JP2000154347A - Adhesive curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive curable composition having improved adhesivity to adherends such as metals and plastics by making the composition containe a specific vinylic polymer, a specific compound, and an adhesivity-accelerating agent. SOLUTION: This composition comprises (A) a vinylic polymer having at least one alkenyl group of the formula: CH2=C(R1) (R1 is H or methyl), (B) a hydrosilyl group-containing compound, (C) an adhesivity-accelerating agent, and, if necessary, (D) an antiageing agent, a filler, a plasticizer, a physical property-adjusting agent, a storage stability-improving agent, etc. The alkenyl group of the formula: CH2=C(R1) as the cross-linking group of the component A includes a hydrocarbon-based alkenyl group of the formula: CH2=C(R1)-R4 (R4 is a direct bond or a 1-20C divalent hydrocarbon group) and an ether bond- containing alkenyl group of the formula: CH2=C(R1)-R5-O [R5 is a direct bond or a (ether bond-containing) 1-20C divalent organic group].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an adhesive curable composition. More specifically, the present invention relates to an adhesive curable composition containing an alkenyl group-containing vinyl polymer, a hydrosilyl group-containing compound and an adhesion promoter as essential components.

[0002]

2. Description of the Related Art JP-A-9-272714 discloses a method for obtaining a curable composition by crosslinking an alkenyl group-containing vinyl polymer with a hydrosilyl group-containing compound.

[0003]

However, this curable composition cannot be said to have sufficient adhesion to metals and plastics, and is used in applications where good adhesion to an adherend is one of the important functions. For use, further improvement in adhesiveness was required.

[0004]

Means for Solving the Problems The present inventors have proposed a curable composition comprising an alkenyl group-containing vinyl polymer and a hydrosilyl group-containing compound as a main component by adding an adhesion promoter. It has been found that the adhesiveness of the object is improved.

That is, the present invention provides the following three components: (A) a vinyl polymer having at least one alkenyl group represented by the general formula (1), CH ₂ ＣC (R ¹ )-(1) In the formula, R ¹ represents hydrogen or a methyl group.) An adhesive curable composition containing (B) a hydrosilyl group-containing compound and (C) an adhesion promoter as essential components.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The present invention comprises the following three components: (A) a vinyl polymer having at least one alkenyl group represented by the general formula (1), CH _{2 、} C (R ¹ )-(1 (Wherein, R ¹ represents hydrogen or a methyl group.) An adhesive curable composition comprising (B) a hydrosilyl group-containing compound and (C) an adhesion promoter as essential components.

The adhesive curable composition of the present invention is described below.
It will be described in detail. [About the vinyl polymer of the component (A)]
The above general formula (1), which is a crosslinkable group of a vinyl polymer.
An alkenyl group represented by the following general formula (3)
A hydrocarbon alkenyl group represented by the general formula (4)
An alkenyl group having an ether bond represented by the general formula
A) having an ester bond represented by (5) and (6);
Lucenyl group and carbonate represented by general formula (7)
To the main chain via an oxygen atom such as an alkenyl group having a bond
An alkenyl group to be bound; CH_Two= C (R¹) -R^Four-(3) (where R¹Is the same as described above. R^FourIs directly
Represents a bond or a divalent hydrocarbon group having 1 to 20 carbon atoms
You. In the above general formula (3), R^FourIs particularly limited
However, for example,-(CH_Two)_n− (N is an integer of 0 to 10
Number), -CH_TwoCH (CH_Three)-, -CH_TwoCH (CH_Three)
CH_Two-And the like. CH_Two= C (R¹) -R^Five-O- (4) CH_Two= C (R¹) -R^Five—OC (O) — (5) CH_Two= C (R¹) -R^Five—C (O) O— (6) CH_Two= C (R¹) -R^Five—OC (O) O— (7) (wherein, R¹Is the same as described above. R^FiveIs directly
May contain a bond or one or more ether bonds.
A divalent organic group having 1 to 20 carbon atoms. ) In the above general formulas (4), (5), (6) and (7)
And R^FiveIs not particularly limited, for example,-(C
H_Two)_n-, (N is an integer of 0 to 20), -CH_TwoCH (C
H_Three)-, -CH_TwoCH (CH_Three) CH_Two-; -CH_TwoOC
H_TwoCH_Two-, -CH_TwoOCH_TwoCH_TwoCH_Two-, -CH_TwoC
H_TwoOCH_TwoCH_Two-, -CH_TwoCH_TwoOCH _TwoCH_TwoCH
_Two-; O-, m-, pC₆H_Four-, O-, m-, pC
H_Two-C₆H_Four-, O-, m-, p-CH_Two-C₆H_Four-CH
_Two-And the like.

Further, a group having an electron withdrawing group represented by the general formula (8) is also exemplified as the alkenyl group of the general formula (1). CH ₂ ＣC (R ¹ ) -R ⁵ -C (R ⁶ ) (R ⁷ )-(8) (wherein R ¹ and R ⁵ are the same as described above. R ⁶ and R ⁷ are both carbanion C ^- an electron-withdrawing group stabilizing R ⁶ and R ⁷ or one of the other with the electron withdrawing group is a hydrogen or an alkyl group or phenyl group having 1 to 10 carbon atoms) the general formula in (8). as the electron withdrawing group is not particularly limited, for example, -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. The substituent R is an alkyl group having 1 to 20 carbon atoms and 6 carbon atoms.
Represents an aryl group having from 20 to 20 or an aralkyl group having from 7 to 20 carbon atoms, and is preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group. As R ⁶ and R ⁷ , —CO ₂ R,
-C (O) R and -CN are particularly preferred.

The monomer forming the main chain of the vinyl polymer as the component (A) 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- (meth) acrylate Butyl, isobutyl (meth) acrylate, -tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (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) 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl- (meth) acrylate
2-perfluorobutylethyl, (meth) acrylic acid-
2-perfluoroethyl, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl (meth) acrylate-
2-perfluoroethylmethyl, (meth) acrylic acid-
(Meth) acrylic acid-based monomers such as 2-perfluorohexylethyl, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-
Styrene monomers such as methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl such as vinyltrimethoxysilane and vinyltriethoxysilane Maleic anhydride, maleic anhydride, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide; Maleimide monomers such as octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide; acrylonitrile, meta Nitrile group-containing vinyl monomers such as Rironitoriru; acrylamide, amide group-containing vinyl monomers such as methacrylamide, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate,
Vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride;
Allyl alcohol and the like can be mentioned. These may be used alone or in combination of two or more. In the above expression format, for example, (meth) acrylic acid indicates acrylic acid and / or methacrylic acid.

The vinyl polymer having at least one alkenyl group represented by the general formula (1) is obtained by synthesizing at least 40% by weight of a (meth) acrylic acid monomer among the above monomers. (Meth) acrylic polymers are more preferable in terms of physical properties. In the vinyl polymer having at least one alkenyl group represented by the general formula (1), among the above monomers, an acrylic acid monomer
Acrylic polymers obtained by synthesizing with 0% by weight or more are more preferable from the viewpoint of physical properties.

The molecular weight distribution of the vinyl polymer having at least one alkenyl group, that is, the weight average molecular weight (M
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) is not particularly limited. However, it is preferable that the molecular weight distribution is narrow in order to keep the viscosity of the curable composition low and to facilitate the handling, and to obtain sufficient cured physical properties. The value of the molecular weight distribution is preferably less than 1.8,
It is more preferably at most 1.7, further preferably at most 1.6, further preferably at most 1.5, further preferably at most 1.4, even more preferably at most 1.3. Most commonly, the molecular weight distribution is measured by gel permeation chromatography (GPC). Chloroform or THF is used as the mobile phase, and a polystyrene gel column is used as the column, and the number average molecular weight and the like can be determined in terms of polystyrene.

The molecular weight of the vinyl polymer having at least one alkenyl group is not particularly limited.
It is preferably in the range of 100 to 100,000. When the molecular weight is 500 or less, the intrinsic properties of the vinyl polymer are hardly exhibited, and when it is 100,000 or more, handling becomes difficult.

The vinyl polymer having at least one alkenyl group can be obtained by various polymerization methods, and the method is not particularly limited. However, from the viewpoint of versatility and easy control of monomers, vinyl polymers having a specific functional group that can be directly introduced into an alkenyl group by a radical polymerization method or converted into an alkenyl group in one or several steps of reaction. And converting the specific functional group into an alkenyl group to obtain a vinyl polymer having at least one alkenyl group.

In a radical polymerization method used in a method for synthesizing a vinyl polymer having a specific functional group containing an alkenyl group, a specific functional group is 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” in which a monomer having a vinyl monomer is simply copolymerized 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 and can be used in the present invention. However, in this method, the monomer is only stochastically introduced into the polymer, so that in order to obtain a polymer having a high functionalization rate, it is necessary to use a considerably large amount of the monomer having the specific functional group. There is a problem that the control range of physical properties is narrowed. Conversely, when the amount of the monomer having the specific functional group is small, there is a problem that the ratio of the polymer into which the specific functional group is not introduced increases. In addition, since it is a free radical polymerization, there is a problem that a polymer having a wide molecular weight distribution and a high viscosity is 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 terminal functional group. It can be classified as a "living radical polymerization method" in which a polymer having a molecular weight substantially as designed can be obtained by growing a polymer growth terminal without causing a termination reaction or the like.

The "chain transfer agent method" is capable of obtaining a polymer having a high functionalization rate as compared with the "general radical polymerization method", but a considerably large amount of a specific amount of the initiator relative to the initiator. A chain transfer agent having a functional group is required, and there is a problem in terms of economy including treatment. Further, as in the above-mentioned "general radical polymerization method", there is also a problem that a polymer having a wide molecular weight distribution and a high viscosity is obtained due to free radical polymerization.

[0018] 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 due to coupling between radicals is likely to occur. The reaction hardly occurs and the molecular weight distribution is narrow (Mw / Mn is 1.
(Approximately 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.

Therefore, 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 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” is not particularly limited as long as it is a radical polymerization that satisfies the above definition. In recent years, various groups have been actively studying this "living radical polymerization method", and examples include:
For example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994
Year, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 27.
Vol., P. 7228, "Atom Transfer Radical Polymerization" using an organic halide or the like as an initiator and a transition metal complex as a catalyst (Atom Transfer Radic)
al 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, p. 7901, Science
e) 1996, vol. 272, p. 866, WO 96/30
No. 421, WO97 / 18247 or S
awamoto et al., Macromolecules (Macro)
1995, Vol. 28, p. 1721.

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.

In order to obtain a crosslinkable vinyl polymer by using this polymerization method, an organic halide having two or more starting points or a sulfonyl halide compound can be used as an initiator. As these specific examples, o-, m-, p-XCH 2 -C 6 H 4 -CH 2 X, o-, m
_{-, p-CH 3 C (} H) (X) -C 6 H 4 -C (H)
_{(X) CH 3, o-,} m-, p- (CH 3) 2 C (X) -
C ₆ H ₄ —C (X) (CH ₃ ) ₂ (wherein C ₆ H ₄ represents a phenylene group; X represents chlorine;
Shows bromine or iodine. _{) RO 2 C-C (H} ) (X) - (CH 2) n -C (H)
_{(X) -CO 2 R, RO} 2 C-C (CH 3) (X) - (C
_{H 2) n -C (CH 3} ) (X) -CO 2 R, RC (O) -C
(H) (X) - ( CH 2) n -C (H) (X) -C (O)
R, RC (O) -C ( CH 3) (X) - (CH 2) n -C
(CH ₃ ) (X) —C (O) R (wherein, R represents an alkyl group, an aryl group or an aralkyl group having 1 to 20 carbon atoms. N represents an integer of 0 to 20, and X represents chlorine. , Bromine and iodine.) XCH ₂ —C (O) —CH ₂ X, H ₃ C—C (H) (X)
—C (O) —C (H) (X) —CH ₃ , (H ₃ C) ₂ C
(X) -C (O) -C (X) (CH 3) 2, C 6 H 5 C
(H) (X) - ( CH 2) n -C (H) (X) C 6 H 5 ( in the above formulas, X represents chlorine, bromine or iodine, n is an integer of 0 to 20.) XCH ₂ CO ₂ — (CH ₂ ) _n —OCOCH ₂ X, CH ₃ C
_{(H) (X) CO 2} - (CH 2) n -OCOC (H)
_{(X) CH 3, (CH} 3) 2 C (X) CO 2 - (CH 2) n -
OCOC (X) (CH ₃ ) ₂ (In the above formula, n represents an integer of 1 to 20.) XCH ₂ C (O) C (O) CH ₂ X, CH ₃ C (H)
(X) C (O) C (O) C (H) (X) CH ₃ , (C
H ₃ ) ₂ C (X) C (O) C (O) C (X) (CH ₃ ) ₂ ,
_{o-, m-, p-XCH 2} CO 2 -C 6 H 4 -OCOCH 2
X, o-, m-, p- CH 3 C (H) (X) CO 2 -C 6
_{H 4 -OCOC (H) (X} ) CH 3, o-, m-, p-
_{(CH 3) 2 C (X} ) CO 2 -C 6 H 4 -OCOC (X)
_{(CH 3) 2, o-,} m-, p-XSO 2 -C 6 H 4 -SO 2
X (In the above formula, X represents chlorine, bromine, or iodine.) The transition metal complex used as the polymerization catalyst is not particularly limited, but is preferably a group 7, 8 or 9 of the periodic table.
It is a metal complex complex containing a Group 10, Group or Group 11 element as a central metal. More preferred are zero-valent copper, 1
Complex of divalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity A ligand such as a polyamine is 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 ) and bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PP
h _{3) 2),} and a divalent bis tributylphosphine complex nickel _{(NiBr 2 (PBu 3) 2} ) are also suitable as catalysts.

The vinyl monomer used in the polymerization is not particularly limited, and any of those already exemplified can be suitably used.

The above polymerization reaction can be carried out without a solvent, but can also be carried out in the following various solvents. The solvent is not particularly limited and includes, for example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene. Solvents: ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, ethanol, propanol, isopropanol, n-butyl alcohol, te
alcohol solvents such as rt-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more. The polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

The polymerization can be carried out in the range of 0 to 200 ° C., preferably in the range of room temperature to 150 ° C.

A method for producing a vinyl polymer having at least one alkenyl group represented by the general formula (1) will be specifically described in the following [A] to [C], but is not limited thereto. Not something. [A] A method in which an alkenyl group is directly introduced into a polymer main chain when a vinyl polymer is synthesized by radical polymerization. [B] at least one halogen represented by the general formula (2)
A method in which the halogen is substituted with an alkenyl group-containing functional group using a vinyl polymer having two or more vinyl polymers. [C] A method of using a vinyl polymer having at least one hydroxyl group and substituting the hydroxyl group with an alkenyl group-containing functional group.

The method of introducing an alkenyl group directly into the polymer main chain in the above-mentioned synthesis method [A] is not particularly limited,
Specifically, the following methods [Aa] to [Ab] can be exemplified.

[Aa] When a vinyl polymer is synthesized by living radical polymerization, a polymerizable alkenyl group and a polymerizable alkenyl group in one molecule represented by the following general formula (9) are added together with a predetermined vinyl monomer. A method in which a compound having an alkenyl group having low polymerizability is also reacted. H ₂ C ＝ C (R ¹ ) -R ⁸ -R ⁹ -C (R ¹ ) = CH ₂ (9) wherein R ¹ represents hydrogen or a methyl group, and may be the same or different. Is also good. R ⁸ is —C (O) O—
(Ester group) or an o-, m- or p-phenylene group. R ⁹ represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may have one or more ether bonds. When R ⁸ is an ester group, it is a (meth) acrylate compound, and when R ⁸ is a phenylene group, it is a styrene compound. R ⁹ in the general formula (9) is not particularly limited, but includes, for example, an alkylene group such as methylene, ethylene, and propylene; an o-, m-, p-phenylene group; an aralkyl group such as a benzyl group; Examples thereof include an alkylene group containing an ether bond such as ₂ CH ₂ —O—CH ₂ — and —O—CH ₂ —.

Among the compounds of the above general formula (9),
The following are preferred in that they are easy to perform. H_TwoC = C (H) C (O) O (CH_Two)_n-CH = CH_Two,
H_TwoC = C (CH_Three) C (O) O (CH_Two)_n-CH = CH
_Two (In each of the above formulas, n represents an integer of 0 to 20.) H_TwoC = C (H) C (O) O (CH_Two)_n-O- (CH_Two)
_mCH = CH_Two, H_TwoC = C (CH_Three) C (O) O (C
H_Two)_n-O- (CH_Two)_mCH = CH_Two (In each of the above formulas, n is an integer of 1 to 20, and m is 0 to
Indicates an integer of 20. ) O-, m-, p-divinylbenzene, o-, m-, p-
H_TwoC = CH-C₆H_Four-CH_TwoCH = CH_Two, O-, m
−, PH_TwoC = CH-C₆H_Four-CH_Two-C (CH_Three) =
CH_Two, O-, m-, pH_TwoC = CH-C₆H_Four-CH_Two
CH_TwoCH = CH_Two, O-, m-, pH_TwoC = CH-C₆
H_Four-OCH_TwoCH = CH_Two, O-, m-, pH_TwoC = C
HC₆H_Four-OCH_Two-C (CH_Three) = CH_Two, O-, m
−, PH_TwoC = CH-C₆H_Four-OCH_TwoCH_TwoCH = C
H_Two, O-, m-, pH_TwoC = C (CH_Three) -C₆H_Four−
C (CH_Three) = CH_Two, O-, m-, pH_TwoC = C (C
H_Three) -C₆H_Four-CH_TwoCH = CH_Two, O-, m-, p-
H_TwoC = C (CH_Three) -C₆H_Four-CH_TwoC (CH_Three) = CH
_Two, O-, m-, pH_TwoC = C (CH_Three) -C₆H_Four-C
H_TwoCH_TwoCH = CH_Two, O-, m-, pH_TwoC = C (C
H_Three) -C₆H_Four-OCH_TwoCH = CH_Two, O-, m-, p
-H_TwoC = C (CH_Three) -C₆H_Four-OCH_Two-C (CH _Three)
= CH_Two, O-, m-, pH_TwoC = C (CH_Three) -C₆H
_Four-OCH_TwoCH_TwoCH = CH_Two (In each of the above equations, C₆H_FourIndicates a phenylene group
You. Note that the polymerizable alkenyl group and the polymerizable
The timing of reacting a compound having a lucenyl group is
Although there is no particular limitation, in living radical polymerization,
At the end of the combined reaction or after the reaction of the given monomer,
It is preferred to react as a second monomer.

[Ab] When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, at least two alkenyl groups having low polymerizability are used as the second monomer. A method of reacting a compound having two or more compounds.

Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (10). ^{_{H 2 C = C (R 1}} ) -R 10 -C (R 1) = CH 2 (10) ( wherein, R ¹ represents a hydrogen or a methyl group, good .R ¹⁰ be the same as or different from each other It represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds.) The compound represented by the general formula (10) is not particularly limited, but is easily available. Therefore, 1,5
-Hexadiene, 1,7-octadiene and 1,9-decadiene are preferred.

In the method for synthesizing a vinyl polymer having at least one alkenyl group by directly introducing an alkenyl group into the polymer main chain in the above-mentioned synthesis method [A],
The method [A-b] is preferred because it is easier to control the alkenyl group introduced per molecule.

The method for synthesizing the vinyl polymer having at least one halogen represented by the general formula (2) in the above synthesis method [B] is preferably an atom transfer radical polymerization method. The method of substituting the alkenyl group-containing functional group for the halogen in the polymer is not particularly limited, but specific examples include the following methods [Ba] to [Bd].

[Ba] A method in which various organic metal compounds having an alkenyl group are allowed to act on a vinyl polymer having at least one halogen represented by the general formula (2) to replace the halogen.

Examples of such organometallic compounds include organic lithium, organic sodium, organic potassium, organic magnesium, organic tin, organic silicon, organic zinc, organic copper and the like. In particular, organotin and organocopper compounds are preferred because they selectively react with the halogen of the general formula (2) and have low reactivity with a carbonyl group.

As an organotin compound having an alkenyl group
Is not particularly limited, but is represented by the following general formula (11)
Compounds are preferred. H_TwoC = C (R¹) C (R¹¹) (R¹²) Sn (R¹³)_Three (11) (where R¹Is the same as described above. R¹¹and
R¹²Is hydrogen, an alkyl group having 1 to 10 carbon atoms, carbon
An aryl group having 6 to 10 carbon atoms, or an aryl group having 7 to 10 carbon atoms
Represents alkyl groups, which are the same or different
May be. R ¹³Is an alkyl group having 1 to 10 carbon atoms,
Indicates an aryl group or an aralkyl group. If specific examples of the organotin compound represented by the general formula (11) are shown,
For example, allyltributyltin, allyltrimethyltin, allyl
Tri (n-octyl) tin, allyltri (cyclohexyl)
G) tin and the like. Organic copper having alkenyl group
Compounds include lithium divinyl copper and diallyl copper lithium.
And lithium lithium diisopropenyl.

[Bb] A stabilized carbanion having an alkenyl group represented by the following general formula (12) is reacted with a vinyl polymer having at least one halogen represented by the general formula (2). Substituting halogen. ^{M + C - (R 6)} (R 7) -R 5 -C (R 1) = CH 2 (12) ( ^{wherein, R 1, R 5, R} 6 and R ⁷ are the same as those described above M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) Alkali metal ions include lithium ions, sodium ions, and potassium ions, and quaternary ammonium ions include tetramethyl ammonium ions, tetraethyl ammonium ions, and trimethyl ions. Specific examples include a benzyl ammonium ion, a trimethyl dodecyl ammonium ion, and a tetrabutyl ammonium ion.

The carbanion of the general formula (12) can be obtained by reacting a basic compound with a precursor thereof to extract active protons.

Precursor compound of carbanion of general formula (12)
Examples of the compound include the following compounds. H_TwoC = CH-CH (CO_TwoCH_Three)_Two, H_TwoC = CH-C
H (CO_TwoC_TwoH_Five)_Two, H_TwoC = CH- (CH_Two)_nCH
(CO_TwoCH_Three)_Two, H_TwoC = CH- (CH_Two)_nCH (CO
_TwoC_TwoH_Five)_Two, O-, m-, pH_TwoC = CH-C₆H_Four−
CH (CO_TwoCH_Three)_Two, O-, m-, pH_TwoC = CH-
C₆H_Four-CH (CO_TwoC_TwoH_Five)_Two, O-, m-, pH_Two
C = CH-C₆H_Four-CH_TwoCH (CO_TwoCH_Three)_Two, O-,
m-, pH_TwoC = CH-C₆H_Four-CH_TwoCH (CO_TwoC_Two
H_Five)_Two, H_TwoC = CH-CH (C (O) CH_Three) (CO_Two
C_TwoH_Five), H_TwoC = CH- (CH_Two)_nCH (C (O) C
H_Three) (CO _TwoC_TwoH_Five), O-, m-, pH_TwoC = CH
-C₆H_Four-CH (C (O) CH_Three) (CO_TwoC_TwoH_Five), O
-, M-, pH_TwoC = CH-C₆H_Four-CH_TwoCH (C
(O) CH_Three) (CO_TwoC_TwoH_Five), H_TwoC = CH-CH
(C (O) CH_Three)_Two, H_TwoC = CH- (CH_Two)_nCH
(C (O) CH_Three)_Two, O-, m-, pH_TwoC = CH-
C₆H_Four-CH (C (O) CH_Three)_Two, O-, m-, pH
_TwoC = CH-C₆H_Four-CH_TwoCH (C (O) CH_Three)_Two, H
_TwoC = CH-CH (CN) (CO_TwoC_TwoH_Five), H_TwoC = C
H- (CH_Two)_nCH (CN) (CO_TwoC_TwoH_Five), O-,
m-, pH_TwoC = CH-C₆H_Four-CH (CN) (CO_Two
C_TwoH_Five), O-, m-, pH_TwoC = CH-C₆H_Four-C
H_TwoCH (CN) (CO_TwoC_TwoH_Five), H_TwoC = CH-CH
(CN)_Two, H_TwoC = CH- (CH_Two)_nCH (CN)_Two,
o-, m-, pH_TwoC = CH-C₆H_Four-CH (C
N)_Two, O-, m-, pH_TwoC = CH-C₆H_Four-CH_Two
CH (CN)_Two, H_TwoC = CH- (CH_Two)_nNO_Two, O
-, M-, pH_TwoC = CH-C₆H_Four-CH_TwoNO_Two, O
-, M-, pH_TwoC = CH-C₆H_Four-CH_TwoCH_TwoN
O_Two, H_TwoC = CH-CH (C₆H_Five) (CO_TwoC_TwoH_Five),
H_TwoC = CH- (CH_Two)_nCH (C₆H_Five) (CO_TwoC
_TwoH_Five), O-, m-, pH_TwoC = CH-C₆H_Four-CH
(C₆H_Five) (CO_TwoC_TwoH_Five), O-, m-, pH_TwoC =
CH-C₆H_Four-CH_TwoCH (C₆H_Five) (CO _TwoC_TwoH_Five(In the above formula, n represents an integer of 1 to 10.) A proton is extracted from the above compound to obtain a compound represented by the general formula (12).
Various basic compounds are used to make rubanion.
It is. These basic compounds include the following compounds
Things can be exemplified. Sodium, potassium, lithium, etc.
Alkali metal; sodium methoxide, potassium methoki
Sid, lithium methoxide, sodium ethoxide, mosquito
Lithium ethoxide, lithium ethoxide, sodium-
tert-butoxide, potassium-tert-butoxy
Metal alkoxides such as sodium carbonate, potassium carbonate
Carbonates such as water, lithium carbonate and sodium hydrogen carbonate; water
Hydroxides such as sodium oxide and potassium hydroxide; hydrogenation
Sodium, potassium hydride, methyl lithium, ethyl
Hydrides such as lithium; n-butyllithium, tert
-Butyl lithium, lithium diisopropylamide,
Organometallics such as titanium hexamethyldisilazide; ammonium
A; trimethylamine, triethylamine, tributyl
Alkylamines such as amines; tetramethylethylenedia
Polyamides such as min, pentamethyldiethylenetriamine
Basic compounds such as pyridine and picoline are used in equivalent or small amounts to the precursor.
An excess amount may be used, preferably 1 to 1.2 equivalents.
You.

A quaternary ammonium salt can also be used as the above carbanion. In this case, it is obtained by preparing an alkali metal salt of a carboxylic acid compound and reacting it with a quaternary ammonium halide. Examples of the quaternary ammonium halide include tetramethylammonium halide, tetraethylammonium halide, trimethylbenzylammonium halide, trimethyldodecylammonium halide, and tetrabutylammonium halide.

Examples of the solvent used for reacting the above-mentioned precursor compound with a basic compound include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; Halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone,
Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate Solvent solvents such as ethylene carbonate and propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide; and sulfoxide solvents such as dimethyl sulfoxide. These can be used alone or in combination of two or more.

By reacting the above precursor with a basic compound, a carbanion represented by the general formula (12) is prepared and reacted with a halogen-terminated vinyl polymer represented by the general formula (2). The desired vinyl polymer having a terminal alkenyl group represented by the general formula (1) can be obtained.

[Bc] A vinyl polymer having at least one halogen represented by the general formula (2) is reacted with a simple metal or an organometallic compound to form an enolate anion. To react with the electrophilic compound.

As the metal simple substance, zinc is particularly preferable because the resulting enolate anion is unlikely to cause a side reaction such as attacking or transferring another ester group. Various kinds of electrophilic compounds having an alkenyl group can be used. Examples thereof include an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. Of these, the use of an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group is preferable because atoms other than carbon are not introduced into the main chain and the weather resistance of the vinyl polymer is not lost.

[Bd] An alkenyl group-containing oxyanion represented by the following general formula (13) or a alkenyl group-containing oxyanion represented by the following general formula (2) 14) A method of reacting the alkenyl group-containing carboxylate anion represented by the above formula to replace the halogen with an alkenyl group-containing substituent. ^{_{CH 2 = C (R 1)}} -R 5 -O - M + (13) (. Wherein, R ^1, R ⁵ and M ⁺ are the same as those described ^{_{above) CH 2 = C (R 1}} ) - R ⁵ -C (O) O ⁻ M ⁺ (14) (wherein R ¹ , R ⁵ and M ⁺ are the same as those described above.) Oxygens represented by the general formulas (13) and (14) The following compounds are used as precursors of the anion: H ₂ C =
_{CH-CH 2 -OH, H 2} C = CH-CH (CH 3) -O
_{H, H 2 C = C (} CH 3) -CH 2 -OH, H 2 C = CH-
(CH _{2) n} -OH _(n represents an integer of 2 to 20.),
_{H 2 C = CH-CH 2} -O- (CH 2) 2 -OH, H 2 C =
CH-C (O) O- ( CH 2) 2 -OH, H 2 C = C (C
_{H 3) -C (O) O-} (CH 2) 2 -OH, o-, m-,
_{p-H 2 C = CH-} C 6 H 4 -CH 2 -OH, o-, m-,
_{p-H 2 C = CH-} CH 2 -C 6 H 4 -CH 2 -OH, o
_{-, m-, p-H 2} C = CH-CH 2 -O-C 6 H 4 -CH
Alcoholic hydroxyl group-containing compounds such as _2- OH; o-, m
_{-, p-H 2 C =} CH-C 6 H 4 -OH, o-, m-, p
_{-H 2 C = CH-CH 2} -C 6 H 4 -OH, o-, m-, p
-H ₂ C = CH-CH phenolic hydroxyl group-containing compounds such as _{2 -O-C 6 H 4 -OH} ; H 2 C = CH-C (O) -O
_{H, H 2 C = C (} CH 3) -C (O) -OH, H 2 C = C
_{H-CH 2 -C (O)} -OH, H 2 C = CH- (CH 2) n
—C (O) —OH (n represents an integer of 2 to 20),
_{H 2 C = CH- (CH 2} ) n -OC (O) - (CH 2) m -
C (O) —OH (m and n are the same or different, and
Indicates an integer of 19. ), O-, m-, p- H 2 C = CH
_{-C 6 H 4 -C (O)} -OH, o-, m-, p-H 2 C =
_{CH-CH 2 -C 6 H 4} -C (O) -OH, o-, m-,
_{p-H 2 C = CH-} CH 2 -O-C 6 H 4 -C (O) -O
H, o-, m-, p- H 2 C = CH- (CH 2) n -OC
A carboxyl group-containing compound such as (O) —C ₆ H ₄ —C (O) —OH (n represents an integer of 0 to 13);

Various basic compounds are used to extract a proton from the above compound to form an anion of the above general formula (13) or (14). All basic compounds used in preparing carbanions are preferably used.
As the reaction solvent, any of those used for preparing carbanions is preferably used.

In the above synthesis method [B], since an alkenyl group can be introduced at a high ratio, an atom transfer radical using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is used. A method of introducing an alkenyl group by converting a halogen of a vinyl polymer having at least one halogen represented by the general formula (2) obtained by a polymerization method by the method of [Bd] is preferable. Among the methods of [Bd], a method of reacting an alkenyl group-containing carboxylate anion represented by the general formula (14) or the like is more preferable.

A method for producing a vinyl polymer, characterized by using an atom transfer radical polymerization method in which a vinyl monomer is polymerized by using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst, When an organic halide having an alkenyl group is used as an initiator, a vinyl polymer having an alkenyl group at one terminal and the other terminal having the structure represented by the general formula (2) can be obtained. By converting the halogen at the terminal end of the polymer thus obtained into an alkenyl group-containing substituent, a vinyl polymer having alkenyl groups at both ends can be obtained. As the conversion method, the method already described can be used.

The organic halide having an alkenyl group is not particularly limited.
Those having the structure shown in FIG. ^{R 14 R 15 C (X)} -R 16 -R 9 -C (R 1) = CH 2 (15) { wherein, R ^1, R ⁹ and X are the same as those described above. R ¹⁴ and R ^{15 each} represent hydrogen or 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 one linked to each other at the other end. R ¹⁶ represents —C (O) O— (ester group), —C
(O)-(keto group) or o-, m-, p-phenylene group.具体 Specific examples of the organic halide having an alkenyl group represented by the general formula (15) 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 ,

[0052]

Embedded image (In each formula mentioned above, X is chlorine, bromine or .n indicating iodine, 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 (C
H 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 ,

[0053]

Embedded image(In each of the above formulas, X represents chlorine, bromine, or iodine.
Show. n represents an integer of 1 to 20, m represents an integer of 0 to 20
You. ) O, m, p-XCH_Two-C₆H_Four− (CH_Two)_n-CH = C
H_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four− (C
H_Two)_n-CH = CH_Two, O, m, p-CH_ThreeCH_TwoC
(H) (X) -C₆H_Four− (CH_Two)_n-CH = CH_Two (In each of the above formulas, X represents chlorine, bromine, or iodine.
Show. n shows the integer of 0-20. ) 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− (CH_Two)_n-O- (CH_Two)_mCH = CH_Two (In each of the above formulas, X represents chlorine, bromine, or iodine.
Show. n represents an integer of 1 to 20, m is an integer of 0 to 20
Is shown. ) O, m, p-XCH_Two-C₆H_Four-O- (CH_Two)_n-CH
= CH_Two, O, m, p-CH_ThreeC (H) (X) -C₆H_Four−
O- (CH_Two)_n-CH = CH_Two, O, m, p-CH _ThreeCH
_TwoC (H) (X) -C₆H_Four-O- (CH_Two)_n-CH = C
H_Two (In each of the above formulas, X represents chlorine, bromine, or iodine.
And n represents 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- (CH_Two)_n-O- (CH_Two) _m-C
H = CH_Two, O, m, p-CH_ThreeCH_TwoC (H) (X)-
C₆H_Four-O- (CH _Two)_n-O- (CH_Two)_m-CH = CH
_Two (In each of the above formulas, X is chlorine, bromine, or iodine.
Is shown. n represents an integer of 1 to 20, and m is an integer of 0 to 20.
Indicates a number. ) The organic halide having an alkenyl group is further
A compound represented by the general formula (16) is exemplified. H_TwoC = C (R¹) -R⁹-C (R¹⁴) (X) -R¹⁷-R¹⁵ (16) ｛where R¹, R⁹, R¹⁴, R¹⁵, X is the same as above
It is like. R¹⁷Is a direct bond, -C (O) O- (ester
), -C (O)-(keto group), or o-, m
-Represents a p-phenylene 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, the carbon-halogen is linked by an adjacent vinyl group.
Is activated, so that R¹⁷As C (O) O
Group or phenylene group is not necessary
It may be a combination. R⁹Is not a direct bond,
In order to activate the halogen-halogen bond, R¹⁷As C
(O) O group, C (O) group and phenylene group are preferred.

Specific examples of the compound of the above formula (16) include the following compounds. CH ₂ ＣＨCHCH ₂ X, CH ₂ ＣC (CH ₃ ) CH ₂ X, C
H ₂ ＣＨCHC (H) (X) CH ₃ , CH ₂ ＣC (CH ₃ ) C
(H) (X) CH ₃ , CH ₂ ＣＨCHC (X) (CH ₃ ) ₂ ,
CH ₂ ＣＨCHC (H) (X) C ₂ H ₅ , CH ₂ ＣＨCHC
(H) (X) CH (CH ₃ ) ₂ , CH ₂ ＣＨCHC (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, C
H ₂ ＣＨCH (CH ₂ ) ₂ C (H) (X) —CO ₂ R, CH _{2
= CH (CH 2) 3 C} (H) (X) -CO 2 R, CH 2 = C
_{H (CH 2) 8 C (} H) (X) -CO 2 R, CH 2 = CHC
_{H 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 formulas, X represents chlorine, bromine or .R showing the iodine is an alkyl group having 1 to 20 carbon atoms, an aryl group,
Represents an aralkyl group. The halogenated sulfonyl compound having an alkenyl group is
Specifically, the following compounds can be exemplified. _{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 each of the above formulas, X represents chlorine, bromine, or iodine; n represents an integer of 0 to 20.) An organic halide having an alkenyl group, or a sulfonyl halide When a compound or the like is used as an initiator, a polymer having an alkenyl group at one terminal and a halogen terminal at the other terminal represented by the general formula (2) can be obtained. A halogen represented by the general formula (2) of the polymer can be substituted;
A vinyl polymer having an alkenyl group at a terminal can also be obtained by coupling halogen terminals with a compound having a total of two or more same or different functional groups.

There is no particular limitation on those having a total of two or more identical or different functional groups capable of substituting a terminal halogen, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides, etc. Is preferred. The following compounds can be exemplified as specific examples of these compounds.

Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,
3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, 1, 5-pentanediol,
1,4-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, , 12-Dodecanediol, 1,2-cyclopentanediol, 1,3-
Cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycerol, 1,2,4-butanetriol, catechol, resorcinol, hydroquinone, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,2′-biphenol, 4,4′-biphenol, bis (4-hydroxyphenyl) methane, 4,4′-isopropylidene Phenol, 3,3 ′-(ethylenedioxy) diphenol, α, α′-dihydroxy-p-xylene, 1,1,
Polyols such as 1-tris (4-hydroxyphenyl) ethane, pyrogallol, 1,2,4-benzenetriol; and alkali metal salts of the above polyol compounds;
Ethylenediamine, 1,3-diaminopropane, 1,2
-Diaminopropane, 1,4-diaminobutane, 1,2
-Diamino-2-methylpropane, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1 , 9-Diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4′-methylenebis (cyclohexylamine), 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane Polyamines such as 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, α, α′-diamino-p-xylene; and alkali metal salts of the above polyamine compounds; oxalic acid, malonic acid ,
Methylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9
-Nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-
Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,
Polycarboxylic acids such as 2,3-benzenetricarboxylic acid and 1,2,4,5-benzenetetracarboxylic acid; and alkali metal salts of the above polycarboxylic acids; 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,
7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethylether, p-xylene-α, α′-dithiol,
Polythiols such as 2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, and the like;
And alkali metal salts of the above polythiol compounds; lithium sulfide, sodium sulfide, and potassium sulfide.

When the above-mentioned polyols, polyamines, polycarboxylic acids and polythiols are used, a basic compound is used in combination to promote the substitution reaction, and specific examples thereof include those already exemplified.

In the above synthesis method [C], at least one hydroxyl group
The method for substituting this hydroxyl group with an alkenyl group-containing functional group using a vinyl polymer having two or more vinyl polymers is not particularly limited, and specific examples thereof include the following [Ca] to [Cd].
And the like.

The vinyl polymer having at least one hydroxyl group is represented by [Da] to [Df] described later.
Can be obtained.

[Ca] After a base such as sodium hydroxide or sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group, it reacts with an alkenyl group-containing halide such as allyl chloride. How to let.

[Cb] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing isocyanate compound such as allyl isocyanate.

[Cc] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine.

[Cd] A method of reacting a vinyl polymer having at least one hydroxyl group with an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.

The method for producing a vinyl polymer having at least one hydroxyl group used in the method [C] is as follows [D]
-A] to [D-f], but are not limited to these methods.

[Da] When a vinyl polymer is synthesized by living radical polymerization, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule represented by the following general formula (17) is used as a second compound. A method of reacting as a monomer. H ₂ C = C (R ¹ ) -R ⁸ -R ⁹ -OH (17) (wherein R ¹ , R ⁸ and R ⁹ are the same as those described above). There is no limitation on the time when the compound having both the alkenyl group and the hydroxyl group is reacted, but if rubbery properties are particularly expected, the reaction may be carried out as the second monomer at the end of the polymerization reaction or after the reaction of a predetermined monomer. Is preferred.

[Db] When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer, alkenyl having low polymerizability in one molecule is used as a second monomer. A method of reacting a compound having a group and a hydroxyl group.

Such a compound is not particularly limited, and examples thereof include a compound represented by the general formula (18). ^{_{H 2 C = C (R 1}} ) -R 10 -OH (18) ( wherein, R ¹ and R ¹⁰ are the same as those described above.) In particular limitation is imposed on the compound represented by the above general formula (18) Not available, but 10-
Alkenyl alcohols such as undecenol, 5-hexenol, allyl alcohol are preferred.

[Dc] The method disclosed in Japanese Patent Application Laid-Open No. 4-132706 discloses a method in which a carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization is reduced to at least one. A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a vinyl polymer having the same with a hydroxyl group-containing compound.

[Dd] A vinyl polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by atom transfer radical polymerization is added to the general polymer (19)
A method of reacting a stabilized carbanion having a hydroxyl group as described in (1) to replace halogen. ^{M + C - (R 6)} (R 7) -R 5 -OH (19) (. Wherein, R ^5, R ⁶ and R ⁷ are the same as those described above) [D-e] atom transfer radical A vinyl-based polymer having at least one carbon-halogen bond represented by the general formula (2) obtained by polymerization is reacted with a simple metal such as zinc or an organometallic compound to prepare an enolate anion, After that, a method of reacting aldehydes or ketones.

[Df] A vinyl-based polymer having at least one halogen represented by the general formula (2) is added to a hydroxyl group-containing oxyanion represented by the following general formula (20) or the like, A) reacting a hydroxyl group-containing carboxylate anion represented by formula (1) or the like to replace the halogen with a hydroxyl group-containing substituent. ^{HO-R 5 -O - M +} (20) ( wherein, the R ⁵ and M ⁺ are the same as those described ^{above.) HO-R 5 -C (} O) O - M + (21) ( in the formula , R ⁵ and M ⁺ are the same as those described above.) In the present invention, when a halogen is not directly involved in a method for introducing a hydroxyl group such as [Da] to [Db], control is easier. In view of this, the method [Db] is more preferable.

In addition, general formulas such as [Dc] to [Df]
At least one carbon-halogen bond represented by the formula (2)
By converting halogen of vinyl polymer
When introducing hydroxyl groups, is it easier to control
The method of [D-f] is more preferable. [About the hydrosilyl group-containing compound of the component (B)]
As the hydrosilyl group-containing compound of the component (B),
Component (A) having at least one alkenyl group
Containing hydrosilyl group that can be cured by cross-linking with phenyl-based polymer
There is no particular limitation as long as it is a compound, and various compounds are used.
be able to. For example, the general formula (22) or (23)
A chain polysiloxane represented by the formula: R¹⁸ _ThreeSiO- [Si (R¹⁸)_TwoO]_a− [Si (H) (R¹⁹) O]_b− [Si (R ¹⁹ ) (R²⁰) O]_c-SiR¹⁸ _Three (22) HR¹⁸ _TwoSiO- [Si (R¹⁸)_TwoO]_a− [Si (H) (R¹⁹) O]_b− [Si (R¹⁹) (R²⁰) O]_c-SiR¹⁸ _TwoH (23) (wherein, R¹⁸And R¹⁹Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ²⁰Is an alkyl having 1 to 10 carbons
Group or aralkyl group. a is 0 ≦ a ≦ 100, b
Is an integer satisfying 2 ≦ b ≦ 100 and c is an integer satisfying 0 ≦ c ≦ 100
Show. A) a cyclic siloxane represented by the general formula (24);

[0072]

Embedded image(Where R^{twenty one}And R^{twenty two}Is an alkyl group having 1 to 6 carbon atoms,
Or a phenyl group, R ^{twenty three}Is an alkyl having 1 to 10 carbons
Group or aralkyl group. d is 0 ≦ d ≦ 8, e is 2
≦ e ≦ 10, f represents an integer of 0 ≦ f ≦ 8, and 3 ≦ d
+ E + f ≦ 10 is satisfied. ))
it can.

These may be used alone or in combination of two or more. Among these siloxanes, from the viewpoint of compatibility with the (meth) acrylic polymer, chain siloxanes represented by the following general formulas (25) and (26) having a phenyl group, and the general formulas (27) and (26) The cyclic siloxane represented by 28) is preferred. _{(CH 3) 3 SiO- [Si} (H) (CH 3) O] g - [Si (C 6 H 5) 2 O] h -S i (CH 3) 3 (25) (CH 3) 3 SiO- [Si (H) (CH ₃ ) O] _g- [Si (CH ₃ ) ｛CH ₂ C (H) (R ²⁴ ) C ₆ H ₅ ｝ O] _h -Si (CH ₃ ) ₃ (26) Wherein R ²⁴ represents hydrogen or a methyl group, and g is 2 ≦ g.
≦ 100, h represents an integer of 0 ≦ h ≦ 100. C ₆ H ₅ represents a phenyl group. )

[0074]

Embedded image (Wherein, R ²⁴ represents hydrogen or a methyl group; i is 2 ≦
i ≦ 10 and j are integers satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10. C ₆ H ₅ represents a phenyl group. As the compound having at least one hydrosilyl group of the component (B), a low molecular weight compound having two or more alkenyl groups in the molecule may further be selected from hydrosilyl groups represented by the general formulas (22) to (28). A compound obtained by subjecting a group-containing compound to an addition reaction so that a part of the hydrosilyl group remains even after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, 1,4
Hydrocarbon compounds such as -pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene;
O'-diallylbisphenol A, ether compounds such as 3,3'-diallylbisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate and tetraallyl pyromellitate, diethylene glycol diallyl carbonate and the like And carbonate-based compounds.

The above-mentioned alkenyl group-containing compound is slowly added dropwise to the excess amount of the hydrosilyl group-containing compound represented by the above general formulas (22) to (28) in the presence of a hydrosilylation catalyst to convert the compound. Obtainable. Among these compounds, the following compounds are preferred in consideration of the availability of raw materials, the ease of removal of excess siloxane, and the compatibility of the component (A) with the polymer.

[0076]

Embedded image The polymer (A) and the curing agent (B) can be mixed in any ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is preferably in the range of 5 to 0.2. And more preferably 2.5 to 0.4. When the molar ratio is 5 or more, only a cured product with insufficient curing and insufficient tackiness is obtained, and when it is less than 0.2, a large amount of active hydrosilyl groups remains in the cured product even after curing. , Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.

The curing reaction between the polymer (A) and the curing agent (B) proceeds by mixing and heating the two components.
To make the reaction proceed more quickly, a hydrosilylation catalyst can be added. Such a hydrosilylation catalyst is not particularly limited, and examples thereof include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited.
For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
Such as 2,5-dimethyl-2,5-di (t-butylperoxy) -3-hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α′-bis (t-butylperoxy) isopropylbenzene Dialkyl peroxides, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as t-butyl perbenzoate, Peroxydicarbonates such as diisopropyl carbonate, di-2-ethylhexyl percarbonate, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) -3,3,5-trimethyl Peroxyke such as cyclohexane It can be mentioned Lumpur and the like.

The transition metal catalyst is not particularly limited. For example, platinum solid, dispersion of platinum solid on a carrier such as alumina, silica or carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Examples include a complex with a ketone or the like, a platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , R
hCl ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl
_{3, PdCl 2 · H 2 O} , NiCl 2, TiCl 4 , and the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but may be 1 to 1 mol of the alkenyl group of the component (A).
It is preferably used in the range of 0 ^-1 to 10 ^-8 mol, and more preferably in the range of 10 ^-3 to 10 ^-6 mol. 10
^If it is less than ^-8 mol, curing does not proceed sufficiently. Since the hydrosilylation catalyst is expensive, it is preferable not to use 10 ^-1 mol or more.

The curing temperature is not particularly limited, but it is generally preferable to cure at 0 ° C. to 200 ° C., preferably 30 ° C. to 150 ° C., more preferably 80 ° C. to 150 ° C. [Adhesion promoter of component (C)] The adhesion promoter of component (C) is a vinyl polymer having at least one alkenyl group of component (A) and a hydrosilyl group-containing compound of component (B). The compound is not particularly limited as long as it imparts adhesiveness to a cured product obtained by crosslinking with the compound, but a crosslinkable silyl group-containing compound is preferable, and a silane coupling agent is more preferable. Among them, a silane coupling agent having both an organic group having an atom other than a carbon atom and a hydrogen atom such as an epoxy group, a (meth) acryl group, an isocyanate group, an isocyanurate group, and a carbamate group and a crosslinkable silyl group in a molecule is preferable. Furthermore, from the viewpoint of curability and adhesiveness,
Alkoxysilanes having an epoxy group or a (meth) acryl group in the molecule are preferred. When these are specifically exemplified, alkoxysilanes having an epoxy group include γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropyltriethoxysilane, 2- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like include alkoxysilanes having a (meth) acryl group as γ-methacryloxypropyltrimethoxysilane, γ -Methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyl And triethoxysilane. These may be used alone or in combination of two or more.

The adhesion promoter is preferably used in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the vinyl polymer (A). If the amount is less than 0.01 part by weight, the effect of improving the adhesion is small, and if it exceeds 20 parts by weight, the physical properties of the cured product are adversely affected. Preferably it is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

In order to further improve the adhesiveness, a crosslinkable silyl group condensation catalyst can be used together with the component (C). Examples of the crosslinkable silyl group condensation catalyst include organic tin compounds such as dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimethoxide, and tin octylate; organic aluminum compounds such as aluminum acetylacetonate; tetraisopropoxytitanium; tetrabutoxytitanium And the like.

The adhesive curable composition of the present invention contains various additives for adjusting physical properties, such as an antioxidant, a filler, a plasticizer, a physical property modifier, and a storage stability improver. May be.

Since the vinyl polymer is inherently a polymer having excellent durability, an antioxidant is not always necessary. Can be.

The filler that can be blended is not particularly limited, and examples thereof include finely divided silica, calcium carbonate, clay,
Talc, titanium oxide, zinc white, diatomaceous earth, barium sulfate,
And carbon black.

As the plasticizer, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate and butyl benzyl phthalate; dioctyl adipate, dioctyl sebacate for the purpose of adjusting physical properties and properties. 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 alkyl diphenyl and partially hydrogenated terphenyl alone. Alternatively, two or more kinds can be used as a mixture, but are not always required. In addition, these plasticizers can be blended at the time of polymer production.

The storage stability improver that can be blended is not particularly limited as long as it can suppress the increase in the viscosity of the composition during storage and the remarkable change in the curing rate after storage. For example, benzothiazole, dimethyl Malate and the like.

The adhesive curable composition of the present invention can be used for various sealing materials, coating materials, adhesives, paints, gaskets and the like which require adhesiveness.

[0089]

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 crosslinked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used, and chloroform was used as a GPC solvent. (Production Example 1) In a 500 mL three-necked flask equipped with a reflux tube,
Cuprous bromide (1.50 g, 10.5 mmol
l), pentamethyldiethylenetriamine (1.65 mL) as a ligand, diethyl-2,5-dibromoadipate (9.42 g, 26.2 mol) as an initiator, acetonitrile (30 mL) as a solvent, and acrylic acid- n-butyl (300 mL) in a nitrogen atmosphere at 70 ° C
When the conversion of n-butyl acrylate is 93%, 1,7-octadiene (38.6 mL, 0.2
61 mol) and heated at the same temperature. The reaction mixture was diluted with ethyl acetate, the catalyst was removed through a column of activated alumina, and volatiles were distilled off under reduced pressure to obtain a polymer [1] having a terminal alkenyl group. The number average molecular weight of the polymer [1] is 13,800, and the molecular weight distribution is 1.
28. The number of alkenyl groups introduced per oligomer-1 molecule was 1.84 by ¹ H NMR analysis. The viscosity of this polymer [1] was 35 Pa · s. (Production Example 2) (Production of carboxylate having alkenyl group)
(245 mL) in 4-pentenoic acid (49 g, 0.48
9 mol), potassium-tert-butoxide (54.
9g, 0.489 mol) and stirred at 0 ° C.
The volatiles were distilled off under reduced pressure to obtain potassium pentenoate shown by the following formula. In K ⁺ (manufacture of poly (butyl -n- acrylate) having an alkenyl group) equipped with a reflux condenser 500mL three-necked ^{_{flask, - CH 2 = CH- (CH}} 2) 2 -CO 2
Cuprous bromide (1.50 g, 10.5 mmol
l), pentamethyldiethylenetriamine (0.69 mL) as a ligand, diethyl-2,5-dibromoadipate (9.42 g, 26.2 mol) as an initiator, and acetonitrile (30 mL) as a solvent. n-butyl (300 mL) in a nitrogen atmosphere at 70 ° C
And a halogen-terminated poly (acrylic acid-
n-butyl). This polymer [2] had a number average molecular weight of 11,300 and a molecular weight distribution of 1.16.

The above-mentioned polymer [2] (5.0 g), the above-mentioned potassium pentenoate (0.12, 8.7 mmol) and dimethylacetamide (10 mL) were charged and reacted at 70 ° C. for 6 hours under a nitrogen atmosphere. I let it. After the volatiles of the mixture were distilled off under reduced pressure, ethyl acetate was added and the insolubles were filtered off. The filtrate [V] was distilled off under reduced pressure to obtain 4.8 g of a polymer [3]. Oligomer -1 alkenyl groups introduced per molecule, from ¹ H NMR analysis, 1.8
There were four. (Example 1) The polymer [1] obtained in Production Example 1 was treated with aluminum silicate (Kyowa Chemical Co., Ltd., Kyoward 700PEL) to remove trace impurities in the polymer. Next, 100 parts of this purified poly (n-butyl acrylate), 10 g of Aerosil (R-974: manufactured by Nippon Aerosil), γ
4 g of glycidoxypropyltrimethoxylane and an average of 5 hydrosilyl groups and an average of 5 α in the molecule
Chain siloxane containing a methylstyrene group and a platinum catalyst (1,1,3,3-tetramethyl-
1,3-divinyldisiloxane complex). (However, the molar ratio of the SiH group of the chain siloxane to the alkenyl group of the polymer = 1.5, and the molar ratio of the platinum atom to the alkenyl group of the polymer = 7 × 10 ⁻⁵ ). This mixture was degassed under reduced pressure, applied on various adherends, and cured by heating at 150 ° C. to obtain a rubber-like cured product. (Example 2) A cured product was produced in the same manner as in Example 1 except that the polymer [3] obtained in Production Example 2 was used instead of the polymer [1] of Example 1. Comparative Example 1 A cured product was prepared in the same manner as in Example 1 except that γ-glycidoxypropyltrimethoxysilane was not used. Comparative Example 2 A cured product was prepared in the same manner as in Example 2 except that γ-glycidoxypropyltrimethoxysilane was not used. (Evaluation) A hand peel test was performed on the cured products of Examples 1 and 2 and Comparative Examples 1 and 3. The results are shown in Table 1.

[0093]

[Table 1] The cured products of Example 1 and Example 2 had good adhesion at the interface, and thus were cohesively broken. On the other hand, the cured products of Comparative Examples 1 and 2 were separated at the interface.

[0094]

According to the present invention, a curable composition having improved adhesiveness, that is, an adhesive curable composition comprising an alkenyl group-containing vinyl polymer, a hydrosilyl group-containing compound and an adhesion promoter as essential components. Things are obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoshiki Nakagawa 1-2-80 Yoshida-cho, Hyogo-ku, Kobe City, Hyogo Prefecture

Claims (9)

[Claims] 1. The following three components: (A) a vinyl polymer having at least one alkenyl group represented by the general formula (1), CH ₂ ＣC (R ¹ )-(1) R ^{1 represents} hydrogen or a methyl group.) An adhesive curable composition comprising (B) a hydrosilyl group-containing compound and (C) an adhesion promoter as essential components. 2. The adhesive curable composition according to claim 1, wherein the molecular weight distribution of the vinyl polymer (A) is less than 1.8. 3. The adhesive curable composition according to claim 1, wherein the vinyl polymer as the component (A) is a (meth) acrylic polymer. 4. The adhesive curable composition according to claim 1, wherein the vinyl polymer as the component (A) is an acrylic polymer. 5. The adhesive curable composition according to claim 1, wherein the vinyl polymer as the component (A) is produced by a living radical polymerization method. 6. The adhesive curable composition according to claim 1, wherein the vinyl polymer as the component (A) is produced by an atom transfer radical polymerization method. 7. The adhesive curing composition according to claim 1, wherein the component (A) is a vinyl polymer having at least one alkenyl group represented by the general formula (1) at the terminal of the molecular chain. Composition. 8. A process for producing a vinyl polymer having a terminal structure represented by the general formula (2) by polymerizing a vinyl monomer by an atom transfer radical polymerization method. , -C (R ² ) (R ³ ) (X) (2) (wherein, R ² and R ³ represent a group bonded to an ethylenically unsaturated group of a vinyl monomer. X represents chlorine, bromine or iodine. (2) A vinyl polymer obtained by converting a terminal halogen of the polymer into a substituent having an alkenyl group represented by the general formula (1). The adhesive curable composition according to the above. 9. The method according to claim 9, wherein the component (A) comprises the following steps: (1) a vinyl polymer is produced by polymerizing a vinyl monomer by a living radical polymerization method;
(2) Subsequently, at least two alkenyl groups having low polymerizability
The adhesive curable composition according to any one of claims 1 to 7, which is a vinyl polymer obtained by reacting a compound having two or more compounds.