or halogen A sulfonyl chloride compound or the like is used as an initiator.

For example,
_{C 6 H 5 -CH 2 X,} C 6 H 5 -C (H) (X) CH 3, C 6 H 5 -C (X) (CH 3) 2
(Wherein C ₆ H ₅ is a phenyl group, X is a chlorine atom, a bromine atom or an iodine atom),
^{_{R 3 -C (H) (X}} ) -CO 2 R 4, R 3 -C (CH 3) (X) -CO 2 R 4, R 3 -C (H) (X) -C (O) R 4 _{^{, R 3 -C (CH 3)}} (X) -C (O) R 4
(Wherein R ³ and R ⁴ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom) ),
R ³ —C ₆ H ₄ —SO ₂ X
(Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, X is a chlorine atom, bromine atom or iodine atom)
Etc.

As an initiator of the atom transfer radical polymerization method, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a structure represented by the general formula (1) at the end of one main chain and the functional group at the other main chain end is produced.
Examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.

The organic halide having the alkenyl group is not particularly limited. For example, the general formula (6):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6)
(In the formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or others. R ⁸ is —C (O) O— (ester group), —C (O) — (keto group) or o-, m-, p-phenylene group, R ⁹ is a direct bond Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds, X is a chlorine atom, a bromine atom or an iodine atom)
What is shown by this is illustrated.

Specific examples of the substituents R ⁶ and R ⁷ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.
Examples of the divalent organic group having 1 to 20 carbon atoms that may contain one or more ether bonds of R ⁹ include, for example, 1 to 20 carbon atoms that may contain one or more ether bonds. An alkylene group etc. are mentioned.

Specific examples of the organic halide having an alkenyl group represented by the general formula (6) include
_{XCH 2 C (O) O (} CH 2) n CH = CH 2,
H ₃ CC (H) (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
(H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n CH═CH ₂ ,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m CH = CH 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m CH = CH 2,

(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -CH = CH 2,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) n -O- (CH 2) m CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -CH = CH 2
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) n -O- (CH 2) m -CH = CH 2
(In the above formulas, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 1-20, m is an integer of 0-20)
Etc.

The organic halide having an alkenyl group is further represented by the general formula (7):
_{^{H 2 C = C (R 5}} ) -R 9 -C (R 6) (X) -R 10 -R 7 (7)
Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ and X are the same as above, R ¹⁰ is a direct bond, —C (O) O— (ester group), —C (O) — (keto group ) Or o-, m-, p-phenylene group)
The compound shown by these is mentioned.

R ⁹ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, a halogen atom is bonded. A vinyl group is bonded to the carbon, and is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, it is not always necessary to have a C (O) O group, a phenylene group or the like as R ¹⁰ , and a direct bond may be used. When R ⁹ is not a direct bond, R ¹⁰ is preferably a C (O) O group, a C (O) group, or a phenylene group in order to activate the carbon-halogen bond.

If the compound represented by the general formula (7) is specifically exemplified,
_{CH 2 = CHCH 2 X, CH} 2 = C (CH 3) CH 2 X,
_{CH 2 = CHC (H) (} X) CH 3, CH 2 = C (CH 3) C (H) (X) CH 3,
_{CH 2 = CHC (X) (} CH 3) 2, CH 2 = CHC (H) (X) C 2 H 5,
_{CH 2 = CHC (H) (} X) CH (CH 3) 2,
_{CH 2 = CHC (H) (} X) C 6 H 5, CH 2 = CHC (H) (X) CH 2 C 6 H 5,
_{CH 2 = CHCH 2 C (H} ) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -CO 2 R,
_{CH 2 = CH (CH 2)} 8 C (H) (X) -CO 2 R,
_{CH 2 = CHCH 2 C (H} ) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 2 C (H) (X) -C 6 H 5,
_{CH 2 = CH (CH 2)} 3 C (H) (X) -C 6 H 5
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

Specific examples of the sulfonyl halide compound having the alkenyl group include
_{o-, m-, p-CH 2} = CH- (CH 2) n -C 6 H 4 -SO 2 X,
_{o-, m-, p-CH 2} = CH- (CH 2) n -O-C 6 H 4 -SO 2 X
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, n is an integer of 0 to 20)
Etc.

The organic halide having a crosslinkable silyl group is not particularly limited. For example, the general formula (8):
^{R 6 R 7 C (X)} -R 8 -R 9 -C (H) (R 5) CH 2 - [Si (R 11) 2-b (Y) b O] m -Si (R 12) 3- _a (Y) _a (8)
(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and X are the same as described above, and R ¹¹ and R ¹² are all alkyl groups, aryl groups, aralkyl groups having 1 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). An organosiloxy group, when two or more R ¹¹ or R ¹² are present, they may be the same or different; Y represents a hydroxyl group or a hydrolyzable group; and Y is two or more When present, they may be the same or different, a is 0, 1, 2 or 3, b is 0, 1 or 2, m is an integer from 0 to 19, provided that a + mb ≧ 1 Satisfy)
The following are exemplified.

If the compound represented by the general formula (8) is specifically exemplified,
XCH ₂ C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (OCH 3) 3,
(CH ₃ ) ₂ C (X) C (O) O (CH ₂ ) _n Si (OCH ₃ ) ₃ ,
_{XCH 2 C (O) O (} CH 2) n Si (CH 3) (OCH 3) 2,
_{CH 3 C (H) (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
_{(CH 3) 2 C (X} ) C (O) O (CH 2) n Si (CH 3) (OCH 3) 2,
(In the above formula, X is a chlorine atom, bromine atom, iodine atom, n is an integer of 0-20),
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (OCH 3) 3,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m Si (OCH 3) 3,
_{XCH 2 C (O) O (} CH 2) n O (CH 2) m Si (CH 3) (OCH 3) 2,
_{H 3 CC (H) (X} ) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{(H 3 C) 2 C (} X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2,
_{CH 3 CH 2 C (H)} (X) C (O) O (CH 2) n O (CH 2) m -Si (CH 3) (OCH 3) 2
(Wherein X is a chlorine atom, bromine atom, iodine atom, n is an integer of 1-20, m is an integer of 0-20),
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 - (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-XCH 2} -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 -Si (OCH 3) 3,
_{o, m, p-CH 3} C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3,
_{o, m, p-CH 3} CH 2 C (H) (X) -C 6 H 4 -O- (CH 2) 2 -O- (CH 2) 3 Si (OCH 3) 3
(In the above formula, X is a chlorine atom, a bromine atom or an iodine atom)
Etc.

The organic halide having a crosslinkable silyl group is further represented by the general formula (9):
_{^{(R 12) 3-a (}} Y) a Si- [OSi (R 11) 2-b (Y) b] m -CH 2 -C (H) (R 5) -R 9 -C (R 6) ( X) -R ¹⁰ -R ⁷ (9)
(Wherein R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , a, b, X, Y are the same as above, m is an integer of 0-19)
What is shown by this is illustrated.

If the compound represented by the general formula (9) is specifically exemplified,
_{(CH 3 O) 3 SiCH 2} CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 2 (CH} 3) SiCH 2 CH 2 C (H) (X) C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 2 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 9 C (H) (X) -CO 2 R,
_{(CH 3 O) 3 Si (} CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 3 C (H) (X) -C 6 H 5,
_{(CH 3 O) 3 Si (} CH 2) 4 C (H) (X) -C 6 H 5,
_{(CH 3 O) 2 (CH} 3) Si (CH 2) 4 C (H) (X) -C 6 H 5,
(In the above formula, X is a chlorine atom, bromine atom or iodine atom, R is an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group)
Etc.

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said hydroxyl group, The following are illustrated.
_{HO- (CH 2) n -OC (} O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said amino group, The following are illustrated.
_{H 2 N- (CH 2) n} -OC (O) C (H) (R) (X)
(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

There is no limitation in particular in the organic halide or halogenated sulfonyl compound which has the said epoxy group, The following are illustrated.

(Wherein X is a chlorine atom, bromine atom or iodine atom, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)

In order to obtain a vinyl polymer having two or more groups represented by the general formula (1) per molecule at the molecular end, an organic halide or sulfonyl halide compound having two or more starting points is used as an initiator. It is preferable to use as. For example,

Etc.
There is no restriction | limiting in particular in the vinyl-type monomer used in this superposition | polymerization, and all already illustrated can be used suitably.

Further, the transition metal complex used as a polymerization catalyst is not particularly limited, but preferably a metal complex having a central metal of Group 7, Group 8, Group 9, Group 11 or Group 11 of the periodic table, for example, copper, It is a metal complex of nickel, ruthenium and iron. More preferable examples include a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable.

Specific examples of the monovalent copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. Is mentioned.
When a copper compound is used, 2,2′-bipyridyl, its derivative, 1,10-phenanthroline, its derivative, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as polyamine can be added.

A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst.
When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator.
Further, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistributylphosphine complex ( NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

The polymerization can be carried out without solvent or in various solvents.
Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more.
Moreover, superposition | polymerization can be performed in room temperature-200 degreeC, Preferably it is 50-150 degreeC.

<Functional group introduction method>
The method for producing the component (A) is not particularly limited. For example, a vinyl polymer having a reactive functional group is produced by the method described above, and the reactive functional group is changed to a substituent having a (meth) acryloyl group. It can be manufactured by converting.
Below, the method to convert the terminal of the vinyl polymer which has a reactive functional group into group represented by General formula (1) is demonstrated.

The method for introducing the (meth) acryloyl group at the terminal of the vinyl polymer is not particularly limited, and examples thereof include the following methods.
(Introduction method 1) A vinyl polymer having a halogen group (halogen atom) at the terminal, and the general formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The method by reaction with the compound shown by these.
As a vinyl polymer having a halogen group at the terminal, the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to an ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
Those having a terminal group represented by are preferred.

(Introduction method 2) A vinyl polymer having a hydroxyl group at the terminal, and the general formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The method by reaction with the compound shown by these.
(Introduction method 3) A vinyl-based polymer having a hydroxyl group at the terminal is reacted with a diisocyanate compound to form a residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The method by reaction with the compound shown by these.

Below, each said method is demonstrated in detail.
[Introduction method 1]
The introduction method 1 is a method by a reaction between a vinyl polymer having a halogen group at the terminal and a compound represented by the general formula (2).
The vinyl polymer having a halogen group at the terminal is not particularly limited, but a vinyl polymer having a terminal group represented by the general formula (3) is preferable.
Examples of the group bonded to the ethylenically unsaturated group of the vinyl monomer in R ¹ and R ² in the general formula (3) include a hydrogen atom, a methyl group, a carbonyl group, a carboxylate group, a toluyl group, a fluoro group, and a chloro group. , Trialkoxysilyl group, phenylsulfonic acid group, carboxylic acid imide group, cyano group and the like.
A vinyl polymer having a halogen group at the terminal, particularly a vinyl polymer having a terminal group represented by the general formula (3), is prepared by using the above-mentioned organic halide or halogenated sulfonyl compound as an initiator and catalyzing a transition metal complex. Is produced by a method of polymerizing a vinyl monomer, or a method of polymerizing a vinyl monomer using a halogen compound as a chain transfer agent, but the former is preferred.

There is no limitation in particular in the compound represented by General formula (2).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (2) are the same as those described above, and specific examples thereof are the same as those described above.
M ⁺ in the general formula (2) is a counter cation of an oxyanion, and examples of the type include alkali metal ions and quaternary ammonium ions.

Examples of the alkali metal ion include lithium ion, sodium ion, and potassium ion.
Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.
Of these, alkali metal ions are preferable, and sodium ions and potassium ions are more preferable.

The usage-amount of the compound shown by General formula (2) becomes like this. Preferably it is 1-5 equivalent with respect to the terminal group shown by General formula (3), More preferably, it is 1.0-1.2 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 2]
The introduction method 2 is a method by a reaction between a vinyl polymer having a hydroxyl group at the terminal and a compound represented by the general formula (4).
There is no limitation in particular in the compound represented by General formula (4).
Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (4) are the same as those described above, and specific examples thereof are the same as those described above.

The vinyl polymer having a hydroxyl group at the terminal is a method of polymerizing a vinyl monomer using the above-mentioned organic halide or sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a compound having a hydroxyl group as a chain transfer agent. Is produced by a method of polymerizing a vinyl monomer, but the former is preferred.

Although there is no limitation in particular in the method of manufacturing the vinyl polymer which has a hydroxyl group at the terminal, For example, the following method is illustrated.
(A) When synthesizing a vinyl polymer by living radical polymerization, the general formula (10):
_{^{H 2 C = C (R 13}} ) -R 14 -R 15 -OH (10)
(In the formula, R ¹³ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ¹⁴ is —C (O) O— (ester group) or o-, m- or p-phenylene group, and R ¹⁵ is a direct bond. Or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds)
A method of reacting a compound having a polymerizable alkenyl group and a hydroxyl group in one molecule as a second monomer.

R ¹³ is preferably a hydrogen atom or a methyl group. Further, when R ¹⁴ is an ester group, it is a (meth) acrylate compound, and when R ¹⁴ is a phenylene group, it is a styrene compound. A specific example of R ¹⁵ is the same as the specific example of R ⁹ .
There is no limitation on the timing of reacting a compound having a polymerizable alkenyl group and hydroxyl group in one molecule, but the end of the polymerization reaction or the completion of the reaction of a predetermined monomer is particularly desired when rubber-like properties are expected. Later, it is preferable to react as the second monomer.

(B) When synthesizing a vinyl polymer by living radical polymerization, it has a low polymerizable alkenyl group and hydroxyl group in the molecule as the second monomer at the end of the polymerization reaction or after completion of the reaction of the predetermined monomer. A method of reacting a compound.
Although there is no limitation in particular in the said compound, For example, General formula (11):
_{^{H 2 C = C (R 13}} ) -R 16 -OH (11)
(In the formula, R ¹³ is the same as described above, and R ¹⁶ represents a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds.)
And the like.
A specific example of R ¹⁶ is the same as the specific example of R ⁹ .

Although there is no limitation in particular in the compound shown by General formula (11), The alkenyl alcohol like 10-undecenol, 5-hexenol, and allyl alcohol is preferable from the point that acquisition is easy.

(C) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization by a method as disclosed in JP-A-4-132706. A method of introducing a hydroxyl group at a terminal by hydrolysis or reaction with a hydroxyl group-containing compound.

(D) To a vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization, the general formula (12):
^{M + C - (R 17)} (R 18) -R 16 -OH (12)
(In the formula, R ¹⁶ and M ⁺ are the same as described above, and R ¹⁷ and R ¹⁸ are both an electron-withdrawing group for stabilizing carbanion C ⁻ or one is the electron-withdrawing group, the other is a hydrogen atom, and 1 to 10 carbon atoms. Represents an alkyl group or a phenyl group)
A method in which a halogen atom is substituted by reacting a stabilized carbanion having a hydroxyl group represented by formula (1).

Examples of the electron withdrawing group include —CO ₂ R (ester group), —C (O) R (keto group), —CON (R ₂ ) (amide group), —COSR (thioester group), —CN (nitrile group). ), —NO ₂ (nitro group) and the like, —CO ₂ R, —C (O) R, —CN are particularly preferable. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group.

(E) A vinyl polymer having at least one carbon-halogen bond represented by the general formula (3) obtained by atom transfer radical polymerization is allowed to react with a metal simple substance or an organometallic compound such as zinc to enolate. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl polymer having at least one halogen atom represented by the general formula (3), preferably a halogen atom at the terminal of the polymer, is represented by the general formula (13):
HO-R ^{< 16 >} -O ^- M ^<+> (13)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A hydroxyl group-containing compound represented by the general formula (14):
HO—R ¹⁶ —C (O) O ⁻ M ⁺ (14)
(Wherein R ¹⁶ and M ⁺ are the same as above)
A method in which the halogen atom is substituted with a hydroxyl group-containing substituent by reacting the hydroxyl group-containing compound represented by formula (1).

In the case where a halogen atom is not directly involved in the method of introducing a hydroxyl group as in (a) to (b), the method of (b) is more preferred because control is easier.
In addition, when a hydroxyl group is introduced by converting a halogen atom of a vinyl polymer having at least one carbon-halogen bond such as (c) to (f), control is easier (f). The method is more preferable.

The usage-amount of the compound shown by General formula (4) becomes like this. Preferably it is 1-10 equivalent with respect to the terminal hydroxyl group of a vinyl type polymer, More preferably, it is 1-5 equivalent.
The solvent for carrying out the reaction is not particularly limited, but is preferably a polar solvent because it is a nucleophilic substitution reaction. For example, tetrahydrofuran, dioxane, diethyl ether, acetone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphoric trimethyl. Amides, acetonitrile and the like are preferably used.
Although reaction temperature does not have limitation in particular, Preferably it is 0-150 degreeC, More preferably, it is 10-100 degreeC.

[Introduction method 3]
In the introduction method 3, a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at the terminal, and the residual isocyanate group and the general formula (5):
HO—R′—OC (O) C (R ^a ) ═CH ₂ (5)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ′ represents a divalent organic group having 2 to 20 carbon atoms)
It is the method by reaction with the compound shown by.

Examples of the organic group having 1 to 20 carbon atoms in R ^a in General Formula (5) are the same as those described above, and specific examples thereof are the same as those described above.
Examples of the divalent organic group having 2 to 20 carbon atoms represented by R ′ in the general formula (5) include an alkylene group having 2 to 20 carbon atoms (ethylene group, propylene group, butylene group, etc.), and 6 to 20 carbon atoms. And an arylene group having 7 to 20 carbon atoms.
Although there is no limitation in particular in the compound shown by General formula (5), As a particularly preferable compound, 2-hydroxypropyl methacrylate etc. are mentioned.
The vinyl polymer having a hydroxyl group at the terminal is as described above.

There is no particular limitation on the diisocyanate compound, and any conventionally known one can be used. Specific examples include toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluylene diisocyanate, hydrogen. Xylylene diisocyanate, isophorone diisocyanate and the like. These may be used alone or in combination of two or more. Moreover, you may use block isocyanate. From the viewpoint of obtaining better weather resistance, it is preferable to use a diisocyanate compound having no aromatic ring, such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate.

The amount of the diisocyanate compound used is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, relative to the terminal hydroxyl group of the vinyl polymer.
The usage-amount of the compound shown by General formula (5) becomes like this. Preferably it is 1-10 equivalent with respect to a residual isocyanate group, More preferably, it is 1-5 equivalent.
The reaction solvent is not particularly limited, but an aprotic solvent is preferable.
Although there is no limitation in particular in reaction temperature, Preferably it is 0-250 degreeC, More preferably, it is 20-200 degreeC.

<< (B) component >>
The redox (redox) initiator of the component (B) is not particularly limited, but is an inorganic peroxide initiator (persulfate initiator such as sodium persulfate, potassium persulfate, ammonium persulfate). And inorganic reducing agents (sodium metabisulfite, sodium bisulfite, etc.); combinations of organic peroxides and tertiary amines, such as benzoyl peroxide / dimethylaniline, cumene hydroperoxide / dimethylaniline, cumene hydro Condensates of peroxide / butyraldehyde and aniline, etc .; combinations of organic peroxides and transition metals, such as cumene hydroperoxide / cobalt naphthate, cumene hydroperoxide / copper naphthate, t-butyl hydroperoxide / cobalt naphth Tate, t-Butyl Hydropa Oxides / copper naphthates, other hydroperoxides / other metal soaps, etc .; transition metal and tertiary amine combinations, for example, copper naphthates / butyraldehyde and aniline condensates, other metal soaps / butyraldehyde and aniline Preferred examples include condensates.
Examples of the other hydroperoxides include diisopropyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxylaurate, t-butyl peroxydecanoate, t- Examples include butyl peroxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, p-methane hydroperoxide, diisopropylbenzene hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, and the like. It is done.
Examples of the other metal soaps include manganese naphthate, cobalt octoate, aluminum stearate, calcium stearate, zinc stearate, magnesium stearate, potassium oleate, and magnesium palmitate.
From the viewpoint of curability and storage stability, a combination of an organic peroxide and a tertiary amine, or a combination of an organic peroxide and a transition metal is more preferable.

(B) As a compounding quantity of a component, from a viewpoint of sclerosis | hardenability and storage stability, Preferably it is 0.01-20 weight part with respect to 100 weight part of (A) component, More preferably, it is 0.1-10 weight Part.

<< (C) component >>
The adhesive composition of the present invention may further contain a vinyl monomer as component (C) in order to improve curability, workability by lowering viscosity, and improving adhesiveness.
(C) Component vinyl monomers include (meth) acryloyl groups such as (meth) acrylic groups, carboxyl groups, styrene groups, acrylonitrile groups, N-vinylpyrrolidone groups, acrylamide groups, conjugated diene groups, vinyl ketones. And vinyl monomers having a group or the like.
Among these, those having a (meth) acryloyl group similar to the vinyl polymer used in the present invention, that is, a (meth) acrylic monomer is preferable.

Specific examples of the vinyl monomers include (meth) acrylate monomers, (meth) acrylic acid monomers, α, β-dicarboxyvinyl monomers, cyclic acrylates, styrene monomers, acrylonitrile, N-vinylpyrrolidone, Examples include acrylamide monomers, conjugated diene monomers, vinyl ketone monomers, and polyfunctional monomers.

(Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, (meth ) Isobutyl acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth ) N-octyl acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate , Phenyl (meth) acrylate, toluyl (meth) acrylate, (meth) acrylic Benzyl, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, ( (Meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxy) propyltrimethoxysilane, (meth) acrylic acid ethylene oxide adduct, (meth) acrylic acid trifluoromethylmethyl, (meta ) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate , Perfluoromethyl (meth) acrylate, (meth) Diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (Meth) acrylic acid 2-perfluorohexadecylethyl; 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate Polyethylene glycol di (meth) acrylate, 2,2-bis [4- (meth) acryloxyphenyl] propane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, trimethylolpropane tri (meth) acrylate, Tiger methylol methane tetra (meth) acrylate, isobornyl acrylate, and the like. Moreover, the compound etc. which are shown by the following Formula can also be mentioned. In the following formula, n represents an integer of 0-20.

Examples of the (meth) acrylic acid monomer include (meth) acrylic acid.
Examples of the α, β-dicarboxyvinyl monomer include itaconic acid, maleic acid, fumaric acid, and acid anhydrides of these monomers.
Examples of the styrenic monomer include styrene and α-methylstyrene.
Examples of acrylamide monomers include acrylamide and N, N-dimethylacrylamide.
Examples of the conjugated diene monomer include butadiene and isoprene.
Examples of the vinyl ketone monomer include methyl vinyl ketone.

Multifunctional monomers include trimethylolpropane triacrylate, neopentyl glycol polypropoxydiacrylate, trimethylolpropane polyethoxytriacrylate, bisphenol F polyethoxydiacrylate, bisphenol A polyethoxydiacrylate, dipentaerythritol polyhexanolide hexa Chlorate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) -5-ethyl-5-acryloyloxymethyl-1 , 3-dioxane, tetrabromobisphenol A diethoxydiacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetra Chi glycol diacrylate, 1,9-nonanediol diacrylate, and ditrimethylolpropane tetraacrylate.

In addition to the component (C), an oligomer component may be added.
Examples of oligomers include bisphenol A type epoxy acrylate resins, phenol novolac type epoxy acrylate resins, cresol novolak type epoxy acrylate resins, and COOH group-modified epoxy acrylate type resins; polyols (polytetramethylene glycol, ethylene glycol and adipine) Acid polyester diol, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanates (tolylene diisocyanate, isophorone diisocyanate, diphenylmethane) Diisocyanate, hexamethylene diisocyanate A urethane resin obtained from a hydroxylate-containing (meth) acrylate {hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.)} Urethane acrylate resin obtained by reaction; resin in which (meth) acrylic group is introduced into the polyol via an ester bond; polyester acrylate resin, poly (meth) acrylic acrylate resin (having a polymerizable reactive group) Poly (meth) acrylic ester resin) and the like.

The number average molecular weight of the component (C) and the oligomer component is preferably 5000 or less. Furthermore, in the case of using the component (C) for the purpose of improving the surface curability and reducing the viscosity for improving the workability, the molecular weight is preferably 1000 or less because the compatibility is good. preferable.
The component (C) may be used alone or in combination of two or more.

When the component (C) is used, the blending amount is preferably based on 100 parts by weight of the component (A) from the viewpoint of the balance of mechanical properties, storage stability, curability improvement, adhesion improvement, and workability improvement. Is 0.1 to 100 parts by weight, more preferably 1 to 50 parts by weight.

In addition, in order to increase the workability improving effect by reducing the viscosity, an organic solvent may be further contained in addition to the component (C).
As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane.
These organic solvents may be used alone or in combination of two or more.

<< (D) component >>
The adhesive composition of the present invention may further contain a compound having an SO ₂ Cl group as component (D) for adjusting the curing rate.
Examples of the component (D) compound having a SO ₂ Cl group include methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, 1-butanesulfonyl chloride, benzenesulfonyl chloride, 4-chloro-3-nitrobenzenesulfonyl chloride, chloro Examples include sulfonylacetamide, 4-acetamidobenzenesulfonyl chloride, chlorosulfonylbenzoic acid, chlorosulfonic acid, chlorosulfonic acid acetyl chloride, 5-chlorothiophene-2-sulfonyl chloride, chlorosulfonated acetanilide and the like.
From the viewpoints of storage stability and curability, methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, chlorosulfonic acid and 4-acetamidobenzenesulfonyl chloride are preferred, and methanesulfonyl chloride, ethanesulfonyl chloride and 4-acetamidobenzenesulfonyl chloride are preferred. Further preferred.

In addition, the component (D) includes a polymer having a SO ₂ Cl group, specifically, chlorosulfonated polyethylene rubber (Hypalon manufactured by DuPont Dow, TOSO-CSM manufactured by Tosoh Corporation, etc.), Examples thereof include alkylated chlorosulfonated polyethylene rubber (TOSO-EXTOS manufactured by Tosoh Corporation).
The polymer having a SO ₂ Cl group is preferably an elastomer.

The component (D) may be used alone or in combination of two or more.
When the component (D) is used, the blending amount is preferably 0.1 to 300 parts by weight, more preferably 1 to 150 parts by weight with respect to 100 parts by weight of the component (A) from the viewpoint of curability. is there.

<< (E) component >>
The adhesive composition of the present invention may further contain a polymer capable of dissolving the components (A) to (D) as the component (E) for the mechanical properties and thixotropy of the cured adhesive.
Examples of the polymer that dissolves the components (A) to (D) include poly (meth) acrylic acid copolymer, synthetic rubber, and natural rubber.
Preferred are polyethyl acrylate, polymethyl methacrylate, polyhexyl / ethyl methacrylate, nitrile rubber, diene copolymer, acrylic modified polybutadiene and the like.
The said (E) component may be used independently or may use 2 or more types together.

When the component (E) is used, the blending amount is preferably 0.1 to 300 parts by weight, more preferably 100 parts by weight with respect to 100 parts by weight of the component (A), from the viewpoint of adjusting the balance between mechanical properties and workability. 1 to 150 parts by weight.

<< (F) component >>
Since the adhesive composition of the present invention is preferably composed mainly of a (meth) acrylic polymer, it is not always necessary to add an adhesion-imparting resin, but in order to further improve the adhesion, If necessary, an adhesion-imparting resin may be further contained as the component (F).
Specific examples of the component (F) adhesion-imparting resin include phenol resin, modified phenol resin, cyclopentadiene-phenol resin, xylene resin, coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin, and the like. Is mentioned.
Of these, terpene phenol resins and rosin ester resins are preferred. When the adhesive composition of the present invention is blended with an adhesive composition using the (A) component whose main chain is a (meth) acrylic polymer, the miscibility is relatively good. When used as an adhesive strength (peeling hardness) can be increased. The reason why the miscibility is good is not clear, but it is presumed that these adhesion imparting resins are in the polarity and three-dimensional structure (solubility parameters are close to those of acrylic resins).
The said (F) component may be used independently or may use 2 or more types together.

When the component (F) is used, the blending amount thereof is preferably 0.1 with respect to 100 parts by weight of the component (A) from the viewpoint of the balance between mechanical properties, heat resistance, oil resistance and adhesiveness of the cured product. -100 parts by weight, more preferably 1-50 parts by weight.

<< Adhesive composition >>
The adhesive composition of the present invention is a composition comprising the component (A) and the component (B) as described above. Moreover, (C), (D), (E), (F) component can be contained as needed.
Furthermore, you may mix | blend various additives etc. in order to adjust a physical property as needed to the adhesive composition of this invention.

<Reinforcing silica>
Reinforcing silica may be added to the adhesive composition of the present invention from the viewpoint of improving the strength of the cured product.
Examples of the reinforcing silica include fumed silica and precipitated silica. Among these, those having a particle diameter of 50 μm or less and a specific surface area of 80 m ² / g or more are preferable from the viewpoint of reinforcing effect. In addition, the measuring method of a specific surface area is as the below-mentioned.

Further, surface-treated silica such as organosilane, organosilazane, diorganocyclopolysiloxane and the like is more preferable because it easily exhibits fluidity suitable for molding.
As a more specific example of the reinforcing silica, there is no particular limitation. However, Nippon Aerosil Co., Ltd., which is one of fumed silica, and Nippon Silica Industry Co., Ltd., which is one of precipitated silicas. Nipsil and the like.

The reinforcing silica may be used alone or in combination of two or more.
When reinforcing silica is used, the addition amount is not particularly limited, but is preferably 0.1 to 100 parts, more preferably 100 parts by weight (hereinafter, also simply referred to as part) of the component (A). 0.5 to 80 parts, more preferably 1 to 50 parts. When the amount is less than 0.1 part, the effect of improving the reinforcing property may not be sufficient, and when it exceeds 100 parts, the workability of the adhesive composition may be deteriorated.

<Filler>
In the adhesive composition of the present invention, various fillers may be used as necessary in addition to the reinforcing silica.
The filler is not particularly limited, but wood powder, pulp, cotton chips, asbestos, glass fiber, carbon fiber, mica, walnut shell powder, rice husk powder, graphite, diatomaceous earth, white clay, dolomite, silicic anhydride, Reinforcing fillers such as hydrous silicic acid and carbon black; heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, bengara, Fillers such as fine aluminum powder, flint powder, zinc oxide, activated zinc white, zinc powder, zinc carbonate and shirasu balloon; fibrous fillers such as asbestos, glass fiber and glass filament, carbon fiber, Kevlar fiber, polyethylene fiber, etc. Is mentioned. Of these fillers, carbon black, calcium carbonate, titanium oxide, talc and the like are preferable. In addition, when it is desired to obtain a cured product having low strength and large elongation, a filler selected mainly from titanium oxide, calcium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. may be added. it can.

In general, when calcium carbonate has a small specific surface area, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient. The larger the specific surface area value, the greater the effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product. Moreover, it is more preferable that the calcium carbonate is subjected to a surface treatment using a surface treatment agent. When the surface-treated calcium carbonate is used, the workability of the composition of the present invention is improved as compared with the case of using the non-surface-treated calcium carbonate, and the adhesiveness and weather resistance of the adhesive composition are improved. The improvement effect is considered to be further improved.

Examples of the surface treatment agent include organic substances such as fatty acids, fatty acid soaps and fatty acid esters, various surfactants, and various coupling agents such as silane coupling agents and titanate coupling agents. Specific examples include, but are not limited to, fatty acids such as caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and oleic acid. Sodium salts and potassium salts of these fatty acids, and alkyl esters of these fatty acids.
Specific examples of surfactants include sodium anion surfactants such as polyoxyethylene alkyl ether sulfates and long-chain alcohol sulfates, sulfate-type anionic surfactants such as potassium salts, alkylbenzene sulfonic acids, alkylnaphthalene sulfonic acids, paraffins Examples thereof include sulfonic acid type anionic surfactants such as sodium salts and potassium salts such as sulfonic acid, α-olefin sulfonic acid and alkylsulfosuccinic acid.

The treatment amount of the surface treatment agent is preferably in the range of 0.1 to 20% by weight (hereinafter referred to as “%”) with respect to calcium carbonate, and more preferably in the range of 1 to 5%. When the treatment amount is less than 0.1%, the workability, adhesion and weather resistance adhesion may not be sufficiently improved. When the treatment amount exceeds 20%, the storage stability of the adhesive composition decreases. Sometimes.

Although there is no particular limitation, when calcium carbonate is used, colloidal calcium carbonate is used when particularly improving effects such as thixotropy of the compound, breaking strength of the cured product, elongation at break, adhesion and weather resistance adhesion are expected. Is preferred.
On the other hand, heavy calcium carbonate may be added for the purpose of lowering the viscosity of the compound, increasing the amount, reducing costs, etc. When using this heavy calcium carbonate, the following may be added as necessary. Can be used.

Heavy calcium carbonate is obtained by mechanically pulverizing and processing natural chalk (chalk), marble, limestone, and the like. There are dry and wet methods for the pulverization method, but wet pulverized products are often not preferred because they often deteriorate the storage stability of the adhesive composition of the present invention. Heavy calcium carbonate becomes a product having various average particle diameters by classification. There is no particular limitation, but when the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product is expected, the specific surface area value is 1.5 m ² / g or more and 50 m ² / g or less. , more preferably from ^2m 2 / g or more ^{50 m} 2 / g or less, more preferably 2.4 m ² / g or more ^{50m 2 / g, 3m 2 /} g or more ^{50 m} 2 / g or less is particularly preferred. When the specific surface area is less than 1.5 m ² / g, the improvement effect may not be sufficient. Of course, this is not the case when the viscosity is simply lowered or only for the purpose of increasing the viscosity.

In addition, the value of the specific surface area means a measurement value by an air permeation method (a method for obtaining a specific surface area from air permeability with respect to a powder packed bed) performed according to JIS K 5101 as a measurement method. As a measuring instrument, it is preferable to use a specific surface area meter SS-100 manufactured by Shimadzu Corporation.

These fillers may be used alone or in combination of two or more according to the purpose and necessity. Although not particularly limited, for example, when heavy calcium carbonate with a specific surface area value of 1.5 m ² / g or more and colloidal calcium carbonate are combined, the increase in the viscosity of the compound is moderately suppressed. The effect of improving the strength at break, elongation at break, adhesion and weather resistance of the cured product can be greatly expected.

When using a filler, the amount added is preferably 5 to 1000 parts, more preferably 20 to 500 parts, based on 100 parts of component (A). , Particularly preferably in the range of 40 to 300 parts. If the blending amount is less than 5 parts, the effect of improving the breaking strength, breaking elongation, adhesion and weather resistance of the cured product may not be sufficient, and if it exceeds 1000 parts, the workability of the adhesive composition May decrease. A filler may be used independently and may be used together 2 or more types.

<Anti-aging agent>
In the adhesive composition of the present invention, an anti-aging agent may be blended in order to adjust physical properties.
An acrylic polymer is originally a polymer excellent in heat resistance, weather resistance, and durability, and therefore, an anti-aging agent is not necessarily required, but a conventionally known antioxidant and light stabilizer may be appropriately used. it can. In addition, the anti-aging agent can be used for polymerization control during polymerization, and physical properties can be controlled.

Various types of antioxidants are known, and are described in, for example, “Antioxidant Handbook” published by Taiseisha, “Degradation and Stabilization of Polymer Materials” (235-242), issued by CM Chemical Co., Ltd. Although various things are mentioned, it is not necessarily limited to these.
Examples of the antioxidant include thioethers such as MARK PEP-36 and MARK AO-23 (all are manufactured by Asahi Denka Co., Ltd.); Irgafos 38, Irgafos 168, Irgafos P-EPQ (all are Ciba Specialty And phosphorous antioxidants such as Chemicals Co., Ltd .; hindered phenolic compounds, and the like. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the hindered phenol compound include the following. 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, mono (or di or tri) (α methylbenzyl) phenol, 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 4, 4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol-bis- [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1 , 3,5-triazine, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di -T-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-) t-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-to Limethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl) calcium, tris -(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N'-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, tris (2,4-di-tert-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2 -[2-Hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyl Enyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5 -Chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-condensate with polyethylene glycol (molecular weight about 300), hydroxyphenylbenzotriazole derivative, 2- (3 5-Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6- Ntamechiru 4-piperidyl), 2,4-di -t- butyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like.

In terms of trade names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack NS-7, Nocrack DAH (all above Also manufactured by Ouchi Shinsei Chemical Co., Ltd.), MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO- 80, MARK AO-15, MARK AO-18, MARK 328, MARK AO-37 (all manufactured by Asahi Denka Co., Ltd.), IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024 , IRG NOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL (all are manufactured by Ciba Specialty Chemicals Co., Ltd.), Sumitizer GA-80 (and above, any Can also be exemplified by, but not limited to, Sumitomo Chemical Co., Ltd.).

Furthermore, a monoacrylate phenolic antioxidant having both an acrylate group and a phenol group, a nitroxide compound, and the like can be given.
Examples of the monoacrylate phenol-based antioxidant include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name Sumilyzer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate (trade name Sumitizer GS) and the like.

Nitroxide compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals, cyclic hydroxyamines, etc. The nitroxy free radicals from are illustrated. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.
Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like.
Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

Antioxidants may be used in combination with light stabilizers, and when used together, the effects are further exerted, and the heat resistance may be particularly improved. Tinuvin C353, Tinuvin B75 (all of which are manufactured by Nippon Ciba Geigy Co., Ltd.) and the like in which an antioxidant and a light stabilizer are mixed in advance may be used.

The monoacrylate phenol-based antioxidant can control the rate and curability of thermal radical curing and improve the elongation of the cured product. Since the physical properties of the cured product can be easily controlled, the same examples as described above are exemplified. The said monoacrylate phenolic antioxidant may be used independently and may be used in combination of 2 or more type.

When using the above various antioxidants including monoacrylate phenolic antioxidants, the amount used is not particularly limited, but for the purpose of giving a good effect on the mechanical properties of the resulting cured product (A) 0.01 part or more is preferable with respect to 100 parts of the component, and 0.05 part or more is more preferable. Moreover, 5.0 parts or less are preferable, 3.0 parts or less are more preferable, and 2.0 parts or less are more preferable.

<Plasticizer>
You may mix | blend a plasticizer with the adhesive composition of this invention.
As a plasticizer, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate, etc. Non-aromatic dibasic acid esters; esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyl and partial water And hydrocarbon oils such as terphenyl. These can be used alone or in admixture of two or more, but are not necessarily required. In addition, these plasticizers can also be mix | blended at the time of polymer manufacture.
When using a plasticizer, the usage-amount is preferable 5-800 parts with respect to 100 parts of (A) component from a viewpoint of elongation provision, workability | operativity, and bleeding prevention from hardened | cured material.

<Solvent>
An organic solvent may be added to the adhesive composition of the present invention from the viewpoints of workability during coating, drying before and after curing, and the like.
As the organic solvent, those having a boiling point of 50 to 180 ° C. are usually preferable because of excellent workability during coating and drying before and after curing. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, isobutanol; methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, etc. Ester solvents; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and cyclic ether solvents such as dioxane. These solvents may be used alone or in combination of two or more.
When using a solvent, the usage-amount is preferable 1-900 parts with respect to 100 parts of (A) component from a viewpoint of the finish of hardened | cured material, workability | operativity, and drying.

<Adhesion improver>
Various adhesive property improvers may be added to the adhesive composition of the present invention in order to improve the adhesiveness to various supports (plastic film or the like).
Examples of adhesion improvers include alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxy Silanes, alkyl isopropenoxy silanes such as γ-glycidoxypropyl methyl diisopropenoxy silane, γ-glycidoxy propyl methyl dimethoxy silane, γ-glycidoxy propyl trimethoxy silane, vinyl trimethoxy silane, vinyl dimethyl methoxy Silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-mercaptopro Le trimethoxysilane, .gamma.-mercaptopropyl alkoxysilanes having a functional group such as a methyl dimethoxy silane; silicone varnishes; polysiloxanes and the like.
When using an adhesive property improving agent, the usage-amount is preferable 0.1-20 parts with respect to 100 parts of (A) component from a viewpoint of the balance of the mechanical property (elongation and intensity | strength) and adhesiveness of hardened | cured material. .

<Preparation of adhesive composition>
The adhesive composition of the present invention can be prepared as a two-component type in which the adhesive component excluding the reducing agent is liquid A and the reducing agent is liquid B, and one liquid in which all the ingredients are pre-blended and sealed It can also be prepared as a mold.

<< Usage >>
The adhesive composition of the present invention is used for adhering surface decorative materials to buildings, bonding methods for tiles and panels that do not use joint seals, and bonding transparent substrates such as glass, acrylic, and carbonate. It can be in the form of a one-part adhesive, a two-part adhesive, a contact adhesive that adheres after the open time, an adhesive, and the like. In addition to the adhesive, it is useful as an elastic sealing agent, particularly a building sealing material, a siding board sealing material, and a glazing sealing material, and can be used as a sealing agent for buildings, ships, automobiles, roads and the like. Moreover, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings alone or with the help of a primer, it can also be used as various types of sealing compositions. Furthermore, it is also useful as a paint, a waterproofing coating film, a food packaging material, a cast rubber material, a molding material, and a foam material. In addition, as an adhesive for mounting electrical and electronic components such as flexible printed wiring boards, build-up wiring boards, rigid wiring boards, TAB (Tape Automated Bonding) tapes, adhesive tapes for semiconductors, peripheral materials for lead frames, laminated materials, etc. Useful.

By using the adhesive composition of the present invention, the curability at normal temperature is good, the adhesive strength can be expressed in a short time (tens of minutes) immediately after bonding, heat resistance, weather resistance, oil resistance, etc. An excellent adhesive can be obtained.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples.
In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) and chloroform as a GPC solvent were used.
In the following examples, “average number of terminal (meth) acryloyl groups” is “number of (meth) acryloyl groups introduced per molecule of polymer”, from the number average molecular weight determined by ¹ H-NMR analysis and GPC. Calculated.
In the following examples, “part” represents “part by weight”.

Production Example 1 (Synthesis of poly (acryloyl group) -terminated poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
Cuprous bromide as catalyst, pentamethyldiethylenetriamine as ligand, diethyl-2,5-dibromoadipate as initiator, n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in 25 / mole Polymerization was performed at a ratio of 46/29 to obtain a terminal bromine group poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 16,500 and a molecular weight distribution of 1.13.
400 g of this polymer was dissolved in N, N-dimethylacetamide (400 mL), 10.7 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 6 hours under a nitrogen atmosphere. A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [1]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [1].
The number average molecular weight of the purified acryloyl group both-end polymer [1] is 16900, the molecular weight distribution is 1.14, and the average number of terminal acryloyl groups is 1.8 (that is, the introduction rate of acryloyl groups at the terminals is 90%). there were.

Production Example 2 (Synthesis of acryloyl group single terminal poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
Cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, ethyl 2-bromobutyrate as an initiator, and n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate in moles of 25/46/29 Polymerization was carried out at a ratio of 1 to 3, thereby obtaining a one-terminal bromine group poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate) having a number average molecular weight of 3700 and a molecular weight distribution of 1.14.
1050 g of this polymer was dissolved in N, N-dimethylacetamide (1050 g), 56.2 g of potassium acrylate was added, and the mixture was heated and stirred at 70 ° C. for 4 hours under a nitrogen atmosphere. A mixture of butyl / ethyl acrylate / 2-methoxyethyl acrylate) (hereinafter referred to as polymer [2]) was obtained. After N, N-dimethylacetamide in the mixed solution was distilled off under reduced pressure, toluene was added to the residue, and the insoluble matter was removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to purify the polymer [2].
The number average molecular weight of the purified acryloyl group single terminal polymer [2] is 3800, the molecular weight distribution is 1.15, and the average terminal acryloyl group number is 1.0 (that is, the introduction rate of acryloyl group at the terminal is almost 100%). Met.

Production Example 3 (Synthesis of methacryloyl group-terminated poly (n-butyl acrylate / ethyl acrylate / 2-methoxyethyl acrylate))
A methacryloyl group-terminated poly (n-butyl acrylate / ethyl acrylate / 2-methoxy) was prepared in the same manner as in Production Example 1, except that 12.1 g of potassium methacrylate was used instead of 10.7 g of potassium acrylate. Ethyl acrylate) (hereinafter referred to as polymer [3]).
After purification, the methacryloyl group-terminated polymer [3] has a number average molecular weight of 17,000, a molecular weight distribution of 1.10, and an average number of terminal methacryloyl groups of 1.8 (that is, the introduction rate of methacryloyl groups at the ends is 90%). there were.

Example 1
100 g of the polymer [1] obtained in Production Example 1, 85 g of methyl acrylate, 15 g of acrylic acid, IRGNOX 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1 g of Ciba Specialty Chemicals) and 0.2 g of cumene hydroperoxide were added and mixed well to prepare a liquid composition.
The liquid composition was applied to an area of 25 × 25 mm ² from a position 5 mm from the end of an aluminum substrate for measuring shear strength (width 25 mm × length 100 mm × thickness 2 mm) to a thickness of 100 μm. In addition, dimethylaniline is applied to another base material of the same size and material at the same position as described above, and the two base materials are bonded together to prepare a sample for measuring shear strength to which the adhesive composition is applied. Produced. After curing this at 150 ° C. for 15 minutes, the shear strength was measured.
Thus, in the said Example, it apply | coats to a base material by using the reducing agent equivalent (dimethylaniline) of (B) component as a primer, and apply | coats the liquid composition containing other than the said component to another base material. These were bonded to obtain a shear strength measurement sample to which the adhesive composition was applied.

Example 2
100 g of the polymer [1] obtained in Production Example 1, 85 g of methyl acrylate, 15 g of acrylic acid, 1 g of IRGNOX 1010, 0.2 g of cumene hydroperoxide and 9.4 g of methanesulfonyl chloride are added and mixed well to form a liquid. A composition was prepared.
Preparation of shear strength measurement sample and shear strength in the same manner as in Example 1 except that the liquid composition was used and cured for 3 days under conditions of 23 ° C. × 55% RH instead of curing at 150 ° C. for 15 minutes. The measurement of was carried out.

Example 3
A sample for shear strength measurement was prepared, cured, and measured in the same manner as in Example 2 except that 2 g of 1,6-hexanediol diacrylate was further added.

Example 4
Sample for measuring shear strength in the same manner as in Example 2, except that 100 g of polymer [1] was changed to 70 g and 30 g of polymer [2] was added instead of 85 g of methyl acrylate in the liquid composition of Example 2. Production, curing, and measurement were carried out.

Example 5
In the liquid composition of Example 2, 100 g of the polymer [1] was changed to 70 g, and 30 g of the polymer [2] was further added. Measurements were performed.

Example 6
100 g of the polymer [3] obtained in Production Example 3, 85 g of methyl methacrylate, 15 g of methacrylic acid, 1 g of IRGNOX1010, 0.2 g of cumene hydroperoxide, and 9.4 g of methanesulfonyl chloride are added and mixed well. A liquid composition was prepared.
Using the liquid composition, a sample for shear strength measurement was prepared, cured, and measured in the same manner as in Example 2.

Example 7
A liquid composition was prepared in the same manner as in Example 2 except that the amount of cumene hydroperoxide added was 1.0 g.
Using the liquid composition, instead of dimethylaniline as a primer, a condensate of butyraldehyde and aniline (trade name; Noxeller 8, manufactured by Ouchi Shinsei Chemical Industry) was used in the same manner as in Example 2, A sample for shear strength measurement was prepared, cured, and measured.

Example 8
In the liquid composition of Example 7, the amount of cumene hydroperoxide added was 0.5 g, and further 30 g of Aerosil R-974 (manufactured by Nippon Aerosil Co., Ltd.) as hydrophobic silica, light ester 1,6HX (1,6-hexane) A sample for measuring shear strength, curing, and measurement were carried out in the same manner as in Example 7 except that 2 g of diol dimethacrylate (manufactured by Kyoeisha Chemical Co., Ltd.) was added.

Example 9
100 g of the polymer [1] obtained in Production Example 1, 85 g of isobornyl acrylate, 15 g of acrylic acid, 30 parts of YS resin TO105 (aromatic modified terpene resin, manufactured by Yashara Chemical Co., Ltd.), IRGNOX 1010 (pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by Ciba Specialty Chemicals) 1 g, 1,6-hexanediol diacrylate 2 g, cumene hydroperoxide 0.5 g, ethanesulfonyl chloride 5 g was added and mixed well to prepare a liquid composition.
Preparation of the sample for shear strength measurement, curing, in the same manner as in Example 2, except that the liquid composition was used and a noxeller 8 (condensate of butyraldehyde and aniline) was applied instead of dimethylaniline as a primer. Measurements were performed.

Example 10
A sample for shear strength measurement was prepared, cured, and measured in the same manner as in Example 9 except that YS resin TO105 was changed to YS resin TR105 (aromatic modified terpene resin, manufactured by Yasuhara Chemical Co., Ltd.).

Example 11
A sample for shear strength measurement was prepared, cured, and measured in the same manner as in Example 9 except that YS Resin TO105 was changed to Mighty Ace G125 (terpene phenol resin, manufactured by Yasuhara Chemical Co., Ltd.).

Example 12
A sample for shear strength measurement was prepared, cured, and measured in the same manner as in Example 9 except that YS resin TO105 was changed to Superester A-100 (special rosin ester resin, manufactured by Arakawa Chemical Industries).

Comparative Example 1
85 g of methyl methacrylate, 15 g of methacrylic acid, 2 g of ethylene glycol dimethacrylate, 100 g of chlorosulfonated polyethylene (Cl content 43%, S content 11%, trade name: Haypalon, manufactured by DuPont-Dow), cumene hydroperoxide 0.2 g, 1 g of IRGANOX 1010 was added and mixed well to prepare an adhesive composition.
The composition was applied to an area of 25 × 25 mm ² from a position 5 mm from the end of an aluminum substrate for measuring shear strength (width 25 mm × length 100 mm × thickness 2 mm) so that the thickness was 100 μm. Further, dimethylaniline was applied to another base material of the same size and material at the same position as described above, and the two base materials were bonded together to produce a sample for measuring shear strength. This was cured at 23 ° C. × 55% RH for 3 days, and then the shear strength was measured.

Comparative Example 2
Add 85 g of methyl methacrylate, 15 g of methacrylic acid, 1 g of ethylene glycol dimethacrylate, urethane acrylate (trade name; Ebecryl 8402, manufactured by Daicel UCB), 0.5 g of cumene hydroperoxide, and 9.4 g of methanesulfonyl chloride. And mixed well to prepare an adhesive composition.
Preparation, curing, and measurement of the sample for measuring shear strength were performed in the same manner as in Comparative Example 1.

The shear strength measurement was performed as follows.
Shear strength was measured by Autograph AG-2000G (manufactured by Shimadzu) at 23 ° C. × 55% RH and a shear rate of 50 mm / min using the samples for shear strength measurement obtained in the above Examples and Comparative Examples.

Further, the samples for shear strength measurement obtained in the above Examples and Comparative Examples were further cured at 150 ° C. for 3 days and subjected to a heat resistance test. Using the sample after the heat resistance test, the shear strength was measured in the same manner as described above.
These results are shown in Table 1.

The adhesive compositions of the examples were excellent in adhesive strength after normal temperature curing and heat curing, and the adhesive strength after the heat resistance test was also maintained. On the other hand, in Comparative Example 1, the adhesion function after the heat resistance test disappeared. In Comparative Example 2, the initial adhesive strength was not sufficiently developed.

By using the adhesive composition of the present invention, an adhesive having excellent heat resistance, weather resistance, oil resistance, etc. that has good curability at normal temperature and can express adhesive strength in a short time immediately after bonding. can get.

Claims (26)

(A) General formula (1):
—OC (O) C (R ^a ) ═CH ₂ (1)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms)
A vinyl polymer having two or more groups represented by the formula (1) and having one or more groups represented by the general formula (1) at the molecular end thereof,
(B) a redox initiator,
An adhesive composition comprising: The adhesive composition according to claim 1, wherein the vinyl monomer constituting the main chain of the component (A) is a (meth) acrylic monomer. The adhesive composition according to claim 1 or 2, wherein the vinyl monomer constituting the main chain of the component (A) is an acrylate ester monomer. The adhesive according to any one of claims 1 to 3, wherein the vinyl monomer constituting the main chain of the component (A) contains at least one selected from butyl acrylate, ethyl acrylate, and 2-methoxyethyl acrylate. Composition. (A) ^Ra in General formula (1) of ^a component is a hydrogen atom or a C1-C20 hydrocarbon group, The adhesive composition in any one of Claims 1-4. The adhesive composition according to claim 5, wherein R ^a in the general formula (1) of the component (A) is a hydrogen atom or a methyl group. The adhesive composition according to any one of claims 1 to 6, wherein the component (B) is a combination of an inorganic peroxide initiator and an inorganic reducing agent. The adhesive composition according to any one of claims 1 to 6, wherein the component (B) is a combination of an organic peroxide and a tertiary amine, or a combination of an organic peroxide and a transition metal. The adhesive composition according to any one of claims 1 to 8, further comprising (C) a vinyl monomer in addition to the component (A) and the component (B). The adhesive composition according to claim 9, wherein the component (C) is a (meth) acrylic monomer. The adhesive composition according to claim 1, further comprising (D) a compound having a SO ₂ Cl group. The adhesive composition according to claim 11, wherein the component (D) is a polymer having a SO ₂ Cl group. The adhesive composition according to claim 12, wherein the component (D) is an elastomer. Furthermore, (E) The adhesive composition in any one of Claims 1-13 formed by containing the polymer which melt | dissolves said (A)-(D) component. Furthermore, the adhesive composition in any one of Claims 1-14 formed by containing (F) adhesiveness imparting resin. The component (A) is
To the vinyl polymer having a halogen group at the end,
General formula (2):
M ^{+ −} OC (O) C (R ^a ) ═CH ₂ (2)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
The adhesive composition according to claim 1, which is produced by reacting a compound represented by the formula: A vinyl polymer having a halogen group at the end is represented by the general formula (3):
-CR ¹ R ² X (3)
(Wherein R ¹ and R ² are groups bonded to the ethylenically unsaturated group of the vinyl monomer, and X represents a chlorine atom, a bromine atom or an iodine atom)
The adhesive composition of Claim 16 which has group shown by these. The component (A) is
To the vinyl polymer having a hydroxyl group at the end,
General formula (4):
X ¹ C (O) C (R ^a ) ═CH ₂ (4)
(Wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ represents a chlorine atom, a bromine atom or a hydroxyl group)
The adhesive composition according to claim 1, which is produced by reacting a compound represented by the formula: The component (A) is
(1) A diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal,
(2) Residual isocyanate group and general formula (5):
HO-R'- OC (O) C (R ^a ) = CH ₂ (5)
(In the formula, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ′ represents a divalent organic group having 2 to 20 carbon atoms)
The adhesive composition according to claim 1, which is produced by reacting with a compound represented by the formula: The adhesive composition according to any one of claims 1 to 19, wherein the main chain of the component (A) is produced by living radical polymerization of a vinyl monomer. The adhesive composition according to claim 20, wherein the living radical polymerization is atom transfer radical polymerization. The adhesive composition according to claim 21, wherein the transition metal complex which is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium or iron. The adhesive composition according to claim 22, wherein the transition metal complex is a copper complex. The adhesive composition according to any one of claims 1 to 19, wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent. The number average molecular weight of the said (A) component is 3000 or more, The adhesive composition in any one of Claims 1-24. The adhesion according to any one of claims 1 to 25, wherein the vinyl polymer of the component (A) has a ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8. Agent composition.