JP2001055551A - Adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To use a vinyl polymer having a narrow molecular weight distribution, a low viscosity, and a high ratio of (meth) acryloyl groups at its terminals to form a high solid and fast-curing pressure-sensitive adhesive composition. Offer things. SOLUTION: The pressure-sensitive adhesive composition contains, as an essential component, a vinyl polymer having at least one (meth) acryloyl group per molecule in a molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a pressure-sensitive adhesive composition. More specifically, it contains a vinyl polymer having a (meth) acryloyl group and a photopolymerization initiator, and has a fast curing property,
The present invention also relates to a pressure-sensitive adhesive composition that can be made into a high solid because the viscosity of the polymer is low.

[0002]

2. Description of the Related Art Acrylic pressure-sensitive adhesives have a well-balanced pressure-sensitive adhesive property without adding a tackifier resin, and are produced in large quantities alongside natural rubber-based pressure-sensitive adhesives. Acrylic pressure-sensitive adhesives have insufficient cohesive strength due to the problems of molecular weight and molecular weight distribution, and are generally improved by crosslinking.
Various types of cross-linking methods have been developed. For example, a method of adding a cross-linking agent such as a polyisocyanate compound, an epoxy compound, a polycarboxylic acid, a polyamine compound, a phenol resin, and a sulfur compound has been proposed.

[0003] The acrylic pressure-sensitive adhesive generally comprises a pressure-sensitive adhesive solution obtained by solution-polymerizing a vinyl-based monomer containing an acrylic monomer as a main component with an organic solvent, or an emulsion obtained by emulsion-polymerizing with an aqueous solution. It is obtained by applying or impregnating a substrate and drying it by heating.

However, when an adhesive solution is used, a large amount of energy is consumed for drying the solution, and there are problems such as pollution of the air and danger of ignition of the solvent.
In addition, even when an emulsion is used, more energy is required to evaporate water than when a solvent is used.Moreover, the monomer species used in terms of performance are limited, and the pressure-sensitive adhesive is required. There was a drawback that it was poorly responsive to various needs.

As a method for solving such problems, a photopolymerizable pressure-sensitive adhesive has been proposed. In this photopolymerizable composition, a low molecular weight compound having a (meth) acryloyl group is used in many cases. However, during and after curing, the odor due to the volatilization of the low-boiling unreacted compound is a serious problem. In addition, in order to uniformly apply a composition mainly composed of a monomer to a substrate, the composition needs to have a certain viscosity and needs to be thickened by some method.

To avoid odor problems, oligomers having (meth) acryloyl groups can be used. However, such oligomers, mainly due to synthetic problems,
It is limited to epoxy acrylates, urethane acrylates, polyester acrylates and the like, and there are few oligomers having a large molecular weight.

[0007] Japanese Patent Application Laid-Open No. 2-60981 discloses that
Add acrylic rubber, epichlorohydrin rubber, etc.
Although a method for thickening the composition is described, in this method, since the added rubber component remains in the pressure-sensitive adhesive as a non-crosslinked product, a decrease in the performance of the pressure-sensitive adhesive is inevitable.

[0008]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide a high-solid-state, fast-curing composition containing, as a main component, a vinyl-based polymer having a high ratio of (meth) acryloyl-based groups at the molecular terminals. It is an object of the present invention to provide a pressure-sensitive adhesive composition having pressure-sensitive adhesive and a pressure-sensitive adhesive comprising the same.

[0009]

SUMMARY OF THE INVENTION The present invention provides a novel pressure-sensitive adhesive composition and a pressure-sensitive adhesive having the following constitutions, which solves the above-mentioned problems. 1) a group represented by the general formula 1 -OC (O) C (R) = CH ₂ (wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms) (Meth) acryloyl-based group] per molecule and a vinyl polymer having at least one in the molecule [hereinafter referred to as polymer (I)] as an essential component; 2) polymer (I) ) Is a pressure-sensitive adhesive composition having at least one (meth) acryloyl-based group at a molecular terminal; 3) a pressure-sensitive adhesive composition wherein R of the (meth) acryloyl-based group is hydrogen or a methyl group. 4) The polymer (I) is subjected to the following steps: a vinyl polymer having a halogen group at a terminal is added to the general formula 2 M ⁺ -OC (O) C (R) = CH ₂ (2) (where R is Hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal ion or a quaternary ammonium ion). 5) The polymer (I) is converted into the following steps: a vinyl polymer having a hydroxyl group at a terminal is added to a general formula 4 XC (O) C (R) = CH ₂ (4) (where R is hydrogen, Or X represents an organic group having 1 to 20 carbon atoms; X represents chlorine, bromine, or a hydroxyl group); and 6) a polymer. (I) comprises the following steps: (1) A vinyl polymer having a hydroxyl group at a terminal is The isocyanate compound is reacted, and (2) the remaining isocyanate group and the general formula 5 HO—R′—OC (O) C (R) = CH ₂ (5) (where R is hydrogen or a carbon number of 1 to 20) R ′ represents a divalent organic group having 2 to 20 carbon atoms.)
7) a pressure-sensitive adhesive composition produced by reacting with a compound represented by the formula: 7) a pressure-sensitive adhesive composition wherein the main chain of the polymer (I) is produced by living radical polymerization of a vinyl monomer. 8) a pressure-sensitive adhesive composition wherein the main chain of the polymer (I) is produced by polymerization of a vinyl monomer using a chain transfer agent; 9) the number average molecular weight of the polymer (I) is: The pressure-sensitive adhesive composition having a molecular weight of 3000 or more. 10) The polymer (I) has a weight average molecular weight (Mw) and a number average molecular weight (Mn) ratio (Mw / Mn) of 1 measured by gel permeation chromatography. A pressure-sensitive adhesive composition having a viscosity of less than 0.8. 11) The pressure-sensitive adhesive composition may contain a photopolymerization initiator or a thermal polymerization initiator. Further, the present invention may be 12) a pressure-sensitive adhesive obtained by curing the pressure-sensitive adhesive composition, or 13) a method using active energy ray irradiation or heat curing as a curing method.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a compound represented by the general formula 1: -OC (O) C (R) = CH ₂ (1) wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms. ) (Hereinafter referred to as (meth) acryloyl-based group) per molecule, and a vinyl-based polymer (hereinafter referred to as polymer (I)) having a molecular terminal as an essential component. Agent composition. <Regarding Polymer (I)> The number of (meth) acryloyl-based groups is not particularly limited. However, from the viewpoint that the polymers (I) are crosslinked with each other, if the number is less than 1 per molecule, the curability deteriorates. The number is preferably one or more, more preferably 1.2 to 4.

The (meth) acryloyl-based group may be present at either the side chain and / or the terminal of the molecule, but is preferably present at the terminal of the molecule from the viewpoint of rubber elasticity.

Specific examples of R of the (meth) acryloyl group are not particularly limited, and include, for example, -H, -CH ₃ , -C
_{H 2 CH 3, - (CH} 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, but -CN, and the like, preferably -H, - CH ₃ .

The vinyl monomer constituting the main chain of the polymer (I) is not particularly limited, and various monomers can be used. For example, (meth) acrylic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) ) -Tert-butyl acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylic acid -N-octyl, (meth)
2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, ( 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2- (meth) acrylate
Hydroxyethyl, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth)
Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acryl 2-trifluoromethylethyl acid, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2- (meth) acrylate
Perfluorobutylethyl, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2- (meth) acrylate
(Meth) acrylic monomers such as perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate Styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene and vinylidene fluoride; vinyltrimethoxysilane, vinyl Silicon-containing vinyl monomers such as triethoxysilane; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methyl ester Maleimide monomers such as imide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; vinyl monomers containing a nitrile group such as acrylonitrile and methacrylonitrile; acrylamide; Vinyl monomers containing an amide group such as methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene Kind;
Examples thereof include vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of them may be copolymerized. Among them, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred from the viewpoint of the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and in such a case, it is preferable that these preferable monomers are contained in a weight ratio of 40% or more.

The molecular weight distribution of the polymer (I) [the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) as measured by gel permeation chromatography] is not particularly limited, but is preferably less than 1.8. Yes, more preferably 1.7 or less, 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. It is. In the GPC measurement in the present invention, a value of the molecular weight is usually determined in terms of polystyrene using a polystyrene gel column or the like using chloroform or tetrahydrofuran as a mobile phase.

The number average molecular weight of the polymer (I) is 500 to 1
The range of 00000 is preferable, and 3000 to 40,000 is more preferable. When the molecular weight is 500 or less, it is difficult for the vinyl polymer to exhibit its original properties,
If it is more than 000, handling becomes difficult. <Regarding Method for Producing Polymer (I)> The method for producing the polymer (I) is not particularly limited. Vinyl polymers are generally
Although it is produced by anionic polymerization or radical polymerization, radical polymerization is preferred because of the versatility of the monomer and the 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.

In the radical polymerization method used in the method for synthesizing the polymer (I), a monomer having a specific functional group and a vinyl monomer are simply prepared by using an azo compound, a peroxide or the like as a polymerization initiator. It can be classified into a "general radical polymerization method" for copolymerization and a "controlled radical polymerization method" in which a specific functional group can be introduced into a controlled position such as a terminal.

The "general radical polymerization method" is a simple method, but in this method, a monomer having a specific functional group is introduced into the polymer only stochastically. If it is intended to obtain such a monomer, it is necessary to use this monomer in a considerably large amount. Conversely, if the monomer is used in a small amount, there is a problem that the proportion of the polymer into which this specific functional group is not introduced becomes large. In addition, since it is free radical polymerization, there is 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 polymerization is carried out using a chain transfer agent having a specific functional group to obtain a vinyl polymer having a functional group at a terminal. The term "living radical polymerization method" can be classified into a "living radical polymerization method" in which a polymer having a molecular weight almost as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like. The “chain transfer agent method” can obtain a polymer having a high functionalization rate, but requires a considerably large amount of a chain transfer agent having a specific functional group with respect to the initiator, and includes a treatment. There is an economic problem. Further, similarly to the above-mentioned "general radical polymerization method", there is also a problem that since it is a free radical polymerization, only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Unlike these polymerization methods, the "living radical polymerization method" is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is easily caused by coupling of radicals. The reaction hardly occurs and the molecular weight distribution is narrow (Mw / Mn is 1.
(About 1 to 1.5) A polymer can be obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.

Accordingly, the "living radical polymerization method" can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer. Therefore, the method for producing a vinyl polymer having the above specific functional group is more preferable.

In the narrow sense of living polymerization,
This refers to polymerization in which the molecular chain grows while the terminal always keeps activity.In general, the pseudo-polymer in which the terminal is inactivated and the terminal that is activated grows in an equilibrium state. Living polymerization is also included. The definition in the present invention is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 2
7, “Atom Transfer Radical Polymerization” using a radical scavenger such as a nitroxide compound as shown in page 7228, and using an organic halide or the like as an initiator and a transition metal complex as a catalyst.
cal Polymerization (ATRP).

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized 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 features of the `` radical polymerization method, '' vinyl-based polymers having specific functional groups have halogens at the terminals that are relatively advantageous for the functional group conversion reaction, and have a high degree of freedom in designing initiators and catalysts. It is more preferable as a method for producing a united product. As this atom transfer radical polymerization method, for example, Mat
yjaszewski et al., Journal of American Chemical Society (J. Am. Chem. So
c. 1995, 117, 5614, Macromolecules 1995.
Year, Volume 28, 7901, Science
e) 1996, 272, 866, WO 96/30
No. 421, WO 97/18247 or S
awamoto et al., Macromolecules (Macro)
1995, Vol. 28, p. 1721.

In the present invention, there is no particular limitation on which of these methods is used. However, basically, controlled radical polymerization is used, and living radical polymerization is preferred in view of easiness of control. A radical polymerization method is preferred.

First, one of the controlled radical polymerizations, polymerization 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.

A method for obtaining a halogen-terminated polymer by using a halogenated hydrocarbon as a chain transfer agent as disclosed in JP-A-4-132706 and JP-A-61-2
No. 71306, Japanese Patent No. 2594402, and Japanese Patent Application Laid-Open No. 54-47782 discloses a method of obtaining a hydroxyl-terminated polymer using a hydroxyl group-containing mercaptan or a hydroxyl group-containing polysulfide as a chain transfer agent.

Next, living radical polymerization will be described.

First, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N
-O.) Is used as a radical capping agent. Such compounds include, but are not limited to, 2, 2,
6,6-substituted-1-piperidinyloxy radicals and 2,
Preferred are nitroxy free radicals from cyclic hydroxyamines, such as 2,5,5-substituted-1-pyrrolidinyloxy radicals. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group and 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, 1,1,3,3-tetramethyl-2-isoindolinyloxy radical,
N, N-di-t-butylamineoxy radical and the like can be mentioned. Instead of the nitroxy free radical, a stable free radical such as galvinoxyl free radical may be used.

The above 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. The combination ratio of both is not particularly limited, but 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. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate; Peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyoctoate, t-
There are alkyl peresters such as butyl peroxybenzoate. Particularly, benzoyl peroxide is preferred. Further, a radical generator such as a radical-generating azo compound such as azobisisobutyronitrile may be used instead of the peroxide.

Macromolecules 199
5, 28, 2993, instead of using a radical capping agent and a radical generator together,
An alkoxyamine compound as shown below may be used as an initiator.

[0032]

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

The polymerization conditions such as the monomer, solvent and polymerization temperature used in the polymerization using the radical scavenger such as the above-mentioned nitroxide compound are not limited, but may be the same as those used for the atom transfer radical polymerization described below. .

Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.

In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl position), Alternatively, a sulfonyl halide 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 (where C ₆ H ₅ is a phenyl group, X is chlorine, bromine, or iodine) 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 or an alkyl group having 1 to 20 carbon atoms, an aryl group or an aralkyl group having a carbon number of 7 to 20,, X is chlorine, bromine or iodine) in ^{_{R 3 -C 6 H 4 -SO 2}} X ( above equations, R ³ is 1 hydrogen atom or a carbon atoms,
An alkyl group having from 20 to 20, an aryl group having from 6 to 20 carbon atoms, or an aralkyl group having from 7 to 20 carbon atoms, X is chlorine, bromine,
Or iodine).

As the initiator of the atom transfer radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group that initiates the polymerization can be used. In such a case, a vinyl polymer having a structure represented by the above general formula 2 at one main chain terminal and a functional group at the other main chain terminal is produced. Such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups,
Examples include an epoxy group, an amino group, and an amide group.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula 6. ^{R 6 R 7 C (X)} -R 8 -R 9 -C (R 5) = CH 2 (6) ( wherein, R ⁵ is hydrogen or methyl, R ^6, R ⁷ is hydrogen or a carbon A monovalent alkyl group, an aryl group, or an aralkyl group of the formulas 1 to 20, or ones linked to each other at the other end, and R ⁸ represents —C (O) O— (ester group), Keto group), or o-, m-, p
A phenylene group, R ⁹ is a direct bond, or has 1 to 2 carbon atoms;
X is a divalent organic group which may contain one or more ether bonds. X is chlorine, bromine, or iodine. Specific examples of the substituents R ⁶ and R ⁷ include hydrogen, methyl, and ethyl. , N-propyl group, isopropyl group, butyl group,
Examples include a pentyl group and a hexyl group. R ⁶ and R ⁷ may be linked at the other end to form a cyclic skeleton.

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 = C
_{H 2, (H 3 C)} 2 C (X) C (O) O (CH 2) n CH = C
H ₂ , CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n CH =
CH ₂ ,

[0039]

Embedded image (In each formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of _{0~20,) XCH 2 C (O} ) O (CH 2) n O (CH 2) m CH = C
H 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 (C
H ₂ ) _m CH = CH ₂ ,

[0040]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (CH_Two)
_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-O- (C
H_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (CH_Two)
_n-O- (CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four− (C
H_Two)_n-O- (CH_Two)_mCH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 1 to 20, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_n-CH = CH _Two(In the above formulas, X represents chlorine, bromine, or iodine.
Prime, n is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-O-
(CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (C
H_Two)_n-O- (CH_Two)_m-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_n-O- (CH _Two)_m-CH = CH_Two(In the above formulas, X represents chlorine, bromine, or iodine.
, N is an integer of 1 to 20, m is an integer of 0 to 20) As an organic halide having an alkenyl group,
The compound represented by the general formula 7 is exemplified. H_TwoC = C (R^Five) -R⁹-C (R⁶) (X) -R^Ten-R⁷(7) (where R^Five, R⁶, R⁷, R⁹, X is the same as above, R
^TenIs a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or o-, m-, p-phenyl
Represents a len group) R⁹Is a direct bond or a divalent organic group having 1 to 20 carbon atoms
(Which may contain one or more ether bonds)
Is a direct bond, the carbon to which the halogen is bonded
With a vinyl group bonded to the halogenated allylic compound
is there. In this case, carbon-halogenation is achieved by adjacent vinyl groups.
Is activated, so that R^TenAs C (O) O
It is not necessary to have a group or phenylene group, etc.
It may be a combination. R⁹Is not a direct bond,
In order to activate the halogen-halogen bond, R^TenAs C
(O) O, C (O) and phenylene groups are preferred.

If the compound of the general formula 7 is specifically exemplified, CH ₂ ＣＨCHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH
₂ X, CH ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (C
H ₃ ) C (H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (C
H ₃ ) ₂ , CH ₂ （CHC (H) (X) C ₂ H ₅ , CH ₂ ＣC
HC (H) (X) CH (CH 3) 2, CH 2 = CHC
(H) (X) C ₆ H ₅ , CH ₂ ＣＨCHC (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 = CH
_{CH 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 each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group,) and the like, etc. it can.

Specific examples of the sulfonyl halide compound having an alkenyl group include: o-, m-, p-CH ₂ ＣＨCH— (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 each formula mentioned above, X is chlorine, bromine or iodine, n represents an integer of 0 to 20,), and the like.

Organic halogen having crosslinkable silyl group
The compound is not particularly limited.
One having a structure is exemplified. R⁶R⁷C (X) -R⁸-R⁹-C (H) (R^Five) CH_Two− [Si (R¹¹)_2-b(Y)_b O]_m-Si (R¹²)_3-a(Y)_a(8) (where R^Five, R⁶, R⁷, R⁸, R⁹, X is the same as above,
R¹¹, R¹²Is an alkyl group having 1 to 20 carbon atoms,
Aryl group, aralkyl group, or (R ′)_ThreeSiO-
(R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms,
The three R's may be the same or different
I) represents a triorganosiloxy group represented by¹¹Ma
Or R¹²When two or more exist, they are the same.
Or may be different. Y is a hydroxyl group or water
A decomposable group, and when two or more Y
They may be one or different. a is 0, 1,
2, or 3, and b represents 0, 1, or 2.
m is an integer of 0-19. Where a + mb ≧ 1
To specifically exemplify the compound of the general formula 8, XCH_Two
C (O) O (CH_Two)_nSi (OCH_Three)_Three, CH_ThreeC
(H) (X) C (O) O (CH_Two)_nSi (OCH_Three)_Three,
(CH_Three)_TwoC (X) C (O) O (CH_Two)_nSi (OCH
_Three)_Three, XCH_TwoC (O) O (CH_Two)_nSi (CH_Three) (O
CH_Three)_Two, CH_ThreeC (H) (X) C (O) O (CH_Two)_n
Si (CH_Three) (OCH_Three)_Two, (CH_Three)_TwoC (X) C
(O) O (CH_Two)_nSi (CH_Three) (OCH_Three)_Two,(Up
In each of the above formulas, X is chlorine, bromine, iodine, and n is 0 to
An integer of 20, XCH_TwoC (O) O (CH_Two)_nO (CH_Two)_mSi (OC
H_Three)_Three, H_ThreeCC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_mSi (OCH_Three)_Three, (H_ThreeC)_TwoC (X) C
(O) O (CH_Two)_nO (CH_Two)_mSi (OCH_Three)_Three, C
H_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO (CH
_Two)_mSi (OCH_Three)_Three, XCH_TwoC (O) O (CH_Two)_n
O (CH_Two)_mSi (CH_Three) (OCH_Three)_Two, H_ThreeCC
(H) (X) C (O) O (CH_Two)_nO (CH_Two)_m-Si
(CH_Three) (OCH_Three)_Two, (H_ThreeC)_TwoC (X) C (O)
O (CH_Two)_nO (CH_Two)_m-Si (CH_Three) (OCH_Three)
_Two, CH_ThreeCH_TwoC (H) (X) C (O) O (CH_Two)_nO
(CH_Two)_m-Si (CH_Three) (OCH_Three)_Two, (Each of the above
In the formula, X is chlorine, bromine, iodine, and n is 1-20.
An integer, m is an integer of 0 to 20) o, m, p-XCH_Two-C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
(CH_Two)_TwoSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_Two
C (H) (X) -C₆H_Four− (CH_Two)_TwoSi (OC
H_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_ThreeS
i (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X)-
C₆H_Four− (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-C
H_ThreeCH_TwoC (H) (X) -C₆H_Four− (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four− (CH_Two)_Two
-O- (CH_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH
_ThreeC (H) (X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)
_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH_TwoC (H)
(X) -C₆H_Four− (CH_Two)_Two-O- (CH_Two)_ThreeSi (O
CH_Three)_Three, O, m, p-XCH_Two-C₆H_Four-O- (C
H_Two)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H)
(X) -C₆H_Four-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Three-Si (OCH_Three)_Three, O, m, p-XCH_Two
-C₆H_Four-O- (CH_Two)_Two-O- (CH_Two)_Three-Si (O
CH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four
-O- (CH_Two)_Two-O- (CH_Two)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH_TwoC (H) (X) -C₆H_Four-O-
(CH_Two)_Two-O- (CH _Two)_ThreeSi (OCH_Three)_Three,(the above
In each formula, X is chlorine, bromine, or iodine), etc.
No.

Further examples of the organic halide having a crosslinkable silyl group include those having a structure 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, m, X, and Y are the same as described above. If such a compound 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) -C
O 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 S
_{i (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 (C
_{H 3) Si (CH 2)} 4 C (H) (X) -C 6 H 5, ( in each formula above, X is chlorine, bromine or iodine, R represents an alkyl group having 1 to 20 carbon atoms, aryl Group, aralkyl group) and the like.

The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. HO- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or an alkyl having 1 to 20 carbon atoms, Group,
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following. H ₂ N- (CH ₂₎ in _{n -OC (O) C (H} ) (R) (X) ( the formulas above, X is chlorine, bromine or iodine, R represents a hydrogen atom or 1 to 20 carbon atoms, An alkyl group of
(Aryl group, aralkyl group, n is an integer of 1 to 20) The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0046]

Embedded image (In each of the above formulas, X is chlorine, bromine, or iodine, 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 polymer having two or more terminal structures in one molecule of the present invention, an organic halide having two or more starting points or halogen Preferably, a sulfonyl halide compound is used as the initiator. To give a concrete example,

[0047]

Embedded image

[0048]

Embedded image And the like.

There are no particular restrictions on the vinyl monomer used in this polymerization, and any of those already exemplified can be suitably used.

The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably 7
It is a metal complex having a Group 8, 8, 9, 10, or 11 element as a central metal. More preferred are complexes of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of the monovalent copper compound include:
Examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate and the like. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-
Ligands such as polyamines such as aminoethyl) amine can be added. 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 are added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ),
Bistriphenylphosphine complex of divalent nickel (Ni
Cl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistributylphosphine complex (NiBr ₂ (PBu ₃ ) ₂ )
Are also suitable as catalysts.

The polymerization can be carried out without solvent or in various solvents. Examples of the solvent 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 ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvent, methanol, ethanol, propanol, isopropanol, n-butyl alcohol, alcohol solvents such as tert-butyl alcohol, acetonitrile, propionitrile, nitrile solvents such as benzonitrile, ethyl acetate, ester solvents such as butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, which may be used alone or in combination of two or more. Further, the polymerization can be carried out in the range of room temperature to 200 ° C, preferably 50 to 150 ° C. <Method for Introducing Functional Group> The method for producing the polymer (I) is not particularly limited. For example, a vinyl polymer having a reactive functional group is produced by the above-described method, and Can be produced by converting into a substituent having Hereinafter, introduction of the terminal functional group of the polymer of the present invention will be described.

The method for introducing a (meth) acryloyl group into the terminal of the vinyl polymer is not limited,
The following methods are mentioned. (Introduction method 1) A method in which a vinyl polymer having a halogen group at a terminal is reacted with a compound represented by the general formula 2. M ⁺ -OC (O) C (R) = CH ₂ (2) (wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal ion or a quaternary ammonium ion. The vinyl polymer having a halogen group at a terminal is preferably a polymer having a terminal structure represented by the following general formula 3. —CR ¹ R ² X (3) (wherein, R ¹ and R ² are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine, or iodine.) Method 2) A method in which a vinyl polymer having a hydroxyl group at a terminal is reacted with a compound represented by the general formula 4. XC (O) C (R) = CH ₂ (4) wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group. 3) A method in which a diisocyanate compound is reacted with a vinyl polymer having a hydroxyl group at a terminal, and the remaining isocyanate group is reacted with a compound represented by the general formula 5. HO-R'-OC (O) C (R) = CH 2 (5) ( wherein, R is hydrogen or a 2 .R 'is C2-20 represents an organic group having 1 to 20 carbon atoms Each of these methods will be described in detail below. <Introducing Method 1> Introducing method 1 is a method in which a vinyl polymer having a halogen group at a terminal is reacted with a compound represented by the general formula 2. M ⁺ -OC (O) C (R) = CH ₂ (2) (wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms. M ⁺ represents an alkali metal ion or a quaternary ammonium ion. Although it does not specifically limit as a vinyl polymer which has a halogen group at a terminal, what has a terminal structure shown by General formula 3 is preferable. —CR ¹ R ² X (3) (wherein, R ¹ and R ² are groups bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine, or iodine). The vinyl polymer having a terminal structure represented by 3 is a method of polymerizing a vinyl monomer using the above-described organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a method of linking a halogen compound It is produced by a method of polymerizing a vinyl monomer as a transfer agent, but the former is preferred.

The compound represented by the general formula 2 is not particularly limited, but specific examples of R include, for example, -H,-
CH ₃ , —CH ₂ CH ₃ , — (CH ₂ ) _n CH ₃ (n is 2 to 1)
Represents an integer of _{9), - C 6 H 5} , -CH 2 OH, -CN,
Etc., and is preferably -H, -CH _3.

[0054] M ⁺ is a counter cation of oxyanion, as the type of M ⁺ alkali metal ion, and specific examples thereof include a lithium ion, sodium ion, potassium ion, and quaternary ammonium ions. Examples of the quaternary ammonium ion include a tetramethylammonium ion, a tetraethylammonium ion, a tetrabenzylammonium ion, a trimethyldodecylammonium ion, a tetrabutylammonium ion, and a dimethylpiperidinium ion, and a sodium ion and a potassium ion are preferable. The use amount of the oxyanion of the general formula 2 is preferably 1 to 5 equivalents, more preferably 1.0 to the halogen terminal of the general formula 3.
~ 1.2 equivalents. The solvent for carrying out this reaction is not particularly limited, but a polar solvent is preferred because it is a nucleophilic substitution reaction. Triamide, acetonitrile,
Are used. The temperature at which the reaction is carried out is not limited, but is generally 0 to 150 ° C, more preferably room temperature to 100 ° C. <Introduction Method 2> The introduction method 2 is a method in which a vinyl polymer having a hydroxyl group at a terminal is reacted with a compound represented by the general formula 4. XC (O) C (R) = CH ₂ (4) (wherein, R represents hydrogen or an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group). in as the compound represented by not particularly limited, specific examples of R, for example, -H, -CH _3, -
_{CH 2 CH 3, - (CH} 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and preferably -H, - CH ₃ .

The vinyl polymer having a hydroxyl group at the terminal is
It is manufactured by a method of polymerizing a vinyl monomer using the above-mentioned organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, or a method of polymerizing a vinyl monomer using a compound having a hydroxyl group as a chain transfer agent. However, the former is preferred. The method for producing a vinyl polymer having a hydroxyl group at a terminal by these methods is not limited, but the following methods are exemplified.

(A) When a vinyl polymer is synthesized by living radical polymerization, a compound represented by the following general formula 10 or the like having both a polymerizable alkenyl group and a hydroxyl group in one molecule is reacted as a second monomer. How to let. H ₂ C ＝ C (R ¹³ ) -R ¹⁴ -R ¹⁵ -OH (10) (wherein, R ¹³ is an organic group having 1 to 20 carbon atoms, preferably hydrogen or methyl group. R ¹⁴ represents —C (O) O— (ester group) or an o-, m- or p-phenylene group, and R ¹⁵ has a direct bond or one or more ether bonds. Represents a divalent organic group having 1 to 20 carbon atoms, wherein R ¹⁴ is an ester group is a (meth) acrylate compound, and R ¹⁴ is a phenylene group is a styrene compound.) There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, if rubbery properties are expected, the second reaction is terminated at the end of the polymerization reaction or after the reaction of a predetermined monomer. It is preferable to react as a monomer of .

(B) When synthesizing a vinyl polymer by living radical polymerization, at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer, an alkenyl group having a low polymerizability in one molecule is used as a second monomer. A method of reacting a compound having a hydroxyl group.

Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula 11. ^{_{H 2 C = C (R 13}} ) -R 16 -OH (11) ( wherein, R ¹³ .R ¹⁶ are carbon atoms which may contain one or more ether bonds is similar to that described above 1 ~ 20
Represents a divalent organic group. The compound represented by the general formula 11 is not particularly limited, but alkenyl alcohols such as 10-undecenol, 5-hexenol, and allyl alcohol are preferable because they are easily available. (C) Halogen of a vinyl polymer having at least one carbon-halogen bond represented by the general formula 2 obtained by atom transfer radical polymerization according to a method disclosed in JP-A-4-132706 and the like. To react with a hydroxyl group-containing compound to introduce a hydroxyl group into the terminal. (D) reacting a vinyl-based polymer having at least one carbon-halogen bond represented by the general formula 2 obtained by atom transfer radical polymerization with a stabilized carbanion having a hydroxyl group as listed in the general formula 12 A method of substituting halogen. ^{M + C - (R 17)} (R 18) -R 16 -OH (12) ( wherein, R ¹⁶ and M ⁺ are the same as those described above.
R ¹⁷ and R ¹⁸ together carbanion C ^- an electron-withdrawing group stabilizing or one, representing the other is hydrogen or an alkyl group or phenyl group having 1 to 10 carbon atoms in the electron-withdrawing group. Examples of the electron withdrawing group for R ¹⁷ and R ¹⁸ include —CO
₂ R (ester group), -C (O) R (keto group), -CO
N (R ₂₎ (amide group), - COSR (thioester group), - CN (nitrile group), - NO ₂ (nitro group), and the like. The substituent R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms.
And preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ¹⁷ and R ¹⁸ , —CO ₂ R, —C (O) R and —CN are particularly preferred. (E) Enolate by reacting a vinyl polymer having at least one carbon-halogen bond represented by the general formula 2 obtained by atom transfer radical polymerization with a simple metal such as zinc or an organometallic compound. A method in which an anion is prepared and then an aldehyde or a ketone is reacted.

(F) A vinyl-containing polymer having at least one halogen at the terminal of the polymer, preferably at least one halogen represented by the general formula 2, is added to a hydroxyl group-containing oxyanion represented by the following general formula 13 or the like. A method of reacting a hydroxyl group-containing carboxylate anion represented by 14 or the like to replace the halogen with a hydroxyl group-containing substituent. ^{HO-R 16 -O - M +} (13) ( wherein, R ¹⁶ and M ⁺ are the same as those described ^{above.) HO-R 16 -C (} O) O - M + (14) ( in the formula , R ¹⁶ and M ⁺ are the same as those described above.) In the present invention, when a halogen is not directly involved in the method for introducing a hydroxyl group as in (a) to (b), control is easier. The method (b) is more preferred.

When a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one carbon-halogen bond as in (c) to (f), the control is easier ( The method f) is more preferred. <Introduction Method 3> In the introduction method 3, a vinyl polymer having a hydroxyl group at a terminal is reacted with a diisocyanate compound.
This is a method in which a residual isocyanate group is reacted with a compound represented by the general formula 5. HO-R'-OC (O) C (R) = CH 2 (5) ( wherein, R is hydrogen or a 2 .R 'is C2-20 represents an organic group having 1 to 20 carbon atoms . represents the valence of the organic groups) is not particularly restricted but includes compounds represented by the general formula 5, as specific examples of R, for example, -H, -CH _3, -
_{CH 2 CH 3, - (CH} 2) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, -CN, etc., and preferably -H, - CH ₃ . Specific compounds include 2-hydroxypropyl methacrylate.

The vinyl polymer having a hydroxyl group at the terminal is
As above.

The diisocyanate compound is not particularly limited, and any conventionally known diisocyanate compound can be used. For example, tolylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, hexamethyl diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate,
Isocyanate compounds such as hydrogenated toluylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate; These can be used alone or in combination of two or more. Further, a blocked isocyanate may be used.

In order to make better use of the weather resistance, it is preferable to use, as the polyfunctional isocyanate compound (b), a diisocyanate compound having no aromatic ring such as hexamethylene diisocyanate and hydrogenated diphenylmethane diisocyanate. <About the pressure-sensitive adhesive composition> The pressure-sensitive adhesive composition of the present invention contains the polymer (I) as an essential component. It is preferable that no other polymerizable monomer is contained in order to eliminate the odor problem caused by the residual monomer, but a polymerizable monomer and / or oligomer and various additives may be used in combination according to the purpose.

As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group or a monomer and / or oligomer having an anion polymerizable group is preferable. Examples of the radical polymerizable group include an acrylic functional group such as a (meth) acryl group, a styrene group, an acrylonitrile group, a vinyl ester group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, a vinyl ketone group, and a vinyl chloride group. Is mentioned. Among them, those having a (meth) acryl group similar to the polymer of the present invention are preferable. Examples of the anionic polymerizable group include a (meth) acryl group, a styrene group, an acrylonitrile group, an N-vinylpyrrolidone group, an acrylamide group,
Examples include a conjugated diene group and a vinyl ketone group. Among them, those having an acrylic functional group similar to the polymer of the present invention are preferred.

Specific examples of the above monomers include (meth) acrylate monomers, cyclic acrylates, N-
Examples include vinylpyrrolidone, styrene-based monomers, acrylonitrile, N-vinylpyrrolidone, acrylamide-based monomers, conjugated diene-based monomers, and vinyl ketone-based monomers. Examples of (meth) acrylate monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and compounds of the following formulas. it can.

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image Styrene-based monomers include styrene, α-methylstyrene, etc., acrylamide-based monomers include acrylamide, N, N-dimethylacrylamide, etc., and conjugated diene-based monomers include butadiene and isoprene.
Examples of the vinyl ketone-based monomer include methyl vinyl ketone.

The polyfunctional monomers include neopentyl glycol polypropoxy diacrylate, trimethylolpropane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, bisphenol A
Polyethoxydiacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) )
-5-ethyl-5-acryloyloxymethyl-1,3
-Dioxane, tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like.

Examples of the oligomer include epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolak type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate resin, polyols (polytetramethylene glycol, ethylene Polyester diol of glycol and adipic acid, 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, hexamethyl Diisocyanates, xylylene diisocyanates, etc.) to obtain hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentaerythritol triacrylate. Examples thereof include a urethane acrylate resin obtained by the reaction, a resin in which a (meth) acryl group is introduced into the above polyol via an ester bond, and a polyester acrylate resin.

These monomers and oligomers are selected according to the purpose.

The number average molecular weight of the monomer and / or oligomer having an acrylic functional group is preferably 2,000 or less, and more preferably 1,000 or less, because of good compatibility.

The pressure-sensitive adhesive composition of the present invention preferably contains a (meth) acrylic polymer as a main component.
It is not always necessary to add a tackifier resin, but various ones can be used as needed. Specific examples include phenolic resins, modified phenolic resins,
Cyclopentadiene-phenol resin, xylene resin,
Coumarone resin, petroleum resin, terpene resin, terpene phenol resin, rosin ester resin and the like.

The pressure-sensitive adhesive composition of the present invention contains various additives such as an antioxidant, a plasticizer,
A physical property modifier, a solvent and the like may be blended.

An acrylic polymer is inherently a polymer having excellent heat resistance, weather resistance and durability. Therefore, an antioxidant is not necessarily required. However, conventionally known antioxidants and ultraviolet absorbers are appropriately used. be able to.

As the 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 such as diethylene glycol dibenzoate;
Esters of polyalkylene glycols such as triethylene glycol dibenzoate; phosphates such as tricresyl phosphate and tributyl phosphate; paraffin chlorides; and hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl alone. Alternatively, two or more kinds can be used as a mixture, but are not necessarily required. In addition, these plasticizers can be blended at the time of polymer production.

Solvents that may be used in the production of the polymer include, for example, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve, methyl ethyl ketone and methyl isobutyl. Ketone solvents such as ketone and diisobutyl ketone are exemplified.

Further, to the pressure-sensitive adhesive composition of the present invention, various adhesion improvers may be added in order to improve the adhesion to various supports (plastic film, paper, etc.).
For example, alkylalkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane; dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxy Alkylisopropenoxysilanes such as propylmethyldiisopropenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane, γ-aminopropyltrisilane Methoxysilane,
N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc. Alkoxysilanes having a functional group; silicone varnishes; polysiloxanes and the like. <Regarding Curing Method> The pressure-sensitive adhesive composition of the present invention is not particularly limited, but is preferably cured with active energy rays such as UV and electron beams or heat. <Active energy ray curing> In the case of curing with active energy rays, a photopolymerization initiator is preferably contained as an adhesive composition.

The photopolymerization initiator is not particularly limited,
Photo-radical initiators and photo-anion initiators are preferred, and photo-radical initiators are particularly preferred. For example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophen, 3-bromo Acetophenone, 4-allylacetophenone, p-
Diacetylbenzene, 3-methoxybenzophenone, 4
-Methylbenzophenone, 4-chlorobenzophenone,
4,4'-dimethoxybenzophenone, 4-chloro-
4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-
Nonyl xanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like can be mentioned. These initiators may be used alone or in combination with other compounds. Specific examples include a combination with an amine such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combined with an iodonium salt such as diphenyliodonium chloride, and a combination with a dye and an amine such as methylene blue. Can be

As the near-infrared light polymerization initiator, a near-infrared light-absorbing cationic dye may be used. As a near-infrared light-absorbing cationic dye, it is excited by light energy in the range of 650 to 1500 nm, for example, as disclosed in JP-A-3-11.
It is preferable to use a near-infrared light-absorbing cationic dye-borate anion complex or the like disclosed in JP-A-1402 and JP-A-5-194609, and it is more preferable to use a boron sensitizer in combination.

The amount of the photopolymerization initiator to be added is not particularly limited since it is only necessary to slightly photofunctionalize the system. preferable.

The active energy ray source is not particularly limited. For example, a high-pressure mercury lamp, a low-pressure mercury lamp, an electron beam irradiator, a halogen lamp, a light emitting diode, a semiconductor laser, etc. Line irradiation. <Heat Curing> In the case of curing by heat, it is preferable to contain a thermal polymerization initiator as an adhesive composition.

The thermal polymerization initiator is not particularly limited, but includes an azo initiator, a peroxide, a persulfuric acid, and a redox initiator.

Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-
2,4-dimethylvaleronitrile) (VAZO 3
3), 2,2'-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,
4-dimethylvaleronitrile) (VAZO 52),
2,2'-azobis (isobutyronitrile) (VAZO
64), 2,2'-azobis-2-methylbutyronitrile (VAZO 67), 1,1-azobis (1-cyclohexanecarbonitrile) (VAZO 88) (all available from DuPont Chemical), 2,
2'-azobis (2-cyclopropylpropionitrile) and 2,2'-azobis (methylisobutyl
G) (V-601) (available from Wako Pure Chemical Industries).

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t- Butylcyclohexyl) peroxydicarbonate (Perkadox)
16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t
-Butyl peroxypivalate (Luppersol 1
1) (available from Elf Atochem), t-butylperoxy-2-ethylhexanoate (Trig
onox 21-C50) (available from Akzo Nobel), and dicumyl peroxide.

[0088] Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate.

Suitable redox (redox) initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; And tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate.

Other initiators include, but are not limited to, pinacols such as tetraphenyl 1,1,2,2-ethanediol.

The thermal radical initiator is preferably selected from the group consisting of an azo initiator and a peroxide initiator. Even more preferred are 2,2'-azobis (methylisobutyrate), t-butylperoxypivalate, and di (4-t-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

[0092] The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is not limited,
Typically, about 0.01 to 5 parts by weight based on 100 parts by weight of the polymer of the present invention having at least one terminal acrylic functional group and the monomer and oligomer mixture added to the other. , More preferably about 0.025
~ 2 parts by weight. If a mixture of initiators is used, the total amount of the mixture of initiators is as if only one initiator was used.

The thermosetting conditions are not particularly limited. The temperature varies depending on the type of the thermal initiator, the polymer (I) and the compound to be used, but is preferably in the range of 50 ° C. to 250 ° C. The temperature is more preferably in the range of 70C to 200C. The curing time varies depending on the used polymerization initiator, monomer, solvent, reaction temperature and the like, but is usually in the range of 1 minute to 10 hours. <About the pressure-sensitive adhesive> The pressure-sensitive adhesive composition of the present invention can be widely applied to tapes, sheets, labels, foils and the like. For example, film, paper, all kinds of cloth, metal foil, metallized plastic foil, asbestos or glass fiber cloth, etc. made of synthetic resin or denatured natural product can be used as a solvent type, emulsion type or hot melt type. The pressure-sensitive adhesive composition may be applied and cured by active energy rays or heat.

[0094]

EXAMPLES Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples.

In the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

In the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)"
Is a gel permeation chromatography (GP
Calculated by standard polystyrene conversion method using C).
However, a GPC column filled with a polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used, and chloroform was used as a GPC solvent.

In the following examples, the “average number of terminal (meth) acryloyl groups” is “the number of (meth) acryloyl groups introduced per polymer molecule”, and is the number average determined by ¹ H NMR analysis and GPC. Calculated by molecular weight. (Production Example 1) (Synthesis of potassium methacrylate) In a flask, methanol (800 mL) was charged, and the flask was cooled to 0 ° C.
And cooled. There, potassium t-butoxide (130
g) was added in several portions. The reaction solution was maintained at 0 ° C., and a methanol solution of methacrylic acid (100 g) was added dropwise. After the completion of the dropwise addition, the temperature of the reaction solution was returned from 0 ° C. to room temperature, and the volatile components of the reaction solution were distilled off under reduced pressure to obtain potassium methacrylate (hereinafter, referred to as compound (1)) represented by the following formula. CH ₂ ＣC (CH ₃ ) CO ₂ K (Production Example 2) (Synthesis of potassium acrylate) A flask was charged with methanol (500 mL), and the flask was cooled to 0 ° C.
And cooled. There, potassium t-butoxide (78 g)
Was added in several portions. This reaction solution was kept at 0 ° C., and a methanol solution of acrylic acid (50 g) was added dropwise. After completion of the dropwise addition, the temperature of the reaction solution is returned from 0 ° C. to room temperature, and volatile components of the reaction solution are distilled off under reduced pressure to obtain potassium acrylate represented by the following formula (hereinafter, referred to as compound (2)).
I got CH ₂ ＣＨCHCO ₂ K (Production Example 3) (methacryloyl-terminated poly (acrylic acid n)
Synthesis of -butyl) n-butyl acrylate was polymerized by using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and diethyl-2,5-dibromoadipate as an initiator to obtain a number average molecular weight of 10,900 and a molecular weight distribution. 1.12 brominated end-terminated poly (n-butyl acrylate) (hereinafter referred to as polymer [1]) was obtained. 20.0 g of the polymer [1] was dissolved in N, N-dimethylacetamide, and 1.46 g of the compound (1) was added, followed by stirring at room temperature for 2 days. The reaction mixture was diluted with ethyl acetate (50 mL), and the insoluble portion was filtered. The filtrate was further diluted with ethyl acetate (150 mL) and washed with water and brine. The organic layer was dried over Na ₂ SO ₄ and volatile matter was distilled off under reduced pressure to obtain methacryloyl group-terminated poly (butyl acrylate) (hereinafter, referred to as polymer [2]).

The average number of terminal methacryloyl groups of the polymer [2] after purification was 1.52. (Production Example 4) (Acryloyl-terminated poly (n-acrylate)
Synthesis of butyl)) n-butyl acrylate was polymerized by using cuprous bromide as a catalyst, pentamethyldiethylenetriamine as a ligand, and diethyl-2,5-dibromoadipate as an initiator to obtain a number average molecular weight of 10800 and a molecular weight distribution of 1 .15 terminal brominated poly (n-butyl acrylate) was obtained.

300 g of this polymer was dissolved in N, N-dimethylacetamide (300 mL) to give compound (2)
8.3 g was added, and the mixture was heated and stirred at 70 ° C. for 3 hours in a nitrogen atmosphere to obtain a mixture of acryloyl group-terminated poly (n-butyl acrylate) (hereinafter, referred to as polymer [3]). After N, N-dimethylacetamide of this mixture was distilled off under reduced pressure, toluene was added to the residue, and insolubles were removed by filtration. The toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [3].
Was purified.

The average number of terminal acryloyl groups in the purified polymer [3] was 2.0. (Example 1) (Photocuring test 1) Benzophenone (25.2 m) was added to 2.0 g of polymer [2].
g, 0.138 mmol), diethanolmethylamine (0.079 mL, 0.691 mmol), and diphenyliodonium chloride (35.0 mg, 0.11
1 mmol) and mixed well.

A part of the composition thus obtained was applied on a glass plate, and a high-pressure mercury lamp (SHL-100U) was used.
VQ-2; manufactured by Toshiba Lighting & Technology Corporation), 50 cm
Irradiation was performed at an irradiation distance of 5 minutes to obtain a rubber-like cured product. (Example 2) (Photocuring test 2) Benzophenone (0.207) was added to 3.0 g of polymer [2].
mmol, 50 wt% ethyl acetate solution), diethanolmethylamine (0.119 mL, 1.036 mmol)
Was added and mixed well.

The composition thus obtained was poured into a mold, and volatile components were distilled off under reduced pressure.
Using HL-100UVQ-2 (manufactured by Toshiba Lighting & Technology Corp.), light was irradiated for 10 minutes at an irradiation distance of 50 cm to obtain a rubber-like cured product.

A No. 3 mini dumbbell test piece was punched out of the cured product, and a tensile test was performed using an autograph manufactured by Shimadzu. The breaking strength was 0.34 MPa and the breaking elongation was 56% (measurement conditions: 23 ° C., tensile speed 200 mm /
Minutes). (Examples 3 to 6) (Photocuring test 3) The polymer [3] and diethoxyacetophenone were mixed well in the ratio shown in Table 1. After filling these compositions in a mold and degassing under reduced pressure, the surface was covered with a glass plate to prepare a sample. For these samples, a high-pressure mercury lamp (SHL-100UV) was used for the irradiation time shown in Table 1.
Q-2; manufactured by Toshiba Lighting & Technology Corp.), a rubber-like cured product was obtained. However, the distance between the high-pressure mercury lamp and the sample was 20 cm.

For the obtained cured product, the gel fraction was measured. However, the gel fraction was determined by the weight ratio of the cured product before and after extraction of the uncured portion of the cured product. Extraction of the uncured portion was performed by immersing the cured product in toluene. The results are shown in Table 1.

[0105]

[Table 1] (Examples 7 to 9) (Thermosetting Test) Polymer [1] and organic peroxide Perhexa 3M (1,
1-di- (t-butylperoxy) -3,3,5-trimethylcyclohexane (manufactured by NOF CORPORATION) was mixed well in the ratio shown in Table 2. These compositions were filled in a mold, degassed under reduced pressure, and then heated at 150 ° C. for 5 minutes to obtain a rubber-like cured product.

The cured product was measured for gel fraction and subjected to a tensile test. The gel fraction was determined from the weight ratio of the cured product before and after extraction of the uncured portion of the cured product. Extraction of the uncured portion was performed by immersing the cured product in toluene. The tensile test was performed by punching a 2 (1/3) -size dumbbell test piece from the sheet-shaped cured product and using an autograph manufactured by Shimadzu (measurement conditions: 23).
° C, 200 mm / min). Table 2 also shows the gel fraction and the results of the tensile test.

[0107]

[Table 2] (Example 10) (Preparation of photocurable pressure-sensitive adhesive sheet and adhesion test) 100 parts of polymer [3], diethoxyacetophenone 1
And 175 parts (70 parts as a tackifier) of a 40% acetone solution of terpene phenol-based tackifier (YS Polystar T115; manufactured by Yasuhara Chemical) were mixed well to obtain a pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition thus obtained was
A 50 μm-thick corona-treated polyethylene terephthalate film (manufactured by Toray Industries, Inc.) was applied so that the thickness after drying became about 40 μm, and dried under reduced pressure at room temperature.
High pressure mercury lamp (SHL-100UVQ) under nitrogen atmosphere
-2; manufactured by Toshiba Lighting & Technology Corp.) for 10 minutes to cure. The adhesive strength of the obtained adhesive tape was measured according to the following method according to JIS Z-0237.

The obtained pressure-sensitive adhesive tape was cut into a width of 25 mm, and the pressure-sensitive adhesive surface was pressure-bonded to a stainless steel plate (SUS # 304) whose surface had been previously polished with a # 240 water-resistant abrasive paper to prepare a test piece. After leaving the test body for 30 minutes, the peeling speed was 300 mm under the conditions of 23 ° C. and 65 RH in a tensile tester.
As a result of measuring the peel strength at 180 ° / min,
It was 8.3 N / 25 mm. (Example 11) (Preparation of thermosetting adhesive sheet and adhesion test) 100 parts of polymer [3], organic peroxide Perhexa 3M
(1,1-di- (t-butylperoxy) -3,3,5
-Trimethylcyclohexane; manufactured by NOF Corporation 1
And 175 parts (70 parts as a tackifier) of a 40% acetone solution of terpene phenol-based tackifier (YS Polystar T115; manufactured by Yasuhara Chemical) were mixed well to obtain a pressure-sensitive adhesive composition.

The pressure-sensitive adhesive composition thus obtained was
A 50 μm-thick corona-treated polyethylene terephthalate film (manufactured by Toray Industries, Inc.) was applied so that the thickness after drying became about 40 μm, and dried under reduced pressure at room temperature.
It was cured by heating at 150 ° C. for 10 minutes in a nitrogen atmosphere.
The adhesive strength of the obtained adhesive tape was measured according to JIS Z-02.
The measurement was carried out according to the following method according to 37.

The obtained pressure-sensitive adhesive tape was cut into a width of 25 mm, and the pressure-sensitive adhesive surface was pressed against a stainless steel plate (SUS # 304) whose surface had been previously polished with a # 240 water-resistant abrasive paper to prepare a test piece. After leaving the test body for 30 minutes, the peeling speed was 300 mm under the conditions of 23 ° C. and 65 RH in a tensile tester.
As a result of measuring the peel strength at 180 ° / min,
It was 19.7 N / 25 mm.

[0112]

The pressure-sensitive adhesive composition of the present invention has a low viscosity because the molecular weight distribution of the vinyl polymer having a (meth) acryloyl group as a main component is narrow, and can be made into a high solid. In addition, it has polymerization activity at the polymer terminal (meth)
Since the acryloyl group is introduced, an active energy ray-curable or thermosetting adhesive can be obtained. Since the introduction ratio of (meth) acryloyl groups to the terminal of the polymer is high, a cured product having a high gel content is obtained, and it is also a rapid curing. Another characteristic is that the main chain of the polymer is a vinyl polymer, so that the weather resistance is high.

Continuation of front page (72) Inventor Masayuki Fujita 1-2-80 Yoshida-cho, Hyogo-ku, Kobe-shi, Hyogo Kanebuchi Chemical Industry Co., Ltd. Functional Materials RD Center Kobe Laboratory F-term (reference) 4J027 AA02 AA08 AB03 AB10 AB15 AB18 AB28 AC02 AC03 AC04 AC06 AC09 AE02 AE03 AE06 AE07 AG02 AG03 AG04 AG05 AG09 AG12 AG23 AG24 AG27 AJ01 AJ04 AJ06 AJ08 BA01 BA04 BA05 BA07 BA10 BA13 BA14 BA15 BA17 BA19 BA23 BA27 CA10 CB02 CB03 FA09 CC09 CC09 FA161 FA171 FA181 FA191 FA201 FA231 HA256 HB41 HC14 HC18 HC22 HD43 JB02 JB07 JB08 JB09 KA12 KA13 KA14 KA18 KA21 LA01 LA05 QA01

Claims (30)

[Claims] 1. A group represented by the general formula 1 -OC (O) C (R) = CH ₂ (1) wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms. At least one per molecule,
An adhesive composition containing a vinyl polymer [Polymer (I)] in a molecule as an essential component. 2. The pressure-sensitive adhesive composition according to claim 1, wherein the polymer (I) has at least one group represented by the general formula 1 at a molecular terminal. 3. The pressure-sensitive adhesive composition according to claim 1, wherein R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms. 4. The pressure-sensitive adhesive composition according to claim 3, wherein R is hydrogen or a methyl group. 5. The pressure-sensitive adhesive composition according to claim 1, wherein the polymer (I) is a (meth) acrylic polymer. 6. The pressure-sensitive adhesive composition according to claim 5, wherein the polymer (I) is an acrylate polymer. 7. The pressure-sensitive adhesive composition according to claim 1, wherein the polymer (I) is a styrene polymer. 8. A polymer (I) having the following steps: a vinyl polymer having a halogen group at a terminal is added to a general formula 2 M ⁺ -OC (O) C (R) = CH ₂ (2) , R represents hydrogen or an organic group having 1 to 20 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion.). The pressure-sensitive adhesive composition according to claim 1. 9. A vinyl polymer having a halogen group at a terminal is represented by the general formula 3-CR ¹ R ² X (3) wherein R ¹ and R ² are bonded to an ethylenically unsaturated group of a vinyl monomer. X is chlorine, bromine or iodine.) The pressure-sensitive adhesive composition according to claim 8, wherein X is chlorine, bromine or iodine. 10. A polymer (I) comprising the following steps: a vinyl polymer having a hydroxyl group at a terminal is added to a vinyl polymer represented by the following general formula: 4 XC (O) C (R) = CH ₂ (4) (where R is hydrogen Or X represents an organic group having 1 to 20 carbon atoms. X represents chlorine, bromine, or a hydroxyl group). The pressure-sensitive adhesive composition according to item 1. 11. A polymer (I) comprising the following steps: (1) reacting a vinyl polymer having a hydroxyl group at a terminal with a diisocyanate compound; OC (O) C (R) = CH ₂ (5) wherein R represents hydrogen or an organic group having 1 to 20 carbon atoms. R ′ represents a divalent organic group having 2 to 20 carbon atoms. Represents.)
The pressure-sensitive adhesive composition according to any one of claims 1 to 7, wherein the pressure-sensitive adhesive composition is produced by reacting a compound represented by the formula: 12. The pressure-sensitive adhesive composition according to claim 1, wherein the main chain of the polymer (I) is produced by living radical polymerization of a vinyl monomer. 13. The pressure-sensitive adhesive composition according to claim 12, wherein the living radical polymerization is atom transfer radical polymerization. 14. The pressure-sensitive adhesive composition according to claim 13, wherein the transition metal complex that is a catalyst for atom transfer radical polymerization is selected from a complex of copper, nickel, ruthenium, and iron. 15. The pressure-sensitive adhesive composition according to claim 14, wherein the transition metal complex is a copper complex. 16. The pressure-sensitive adhesive composition according to claim 1, wherein the main chain of the polymer (I) is produced by polymerization of a vinyl monomer using a chain transfer agent. 17. The polymer (I) having a number average molecular weight of 300
The pressure-sensitive adhesive composition according to any one of claims 1 to 16, which is 0 or more. 18. The polymer (I) wherein the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8.
8. The pressure-sensitive adhesive composition according to any one of 7 above. 19. The pressure-sensitive adhesive composition according to claim 1, further comprising a monomer and / or oligomer having a radical polymerizable group. 20. The pressure-sensitive adhesive composition according to claim 1, further comprising a monomer and / or oligomer having an anion-polymerizable group. 21. The pressure-sensitive adhesive composition according to claim 19, further comprising a monomer and / or oligomer having a (meth) acryloyl group. 22. A monomer and / or monomer having a (meth) acryloyl group and having a number average molecular weight of 2,000 or less.
Or containing an oligomer.
The pressure-sensitive adhesive composition according to item 1. 23. The pressure-sensitive adhesive composition according to claim 1, further comprising a photopolymerization initiator. 24. The pressure-sensitive adhesive composition according to claim 23, wherein the photopolymerization initiator is a photoradical initiator. 25. The pressure-sensitive adhesive composition according to claim 24, wherein the photopolymerization initiator is a photoanion initiator. 26. The pressure-sensitive adhesive composition according to claim 1, further comprising a thermal polymerization initiator. 27. The adhesive according to claim 26, wherein the thermal polymerization initiator is selected from the group consisting of an azo-based initiator, a peroxide, a persulfate, and a redox initiator. Composition. A pressure-sensitive adhesive obtained from the pressure-sensitive adhesive composition according to any one of claims 1 to 27. 29. An adhesive obtained by irradiating the adhesive composition according to claim 1 with an active energy ray. 30. A pressure-sensitive adhesive obtained by thermosetting the pressure-sensitive adhesive composition according to any one of claims 1 to 27.