JP3112711B2 - Alkenyl ether compounds and uses thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a linear, triple-stranded or quadruple star such as linear polyalkenyl ether, triple-stranded star polyalkenyl ether and quadruple-star polyalkenyl ether. And an adhesive composition, a pressure-sensitive adhesive composition and a room temperature-curable resin composition containing an alkenyl ether compound.

[0002]

2. Description of the Related Art Alkenyl ethers are polymerized only by cationic polymerization. However, in normal cationic polymerization, growing carbon cations are unstable, making it difficult to suppress migration and termination reactions. It was difficult to produce a disperse polymer or block copolymer.

However, the present inventors have proposed that cation-supplying compounds HI and I ₂ , ZnI ₂ or metal halides (ZnI ₂ , ZnBr ₂ , ZnCl ₂ , SnI ₂ , SnI
It has been found that when a binary initiator composed of Cl ₂ , MgCl ₂ , BF ₃ OEt ₂ , and SnCl ₄ ) is used, isobutyl vinyl ether can be subjected to living polymerization to produce a polymer or a block copolymer having a narrow molecular weight distribution (HI / for I _2-based initiator Macromolecules, 19
84, 17 , 3, 265-272 and HI / ZnI2 are described in Macromolecules, 1987, 20 , 11, 269.
3-2696, Macromol for HI / metal halide
ecules, 1989, 22 , 4,1552-1557).

[0004] Linear polyalkenyl ethers, triple-stranded or quadruple-star polymers are polymers having two, three or four branched chains extending from one common center to both sides or radially. It is a polymer having two, three, or four active terminals, and can be applied to various applications by utilizing the physical properties derived from such a unique structure, and is expected as a useful polymer material.

[0005]

However, in the living cationic polymerization of the alkenyl ether, the initiator is an adduct of a monofunctional alkenyl ether and a cation-providing compound. Thus, the synthesis of the linear polyalkenyl ether, triple-stranded star polymer or quadruple-stranded star polymer was impossible.

In view of the above, an object of the present invention is to provide a linear,
An object of the present invention is to provide a novel alkenyl compound having a three- or four-chain star configuration.

Another object of the present invention is to provide an adhesive composition, a pressure-sensitive adhesive composition and a room-temperature adhesive composition containing the above-mentioned linear, three- or four-chain alkenyl ether compound. An object of the present invention is to provide a curable resin composition.

[0008]

The linear, triple-stranded or quadruple-star alkenyl ether compounds according to the present invention have the general formula

[0009]

Embedded image

(Wherein R ¹ is a hydrogen atom or a methyl group,
n is an integer 2, 3 or 4, R ² is a divalent organic group when n is 2, a trivalent organic group when n is 3, a tetravalent organic group when n is 4, R ³ is a hydrogen atom Or a methyl group, R ⁴ is a monovalent organic group, R ⁵ is a divalent organic group containing a nitrogen atom or a sulfur atom , R ⁶ , R ⁷ and R ⁸ are the same or different and are an alkyl group, an aryl group or an alkoxy group. At least one of which is an alkoxy group, x is 1 to 10,000,
(Hereinafter, this means the alkenyl ether compound of the present invention).

The definition of the structural formula of the alkenyl ether compound of the present invention will be described in detail.

R ¹ is a hydrogen atom or a methyl group.

N is an integer 2, 3 or 4.

Specific examples of the divalent organic group as R ² include those shown in Tables 1 and 2 below.

Specific examples of the trivalent organic group as R ² include those shown in Tables 3 to 8 below.

Specific examples of the tetravalent organic group as R ² include those shown in Tables 9 and 10 below.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

[0024]

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

R ³ is a hydrogen atom or a methyl group.

R ⁴ is a monovalent organic group.

Examples of R ⁴ representing a monovalent organic group include the following.

That is, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, tert-butyl, n-pentyl, isopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, 2-ethylbutyl, 1,3-dimethylbutyl,
n-heptyl, isoheptyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, 2-methyloctyl, n-decyl, 1-pentylhexyl,
-Ethyl-1-methyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n
-Alkyl groups such as eicosyl and n-docosyl: cycloalkyl groups such as cyclohexyl: cycloalkylalkyl groups such as cyclohexylmethyl, terpenyl, menthyl, bornyl, isobornyl: benzyl, p-methylbenzyl, p-chlorobenzyl, p-phenyl Aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenylpropyl, 3-phenylpropyl, 1,1-dimethylbenzyl, benzhydryl, 3-phenylpropan-2-yl: cinnamyl, 1-methylcinna Arylalkenyl groups such as mill, 3-methylcinnamyl, 3-phenylcinnamyl, 2-phenylallyl, 1-methyl-2-phenylallyl: phenyl, o
-Tolyl, m-tolyl, p-tolyl, p-tert-butylphenyl, mesityl, p-isohexylphenyl,
p-isooctylphenyl, o-chlorophenyl, m-
Chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl, p-bromophenyl, o-
Aryl groups such as methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl and 2,4-dinitrophenyl: 1-chloroethyl, 2-chloroethyl, 2-bromoethyl , 2-iodoethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-chloropropyl and other haloalkyl groups: methoxyethyl, ethoxyethyl, 2-ethoxyethoxyethyl and other alkoxyalkyl groups, phenoxyethyl, p Aryloxyalkyl groups such as -chlorophenoxyethyl, p-bromophenoxyethyl, p-fluorophenoxyethyl, p-methoxyphenoxyethyl and the like: 2-acetoxyethyl, 2-benzoxyethyl, 2- (p-methoxybenzoxy) ethyl , 2- ( Acyloxyalkyl groups such as -chlorobenzoxy) ethyl and the like: iminoalkyl groups such as 2-phthaliminoethyl and 2- (di-tert-butylcarboxyimino) ethyl: malonyl such as 2-diethylmalonylethyl and 2-diphenylmalonylethyl Alkyl group: Allyloxyalkyl group such as 2-acryloxyethyl, 2-methacryloxyethyl, 2-cinnamyloxyethyl, 2-sorbyloxyethyl and the like.

Examples of the divalent organic group R ⁵ containing a nitrogen atom or a sulfur atom include 3 -aminopropyl, 3-aminobutyl, 3-aminophenyl, 3- (2-aminoethylamino) propyl, and 3-piperazine A divalent organic group containing a nitrogen atom in which both ends of a group such as nopropyl and 3-anilinopropyl are a bond, and a sulfur atom in which both ends of a group such as 3-mercaptopropyl are a bond. And a divalent organic group containing

As the alkyl group represented by R ⁶ , R ⁷ and R ⁸ , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, te
rt-butyl, n-pentyl, isopentyl, 1,2-
Dimethylpropyl, n-hexyl, isohexyl, 2-
Ethylbutyl, 1,3-dimethylbutyl, n-heptyl, isoheptyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, n-nonyl, 2-methyloctyl, n-decyl, 1-pentylhexyl, 4-ethyl- Examples thereof include 1-methyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl and the like.

The aryl group represented by R ⁶ , R ⁷ and R ⁸ includes phenyl, o-tolyl, m-tolyl, p-
Tolyl, p-tert-butylphenyl, mesityl, p
-Isohexylphenyl, p-isooctylphenyl,
o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-bromophenyl, m-bromophenyl,
p-bromophenyl, o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl, o-nitrophenyl, m-nitrophenyl, p-nitrophenyl, 2,
4-dinitrophenyl and the like are exemplified.

The alkoxy groups represented by R ⁶ , R ⁷ and R ⁸ include methoxy, ethoxy, n-propoxy,
Isopropoxy, n-butoxy, isobutoxy, sec
-Butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, 1,2-dimethylpropoxy, n-hexyloxy, isohexyloxy, 2-ethylbutoxy, 1,3-dimethylbutoxy, n-heptyloxy, iso- Heptyloxy, n-octyloxy,
1-methylheptyloxy, 2-ethylhexyloxy, n-nonyloxy, 2-methyloctyloxy, n
-Decyloxy, 1-pentylhexyloxy, 4-ethyl-1-methyloctyloxy, n-dodecyloxy, n-tetradecyloxy, n-hexadecyloxy, n-octadecyloxy, n-eicosyloxy,
Examples are n-docosyloxy and the like.

X is 1 to 10000, preferably 1 to 10
00.

Next, a method for producing an alkenyl ether according to the present invention will be described.

The alkenyl ether of the present invention has the general formula

[0038]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
n is an integer 2, 3 or 4, R ² is a divalent organic group when n is 2, a trivalent organic group when n is 3, and a tetravalent organic group when n is 4) Using an adduct of a polyfunctional alkenyl ether represented by the formula and a cation-providing compound as an initiator, (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group, respectively), and then produced by introducing an alkoxysilyl group to the polymer terminal. .

First, a method for producing a linear compound will be described.

General formula CHR ¹ ＣＨCH—O—R ² —O—CH ＝ CHR ¹ (Ia) wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent organic group. Using an adduct of a bifunctional alkenyl ether represented by (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group, respectively), and then an alkoxysilyl group is introduced into a terminal of the polymer.

[0042]

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(Where x is 1 to 10,000, R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same meaning as described above).

Next, a method for producing a three-stranded star compound will be described.

General formula (Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a trivalent organic group) and an adduct of a cation-providing compound and a trifunctional alkenyl ether represented by the general formula: (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group, respectively), and then an alkoxysilyl group is introduced into a polymer terminal to obtain a compound represented by the general formula:

[0046]

Embedded image

(Where x is 1 to 10000, R ¹ ,
Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same meaning as described above).

Next, a method for producing a four-stranded star compound will be described.

General formula

[0050]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² represents a tetravalent organic group), and an adduct of a tetrafunctional alkenyl ether represented by (Wherein, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group, respectively), and then an alkoxysilyl group is introduced into a polymer terminal to obtain a compound represented by the general formula:

[0052]

Embedded image

(Where x is 1 to 10,000, R ¹ ,
^{R 2, R 3, R 4} , R 5, R 6, R 7 and R ⁸ to produce a quadruplex star alkenyl ether represented by have the same meaning as above).

In the production of the linear compound, specific examples of the bifunctional alkenyl ether [Ia] are those described in Tables 1 and 2 above.

Specific examples of the trifunctional alkenyl ether [Ib] in the production of the three-chain star compound are shown in Tables 3 to 8 above.
It is described in.

Among the bifunctional alkenyl ethers [Ia] and the trifunctional alkenyl ethers [Ib], those compounds in which the group R ² has an ether bond can be prepared, for example, by converting the corresponding bifunctional alcohol and trifunctional alcohol into dimethyl sulfoxide, respectively. And chloroethyl vinyl ether or chloroethyl propenyl ether in the presence of sodium hydroxide.

Further, bifunctional alkenyl ether [Ia]
And the trifunctional alkenyl ether [Ib]
^The compound in which ² has an ester bond is, for example, 2-hydroxyethyl vinyl ether or 2-hydroxyethyl propenyl ether is converted into a sodium salt with sodium hydroxide or sodium hydride in toluene,
It is obtained by reacting this with the corresponding trifunctional carboxylic acid chloride.

In the production of the four-chain star compound, specific examples of the tetrafunctional alkenyl ether [Ic] are shown in Tables 9-1.
0.

The tetrafunctional alkenyl ether [Ic] is obtained, for example, by reacting tetrakis (4-hydroxyphenyl) cyclohexane with chloroethyl vinyl ether or chloroethyl propenyl ether in dimethyl sulfoxide in the presence of sodium hydroxide. can get.

In the present production method, examples of the cation supply compound include CF ₃ COOH, CCl ₃ COOH,
H ₃ COOH, HCOOH, H ₃ PO ₄ , HOPO (O
C ₄ H ₇ ) ₂ , HOPO (OC ₆ H ₅ ) ₂ , HOPO
(C ₆ H ₅ ) ₂ , HI, HCl, HBr and the like.

In this method, an adduct of a polyfunctional alkenyl ether [I] and a cation-supplying compound, that is, an adduct of a bifunctional alkenyl ether [Ia] and a cation-supplying compound, and a trifunctional alkenyl ether [Ib] and a cation-supplying compound An adduct of a compound or an adduct of a tetrafunctional alkenyl ether [Ic] and a cation-providing compound is used as an initiator. When the cation-providing compound is represented by HA, this adduct has the general formula

[0062]

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(Wherein R ¹ , R ² and n have the same meanings as described above, and A means the cation supply residue of the cation supply compound).

As a general method for synthesizing the adduct [IV], an inert solvent such as carbon tetrachloride, n-hexane or toluene (preferably the same as the polymerization reaction solvent) at room temperature under a nitrogen stream is used. An example is a method in which a polyfunctional alkenyl ether [I] is dissolved therein, and an equivalent amount of the cation-providing compound HA is added thereto for reaction. Bifunctional alkenyl ether [Ia] used and cation-providing compound H
The molar ratio of the trifunctional alkenyl ether [Ib] to the cation-supplying compound HA is substantially 1: 3, and the molar ratio of the trifunctional alkenyl ether [Ib] to the cation-providing compound HA is substantially 1: 2. The molar ratio with the feed compound is substantially 1: 4. The reaction temperature is usually set appropriately in the range of -90C to 100C. The reaction pressure is usually normal pressure,
Pressurization is also possible. Reaction time is 10 seconds to 24
Time, preferably 5 minutes to 1 hour. According to this synthesis method, the reaction proceeds quickly and the adduct [I
V]. Further, the adduct [I
V] may be isolated, but it is also possible to subject it to polymerization in the state of the above solution without isolation.

Since the degree of polymerization of the polymer is determined by the molar ratio of the olefin compound [II] to the adduct [IV] (100% conversion), the amount of the adduct [IV] used is important. The molecular weight can be set by determining the molar ratio between the olefin compound [II] and the adduct [IV] according to the desired degree of polymerization. The molar ratio is 2 or more when a double-stranded star compound is obtained, 3 or more when a triple-stranded star compound is obtained, and 4 or more when a four-stranded star compound is obtained. Is appropriately determined according to the conditions.

The alkenyl ethers [II] may be used alone or in combination of two or more.

In the method using alkenyl ether [II], it is preferable to adopt a method for promoting polymerization (living polymerization), and the following two methods are available.

The first method is a method in which a side reaction is prevented by protecting the growing carbon cation with a Lewis base, and living polymerization is carried out using an organoaluminum as a catalyst. The second method is a counter anion to the growing carbon cation. Is a method in which the nucleophilicity of is controlled by a Lewis acid to prevent side reactions and to perform living polymerization.

These methods will be described in more detail.

In the first method, an organoaluminum represented by the following general formula [V] is used as a catalyst in the presence of a Lewis base.

R ⁹ _r AlX _s [V] (wherein R ⁹ represents a monovalent organic group, X represents a halogen atom, r and s are integers, r + s = 3, and 0 ≦ r
<3, 0 ≦ s <3. Examples of the organic aluminum compound [V] include, for example, trichloroaluminum, tribromoaluminum, ethylaluminum dichloride, ethylaluminum dibromide, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum diiodo, ethylaluminum difluoride, methyl Aluminum dichloride, methylaluminum dibromide, dimethylaluminum chloride, dimethylaluminum bromide and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more kinds. The amount of the organoaluminum compound is generally in the range of olefin [II] / organoaluminum compound [V] = 2 to 10,000 in molar ratio, Preferably 10-5
000.

Specific examples of the coexisting Lewis base include, for example, ethyl acetate, n-butyl acetate, phenyl acetate, ethyl benzoate, ethyl p-chlorobenzoate and p-chlorobenzoate.
-Ester compounds such as ethyl methyl benzoate, ethyl p-methoxy benzoate, methyl acetate, isopropyl acetate, and t-butyl acetate: 1,4-dioxane, diethyl ether, tetrahydrofuran, di-n-hexyl ether, diisopropyl ether, diisopropyl ether -N-butyl ether, methoxytoluene, propylene oxide, 1,2-
Ether compounds such as diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and acetal: pyridine;
2,6-dimethylpyridine, 2-methylpyridine, 2,
Examples thereof include pyridine derivatives such as 4,6-trimethylpyridine, 2,4-dimethylpyridine, and 2,6-di-t-butylpyridine.

These Lewis bases can be used alone or in combination of two or more. These can be used in a bulk state or in a solution state in an inert solvent. These Lewis bases are added to the reaction system in an amount according to the basicity of the Lewis base within the following relationship between the amount of the Lewis base used and the amount of the alkenyl ether [I] used.

0.001 ≦ used amount of Lewis base / used amount of polyfunctional alkenyl ether [I] ≦ 100 In the above relationship, the ratio of the used amount of Lewis base to the used amount of polyfunctional alkenyl ether [I] is: When it is less than 0.001, or when it exceeds 100, it is difficult to obtain a complete living system, which is not preferable.

In the second method, a Lewis acid is used to appropriately activate a counter anion to a growing carbon cation. Examples of the Lewis acid include iodine, zinc (II) halide, and halogen (II). And tin (II) oxide. Particularly, I ₂ , ZnI ₂ , ZnBr ₂ , ZnC
l ₂ , SnI ₂ and SnCl ₂ are preferably used. The Lewis acids are used alone or in combination of two or more. The amount used is generally such that the molar ratio of polyfunctional alkenyl ether [I] / Lewis acid is in the range of 2 to 100,000, preferably 10 to 10,000.

In the present invention, the polymerization reaction forms include:
Usually, a solution polymerization method is employed, but a bulk polymerization method or the like can also be employed. In solution polymerization, as a solvent,
n-hexane, cyclohexane, benzene, toluene,
An inert solvent such as carbon tetrachloride or ethylene chloride is used. The reaction temperature is appropriately set usually in the range of -40C to 100C. The reaction pressure is usually normal pressure, but can be increased. The reaction time is 3 seconds to 7 days, preferably 1 minute to 24 hours.

The following two methods are exemplified as a method for introducing an alkoxysilyl group into a polymer terminal.

I) As a terminator, a general formula

[0079]

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(Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same meanings as described above), and the polymerization reaction is stopped.

Such terminating agents include the following substances: 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 4-aminobutyltriethoxysilane, P-aminophenyltrimethoxysilane,
3- (2-aminoethylamino) propyldimethoxymethylsilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, P-aminophenyltriethoxysilane,
3-piperazinopropyltrimethoxysilane, 3-piperazinopropylmethyldimethoxysilane, P-aminophenylmethyldimethoxysilane, P-aminophenylmethyldiethoxysilane, P-aminophenyldimethylmethoxysilane, P-aminophenyldimethyl Ethoxysilane, 3-aminopropylmethyldimethoxysilane, 3
Amines such as aminopropylmethyldiethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropyldimethylethoxysilane, and 3-anilinopropyltrimethoxysilane;

Thiols such as dimethoxy-3-mercaptopropylmethylsilane and 3-mercaptopropyltrimethoxysilane .

[0083]

Ii) In the second method, after introducing an unsaturated group into the polymer terminal, the unsaturated group is added to the unsaturated group in the presence of a platinum-based catalyst.

[0085]

Embedded image

Wherein R ⁶ , R ⁷ and R ⁸ have the same meanings as described above, respectively.

As a method for introducing an unsaturated group into the polymer terminal, amines having an unsaturated group such as an allyl group,
There is a method of terminating polymerization with thiols .

The degree of polymerization x in the alkenyl ether compound of the present invention is from 1 to 10,000, preferably from 4 to 5,000,
More preferably, it is in the range of 10 to 1,000.

The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight of the alkenyl ether compound of the present invention is preferably from 1 to 1.3.

Since the alkenyl ether compound of the present invention is cross-linked and cured by moisture in the air, it is preferable to store it in a moisture-free state until it is used.

Next, the use of the alkenyl ether compound of the present invention will be described.

A) The first use of the alkenyl ether compound of the present invention is as an adhesive composition which is applied to a substrate without a solvent, has excellent tackiness before curing, and becomes a strong adhesive after curing. About.

Conventionally, adhesives used in the fields of building materials, electronic materials, automobile parts and the like often contain solvents such as rubber-based adhesives. However, it is desirable that these adhesives be solvent-free in view of problems such as air pollution of the used solvents, danger of fire, and toxicity to human bodies.

To meet these demands, many solventless adhesives have been developed. For example, hot melt adhesives of polyolefin resins and solventless reactive adhesives mainly composed of epoxy resins and urethane resins have been reported.

However, in the former, temporary bonding cannot be performed, and in the latter, there are many two-pack types of a main agent and a curing agent, which are disadvantageous in that workability is poor and temporary bonding cannot be performed. .

According to the present invention, there is provided an adhesive which is of a solventless type and has a balance between the adhesive strength and the adhesive strength before curing and has a high peeling adhesive strength after curing.

The adhesive composition according to the present invention comprises the alkenyl ether compound of the present invention and an epoxy resin.

In the adhesive composition according to the present invention, the alkenyl ether compound of the present invention is preferably a compound in which an alkoxysilyl group is introduced into a polymer terminal using the amines or thiols exemplified above as the terminating agent. . In such an alkenyl ether compound, an amino group or a thiol reacts with the epoxy resin to form a strong crosslinked product.

In curing the composition of the present invention, it is preferable to use a catalyst which promotes curing. As the catalyst, a silanol condensation catalyst is effectively used. SB-65, DT of Shared Equipment Co., Ltd.
L, No. 2377, RG-40FT, and dibutyltin phthalate catalyst) are preferred.

The epoxy resin has at least two epoxy groups in the molecule. Examples thereof include bisphenol A type, bisphenol F type, and tetrabromobisphenol A type epoxy resins and hydrogenated products thereof, and aliphatic epoxy resins. , Polyglycol-type epoxy resin, polybutadiene-modified epoxy resin, novolak-type epoxy resin, and the like.

The mixing ratio of the epoxy resin is preferably 5 to 100 parts by weight of the alkenyl ether compound of the present invention.
To 100 parts by weight, more preferably 10 to 80 parts by weight. If the amount of the epoxy resin is too small, the curing becomes insufficient, and if the amount is too large, the resin tends to flow at a low temperature.

In order to change the curing temperature and the curing time, N, N'-dimethylaniline, N, N'-dimethylparatoluidine, triethylamine, triethanolamine, triethylenetetramine, isophoronediamine,
A curing aid such as 2,4,6-tris (dimethylaminomethyl) phenol, trimethylenetetramine, ancamine and dicyandiamide may be added.

The adhesive composition according to the present invention comprises a filler,
It is also possible to optionally add additives such as a tackifier, a plasticizer and an antioxidant.

B) A second use of the alkenyl ether compound of the present invention relates to a pressure-sensitive adhesive excellent in tackiness, adhesion and cohesion.

Conventionally, as a pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive mainly composed of a natural rubber or a synthetic rubber and containing a tackifier resin, a softener, a filler and the like, and an acrylic ester are mainly used. An acrylic pressure-sensitive adhesive obtained by copolymerizing a polar monomer represented by acrylic acid as a monomer is widely used for packaging, stationery, medical use, industrial use, and the like.

Among them, the rubber-based rubber has the advantage that it can be adhered to a relatively large number of adherends, but has the durability (weather resistance, weather resistance, etc.) due to the double bond of the diene portion of the rubber as the main component.
Heat resistance) and has the disadvantage that it cannot be used in the permanent or semi-permanent adhesive field.

On the other hand, acrylic materials have been increasingly used in recent years, taking advantage of their excellent weather resistance. However, in the case of an acrylic resin, its weight average molecular weight is 10 due to problems in the conventional polymerization technology and coating technology.
It had to be less than 10,000. Therefore, it was possible to obtain an acrylic pressure-sensitive adhesive having excellent tackiness and adhesive strength, but only very poor holding power, that is, cohesive strength was obtained.

As a means for compensating for the lack of cohesion, it is conceivable to add a composition which is crosslinked by moisture to the acrylic copolymer.

According to the present invention, there is provided a pressure-sensitive adhesive composition which solves the drawbacks of the above-mentioned conventional acrylic pressure-sensitive adhesives, achieves an appropriate cross-linked structure, and is excellent in tackiness, adhesion and cohesion. Provided.

The pressure-sensitive adhesive composition according to the present invention comprises the alkenyl ether compound of the present invention and a (meth) acrylate copolymer.

In curing the composition of the present invention, it is preferable to use a catalyst that promotes curing. As the catalyst, a silanol condensation catalyst is effectively used. SB-65, DT of Shared Equipment Co., Ltd.
L, No. 2377, RG-40FT, and dibutyltin phthalate catalyst) are preferred.

Examples of the (meth) acrylate in the copolymer containing the (meth) acrylate as a polymer constituent unit include, for example, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate , Lauryl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, lauryl acrylate, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate, Examples include methyl methacrylate and methyl acrylate. Further, a monomer copolymerizable with the above main monomer, for example, sretine, vinyl acetate, acrylonitrile, acrylamide, maleic anhydride, acrylic acid, methacrylic acid, etc. may be copolymerized.

The proportion of the (meth) acrylate copolymer is preferably 5 to 1000 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the alkenyl ether compound of the present invention. If the amount of the (meth) acrylic acid ester copolymer is too small, the strength becomes insufficient, and if it is too large, the curing becomes insufficient.

The pressure-sensitive adhesive composition according to the present invention may optionally contain additives such as a tackifying resin, a filler, a plasticizer, and an antioxidant.

C) A third use of the alkenyl ether compound of the present invention is a type in which the alkenyl ether compound is applied to a substrate without a solvent and is cured by contact with moisture on the substrate, and has excellent cohesive strength, tackiness and durability. Pressure-sensitive adhesive.

Conventional rubber-based or acrylic pressure-sensitive adhesives are all dissolved in an organic solvent.
When this is applied to a substrate, there is a drawback in that the removal or recovery of the solvent is costly. Therefore, a solventless pressure-sensitive adhesive is desired.

According to the present invention, there is provided a solvent-free pressure-sensitive adhesive composition excellent in cohesive strength, tackiness and durability.

The pressure-sensitive adhesive composition according to the present invention comprises the alkenyl ether compound of the present invention and a tackifier.

In curing the composition of the present invention, it is preferable to use a catalyst that promotes curing. As the catalyst, a silanol condensation catalyst is effectively used. SB-65, DT of Shared Equipment Co., Ltd.
L, No. 2377, RG-40FT, and dibutyltin phthalate catalyst) are preferred.

Examples of the tackifying resin include rosin (rosin, modified rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin ester, rosin glycerin ester) and polyterpene (α-pinene polymer, β-pinene polymer, terpene). -Phenol copolymer, α-pinene-phenol copolymer) and petroleum resin (indene, styrene, methylindene, α-methylstyrene, isoprene, cyclopentadiene, 1,3-pentadiene, 1-pentene, 2-pentene, dipentene) Cyclopentadiene, homo- and copolymers of 1,3-pentadiene) and the like. These tackifying resins may be used alone or in combination of two or more.

The mixing ratio of the tackifier is preferably 5 to 100 parts by weight of the alkenyl ether compound of the present invention.
To 100 parts by weight, more preferably 10 to 80 parts by weight. If the amount of the tackifying resin is too small, the tackiness becomes insufficient, and if it is too large, the resin flows at a low temperature.

The pressure-sensitive adhesive composition according to the present invention may optionally contain additives such as a filler, a plasticizer, and an antioxidant.

D) A fourth application of the alkenyl ether compound of the present invention relates to a room temperature-curable resin composition which can be cured at room temperature to an elastic material when exposed to moisture. The composition can be used as a room temperature-curable elastic sealing agent.

The silicone-based room-temperature-curable elastic sealing materials are roughly classified into silicone-based and modified silicone-based sealing materials, but these have many problems. With respect to silicone-based sealing, paint has poor adhesion, and contamination due to oozing of silicone into the base is remarkable. Further, a modified silicone system composed of a propylene oxide polymer cannot be used for glass because the adhesion to a glass surface is significantly deteriorated by sunlight (Japanese Patent Publication Nos. 61-18570 and 61-18852, and Sealing Manufacturers Association: See Sealant Handbook).

According to the present invention, a high-performance room-temperature-curable resin composition is provided.

The room temperature-curable resin composition of the present invention contains the alkenyl ether compound of the present invention as a main component.

In curing the composition of the present invention, it is preferable to use a catalyst which promotes curing. As the catalyst, a silanol condensation catalyst is effectively used. SB-65, DT of Shared Equipment Co., Ltd.
L, No. 2377, RG-40FT, and dibutyltin phthalate catalyst) are preferred.

By adding various fillers to the composition of the present invention, a cured composition having high strength can be obtained. Examples of the filler include calcium carbonate, magnesium carbonate, hydrated silicic acid, silicic anhydride, calcium silicate / silica, carbon black, titanium dioxide, clay, and talc. These fillers may be used alone,
Two or more types may be used.

Further, by adding a plasticizer to the composition of the present invention, the elongation of the cured product can be increased and a large amount of filler can be mixed. Examples of the plasticizer include phosphate esters such as tributyl phosphate and tricresyl phosphate; phthalate esters such as dioctyl phthalate and di-2-ethylhexyl phthalate; aliphatic monobasic acid esters such as glycerin monooleate; and adipine. Dibutyl acid, di-adipate
aliphatic dibasic acid esters such as n-hexyl; dihydric alcohol esters such as triethylene glycol di-2-ethylbutyrate; oxyacid esters such as tributyl acetylcitrate; chlorinated paraffin; methyl abietic acid; . These can be used alone or in combination of two or more.

The composition of the present invention may optionally contain additives such as pigments and antioxidants.

The composition obtained according to the present invention is useful as an elastic sealing material and can be used as a sealing material for buildings and automobiles.

[0132]

According to the present invention, it is possible to obtain a linear compound or a star compound having two, three or four chains of uniform length and a narrow molecular weight distribution.

According to the present invention, it is possible to obtain an adhesive which is of a solventless type, has a good balance between the adhesive strength and the adhesive strength before curing, and has a large peeling adhesive strength after curing.

According to the present invention, it has an appropriate crosslinked structure,
A pressure-sensitive adhesive composition having excellent tackiness, adhesion and cohesion can be obtained.

According to the present invention, it is possible to obtain a solvent-free pressure-sensitive adhesive composition excellent in cohesive strength, tackiness and durability.

Further, according to the present invention, a high-performance room-temperature-curable resin composition can be obtained.

[0137]

Embodiments of the present invention will be described below. In the following examples, the molar concentration (mol / l) indicates the mol of the compound used with respect to the total volume of the polymerization reaction system, and the weight average molecular weight Mw, number average molecular weight Mn, and ratio Mw / Mn are light scattering gel permeation.・ Chromatography GPC (Tosoh “LS8000 system”, column; Showa Denko “Polystyrene gel KF-802, KF-803, K”
F-804; inner diameter 8 mm, length 300 mm).
The chemical structure of the polymer is ¹ H-NMR (GSX manufactured by JEOL Ltd.
-270, 270 MHz). For infrared absorption, use an infrared spectrophotometer (Hitachi Ltd., "270-30")
The melting point is a trace melting point measuring device (Yanagimoto Seisakusho, "MP-S
₃ )).

The adduct of the polyfunctional alkenyl ether [I] and the cation-providing compound used in each Example was obtained at room temperature.
Dissolve the polyfunctional alkenyl ether [I] in an inert solvent (same as the polymerization reaction solvent) which has been sufficiently purified and dried under a nitrogen stream, add an equivalent amount of the cation supply compound HA thereto, and stir for 15 minutes. Prepared by the following method. The obtained adduct was subjected to a polymerization reaction in a solution without isolation.

Reference Examples 1 to 3 relate to the preparation of polyfunctional alkenyl ether, Examples 1 to 19 relate to the preparation of the alkenyl ether compound of the present invention, and Examples 20 to 27 and Comparative Examples 1 to 4 correspond to the adhesive composition. Examples 28 to 3
5 and Comparative Examples 5 to 8 relate to a pressure-sensitive adhesive composition, Examples 36 to 44 and Comparative Examples 9 to 10 relate to another pressure-sensitive adhesive composition, and Examples 45 to 53 and Comparative Examples 11 to 12. Relates to a room temperature-curable resin composition.

Reference Example 1 (Preparation of trifunctional alkenyl ether) 9.96 g (113 mmol) of 2-hydroxyethyl vinyl ether in 50 ml of toluene under a nitrogen atmosphere in a glass three-necked flask equipped with a condenser and a stirrer.
Was dissolved, and 2.71 g of sodium hydride powder was added to the solution.
(113 mmol) was added and the solution was stirred at room temperature for 1 hour. Then, 10.0 g of trimesic acid chloride was added to this solution.
(33.7 mmol) and 0.5 g of tetra-n-butylammonium chloride were added and reacted at 80 ° C. for 4 hours. After the reaction mixture was extracted with diethyl ether, the extract was dried to obtain crude crystals. This is toluene /
Recrystallization from hexane (1: 1) gave tri (2-vinyloxy) ethyl 1,3,5-benzenetricarboxylate (first compound in Table 3). Yield: 62%, melting point: 32-
34 ° C (pale yellow crystal), infrared absorption spectrum (Nujol):
ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm ⁻¹ .

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured:

[0142]

Embedded image

Δ (ppm): peak c 4.00 (t, 6H, —CH ₂
−) E 4.00 and 4.15 (dd, 6H, = CH ₂ ) b 4.50 (t, 6H, —CH ₂ −) d 6.30 (dd, 3H, = CH) a 8.80 (s, 3H, aromatic) Reference Example 2 (Preparation of trifunctional alkenyl ether) 75 ml of dimethyl sulfoxide in a three-neck glass flask equipped with a condenser and a stirrer under a nitrogen atmosphere.
Was dissolved in 10.0 g (32.6 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane, and 23.5 g (587 mmol) of sodium hydroxide powder was added to the solution. Stir for 3 hours. Then, 59.7 ml of 2-chloroethyl vinyl ether (58
7 mmol) and reacted at 80 ° C. for 5 hours.
The reaction mixture was purified in the same manner as in Reference Example 1, and 1,1,1
-Tris [4- (2-vinyloxy) ethoxyphenyl]
Ethane (the second compound in Table 4) was obtained. Yield: 62
%, Melting point: 92-93 ° C. (pale yellow crystal), infrared absorption spectrum (Nujol): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 83
0 cm ^-1 .

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured:

[0145]

Embedded image

Δ (ppm): peak a 2.05 (s, 3H, CH ₃ ) d 4.00 (t, 6H, —CH ₂ —) e 4.15 (t, 6H, —CH ₂ —) g 4.00 and 4.25 (dd, 6H, = CH ₂ ) f 6.50 (dd, 3H, = CH) b 6.80 (d, 6H, aromatic) c 7.00 (d, 6H, aromatic) Reference Example 3 (Preparation of tetrafunctional alkenyl ether) Condenser and stirrer 75 ml of dimethyl sulfoxide in a glass three-necked flask equipped with
Was dissolved in 10.0 g (22.1 mmol) of 1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane, and 21.2 g of sodium hydroxide powder was added to the solution.
(30 mmol) was added and the solution was stirred at 75 ° C. for 3 hours. Then, 53.9 ml (530 mmol) of 2-chloroethyl vinyl ether was added to the solution, and the mixture was reacted at 80 ° C. for 5 hours. The reaction mixture was purified in the same manner as in Reference Example 1 to give 1,1,4,4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane (1 in Table 9).
Th compound) was obtained. Yield: 48%, melting point: 137.
5 to 139 ° C (pale yellow crystal), infrared absorption spectrum (Nuj
ol): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm ⁻¹ .

[0147]

Embedded image

¹ H NMR spectrum (270 MHz, C
Measured value of DCl ₃ ): δ (ppm): peak a 2.25 (m, 8H, cyclohexane ring) d 4.00 (t, 8H, —CH ₂ −) e 4.15 (t, 8H, —CH ₂ −) g 4.00 4.25 (dd, 8H, = CH ₂ ) f 6.50 (dd, 4H, = CH) b 6.80 (d, 8H, aromatic) c 7.00 (d, 8H, aromatic) Example 1 Purification sufficiently under nitrogen atmosphere Dried n-hexane 1.5
2.0 ml of isobutyl vinyl ether
(3.0 mol / l), and 0.5 ml (1.2
Mol / l) of 1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. There, an adduct of 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (the compound of Reference Example 2) diluted with n-hexane and trifluoroacetic acid (CF ₃ COOH) was added. 5 ml (1.7
(Mmol / l) and 0.5 ml (5.0 mmol / l) of a hexane solution of ethylaluminum dichloride were added in this order to start polymerization, and the polymerization was continued at 0 ° C for 3 hours. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a three-chain star-shaped polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.04) was obtained. This value of Mn was in good agreement with the calculated value of 1.8 × 10 ^{5, which} is assumed to produce three chain molecules from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, C
Measured value of DCl ₃ ): <Trifunctional initiator>

[0151]

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Δ (ppm): peak g 1.50 (s, 9H, CH ₃ ) a 2.05 (s, 3H, CH ₃ ) d + e 4.00 (m, 12 H, —CH ₂ −) f 6.15 (q, 3H, CH) b 6.70 (d, 6H, aromatic) c 6.90 (d, 6H, aromatic) <Alkoxysilyl terminal triple-chain polyvinyl ether>

[0153]

Embedded image

Δ (ppm): peak o 1.00 (9H, CH ₃ ) m 0.50 to 2.50 (18 H, —CH ₂ −) k 0.90 (18 × H, CH ₃ ) f 1.20 (9 H, CH ₃ ) g + j 1.40 to 2.00 ( 9 × H, —CH ₂ —) a 2.10 (3H, CH ₃ ) l 2.50 (24 H, piperazine ring) d, e, h, i 3.00 to 4.00 n 3.55 (18H, OCH ₃ ) c 4.10 (6H, —CH ₂ −) B) 6.75 to 7.00 (12H, aromatic) Example 2 Polymerization was carried out in the same manner as in Example 1, and then 1 ml
Was stopped by adding P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a three-chain star polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.04) was obtained. This value of Mn was in good agreement with the calculated value of 1.8 × 10 ^{5, which} is assumed to produce three chain molecules from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, CD
Cl ₃ ): <Terminal alkoxysilyl triple-chain polyvinyl ether>

[0157]

Embedded image

Δ (ppm): peak o 1.00 (9H, CH ₃ ) k 0.90 (18 × H, CH ₃ ) f 1.20 (9 H, CH ₃ ) g + j 1.40 to 2.00 (9 × H, —CH ₂ −) a 2.10 (3H, _{CH 3) d, e, h} , i, l 3.00~4.00 n 3.55 (18H, OCH 3) c 4.10 (6H, -CH 2 -) b 6.75~7.00 (12H, aromatic) m 7.30 (12H, aromatic Example 3 50 ml of ethyl vinyl ether was dissolved in 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere.
5 ml of 1,4-dioxane are added and the temperature of the solution is reduced to 0.
C. was maintained. 2,2-Bis (4-vinyloxyethoxyphenyl) propane (first compound in Table 1) diluted with toluene and trifluoroacetic acid (CF ₃ COO)
5 ml of a 1 mol / l toluene solution of the adduct with H) and 5 ml of a 1 mol / l hexane solution of ethylaluminum dichloride were added in this order to initiate polymerization.
For 3 hours. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropyltrimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to obtain a viscous liquid. As a result, polyethyl vinyl ether having a trimethoxysilyl group at both terminals (Mn = 740)
0, Mw / Mn = 1.03).

¹ H NMR spectrum (270 MHz, CD
Measured value of Cl ₃ ): <Terminal alkoxysilyl telechelic polyvinyl ether>

[0160]

Embedded image

Δ (ppm): peak l 0.50 to 2.50 (12
H, —CH ₂ —) f 1.20 (6H, CH ₃ ) j 1.20 (6 × H, CH ₃ ) g 1.40 to 2.00 (4 × H, —CH ₂ —) a 2.10 (6H, CH ₃ ) k 2.50 (16H, piperazine ring) ) D, e, h, i 3.00 to 4.00 m 3.55 (18H, OCH ₃ ) c 4.10 (4H, —CH ₂ —) b 6.75 to 7.00 (8H, aromatic) Example 4 In the same manner as in Example 3, After polymerization, 1 ml
Was stopped by adding P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, polyethyl vinyl ether having a methyldimethoxysilyl group at both terminals (Mn = 740)
0, Mw / Mn = 1.03).

¹ H NMR spectrum (270 MHz, CD
Measured value of Cl ₃ ): <Terminal alkoxysilyl telechelic polyvinyl ether>

[0164]

Embedded image

Δ (ppm): peak n 1.00 (6H, CH ₃ ) f 1.20 (6 H, CH ₃ ) j 1.20 (6 × H, CH ₃ ) g 1.40 to 2.00 (4 × H, —CH ₂ —) a 2.10 (6H, CH ₃ −) CH ₃ ) d, e, h, i, l 3.00 to 4.00 m 3.55 (12H, OCH ₃ ) c 4.10 (4H, —CH ₂ —) b 6.75 to 7.00 (8H, aromatic) m 7.30 (8H, aromatic Example 5 n-hexane 1.5 fully purified and dried under a nitrogen atmosphere
2.0 ml of isobutyl vinyl ether
(3.0 mol / l), and 0.5 ml (1.2
Mol / l) of 1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. There, 1, diluted with n-hexane
Tri (2-vinyloxyethyl) 3,5-benzenetricarboxylate (compound of Reference Example 2) and trifluoroacetic acid (C
0.5 ml (1.7 mmol / 1) of an adduct with F3 COOH) and 0.5 ml (5.0 mmol / l) of a hexane solution of ethylaluminum dichloride were added in this order to initiate polymerization. The polymerization was continued at 3 ° C. for 3 hours. Thereafter, the polymerization was stopped by adding 1 ml of P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a three-branched star-type polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.04) was obtained. This value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁵ where three side chain molecules were generated from one molecule of the adduct.

¹ H NMR spectrum (270 MHz, CD
Cl ₃ ): <Trifunctional initiator>

[0168]

Embedded image

¹ H NMR δ (ppm): peak e 1.50 (s, 9 H, CH ₃ ) c 4.00 (m, 6 H, —CH ₂ ) b 4.50 (m, 6 H, —CH ₂ ) d 6.10 (q, 3 H, CH) a 8.80 (s, 3H, aromatic) <alkoxy terminal silyl tri-chain polyvinyl ether>

[0170]

Embedded image

Δ (ppm): peak n 1.00 (9H, CH ₃ ) j 1.20 (18 × H, CH ₃ ) f + i 1.40 to 2.00 (9 × H, —CH ₂ —, CH) c, d, g, h, k 3.00 to 4.00 m 3.55 (18H, OCH ₃ ) b 4.50 (6H, -CH _2- ) l 7.30 (12H, aromatic) a 8.80 (3H, aromatic) Example 6 Polymerization was carried out in the same manner as in Example 1, Then 1ml
When the polymerization was terminated by the addition of allylamine, a three-chain polyisobutyl vinyl ether having an allyl group at each terminal (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.03)
was gotten. Here, 1.0 g of methyldimethoxysilane
And 1.0 ml of a solution of chloroplatinic acid in isopropanol / tetrahydrofuran (containing 0.001 g of chloroplatinic acid), and reacted at 80 ° C. for 3 hours. As a result, at each end, A three-branched star-type polyisobutyl vinyl ether having the following structural formula having a group was obtained.

[0172]

Embedded image

O 1.00 (9H, CH ₃ ) m 0.50 to 2.50 (18 H, —CH ₂ −) δ (ppm): peak k 0.90 (18 × H, CH ₃ ) f 1.20 (9 H, CH ₃ ) g + j 1.40 to 2.00 ( 9 × H, —CH ₂ —) a 2.10 (3H, CH ₃ ) d, e, h, i, l 3.00 to 4.00 n 3.55 (18H, OCH ₃ ) c 4.10 (6H, —CH ₂ −) b 6.75 to 7.00 ( 12H, aromatic) Example 7 50 ml (3.0 mol / l) of isobutyl vinyl ether was dissolved in 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere, and 25 ml of 1,4-dioxane was added thereto. The temperature of the solution was kept at 0 ° C. There, 1,1,4,4-tetrakis [4- (2-
Vinyloxy) ethoxyphenyl] 1 mol / adduct of cyclohexane and trifluoroacetic acid (CF ₃ COOH)
1 ml of a toluene solution (40 mmol / l) and 5 ml of a 1 mol / l hexane solution of ethylaluminum dichloride were added in this order to initiate polymerization.
The polymerization was continued for 0 minutes. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to obtain a viscous liquid.

Thus, a four-chain polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn
= 7400, Mw / Mn = 1.05).

¹ H NMR spectrum (270 MHz, CD
Cl ₃ ): <Tetrafunctional initiator>

[0176]

Embedded image

Δ (ppm): peak g 1.50 (s, 12H, CH ₃ ) a 2.25 (m, 8H, cyclohexane ring) d + e 4.00 (m, 16H, —CH ₂ —) f 6.15 (q, 4H, CH) b 6.70 (d, 8H, aromatic) c 6.90 (d, 8H, aromatic) <alkoxy terminal silyl quadruplex polyisobutyl vinyl ether>

[0178]

Embedded image

Δ (ppm): peak m 0.50 to 2.50 (24
_{H, -CH 2 -) k 0.90} (24xH, CH 3) o 1.00 (12H, CH 3) f 1.20 (12H, CH 3) g + j 1.40~2.00 (12xH, -CH 2 -, - CH
−) A 2.10 to 2.40 (8H, cyclohexane ring) l 2.50 (32H, piperazine ring) d, e, h, i 3.00 to 4.00 n 3.55 (24H, OCH ₃ ) c 4.10 (8H, —CH ₂ −) b 6.75 7.07.00 (16H, aromatic) Example 8 Polymerization was carried out in the same manner as in Example 7, and then 1 ml
Was stopped by adding P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a four-chain polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn
= 7100, Mw / Mn = 1.04).

¹ H NMR spectrum (270 MHz, CD
Cl ₃ ): <Alkoxysilyl-terminal four-chain polyisobutyl vinyl ether>

[0182]

Embedded image

Δ (ppm): peak k 0.90 (24 × H,
_{CH 3) o 1.00 (12H,} CH 3) f 1.20 (12H, CH 3) g + j 1.40~2.00 (12xH, -CH 2 -) a 2.10~2.40 (8H, cyclohexane ring) d, e, h, i , l _{3.00~4.00 n 3.55 (24H, OCH 3} ) c 4.10 (8H, -CH 2 -) b 6.75~7.00 (16H, aromatic) m 7.30 (16H, aromatic) sufficiently purified dried under example 9 nitrogen atmosphere 50 ml of ethyl vinyl ether (4.2 mol /
l) Dissolved, 25 ml of 1,4-dioxane was added thereto, and the temperature of the solution was kept at 0 ° C. There, 5 ml of 1 mol / l toluene of an adduct of 1,1,4,4-teratox [4- (2-propenyloxy) ethoxyphenyl] cyclohexane and trifluoroacetic acid (CF ₃ COOH) diluted with toluene ( 40 mmol / l)) and 5 ml (40 mmol / l) of a 1 / l solution of ethylaluminum dichloride in hexane were added in this order to start the polymerization, and the polymerization was continued at 0 ° C. for 3 days. Then 1ml
The polymerization was terminated by the addition of 3-piperazinopropyltrimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to obtain a viscous liquid. As a result, a four-chain polyethyl vinyl ether having a trimethoxysilyl group at each terminal (Mn = 7200, Mw / Mn = 1.04) was obtained.

¹ H NMR spectrum (270 MHz, CD
Cl ₃ ) measured value: <Terminal alkoxysilyl quadruplex polyethyl vinyl ether>

[0185]

Embedded image

Δ (ppm): peak l 0.50 to 2.50 (24
H, —CH ₂ —) f 1.20 (12H, CH ₃ ) g + j 1.40 to 2.00 (20 × H, —CH ₂ —) a 2.10 to 2.40 (8H, cyclohexane ring) k 2.50 (32H, piperazine ring) d, e, h , i 3.00 to 4.00 m 3.55 (36H, OCH ₃ ) c 4.10 (8H, -CH _2- ) b 6.75 to 7.00 (16H, aromatic) Example 10 Polymerization was carried out in the same manner as in Example 9; 1 ml
Was stopped by adding P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a four-chain polyethyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 7)
200, Mw / Mn = 1.04).

¹ H NMR spectrum (270 MHz, CD
Cl ₃ ) measured value: <Terminal alkoxysilyl quadruplex polyethyl vinyl ether>

[0189]

Embedded image

Δ (ppm): peak n 1.00 (12H, CH ₃ ) f + j 1.20 (12 H, CH ₃ ) g + i 1.40 to 2.00 (16 × H, —CH ₂ —) a 2.10 (8 H, cyclohexane ring) d, e, h , k 3.00 to 4.00 m 3.55 (24H, OCH ₃ ) c 4.10 (8H, —CH ₂ —) b 6.75 to 7.00 (16H, aromatic) l 7.30 (16H, aromatic) Example 11 Same as Example 7 Perform polymerization by operation, then 1 ml
When the polymerization was terminated by the addition of allylamine, a four-chain polyisobutyl vinyl ether having an allyl group at each terminal (Mn = 7500, Mw / Mn = 1.03) was obtained. To this, 1.0 g of methyldimethoxysilane and 1.0 ml of a solution of chloroplatinic acid in isopropanol / tetrahydrofuran (including 0.001 g of chloroplatinic acid) were added and reacted at 80 ° C. for 3 hours. As a result, at each end,

[0191]

Embedded image

A three-branched star-type polyisobutyl vinyl ether having the following structural formula having a group was obtained.

H ¹ NMR spectrum (270 MHz, CD
Measured value of Cl ₃ ): <Terminal alkoxysilyl quadruple-chain polyisobutyl vinyl ether>

[0194]

Embedded image

Δ (ppm): peak m 0.50 to 2.50 (24
_{H, -CH 2 -) k 0.90} (24xH, CH 3) o 1.00 (12H, CH 3) f 1.20 (12H, CH 3) g + j 1.40~2.00 (12xH, -CH2 -) a 2.10~2.40 (8H, Cyclohexane ring) d, e, h, i, l 3.00 to 4.00 n 3.55 (24H, OCH ₃ ) c 4.10 (8H, —CH ₂ —) b 6.75 to 7.00 (16H, aromatic) Example 12 Under a nitrogen atmosphere 50 ml (3.0 mol / l) of isobutyl vinyl ether was dissolved in 50 ml of sufficiently purified and dried toluene, 25 ml (mol / l) of 1,4-dioxane was added thereto, and the temperature of the solution was reduced to 0 ° C. Held. Thereto, 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (the compound of Reference Example 2) diluted with toluene and trifluoroacetic acid (CF ₃ CO
5 ml of a 1 mol / l toluene solution of the adduct with OH)
(40 mmol / l) and 5 ml (mmol / l) of a 1 mol / l solution of ethylaluminum dichloride in hexane were added in this order to initiate polymerization.
The polymerization was continued for 0 minutes. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a three-chain star-shaped polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 7,500, Mw / Mn = 1.05) was obtained. Example 13 After polymerization was carried out in the same manner as in Example 12, the polymerization was stopped by adding 1 ml of p-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture.
A viscous liquid was collected.

As a result, a three-chain star-shaped polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 7,400, Mw / Mn = 1.04) was obtained. Example 14 50 ml of ethyl vinyl ether (4.2 mol / l) was added to 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere.
l) Dissolved, 25 ml of 1,4-dioxane was added thereto, and the temperature of the solution was kept at 0 ° C. Thereto, 1,4-divinyloxyethoxybenzene (third compound in Table 1) diluted with toluene and trifluoroacetic acid (CF ₃ CO
5 ml of a 1 mol / l toluene solution of the adduct with OH)
(40 mmol / l) and 5 ml (40 mmol / l) of a 1 mol / l hexane solution of ethylaluminum dichloride were added in this order to start polymerization, and the polymerization was continued at 0 ° C. for 3 hours. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropyltrimethoxysilane,
The solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a linear polyethyl vinyl ether having a trimethoxysilyl group at both terminals (Mn = 7.4
00, Mw / Mn = 1.03).

Example 15 After polymerization was carried out in the same manner as in Example 14, the polymerization was stopped by adding 1 ml of p-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture.
A viscous liquid was collected.

As a result, linear polyethyl vinyl ether having a methyldimethoxysilyl group at both terminals (Mn =
7,400, Mw / Mn = 1.03) were obtained.

Example 16 50 ml (3.0 mol / l) of isobutyl vinyl ether was dissolved in 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere, and 25 ml of 1,4-dioxane was added thereto. The temperature was kept at 0 ° C. There, 1,1,4,4-tetrakis [4- (2-
Vinyloxy) ethoxyphenyl] cyclohexane (compound of Reference Example 3) and trifluoroacetic acid (CF ₃ COOH)
5 ml of a 1 mol / l toluene solution of the adduct with (40 mmol / l), and 5 ml of a 1 mol / l hexane solution of ethylaluminum dichloride (40 mmol / l)
Was added in this order to start polymerization, and the polymerization was continued at 0 ° C. for 30 minutes. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a four-chain star-shaped polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 7,400, Mw / Mn = 1.05) was obtained. Example 17 After polymerization was carried out in the same manner as in Example 16, the polymerization was stopped by adding 1 ml of p-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture.
A viscous liquid was collected.

As a result, a quadruple star polyisobutyl vinyl ether having a methyldimethoxysilyl group at each terminal (Mn = 7,100, Mw / Mn = 1.04) was obtained. Example 18 In 50 ml of toluene sufficiently purified and dried under a nitrogen atmosphere, 50 ml of ethyl vinyl ether (4.2 mol /
l) Dissolved, 25 ml of 1,4-dioxane was added thereto, and the temperature of the solution was kept at 0 ° C. Thereto, 1,1,4,4-tetrakis [4- (2-propenyloxy) ethoxyphenyl] cyclohexane (the second compound in Table 9) diluted with toluene and trifluoroacetic acid (CF ₃ CO
5 ml of a 1 mol / l toluene solution of the adduct with OH)
(40 mmol / l) and 5 ml (40 mmol / l) of a 1 mol / l hexane solution of ethylaluminum dichloride were added in this order to start polymerization, and the polymerization was continued at 0 ° C. for 3 hours. Thereafter, the polymerization was stopped by adding 1 ml of 3-piperazinopropyltrimethoxysilane,
The solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a four-chain star-shaped polyethyl vinyl ether having a trimethoxysilyl group at each terminal (Mn =
7,200, Mw / Mn = 1.04) were obtained.

Example 19 After polymerization was carried out in the same manner as in Example 18, the polymerization was stopped by adding 1 ml of p-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture.
A viscous liquid was collected.

As a result, a four-chain star-shaped polyethyl vinyl ether having a methyldimethoxysilyl group at each terminal (M
n = 7,200 and Mw / Mn = 1.04) were obtained.

Example 20 To 100 parts by weight of the polymer obtained in Example 12, 20 parts by weight of a bisphenol A type epoxy resin (trade name “Epicoat 828” manufactured by Yuka Shell Epoxy Co.) was added.
Further, 2 parts by weight of dibutyltin laurate and 5 parts by weight of dicyandiamide were added, and the whole was mixed. The resulting mixture is applied to a sheet substrate to a thickness of 100 μm, left at room temperature for 1 day under a humidity of 60%, and then dried at 130 ° C. for 3 days.
It was cured over time to form an adhesive sheet. This sheet was measured for SP adhesive strength, T peel adhesive strength, and shear adhesive strength.

The above measurement was carried out by changing the addition amount of the bisphenol A type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Example 21 To 100 parts by weight of the polymer obtained in Example 13, 20 parts by weight of a phenol novolak type epoxy resin (trade name “Epicoat 152” manufactured by Yuka Shell Epoxy Co., Ltd.) was added, and dibutyltin laurate was further added. Was added and 5 parts by weight of triethylenetetramine were added, and the whole was mixed. The obtained mixture was applied to a sheet substrate so as to have a thickness of 100 μm, and cured at 50 ° C. for 3 days under a humidity of 60% to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 20.

The above measurement was carried out by changing the addition amount of the phenol novolak type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Example 22 The above bisphenol A type epoxy resin “Epicoat 82” was added to 100 parts by weight of the polymer obtained in Example 14.
8 "was added, 2 parts by weight of dibutyltin laurate and 5 parts by weight of isophoronediamine were added, and the whole was mixed. The resulting mixture is 100 μm thick.
Was applied to the sheet base material and cured at room temperature under a humidity of 60% at 50 ° C. for 3 days to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 20.

The above measurement was carried out by changing the amount of the bisphenol A type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Example 23 100 parts by weight of the polymer obtained in Example 15 was mixed with the above-mentioned phenol novolak type epoxy resin “Epicoat 1”.
52 ", 20 parts by weight of dibutyltin laurate and 2 parts by weight of BF ₃ amine complex (Anchor Chemi
cal Co., trade name "Anchor 1171") was added in an amount of 3 parts by weight, and the whole was mixed. The resulting mixture is 100 μm thick.
m on the sheet substrate, and 1% under 60% humidity.
The adhesive was cured at 00 ° C. for 7 hours to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 20.

The above measurement was carried out by changing the addition amount of the phenol novolak type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Comparative Example 1 After polymerization was carried out in the same manner as in Example 12, the polymerization was stopped by adding 1 ml of methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid. As a result, a three-chain star-shaped polyisobutyl vinyl ether having a methoxy group at each terminal (Mn = 7,500, Mw / Mn =
1.04) was obtained.

The bisphenol A type epoxy resin “Epicoat 828” was added to 2 parts by weight of 100 parts by weight of the polymer.
0 parts by weight, 2 parts by weight of dibutyltin laurate and 5 parts by weight of dicyandiamide were further added, and the whole was mixed. Using the obtained mixture, an adhesive sheet was prepared in the same manner as in Example 20, and the physical properties of this sheet were measured.

Comparative Example 2 After the polymerization was carried out in the same manner as in Example 15, the polymerization was stopped by adding 1 ml of methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid. As a result, linear polyethyl vinyl ether having methoxy groups at both ends (Mn = 7,300, Mw / Mn = 1.04)
was gotten.

The phenol novolak type epoxy resin “Epicoat 152” was added to 100 parts by weight of the polymer.
And 20 parts by weight of dibutyltin laurate.
Parts by weight, and BF ₃ amine complex (Anchor Chemical C
o. 3 anchors (trade name, “Anchor 1171”), and the whole was mixed. Example 2 was obtained using the obtained mixture.
An adhesive sheet was prepared in the same manner as in No. 3, and the physical properties of this sheet were measured.

Table 11 shows the results of these measurements.

[0220]

[Table 11]

In Table 11, the SP adhesive strength was determined by adhering a sample having a width of 15 mm to a stainless steel plate, pressing the sample with five reciprocations of a 2 kg roll, and leaving it to stand for 15 minutes. It shows the strength when peeled off from the stainless steel plate at a speed, and shows the adhesive strength and the condensing strength.

The T-peeling adhesive strength was measured by applying the adhesive composition to one side of a release-treated double-sided release paper, and having a thickness of 0.6 mm and a width of 25 mm.
The above adhesive sheet is stuck on an aluminum plate of mm, the release paper is peeled off and another aluminum plate is stuck, and the pressure is 2 kg /
pressurized 2 min cm ² and temporarily bonded, to prepare a test piece by performing heat curing under conditions of 30 minutes at 110 ° C., a value measured in compliance with ASTMD-1876 This test piece.

The shear adhesive strength was determined by bonding the above-mentioned adhesive sheet to an area of 25 mm × 13 mm between two aluminum plates having a thickness of 1.5 mm, pressure-bonding 5 times with a 2 kg roll, and pressing at 110 ° C. 30 times.
ASTM D-1002 after heat curing under the condition of
It measured according to.

Epicoat 828: Bisphenol A type epoxy resin Epicoat 152: Phenol novolak type epoxy resin Example 24 100 parts by weight of the polymer obtained in Example 16 was added to a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.). Name "Epicoat 828"),
Further, 2 parts by weight of dibutyltin laurate and 5 parts by weight of dicyandiamide were added, and the whole was mixed. The resulting mixture is applied to a sheet substrate to a thickness of 100 μm, left at room temperature for 1 day under a humidity of 60%, and then dried at 130 ° C. for 3 days.
It was cured over time to form an adhesive sheet. This sheet was measured for SP adhesive strength, T peel adhesive strength, and shear adhesive strength.

Further, the above measurement was carried out by changing the amount of the bisphenol A type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Example 25 To 100 parts by weight of the polymer obtained in Example 17, 20 parts by weight of a phenol novolak type epoxy resin (trade name “Epicoat 152” manufactured by Yuka Shell Epoxy Co., Ltd.) was added, and dibutyltin laurate was further added. Was added and 5 parts by weight of triethylenetetramine were added, and the whole was mixed. The obtained mixture was applied to a sheet substrate so as to have a thickness of 100 μm, and cured at 50 ° C. for 3 days under a humidity of 60% to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 24.

The above measurement was carried out by changing the amount of the phenol novolak type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Example 26 The bisphenol A type epoxy resin “Epicoat 82” was added to 100 parts by weight of the polymer obtained in Example 18.
8 "was added, 2 parts by weight of dibutyltin laurate and 5 parts by weight of isophoronediamine were added, and the whole was mixed. The resulting mixture is 100 μm thick.
Was applied to the sheet base material and cured at room temperature under a humidity of 60% at 50 ° C. for 3 days to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 24.

The above measurement was carried out by changing the amount of the bisphenol A type epoxy resin added to 50 parts by weight, and performing the other operations in the same manner as described above.

Example 27 100 parts by weight of the polymer obtained in Example 19 was added to the above-mentioned phenol novolak type epoxy resin “Epicoat 1”.
52 ", 20 parts by weight of dibutyltin laurate and 2 parts by weight of BF ₃ amine complex (Anchor Chemi
cal Co., trade name "Anchor 1171") was added in an amount of 3 parts by weight, and the whole was mixed. The resulting mixture is applied to a thickness of 100
The composition was applied to a sheet substrate so as to have a thickness of μm, and cured at 100 ° C. for 7 hours under a humidity of 60% to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 24.

The above measurement was carried out by changing the addition amount of the phenol novolak type epoxy resin to 50 parts by weight and performing the other operations in the same manner as described above.

Comparative Example 3 After polymerization was carried out in the same manner as in Example 16, the polymerization was stopped by adding 1 ml of methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid. As a result, a quadruple star polyisobutyl vinyl ether having a methoxy group at each terminal (Mn = 7,100, Mw / Mn =
1.05) was obtained.

The bisphenol A type epoxy resin “Epicoat 828” was added to 2 parts by weight of 100 parts by weight of the polymer.
0 parts by weight, 2 parts by weight of dibutyltin laurate and 5 parts by weight of dicyandiamide were further added, and the whole was mixed. Using the obtained mixture, an adhesive sheet was prepared in the same manner as in Example 24, and the physical properties of this sheet were measured.

Comparative Example 4 After polymerization was carried out in the same manner as in Example 18, the polymerization was stopped by adding 1 ml of methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid. As a result, a quadruple star polyethyl vinyl ether having a methoxy group at each terminal (Mn = 7,200, Mw / Mn = 1.
04) was obtained.

The phenol novolak type epoxy resin “Epicoat 152” was added to 100 parts by weight of the polymer.
And 20 parts by weight of dibutyltin maleate.
Parts by weight, and BF ₃ amine complex (Anchor Chemical C
o. 3 anchors (trade name, “Anchor 1171”), and the whole was mixed. Example 2 was obtained using the obtained mixture.
An adhesive sheet was prepared in the same manner as in No. 4, and the physical properties of this sheet were measured.

Table 12 shows the results of these measurements.

[0237]

[Table 12]

SP adhesive strength, T peel adhesive strength, shear adhesive strength,
Epicoat 828 and Epicoat 152 are the same as those in Table 11.

Example 28 To 100 parts by weight of the polymer obtained in Example 12, n
-Butyl acrylate / 2-ethylhexyl acrylate / β-hydroxyethyl methacrylate (60/35
/ 5) Copolymer A (Mw = 260,000, Mw / Mn
= 3.11), and 2 parts by weight of dibutyltin maleate were further added. The obtained mixture was made into a 40% solution of ethyl acetate, and then the undercoat was applied to a thickness of 35%.
40μm on one side of polyester film of μm
And dried to produce a pressure-sensitive adhesive tape. The SP adhesive strength, ball talc and holding power of this tape were measured.

Further, the amount of the copolymer A was changed to 800 parts by weight, and the others were carried out in the same manner as described above, and the above measurement was carried out.

Example 29 n was based on 100 parts by weight of the polymer obtained in Example 13.
-Butyl acrylate / 2-ethylhexyl acrylate / acrylic acid / hydroxypropyl acrylate (5
5/30/10/5) Copolymer B (Mw = 24,000
0, Mw / Mn = 2.80), and 2 parts by weight of dibutyltin maleate were further added, and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 28. The physical properties of this sheet were measured as in Example 28.

Also, the amount of copolymer B was changed to 800 parts by weight, and the other steps were carried out in the same manner as above, and the above measurement was carried out.

Example 30 To 100 parts by weight of the polymer obtained in Example 14, 200 parts by weight of the same copolymer A as that of Example 28 was added.
Further, 2 parts by weight of dibutyltin maleate was added and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 28. The physical properties of this sheet were measured as in Example 28.

Also, the amount of copolymer B was changed to 800 parts by weight, and the other steps were carried out in the same manner as above, and the above measurement was carried out.

Example 31 To 100 parts by weight of the polymer obtained in Example 15, 200 parts by weight of the same copolymer B as in Example 29 was added.
Further, 2 parts by weight of dibutyltin maleate was added and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 28. The physical properties of this sheet were measured as in Example 28.

Also, the amount of the copolymer B was changed to 800 parts by weight, and the others were carried out in the same manner as above, and the above measurement was carried out.

Comparative Example 5 The copolymer A of Example 28 was used alone, and the other points were the same as in Example 28, and the physical properties were measured.

Comparative Example 6 The copolymer B of Example 29 was used alone, and the other points were the same as in Example 29, and the physical properties were measured.

Table 13 shows the results of these measurements.

[0250]

[Table 13]

In Table 13, the amount of the copolymer is the amount of the (meth) acrylate copolymer added to 100 parts by weight of the polyalkenyl ether.

The SP adhesion is the same as that in Table 11.

The ball tack was obtained from J.I. It is based on the Dow method and represents adhesive strength.

The holding force was such that the sample was adhered to a stainless steel plate such that the size of the adhesive surface was 25 mm in width and 25 mm in length, and further pressed by one reciprocation of a 2 kg roll.
After standing for 15 minutes, one end of the stainless steel plate is fixed, and 500 g (for an atmosphere of 80 ° C.) and 1 kg (for an atmosphere of 40 ° C.) are suspended from the other end of the sample until the weight falls. , Which indicates the cohesive force.

Copolymer A: n-butyl acrylate / 2
-Ethylhexyl acrylate / β-hydroxyethyl methacrylate (60/35/5, Mw = 260,00
0, Mw / Mn = 3.11) Copolymer B: n-butyl acrylate / 2-ethylhexyl acrylate / acrylic acid / hydroxypropyl acrylate (55/30/10/5, Mw = 24,000)
0, Mw / Mn = 2.80) Example 32 With respect to 100 parts by weight of the polymer obtained in Example 16, n
-Butyl acrylate / 2-ethylhexyl acrylate / β-hydroxyethyl methacrylate (60/35
/ 5) Copolymer A (Mw = 260,000, Mw / Mn
= 3.11), and 2 parts by weight of dibutyltin maleate were further added. The obtained mixture was made into a 40% solution of ethyl acetate, and then the undercoat was applied to a thickness of 35%.
40μm on one side of polyester film of μm
And dried to produce a pressure-sensitive adhesive tape. The SP adhesive strength, ball talc and holding power of this tape were measured.

Also, the amount of the copolymer A was changed to 800 parts by weight, and the others were carried out in the same manner as described above, and the above measurement was carried out.

Example 33 n was based on 100 parts by weight of the polymer obtained in Example 17.
-Butyl acrylate / 2-ethylhexyl acrylate / acrylic acid / hydroxypropyl acrylate (5
5/30/10/5) Copolymer B (Mw = 24,000
0, Mw / Mn = 2.80), and 2 parts by weight of dibutyltin maleate were further added, and the whole was mixed. Using the resulting mixture, an adhesive tape was prepared in the same manner as in Example 32. The physical properties of this sheet were measured as in Example 32.

Also, the amount of the copolymer B was changed to 800 parts by weight, and the other steps were carried out in the same manner as above, and the above measurement was carried out.

Example 34 To 100 parts by weight of the polymer obtained in Example 18, 200 parts by weight of the same copolymer A as that of Example 32 was added.
Further, 2 parts by weight of dibutyltin maleate was added and the whole was mixed. Using the resulting mixture, an adhesive tape was prepared in the same manner as in Example 32. The physical properties of this sheet were measured as in Example 32.

Also, the amount of the copolymer B was changed to 800 parts by weight, and the other steps were carried out in the same manner as above, and the above measurement was carried out.

Example 35 To 100 parts by weight of the polymer obtained in Example 19, 200 parts by weight of the same copolymer B as that of Example 33 was added.
Further, 2 parts by weight of dibutyltin maleate was added and the whole was mixed. Using the resulting mixture, an adhesive tape was prepared in the same manner as in Example 32. The physical properties of this sheet were measured as in Example 32.

Also, the amount of the copolymer B was changed to 800 parts by weight, and the others were carried out in the same manner as above, and the above measurement was carried out.

Comparative Example 7 The copolymer A of Example 32 was used alone, and the other points were the same as in Example 32, and the physical properties were measured.

Comparative Example 6 The copolymer B of Example 33 was used alone, and the other points were the same as in Example 33, and the physical properties were measured.

Table 14 shows the results of these measurements.

[0266]

[Table 14]

In Table 14, the copolymer addition amount, SP adhesive strength,
Ball tack, holding power, copolymer A and copolymer B
Are the same as those in Table 13.

Example 36 To 100 parts by weight of the polymer obtained in Example 12, 30 parts by weight of ester gum A (rosin type, manufactured by Arakawa Kagaku Co.) was added, and 2 parts by weight of dibutyltin maleate was further added. The obtained mixture was applied to one surface of a 35 μm-thick polyester film so that the paste thickness was 40 μm, and was cured with hot air at a temperature of 90 ° C. for 10 minutes under a humidity of 60% to prepare a pressure-sensitive adhesive tape. The SP adhesive strength, ball talc and holding power of this tape were measured.

The amount of the ester gum A was 0,
The measurement was carried out by changing the amount to 80 and 120 parts by weight, and performing the other operations in the same manner as described above.

Example 37 To 100 parts by weight of the polymer obtained in Example 13, Y
30 parts by weight of S resin Px (β-pinene polymer, Yasuhara Yushi) was added, and 2 parts by weight of dibutyltin maleate was further added, and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 36. The physical properties of this sheet were measured as in Example 36.

The amount of the YS resin Px to be added was 80
The above measurement was carried out by changing the parts to parts by weight and performing the other operations in the same manner as described above.

Example 38 100 parts by weight of the polymer obtained in Example 14 was mixed with 30 parts of Escolets 1103U (oil-based, manufactured by Esso Chemical Co., Ltd.).
2 parts by weight of dibutyltin maleate were further added, and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 36. The physical properties of this sheet were measured as in Example 36.

Further, the above-mentioned measurement was carried out by changing the amount of the above-mentioned ESCOLETS 1103U to 0, 80, and 120 parts by weight, and performing the other operations in the same manner as above.

Example 39 To 100 parts by weight of the polymer obtained in Example 15 was added Hiretsu T-100X (petroleum system, manufactured by Mitsui Petrochemical Co.), and 2 parts by weight of dibutyltin maleate was further added. did. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 36. The physical properties of this sheet were measured as in Example 36.

Further, the above measurement was carried out by changing the amount of Hiretsu T-100X to 80 parts by weight and performing the other operations in the same manner as described above.

Comparative Example 9 After polymerization was carried out in the same manner as in Example 12, the polymerization was stopped by adding 1 ml of methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid. As a result, a three-chain star-shaped polyisobutyl vinyl ether having a methoxy group at each terminal (Mn = 7,300, Mw / Mn =
1.03) was obtained.

To 100 parts by weight of the polymer, 30 parts by weight of YS resin Px (β-pinene polymer, Yasuhara Yushi) was added, and 2 parts by weight of dibutyltin maleate was further added, followed by mixing. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 36. The physical properties of this sheet were measured as in Example 36.

The amount of the YS resin Px to be added was 80
The above measurement was carried out by changing the parts to parts by weight and performing the other operations in the same manner as described above.

Table 15 shows the results of these measurements.

[0280]

[Table 15]

In Table 15, the copolymer addition amount, SP adhesive strength,
Ball tack and retention are the same as those in Table 13.

The SP adhesion, ball tack and holding power are the same as those in Table 13.

Ester gum A: Rosin-based tackifier resin, Arakawa Chemical Co., Ltd. YS resin Px: β-pinene polymer tackifier resin, Yasuhara Yushi Escolets 1103U: Petroleum-based tackifier resin, Esso Chemical Co., Ltd. Hailetsu T-100X: Petroleum-based tackifying resin, manufactured by Mitsui Petrochemical Co., Ltd. Example 40 To 100 parts by weight of the polymer obtained in Example 16, 30 parts by weight of ester gum A (rosin type, manufactured by Arakawa Chemical Co., Ltd.) was added, and dibutyltin maleate was further added. Was added in 2 parts by weight. The obtained mixture was applied to one surface of a 35 μm-thick polyester film so that the paste thickness was 40 μm, and was cured with hot air at a temperature of 90 ° C. for 10 minutes under a humidity of 60% to prepare a pressure-sensitive adhesive tape. The SP adhesive strength, ball talc and holding power of this tape were measured.

The amount of the ester gum A was 0,
The measurement was carried out by changing the amount to 80 and 120 parts by weight, and performing the other operations in the same manner as described above.

Example 41 To 100 parts by weight of the polymer obtained in Example 17, Y was added.
30 parts by weight of S resin Px (β-pinene polymer, Yasuhara Yushi) was added, and 2 parts by weight of dibutyltin maleate was further added, and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 40. The physical properties of this sheet were measured as in Example 40.

The amount of the YS resin Px to be added was 80%.
The above measurement was carried out by changing the parts to parts by weight and performing the other operations in the same manner as described above.

Example 42 To 100 parts by weight of the polymer obtained in Example 18, 30 parts of Escolets 1103U (oil-based, manufactured by Esso Chemical Co., Ltd.) was added.
2 parts by weight of dibutyltin maleate were further added, and the whole was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 40. The physical properties of this sheet were measured as in Example 40.

Further, the above-mentioned measurement was carried out by changing the amount of the above-mentioned ESCOLET 1103U to 0, 80, and 120 parts by weight, and conducting the other steps in the same manner as above.

Example 43 To 100 parts by weight of the polymer obtained in Example 19, 100 parts by weight of Hirets T-100X (petroleum system, manufactured by Mitsui Petrochemical Co., Ltd.), 2 parts by weight of dibutyltin maleate, and 2 parts by weight were mixed. did. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 40. The physical properties of this sheet were measured as in Example 40.

Further, the above measurement was carried out by changing the amount of HIREZ T-100X added to 80 parts by weight and performing the other operations in the same manner as described above.

Example 44 To 100 parts by weight of the polymer obtained in Example 11, 30 parts by weight of ester gum A (rosin type, manufactured by Arakawa Chemical Co., Ltd.) and 2 parts by weight of dibutyltin maleate were added. Was mixed. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 40. The physical properties of this sheet were measured as in Example 40.

The amount of the ester gum A was 80
The above measurement was carried out by changing the parts to parts by weight and performing the other operations in the same manner as described above.

Comparative Example 10 After the polymerization was carried out in the same manner as in Example 16, the polymerization was stopped by adding 1 ml of methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid. As a result, a four-chain star polyisobutyl vinyl ether having a methoxy group at each terminal (Mn = 7,300, Mw / Mn =
1.03) was obtained.

To 100 parts by weight of the polymer, 30 parts by weight of YS resin Px (β-pinene polymer, Yasuhara Yushi) was added, and 2 parts by weight of dibutyltin maleate was further added, followed by mixing. Using the obtained mixture, an adhesive tape was prepared in the same manner as in Example 40. The physical properties of this sheet were measured as in Example 40.

Further, the addition amount of the YS resin Px was 80
The above measurement was carried out by changing the parts to parts by weight and performing the other operations in the same manner as described above.

Table 16 shows the results of these measurements.

[0297]

[Table 16]

In Table 16, the SP adhesive strength, ball tack and holding power are the same as those in Table 13.

Ester gum A, YS resin Px, Escolec 1103U and Hiretz T-100X are shown in Table 15
Are the same as those of

Example 45 To 100 parts by weight of the polymer obtained in Example 12, 20 parts by weight of chlorinated paraffin (chlorine content: 40%), 20 parts by weight of titanium dioxide, and 50 parts by weight of calcium carbonate were added. Was mixed with three rolls.

To this mixture, 2 parts by weight of dibutyltin maleate was added, and the mixture was further mixed.
% At a temperature of 7% to prepare a cured product sheet having a thickness of 2 mm.

A tensile test was performed on this sheet in accordance with JIS6301 to find that the strength at break was 15.2 kg.
/ Cm ² and elongation at break of 450%. Further, when the exposure test was performed for 500 hours, no whitening or cracking occurred.

Example 46 20 parts by weight of tricresyl phosphate, 20 parts by weight of carbon black and 50 parts by weight of silicic anhydride were added to 100 parts by weight of the polymer obtained in Example 13, and the mixture was rolled with three rolls. Mixed. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 45, and a tensile test was performed. As a result, a strength at break of 13.1 kg / cm ² and an elongation at break of 4 were obtained.
A result of 80% was obtained. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Example 47 To 100 parts by weight of the polymer obtained in Example 14, 20 parts by weight of dioctyl phthalate, 20 parts by weight of titanium dioxide, and 50 parts by weight of magnesium carbonate were added, and a blend was prepared.
The mixture was mixed with this roll. Example 4 using the obtained mixture
A cured product sheet was prepared in the same manner as in Example 5, and a tensile test was carried out. As a result, it was found that the strength at break was 11.2 kg / cm ² and the elongation at break was 600%. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Example 48 To 100 parts by weight of the polymer obtained in Example 15, 20 parts by weight of triethylene glycol di-2-ethylbutyrate, 20 parts by weight of carbon black and 50 parts by weight of talc were added. Was mixed with three rolls. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 45 and subjected to a tensile test.
The results were 4 kg / cm ² and 550% elongation at break. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Comparative Example 11 As a resin, polypropylene oxide having a methyldimethoxysilyl group at both terminals (Mn = 7.400, Mw /
Using Mn = 1.03), the same additives as in Example 48 were added to 100 parts by weight of the polymer, and the mixture was mixed with three rolls. Example 45 was performed using the obtained mixture.
A cured product sheet was prepared in the same manner as described above, and a tensile test was conducted. As a result, it was found that the strength at break was 11.3 kg / cm ² and the elongation at break was 480%. When an exposure test was further performed for 500 hours, a crack having a length of up to 5 mm was formed on the entire surface of the cured product.

Example 49 To 100 parts by weight of the polymer obtained in Example 16, 20 parts by weight of chlorinated paraffin (chlorine content: 40%), 20 parts by weight of titanium dioxide, and 50 parts by weight of calcium carbonate were added. Was mixed with three rolls.

To this mixture was added 2 parts by weight of dibutyltin maleate, and the mixture was further mixed.
% At a temperature of 7% to prepare a cured product sheet having a thickness of 2 mm.

A tensile test was performed on this sheet in accordance with JIS6301.
/ Cm ² and an elongation at break of 280%. Further, when the exposure test was performed for 500 hours, no whitening or cracking occurred.

Example 50 20 parts by weight of tricresyl phosphate, 20 parts by weight of carbon black, and 50 parts by weight of silicic anhydride were added to 100 parts by weight of the polymer obtained in Example 17, and the mixture was rolled with three rolls. Mixed. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 49, and a tensile test was carried out. As a result, the strength at break was 21.3 kg / cm ² , and the elongation at break was 2
A result of 60% was obtained. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Example 51 To 100 parts by weight of the polymer obtained in Example 18, 20 parts by weight of dioctyl phthalate, 20 parts by weight of titanium dioxide, and 50 parts by weight of magnesium carbonate were added.
The mixture was mixed with this roll. Example 4 using the obtained mixture
A cured product sheet was prepared in the same manner as in Example 9, and a tensile test was carried out. As a result, it was found that the strength at break was 26.5 kg / cm ² and the elongation at break was 210%. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Example 52 To 100 parts by weight of the polymer obtained in Example 19, 20 parts by weight of triethylene glycol di-2-ethylbutyrate, 20 parts by weight of carbon black and 50 parts by weight of talc were added. Was mixed with three rolls. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 49, and subjected to a tensile test.
The results were 3 kg / cm ² and elongation at break 240%. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Example 53 To 100 parts by weight of the polymer obtained in Example 11, 20 parts by weight of chlorinated paraffin (chlorine content 40%), 20 parts by weight of titanium dioxide and 50 parts by weight of calcium carbonate were added. Was mixed with three rolls. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 49,
When a tensile test was performed, the strength at break was 19.1 kg /
cm ² and elongation at break of 320% were obtained. When an exposure test was further performed for 500 hours, no whitening or cracking occurred.

Comparative Example 11 As a resin, a polypropylene oxide having a methyldimethoxysilyl group at both terminals (Mn = 7.400, Mw /
(Mn = 1.03), the same additives as in Example 52 were added to 100 parts by weight of the polymer, and the mixture was mixed with a three-roll mill. Example 49 was obtained using the obtained mixture.
A cured product sheet was prepared in the same manner as described above, and a tensile test was conducted. As a result, it was found that the strength at break was 11.3 kg / cm ² and the elongation at break was 480%. When an exposure test was further performed for 500 hours, a crack having a length of up to 5 mm was formed on the entire surface of the cured product.

Claims (5)

(57) [Claims] 1. A compound of the general formula (Wherein, R ¹ is a hydrogen atom or a methyl group, n is an integer 2,
3 or 4, R ² is a divalent organic group when n is 2, n is 3
Is a trivalent organic group, when n is 4, a tetravalent organic group, R ³
Is a hydrogen atom or a methyl group, R ⁴ is a monovalent organic group, R ⁵
Is a divalent organic group containing a nitrogen atom or a sulfur atom , R ⁶ ,
R ⁷ and R ⁸ are the same or different and are an alkyl group, an aryl group or an alkoxy group,
Are alkoxy groups, and x represents 1 to 10,000, respectively). 2. An adhesive composition comprising the alkenyl ether compound according to claim 1 and an epoxy resin. 3. A pressure-sensitive adhesive composition comprising the alkenyl ether compound according to claim 1 and a (meth) acrylate copolymer. 4. A pressure-sensitive adhesive composition comprising the alkenyl ether compound according to claim 1 and a tackifier. 5. A room temperature curable resin composition comprising the alkenyl ether compound according to claim 1.