JPH0543615A - Alkenyl ether compound and use thereof - Google Patents

Abstract

PURPOSE:To obtain an alkenyl ether compound which has a specific linear, three-chain star, or four-chain star structure and is hence useful as an ingredient for a high-performance adhesive composition, pressure-sensitive adhesive composition, and room temperature-curing resin composition. CONSTITUTION:The title compound is represented by the formula (wherein R<1> is H or CH3; n is 2, 3, or 4; R<2> is a divalent, trivalent, or tetravalent organic group when n is 2, 3, or 4, respectively; R<3> is H or CH3; R<4> is a monovalent organic group; R<5> is a divalent organic group; R<6>, R<7>, and R<8> each is an alkyl, an aryl, or an alkoxy, provided that at least one of R<6> to R<8> is an alkoxy; and X is 1 to 10,000). This compound is a linear or star compound having two, three, or four chains uniform in length and having a narrow molecular-weight distribution. This compound can be used to produce a solvent-free, pressure- sensitive adhesive composition which is excellent in cohesive force, tackiness, and durability, or to produce a room temperature-curing resin composition having high performance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to linear polyalkenyl ethers, three-chain star polyalkenyl ethers, four-chain star polyalkenyl ethers, and other linear, three-chain star or four-chain star And an adhesive composition, a pressure-sensitive adhesive composition and a room temperature curable resin composition containing the alkenyl ether compound.

[0002]

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

However, the present inventors have found that cation supplying compounds HI and I ₂ , ZnI ₂ or metal halides (ZnI ₂ , ZnBr ₂ , ZnCl ₂ , SnI ₂ , Sn).
It has been found that when a binary initiator composed of Cl ₂ , MgCl ₂ , BF ₃ OEt ₂ , SnCl ₄ ) is used, isobutyl vinyl ether undergoes living polymerization to produce a polymer having a narrow molecular weight distribution or a block copolymer (HI / For I ₂ type initiators, see Macromolecules, 19
84, 17 , 3,265-272, and HI / ZnI2, Macromolecules, 1987, 20 , 11,26
3-2696, Macrol for HI / metal halides
ecules, 1989, 22 , 4, 1552-1557).

A linear polyalkenyl ether, a three-chain star polymer or a four-chain star polymer is a polymer 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 it is expected to be a useful polymer material because it can be applied to various applications by utilizing the physical properties of such a unique structure.

[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, which is one per molecule. It was impossible to synthesize the above-mentioned linear polyalkenyl ether, the three-chain star polymer or the four-chain star polymer, because only the active sites of

In view of the above points, an object of the present invention is to provide a linear shape,
It is intended to provide a novel three-chain star-type or four-chain star-type alkenyl compound.

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

[0008]

The linear, three-chain star or four-chain star alkenyl ether compound according to the present invention has the general formula

[0009]

[Chemical 2]

(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, R ⁶ , R ⁷ and R
⁸ are the same or different and each represents an alkyl group, an aryl group or an alkoxy group, at least one of which means an alkoxy group and x is 1 to 10000) (hereinafter, this is referred to as the alkenyl ether of the present invention). Compound).

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 which represents 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, 4
-Ethyl-1-methyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n
-Alkyl group such as eicosyl and n-docosyl: Cycloalkyl group such as cyclohexyl: Cycloalkylalkyl group such as cyclohexylmethyl, terpenyl, menthyl, bornyl and 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 mil, 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, 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: 2-acetoxyethyl, 2-benzoxyethyl, 2- (p-methoxybenzoxy) ethyl , 2- ( Acyloxyalkyl groups such as -chlorobenzoxy) ethyl: 2-phthaliminoethyl, iminoalkyl groups such as 2- (di-tert-butylcarboxyimino) ethyl: 2-dienylmalonylethyl, malonyl such as 2-diphenylmalonylethyl Alkyl group: an allyloxyalkyl group such as 2-acryloxyethyl, 2-methacryloxyethyl, 2-cinnamyloxyethyl, 2-sorbyloxyethyl and the like.

Examples of the divalent organic group R ⁵ include alkylene groups such as methylene, ethylene, propylene and butylene: arylene groups such as phenylene and ethylphenylene, and further 3-aminopropyl, 3-aminobutyl,
3-aminophenyl, 3- (2-aminoethylamino)
Both ends of groups such as propyl, 3-piperazinopropyl, 3-anilinopropyl are used as bonds, and both ends of groups such as divalent organic groups containing a nitrogen atom: 3-mercaptopropyl are used as bonds. Examples thereof include divalent organic groups containing a sulfur atom.

Examples of the alkyl group represented by R ⁶ , R ⁷ and R ⁸ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and 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- 1-Methyloctyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl, etc. are illustrated.

The aryl group represented by R ⁶ , R ⁷ and R ⁸ is 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 etc. are illustrated.

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,
N-docosyloxy etc. are illustrated.

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

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

The alkenyl ether of the present invention has the general formula

[0038]

[Chemical 3]

(In the formula, 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) are polymerized, and then an alkoxysilyl group is introduced at the polymer terminal. ..

Of the present production method, the production method of the linear compound will be described first.

General formula CHR ¹ ═CH—O—R ² —O—CH═CHR ¹ ... [Ia] (In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent organic group. A) an adduct of a bifunctional alkenyl ether represented by (In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a monovalent organic group), the alkenyl ether represented by the following formula is polymerized, and then an alkoxysilyl group is introduced at the polymer terminal,

[0042]

[Chemical 4]

(In the formula, x is 1 to 10000, R ¹ ,
A linear alkenyl ether represented by R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ has the same meaning as above.

Next, a method for producing a three-chain 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, respectively) using an adduct of a trifunctional alkenyl ether 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) are polymerized, and then an alkoxysilyl group is introduced into the polymer terminal to give

[0046]

[Chemical 5]

(In the formula, x is 1 to 10000, R ¹ ,
^{R 2, R 3, R 4} , R 5, R 6, R 7 and R ⁸ to produce a three-Kusariboshi type alkenyl ether represented by have the same meaning as above).

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

General formula

[0050]

[Chemical 6]

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

[0052]

[Chemical 7]

(Where x is 1 to 10000, 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).

Specific examples of the bifunctional alkenyl ether [Ia] in the production of the linear compound 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.
As described in.

Among the bifunctional alkenyl ethers [Ia] and the trifunctional alkenyl ethers [Ib], the compounds in which the group R ² has an ether bond are, for example, the corresponding difunctional alcohols and trifunctional alcohols in dimethyl sulfoxide, respectively. At room temperature in the presence of sodium hydroxide with chloroethyl vinyl ether or chloroethyl propenyl ether.

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

Specific examples of the tetrafunctional alkenyl ether [Ic] in the production of the four-chain star compound are shown in Tables 9 to 1 above.
0.

Tetrafunctional alkenyl ethers [Ic] are obtained, for example, by reacting tetrakis (4-hydroxyphenyl) cyclohexane with chloroethyl vinyl ether or chloroethyl propenyl ether in dimethylsulfoxide in the presence of sodium hydroxide. can get.

In the present production method, examples of the cation supplying compound include CF ₃ COOH, CCl ₃ COOH and C
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 the present 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, a trifunctional alkenyl ether [Ib] and a cation supplying compound. An adduct with a compound or an adduct of a tetrafunctional alkenyl ether [Ic] with a cation-providing compound is used as an initiator. Expressing the cation-providing compound as HA, this adduct has the general formula

[0062]

[Chemical 8]

(In the formula, R ¹ , R ² and n have the same meanings as described above, and A means the cation-feeding balance of the cation-feeding compound).

As a general method for synthesizing this adduct [IV], an inert solvent such as carbon tetrachloride, n-hexane, or toluene (preferably the same kind as the polymerization reaction solvent) at room temperature under a nitrogen stream. An example is a method in which a polyfunctional alkenyl ether [I] is dissolved therein, and an equivalent amount of a cation-providing compound HA is added thereto and reacted. Bifunctional alkenyl ether [Ia] and cation-providing compound H used
The molar ratio with A is substantially 1: 2, the molar ratio between the trifunctional alkenyl ether [Ib] and the cation supplying compound HA is substantially 1: 3, and the tetrafunctional alkenyl ether [Ic] with the cation. The molar ratio with the feed compound is substantially 1: 4. The reaction temperature is usually set appropriately in the range of -90 ° C to 100 ° C. The reaction pressure is usually atmospheric pressure,
It is also possible to apply pressure. Reaction time is 10 seconds to 24
The time is preferably 5 minutes to 1 hour. According to this synthetic method, the reaction proceeds rapidly and the above-mentioned adduct [I
V] solution is obtained. Furthermore, the adduct [I
V] may be isolated, but it may be subjected 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 (100% polymerization rate) of the olefin compound [II] and the adduct [IV], the amount of the adduct [IV] used is important. The molecular weight can be set by determining the molar ratio of the olefin compound [II] and the adduct [IV] according to the desired degree of polymerization. This molar ratio is 2 or more for obtaining a double-strand star compound, 3 or more for obtaining a three-chain star compound, and 4 or more for obtaining a four-chain star compound. It is appropriately determined according to.

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

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

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

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 organoaluminum compound [V] include, for example, trichloroaluminum, tribromoaluminum, ethylaluminum dichloride, ethylaluminum dibromide, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum diiodo, ethylaluminum difluoride, methyl. Aluminum dichloride, methyl aluminum dibromide, dimethyl aluminum chloride, dimethyl aluminum bromide and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more, and the amount thereof is generally in a molar ratio of olefin [II] / organoaluminum compound [V] = 2 to 10,000, Preferably 10-5
It is in the range of 000.

Specific examples of coexisting Lewis bases include, for example, ethyl acetate, n-butyl acetate, phenyl acetate, ethyl benzoate, p-chlorobenzoate, p.
-Ester compounds such as ethyl methyl benzoate, ethyl p-methoxybenzoate, methyl acetate, isopropyl acetate, t-butyl acetate: 1,4-dioxane, diethyl ether, tetrahydrofuran, di-n-hexyl ether, diisopropyl ether, di -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, 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 kinds. In addition, they can be used in bulk or in solution in an inert solvent. Further, these Lewis bases are added to the reaction system in an amount according to the basicity of the Lewis base within the range of the following relationship between the used amount of the Lewis base and the used amount of the alkenyl ether [I].

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

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

In the present invention, the polymerization reaction form is as follows:
Usually, a solution polymerization method is adopted, but a bulk polymerization method or the like can also be adopted. 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 usually appropriately set in the range of -40 ° C to 100 ° C. The reaction pressure is usually normal pressure, but it can be increased. The reaction time is 3 seconds to 7 days, preferably 1 minute to 24 hours.

The following three methods are exemplified as the method of introducing the alkoxysilyl group into the polymer terminal.

I) As a terminating agent, a compound represented by the general formula

[0079]

[Chemical 9]

The polymerization reaction is terminated by using a compound having an alkoxysilyl group represented by the formula (wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same meanings as described above).

Such terminators 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. And lithium salts such as P-trimethoxysilylphenyllithium, P-methyldimethoxysilylphenyllithium, P-triethoxysilylphenyllithium, and P-methyldiethoxysilylphenyllithium.

Examples thereof include granule reagents such as P-trimethoxysilylphenyl magnesium bromide, P-methyldimethoxysilylphenyl magnesium bromide, P-triethoxysilylphenyl magnesium bromide and P-methyldiethoxysilyl magnesium bromide.

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

[0085]

[Chemical 10]

A silicon hydride compound represented by the formula (wherein R ⁶ , R ⁷ and R ⁸ have the same meanings as described above) is reacted.

As a method for introducing an unsaturated group into the polymer terminal, amines having an unsaturated group such as an allyl group,
A method to stop the polymerization with thiols or lithium salts,
There is a method in which the polymerization is terminated with an alcohol such as methanol, ethanol, propanol, isopropanol, butanol and the acetal group formed at the polymer terminal is dealcoholized with an acid catalyst. When methanol is used as the terminating agent, it is preferable to use aqueous ammonia together with this. Ammonia has a function of deactivating the activity of the organoaluminum [V] Lewis acid and the metal halide. The molar ratio of the polymerization terminator to the cation-providing compound HA is 1-10000, preferably 1-1000.

The degree of polymerization x in the alkenyl ether compound of the present invention is 1-10000, preferably 4-5000.
More preferably, it is in the range of 10 to 1000.

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 1 to 1.3.

Since the alkenyl ether compound of the present invention is crosslinked 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 an adhesive composition which is applied to a substrate without solvent and has excellent tackiness before curing and can be a strong adhesive after curing. Regarding

Many adhesives conventionally used in the fields of building materials, electronic materials, automobile parts and the like contain a solvent such as a rubber adhesive. However, it is desirable to make these adhesives solvent-free because of problems such as air pollution of the solvent used, danger of flame, and toxicity to human body.

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

However, in the former case, temporary adhesion cannot be performed, and in the latter case, there are many two-component types of a main agent and a curing agent, which have poor workability and cannot be temporarily adhered. ..

According to the present invention, it is possible to provide an adhesive which is solvent-free, has a good balance of adhesive strength and adhesive strength before curing, and has a large peel adhesion 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 one in which an alkoxysilyl group is introduced at the terminal of the polymer using the amines and thiols exemplified above as the above terminator. .. In such an alkenyl ether compound, an amino group and a thiol react with an epoxy resin to form a strong crosslinked product.

In curing the composition of the present invention, it is preferable to use a catalyst that accelerates the curing, and a silanol condensation catalyst is effectively used as the catalyst. Shared machine SB-65, DT
L, No2377, RG-40FT, and dibutyltin phthalate-based catalyst) are preferred.

The epoxy resin has at least two epoxy groups in the molecule, and is, for example, a bisphenol A type, a bisphenol F type or a tetrabromobisphenol A type epoxy resin and its hydrogenated product, an aliphatic epoxy resin. , Polyglycol type epoxy resin, polybutadiene modified epoxy resin, novolac type epoxy resin and the like.

The mixing ratio of the epoxy resin is preferably 5 with respect 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 compounded is too small, the curing will be insufficient, and if it is too large, the epoxy resin will easily 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 includes a filler,
Additives such as a tackifier, a plasticizer and an anti-aging agent can be optionally added.

B) The second use of the alkenyl ether compound of the present invention relates to a pressure-sensitive adhesive excellent in tackiness, adhesiveness and cohesive force.

Conventionally, as the pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive mainly composed of natural rubber or synthetic rubber, which is blended with a tackifying resin, a softening agent, a filler and the like, and an acrylic ester are mainly used. An acrylic pressure-sensitive adhesive obtained by copolymerizing a polar monomer typified by acrylic acid as a monomer is widely used for packaging, stationery, medical use, industrial use and the like.

Of these, the rubber type has the advantage that it can be adhered to a relatively large number of adherends, but on the other hand, due to the double bond of the diene portion of the main component rubber, durability (weather resistance,
It has a poor heat resistance and cannot be used in the permanent or semi-permanent bonding field.

On the other hand, the acrylic type has been used in many more applications in recent years by taking advantage of its excellent weather resistance. However, in the case of an acrylic type, its weight average molecular weight is 10 due to problems in conventional polymerization technology and coating technology.
It had to be less than 10,000. Therefore, although it is possible to obtain an acrylic pressure-sensitive adhesive excellent in its tackiness and adhesive force, only a very low holding force, that is, cohesive force was obtained.

As a means for compensating for this lack of cohesive strength, 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 eliminates the above-mentioned drawbacks of conventional acrylic pressure-sensitive adhesives, leads to an appropriate crosslinked structure, and is excellent in tackiness, adhesiveness and cohesive strength. Provided.

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

In curing the composition of the present invention, it is preferable to use a catalyst that accelerates the curing, and a silanol condensation catalyst is effectively used as the catalyst. Shared machine SB-65, DT
L, No2377, RG-40FT, and dibutyltin phthalate-based catalyst) are preferred.

Examples of the (meth) acrylic acid ester in the copolymer containing the (meth) acrylic acid ester as a polymerized structural unit include, for example, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, isoamyl acrylate and 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 thereof include methyl methacrylate and methyl acrylate. Further, a monomer copolymerizable with the main monomer, for example, threthin, vinyl acetate, acrylonitrile, acrylamide, maleic anhydride, acrylic acid, methacrylic acid or the like may be copolymerized.

The blending ratio of the (meth) acrylic acid ester 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 blending amount of the (meth) acrylic acid ester copolymer is too small, the strength will be insufficient, and if it is too large, the curing will be insufficient.

Additives such as tackifying resins, fillers, plasticizers and antioxidants can be optionally added to the pressure-sensitive adhesive composition according to the present invention.

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

Since all the conventional rubber-based or acrylic pressure-sensitive adhesives are dissolved in an organic solvent,
When this is applied to a base material, there is a problem that it takes a high cost to remove or recover the solvent. Therefore, a solventless pressure-sensitive adhesive is desired.

According to the present invention, there is provided a solvent-free pressure-sensitive adhesive composition which is 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 tackifying substance.

In curing the composition of the present invention, it is preferable to use a catalyst that accelerates the curing, and a silanol condensation catalyst is effectively used as the catalyst. Shared machine SB-65, DT
L, No2377, RG-40FT, and dibutyltin phthalate-based catalyst) are preferred.

Examples of the tackifying resin include rosin resins (rosin, modified rosin, polymerized rosin, partially hydrogenated rosin, fully hydrogenated rosin ester, rosin glycerin ester), polyterpene resins (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, diene Cyclopentadiene, homopolymers and copolymers of 1,3-pentadiene) and the like. These tackifying resins may be used alone or in combination of two or more.

The compounding ratio of the tackifier is preferably 5 with respect 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. When the compounding amount of the tackifying resin is too small, the tackiness becomes insufficient, and when it is too large, it flows at a low temperature.

It is possible to optionally add additives such as a filler, a plasticizer and an antiaging agent to the pressure-sensitive adhesive composition according to the present invention.

D) The fourth use of the alkenyl ether compound of the present invention relates to a room temperature curable resin composition capable of being room temperature cured into an elastic body when exposed to moisture. The composition can be used as a room temperature curable elastic sealing agent.

Silicone-based room temperature-curable elastic sealing materials are roughly classified into silicone-based ones and modified silicone-based ones, but they have many problems. With respect to silicone-based sealing, the paint is poorly glued, and the contamination due to the exudation of silicone into the base material is significant. Further, the modified silicone type composed of a propylene oxide polymer cannot be used for glass because the adhesion to the glass surface is significantly deteriorated by sunlight (Japanese Patent Publication No. 61-18570, Japanese Patent Publication No. 61-18582, and Japanese Patent Publication No. 61-18582). Sealing Industry Association: See Sealing Material Handbook).

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

The room temperature curable resin composition according to the present invention contains the alkenyl ether compound of the present invention as a main constituent.

In curing the composition of the present invention, it is preferable to use a catalyst that accelerates the curing, and a silanol condensation catalyst is effectively used as the catalyst. Shared machine SB-65, DT
L, No2377, RG-40FT, and dibutyltin phthalate-based 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, hydrous silicic acid, anhydrous silicic acid, calcium silicate / silica, carbon black, titanium dioxide, clay and talc. These fillers may be used alone,
You may use 2 or more types.

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 phosphates such as tributyl phosphate and tricresyl phosphate, dioctyl phthalate, phthalates such as di-2-ethylhexyl phthalate, aliphatic monobasic esters such as glycerin monooleate, and adipine. Dibutyl acid, adipic acid di-
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 and the like can be mentioned. .. These can be used alone or in combination of two or more.

It is also possible to optionally add an additive such as a pigment or an anti-aging agent to the composition of the present invention.

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

[0132]

INDUSTRIAL APPLICABILITY According to the present invention, a linear compound or star compound having two, three or four chains of uniform length and having a narrow molecular weight distribution can be obtained.

According to the present invention, it is possible to obtain an adhesive which is solvent-free and has a high balance of adhesive strength and adhesive strength before curing and high peel adhesive strength after curing.

According to the present invention, it has a proper crosslinked structure,
A pressure-sensitive adhesive composition having excellent tackiness, adhesiveness and cohesive force can be obtained.

According to the present invention, it is possible to obtain a pressure-sensitive adhesive composition which is solventless and has excellent cohesive strength, tackiness and durability.

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

[0137]

EXAMPLES Examples of the present invention will be described below. In the following examples, the molar concentration (mol / l) indicates the mole of the compound used with respect to the total volume of the polymerization reaction system, and the weight average molecular weight Mw, the number average molecular weight Mn, and the 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 (JSX GSX
-270, 270 MHz). Infrared absorption is an infrared spectrophotometer (Hitachi, "270-30")
The melting point is a trace melting point measuring device (Yanamoto Co., Ltd., “MP-S
₃ ").

The adduct of the polyfunctional alkenyl ether [I] and the cation-providing compound used in each Example was
Under a nitrogen stream, dissolve the polyfunctional alkenyl ether [I] in a sufficiently purified and dried inert solvent (the same kind as the polymerization reaction solvent), add an equivalent amount of the cation-providing compound HA thereto, and stir for 15 minutes. It was prepared by. The obtained adduct was subjected to a polymerization reaction in a solution state without isolation.

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

Reference Example 1 (Preparation of Trifunctional Alkenyl Ether) In a glass three-necked flask equipped with a condenser and a stirrer, 9.96 g (113 mmol) of 2-hydroxyethyl vinyl ether in 50 ml of toluene under a nitrogen atmosphere.
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 tetra-n-butylammonium chloride 0.5 g were added, and the reaction was carried out at 80 ° C. for 4 hours. The reaction mixture was extracted with diethyl ether and the extract was dried to give crude crystals. 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 ) measurements:

[0142]

[Chemical 11]

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) Example 2 (Preparation of trifunctional alkenyl ether) 75 ml of dimethyl sulfoxide under a nitrogen atmosphere in a glass three-necked flask equipped with a condenser and a stirrer.
1,1,1-tris (4-hydroxyphenyl) ethane (10.0 g, 32.6 mmol) was dissolved in the solution, and sodium hydroxide powder (23.5 g, 587 mmol) was added to the solution. Stir for 3 hours. Then, 59.7 ml of 2-chloroethyl vinyl ether (58
7 mmol) was added and the reaction was carried out at 80 ° C. for 5 hours.
The reaction mixture was purified as in Reference Example 1 to give 1,1,1
-Tris [4- (2-vinyloxy) ethoxyphenyl]
Ethane (second compound in Table 4) was obtained. Yield: 62
%, Melting point: 92 to 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 ) measurements:

[0145]

[Chemical formula 12]

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 under nitrogen atmosphere in a glass three-necked flask equipped with
1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane 10.0 g (22.1 mmol) was dissolved in the solution, and sodium hydroxide powder 21.2 g (5
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 this liquid, and the reaction was carried out 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 ℃ (pale yellow crystal), infrared absorption spectrum (Nuj
ol): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm ⁻¹ .

[0147]

[Chemical 13]

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measured value: 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 and 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 Sufficient purification under nitrogen atmosphere Dried n-hexane 1.5
2.0 ml of isobutyl vinyl ether in ml
Dissolve (3.0 mol / l) and add 0.5 ml (1.2
Mol / l) 1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. An adduct of 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (compound of Reference Example 2) diluted with n-hexane and trifluoroacetic acid (CF ₃ COOH) was added thereto. 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 the polymerization, and the polymerization was continued at 0 ° C. for 3 hours. Then, the polymerization was terminated by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to collect a viscous liquid.

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

¹ H NMR spectrum (270 MHz, C
DCl ₃ ) measurements: <Trifunctional Initiator>

[0151]

[Chemical 14]

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

[0153]

[Chemical 15]

Δ (ppm): peak o 1.00 (9H, CH ₃ ) m 0.50 to 2.50 (18H, —CH ₂ —) k 0.90 (18xH, CH ₃ ) f 1.20 (9H, CH ₃ ) g + j 1.40 to 2.00 ( _{9xH, -CH 2 -) a 2.10} (3H, CH 3) l 2.50 (24H, piperazine ring) d, e, h, i 3.00~4.00 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.
Polymerization was stopped by the addition 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-chain star-shaped polyisobutyl vinyl ether having a methyldimethoxysilyl group at each end (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.04) was obtained. The value of Mn was in good agreement with the calculated value of 1.8 × 10 ⁵ that three chain molecules were generated from one molecule of the adduct.

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

[0157]

[Chemical 16]

Δ (ppm): peak o 1.00 (9H, CH ₃ ) k 0.90 (18xH, CH ₃ ) f 1.20 (9H, CH ₃ ) g + j 1.40 to 2.00 (9xH, -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, and 2 ml thereof was added thereto.
5 ml of 1,4-dioxane was added and the temperature of the solution was adjusted to 0
Hold at 0 ° C. There, 2,2-bis (4-vinyloxyethoxyphenyl) propane (first compound in Table 1) diluted with toluene and trifluoroacetic acid (CF ₃ COO
1 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, and the mixture was heated to 0 ° C.
The polymerization was continued for 3 hours. After that, the polymerization was stopped by adding 1 ml of 3-piperazinopropyltrimethoxysilane, and the solvent and the like were distilled off from the reaction mixture, whereby a viscous liquid was obtained. As a result, polyethyl vinyl ether having a trimethoxysilyl group at both ends (Mn = 740
0, Mw / Mn = 1.03) was obtained.

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

[0160]

[Chemical 17]

Δ (ppm): peak l 0.50 to 2.50 (12
H, chromatography _{CH 2 -) f 1.20 (6H} , CH 3) j 1.20 (6xH, CH 3) g 1.40~2.00 (4xH, -CH 2 -) a 2.10 (6H, CH 3) k 2.50 (16H, piperazine ring ) d, e, h, i 3.00~4.00 m 3.55 (18H, OCH 3) c 4.10 (4H, -CH 2 -) b 6.75~7.00 (8H, aromatic) in the same manner as in example 4 example 3 Polymerize, then 1 ml
Polymerization was stopped by the addition of 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 ends (Mn = 740
0, Mw / Mn = 1.03) was obtained.

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

[0164]

[Chemical 18]

Δ (ppm): peak n 1.00 (6H, CH ₃ ) f 1.20 (6H, CH ₃ ) j 1.20 (6xH, CH ₃ ) g 1.40 to 2.00 (4xH, -CH _2- ) a 2.10 (6H, _{CH 3) d, e, h} , i, l 3.00~4.00 m 3.55 (12H, OCH 3) c 4.10 (4H, -CH 2 -) b 6.75~7.00 (8H, aromatic) m 7.30 (8H, aromatic Example 5 n-hexane 1.5 sufficiently purified and dried under a nitrogen atmosphere
2.0 ml of isobutyl vinyl ether in ml
Dissolve (3.0 mol / l) and add 0.5 ml (1.2
(Mol / l) 1,4-dioxane was added and the temperature of the solution was kept at 0 ° C. 1, diluted with n-hexane
Tri (2-vinyloxyethyl) 3,5-benzenetricarboxylate (compound of Reference Example 2) and trifluoroacetic acid (C
F3 COOH) adduct 0.5 ml (1.7 mmol / 1) and ethylaluminum dichloride hexane solution 0.5 ml (5.0 mmol / l) were added in this order to initiate polymerization, and Polymerization was continued at ℃ 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 triple-branched star-shaped polyisobutyl vinyl ether (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.04) having a methyldimethoxysilyl group at each end was obtained. This Mn value was in good agreement with the calculated value of 1.8 × 10 ⁵ that three side chain molecules were generated from one adduct molecule.

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

[0168]

[Chemical 19]

¹ HNMR δ (ppm): peak e 1.50 (s, 9H, CH ₃ ) c 4.00 (m, 6H, —CH ₂ ) b 4.50 (m, 6H, —CH ₂ ) d 6.10 (q, 3H, CH) a 8.80 (s, 3H, aromatic) <Terminal alkoxysilyl triple-chain polyvinyl ether>

[0170]

[Chemical 20]

Δ (ppm): peak n 1.00 (9H, CH ₃ ) j 1.20 (18xH, CH ₃ ) f + i 1.40 ~ 2.00 (9xH, -CH _2- , CH) c, d, g, h, k 3.00 ~ 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 1 ml
Polymerization was stopped by the addition of allylamine, and triple-chain polyisobutyl vinyl ether having an allyl group at each end (Mn = 1.6 × 10 ⁵ , Mw / Mn = 1.03)
was gotten. Here, 1.0 g of methyldimethoxysilane
And 1.0 ml of an isopropanol / tetrahydrofuran solution of chloroplatinic acid (including 0.001 g of chloroplatinic acid) were added, and the mixture was reacted at 80 ° C. for 3 hours. As a result, at each end, A tri-branched polyisobutyl vinyl ether having the following structural formula having a group was obtained.

[0172]

[Chemical 21]

O 1.00 (9H, CH ₃ ) m 0.50 to 2.50 (18H, --CH _2- ) δ (ppm): peak k 0.90 (18xH, CH ₃ ) f 1.20 (9H, CH ₃ ) g + j 1.40 to 2.00 ( _{9xH, -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) Example 7 50 ml of isobutyl vinyl ether (3.0 mol / l) was dissolved in 50 ml of toluene 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] cyclohexane / trifluoroacetic acid (CF ₃ COOH) 1 mol / mol
5 ml (40 mmol / l) of a toluene solution of 1 and 5 ml of a 1 mol / l hexane solution of ethylaluminum dichloride were added in this order to start the polymerization, and the mixture was stirred at 0 ° C. for 3 minutes.
Polymerization was continued for 0 minutes. Then, the polymerization was stopped by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture, and a viscous liquid was obtained.

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

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

[0176]

[Chemical formula 22]

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) <Terminal alkoxysilyl four-chain polyisobutyl vinyl ether>

[0178]

[Chemical formula 23]

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 2.10~2.40 (8H, cyclohexane ring) l 2.50 (32H, piperazine ring) d, e, h, i 3.00~4.00 n 3.55 (24H, OCH 3) c 4.10 (8H, -CH 2 -) b 6.75 ~ 7.00 (16H, aromatic) Example 8 Polymerization was performed in the same manner as in Example 7, and then 1 ml was used.
Polymerization was stopped by the addition of P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

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

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

[0182]

[Chemical formula 24]

Δ (ppm): peak 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 -) 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 / mol) in 50 ml of toluene.
l) It melt | dissolved, 25 ml of 1, 4-dioxane was added there, and the temperature of the solution was hold | maintained at 0 degreeC. 5 ml of 1 mol / l toluene of an adduct of 1,1,4,4-teratokis [4- (2-propenyloxy) ethoxyphenyl] cyclohexane diluted with toluene and trifluoroacetic acid (CF ₃ COOH) was added thereto. 40 mmol / l)) and 5 ml (40 mmol / l) of a 1 / l hexane solution of ethylaluminum dichloride were added in this order to initiate the polymerization, and the polymerization was continued at 0 ° C. for 3 days. Then 1 ml
Polymerization was stopped 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 end (Mn = 7200, Mw / Mn = 1.04) was obtained.

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

[0185]

[Chemical 25]

Δ (ppm): peak 1 0.50 to 2.50 (24
_{H, -CH 2 -) f 1.20} (12H, CH 3) g + j 1.40~2.00 (20xH, -CH 2 -) a 2.10~2.40 (8H, cyclohexane ring) k 2.50 (32H, piperazine ring) d, e, h , i 3.00~4.00 m 3.55 (36H, OCH 3) c 4.10 (8H, -CH 2 -) b 6.75~7.00 (16H, aromatic) and subjected to polymerization in the same manner as in example 10 example 9, then, 1 ml
Polymerization was stopped by the addition of P-aminophenylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

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

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

[0189]

[Chemical formula 26]

Δ (ppm): peak n 1.00 (12H, CH ₃ ) f + j 1.20 (12H, CH ₃ ) g + i 1.40 to 2.00 (16xH, -CH _2- ) a 2.10 (8H, 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 Similar to Example 7 Polymerize by operation, then 1 ml
When the polymerization was stopped by the addition of allylamine, a four-chain polyisobutyl vinyl ether having an allyl group at each end (Mn = 7500, Mw / Mn = 1.03) was obtained. To this, 1.0 g of methyldimethoxysilane and 1.0 ml of an isopropanol / tetrahydrofuran solution of chloroplatinic acid (including 0.001 g of chloroplatinic acid) were added and reacted at 80 ° C. for 3 hours. As a result, at each end,

[0191]

[Chemical 27]

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

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

[0194]

[Chemical 28]

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 3.00~4.00 n 3.55 (24H, OCH 3) c 4.10 (8H, -CH 2 -) b 6.75~7.00 (16H, aromatic) under example 12 a nitrogen atmosphere 50 ml (3.0 mol / l) of isobutyl vinyl ether was dissolved in 50 ml of sufficiently purified and dried toluene, and 25 ml (mol / l) of 1,4-dioxane was added thereto, and the temperature of the solution was adjusted to 0 ° C. Held There, 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (compound of Reference Example 2) diluted with toluene and trifluoroacetic acid (CF ₃ CO) were added.
OH) adduct with 1 mol / l toluene solution 5 ml
(40 mmol / l), and 5 ml (mmol / l) of a 1 mol / l hexane solution of ethylaluminum dichloride were added in this order to initiate polymerization, and the mixture was stirred at 0 ° C. for 3 minutes.
Polymerization was continued for 0 minutes. Then, the polymerization was terminated by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to collect a viscous liquid.

As a result, a triple-chain star-shaped polyisobutyl vinyl ether (Mn = 7,500, Mw / Mn = 1.05) having a methyldimethoxysilyl group at each end 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 triple-chain star-shaped polyisobutyl vinyl ether having a methyldimethoxysilyl group at each end (Mn = 7,400, Mw / Mn = 1.04) was obtained. Example 14 50 ml of ethyl vinyl ether (4.2 mol / mol) was added to 50 ml of toluene sufficiently purified and dried under a nitrogen atmosphere.
l) It melt | dissolved, 25 ml of 1, 4-dioxane was added there, and the temperature of the solution was hold | maintained at 0 degreeC. Then, 1,4-divinyloxyethoxybenzene diluted with toluene (the third compound in Table 1) and trifluoroacetic acid (CF ₃ CO
OH) adduct with 1 mol / l toluene solution 5 ml
(40 mmol / l) and 5 ml of a 1 mol / l hexane solution of ethylaluminum dichloride (40 mmol / l) were added in this order to start the polymerization, and the polymerization was continued at 0 ° C. for 3 hours. Then the polymerization was stopped by the addition of 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, linear polyethyl vinyl ether having a trimethoxysilyl group at both ends (Mn = 7,4)
00, Mw / Mn = 1.03) was obtained.

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 ends (Mn =
7,400, Mw / Mn = 1.03) was obtained.

Example 16 50 ml of isobutyl vinyl ether (3.0 mol / l) was dissolved in 50 ml of toluene that had been sufficiently purified and dried under a nitrogen atmosphere, and 25 ml of 1,4-dioxane was added thereto to prepare a solution. 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 (40 mmol / l) of a 1 mol / l toluene solution of the adduct with and 5 ml (40 mmol / l) of a 1 mol / l hexane solution of ethylaluminum dichloride.
Were added in this order to start the polymerization, and the polymerization was continued at 0 ° C. for 30 minutes. Then, the polymerization was terminated by adding 1 ml of 3-piperazinopropylmethyldimethoxysilane, and the solvent and the like were distilled off from the reaction mixture to collect a viscous liquid.

As a result, a four-chain star polyisobutyl vinyl ether having a methyldimethoxysilyl group at each end (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 four-chain star polyisobutyl vinyl ether (Mn = 7,100, Mw / Mn = 1.04) having a methyldimethoxysilyl group at each end was obtained. Example 18 50 ml of ethyl vinyl ether (4.2 mol / mol) was added to 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere.
l) It melt | dissolved, 25 ml of 1, 4-dioxane was added there, and the temperature of the solution was hold | maintained at 0 degreeC. Thereto was diluted with toluene 1,1,4,4-tetrakis [4- (2-Puropenirokishi) ethoxyphenyl] cyclohexane (second compound of Table 9) and trifluoroacetic acid (CF ₃ CO
OH) adduct with 1 mol / l toluene solution 5 ml
(40 mmol / l) and 5 ml of a 1 mol / l hexane solution of ethylaluminum dichloride (40 mmol / l) were added in this order to start the polymerization, and the polymerization was continued at 0 ° C. for 3 hours. Then the polymerization was stopped by the addition of 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 poly (vinyl vinyl ether) having a trimethoxysilyl group at each end (Mn =
7,200, Mw / Mn = 1.04) was 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 (M having a methyldimethoxysilyl group at each end) (M
n = 7,200, Mw / Mn = 1.04) was obtained.

Example 20 To 100 parts by weight of the polymer obtained in Example 12, 20 parts by weight of bisphenol A type epoxy resin (trade name "Epicoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.) 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 was applied to a sheet base material so as to have a thickness of 100 μm, allowed to stand at room temperature for 1 day under a humidity of 60%, and then at 130 ° C. for 3 days.
The adhesive sheet was prepared by curing over time. SP adhesion, T-peel adhesion and shear adhesion were measured for this sheet.

Further, the addition amount of the bisphenol A type epoxy resin was changed to 50 parts by weight, and the others were carried out in the same manner as above, and the above measurement was carried out.

Example 21 To 100 parts by weight of the polymer obtained in Example 13, 20 parts by weight of a phenol novolac type epoxy resin (trade name "Epicoat 152" manufactured by Yuka Shell Epoxy Co., Ltd.) was added, and further dibutyltin laurate was added. 2 parts by weight and 5 parts by weight of triethylenetetramine were added, and the whole was mixed. The obtained mixture was applied to a sheet base material so as to have a thickness of 100 μm, and cured at 50 ° C. under humidity of 60% for 3 days to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 20.

Further, the above-mentioned measurement was carried out by changing the addition amount of the above-mentioned phenol novolac type epoxy resin to 50 parts by weight, and otherwise performing the same as above.

Example 22 With respect to 100 parts by weight of the polymer obtained in Example 14, the above-mentioned bisphenol A type epoxy resin "Epicoat 82" was used.
8 ", 20 parts by weight, 2 parts by weight of dibutyltin laurate and 5 parts by weight of isophoronediamine were added, and the whole was mixed. The resulting mixture has a thickness of 100 μm
To a sheet base material and cured at room temperature and 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.

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

Example 23 To 100 parts by weight of the polymer obtained in Example 15, the above phenol novolac type epoxy resin "Epicoat 1" was added.
52 parts by weight, 2 parts by weight of dibutyltin laurate, and BF ₃ amine complex (Anchor Chemi
Cal Co., trade name "anchor 1171") was added 3 parts by weight, and the whole was mixed. The resulting mixture is 100μ thick
It is applied to the sheet base material so that
Curing was carried out at 00 ° C. for 7 hours to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 20.

Further, the above-mentioned measurement was carried out by changing the addition amount of the above-mentioned phenol novolac type epoxy resin to 50 parts by weight, and otherwise performing the same as above.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 12, then 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 end (Mn = 7,500, Mw / Mn =
1.04) was obtained.

To 100 parts by weight of the polymer, 2 parts of the above bisphenol A type epoxy resin "Epicoat 828" is added.
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. An adhesive sheet was prepared using the obtained mixture in the same manner as in Example 20, and the physical properties of this sheet were measured.

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

With respect to 100 parts by weight of the polymer, the above-mentioned phenol novolac type epoxy resin "Epicoat 152" was used.
20 parts by weight of dibutyltin laurate and 2 parts by weight of
Parts by weight, and BF ₃ amine complex (Anchor Chemical C
o. 3 parts by weight of "Anchor 1171" (trade name, manufactured by the company) was added and the whole was mixed. Example 2 using the resulting mixture
An adhesive sheet was prepared in the same manner as in 3, and the physical properties of this sheet were measured.

Table 11 shows the results of these measurements.

[0220]

[Table 11]

[0221] In Table 11, the SP adhesive strength was such that a sample having a width of 15 mm was adhered to a stainless steel plate, further pressed by 5 reciprocations of a 2 kg roll, left for 15 minutes and then 300 mm / min at a folding angle of 180 degrees. It shows the strength when peeled from a stainless steel plate at a speed, and represents the adhesive force and the condensation force.

The T-peel adhesion was 25 mm wide and 25 mm wide when the adhesive composition was applied to one side of release-treated double-sided release paper.
The above adhesive sheet is attached to an aluminum plate of mm, the release paper is peeled off and another aluminum plate is attached, and the pressure is 2 kg /
It is a value measured in accordance with ASTM D-1876 for a test piece prepared by applying a pressure of 2 cm ² for provisional adhesion, heat curing at 110 ° C. for 30 minutes, and preparing the test piece.

The shear adhesive strength is such that the above-mentioned adhesive sheet is adhered to an area of 25 mm × 13 mm between two aluminum plates having a thickness of 1.5 mm, and pressure is applied back and forth 5 times with a 2 kg roll at 30 ° C. at 110 ° C.
After heat-curing under the condition of 1 minute, ASTM D-1002
It was measured according to.

Epicoat 828: Bisphenol A type epoxy resin Epicoat 152: Phenol novolac type epoxy resin Example 24 Based on 100 parts by weight of the polymer obtained in Example 16, a bisphenol A type epoxy resin (produced by Yuka Shell Epoxy Co., Ltd., a product 20 parts by weight of "Epicote 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 was applied to a sheet base material so as to have a thickness of 100 μm, allowed to stand at room temperature for 1 day under a humidity of 60%, and then at 130 ° C. for 3 days.
The adhesive sheet was prepared by curing over time. SP adhesion, T-peel adhesion and shear adhesion were measured for this sheet.

Further, the addition amount of the above-mentioned bisphenol A type epoxy resin was changed to 50 parts by weight, and the other operations were performed in the same manner as above, and the above-mentioned measurement was carried out.

Example 25 To 100 parts by weight of the polymer obtained in Example 17, 20 parts by weight of a phenol novolac type epoxy resin (trade name "Epicoat 152" manufactured by Yuka Shell Epoxy Co., Ltd.) was added, and further dibutyltin laurate was added. 2 parts by weight and 5 parts by weight of triethylenetetramine were added, and the whole was mixed. The obtained mixture was applied to a sheet base material so as to have a thickness of 100 μm, and cured at 50 ° C. under humidity of 60% for 3 days to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 24.

Further, the above-mentioned measurement was carried out by changing the addition amount of the above-mentioned phenol novolac type epoxy resin to 50 parts by weight, and otherwise performing the same as above.

Example 26 To 100 parts by weight of the polymer obtained in Example 18, the above bisphenol A type epoxy resin "Epicoat 82" was used.
8 ", 20 parts by weight, 2 parts by weight of dibutyltin laurate and 5 parts by weight of isophoronediamine were added, and the whole was mixed. The resulting mixture has a thickness of 100 μm
To a sheet base material and cured at room temperature and 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 amount of the bisphenol A type epoxy resin added was changed to 50 parts by weight, and the other operations were performed in the same manner as above, and the above measurement was carried out.

Example 27 With respect to 100 parts by weight of the polymer obtained in Example 19, the above phenol novolac type epoxy resin "Epicoat 1" was used.
52 parts by weight, 2 parts by weight of dibutyltin laurate, and BF ₃ amine complex (Anchor Chemi
Cal Co., trade name "anchor 1171") was added 3 parts by weight, and the whole was mixed. The resulting mixture is made to a thickness of 100
It was applied to a sheet base material so as to have a thickness of μm, and cured at 100 ° C. under humidity of 60% for 7 hours to prepare an adhesive sheet. The physical properties of this sheet were measured as in Example 24.

The amount of the phenol novolac type epoxy resin added was changed to 50 parts by weight, and the other operations were carried out in the same manner as above, and the above measurement was carried out.

Comparative Example 3 Polymerization was carried out in the same manner as in Example 16, then 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-shaped polyisobutyl vinyl ether having a methoxy group at each end (Mn = 7,100, Mw / Mn =
1.05) was obtained.

To 100 parts by weight of the polymer, 2 parts of the above bisphenol A type epoxy resin "Epicoat 828" is added.
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. An adhesive sheet was prepared in the same manner as in Example 24 using the obtained mixture, and the physical properties of this sheet were measured.

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

With respect to 100 parts by weight of the polymer, the above phenol novolac type epoxy resin "Epicoat 152" was used.
20 parts by weight of dibutyl tin maleate
Parts by weight, and BF ₃ amine complex (Anchor Chemical C
o. 3 parts by weight of "Anchor 1171" (trade name, manufactured by the company) was added and the whole was mixed. Example 2 using the resulting mixture
An adhesive sheet was prepared in the same manner as in 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 With respect 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) was added in an amount of 200 parts by weight, and dibutyltin maleate was further added in an amount of 2 parts by weight. The resulting mixture was made into a 40% solution of ethyl acetate and then undercoated to a thickness of 35
One side of the μm polyester film has a thickness of 40 μm
To obtain a pressure-sensitive adhesive tape. SP adhesive strength, ball talc and holding power of this tape were measured.

Further, the addition amount of the above copolymer A was changed to 800 parts by weight, and the other conditions were the same as above, and the above measurement was carried out.

Example 29 With respect to 100 parts by weight of the polymer obtained in Example 13, n
-Butyl acrylate / 2-ethylhexyl acrylate / acrylic acid / hydroxypropyl acrylate (5
5/30/10/5) Copolymer B (Mw = 24,000)
0, Mw / Mn = 2.80) was added in an amount of 200 parts by weight, dibutyltin maleate was further added in an amount of 2 parts by weight, 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.

Further, the addition amount of the above-mentioned copolymer B was changed to 800 parts by weight, and the others were carried out in the same manner as above, and the above-mentioned 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 in Example 28 was added,
Further, 2 parts by weight of dibutyl tin 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.

The amount of the above-mentioned copolymer B was changed to 800 parts by weight, and the others were carried out in the same manner as above, and the above-mentioned 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 dibutyl tin 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.

Further, the addition amount of the copolymer B was changed to 800 parts by weight, and the others were performed 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, 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, 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 added amount of the copolymer is the added amount of the (meth) acrylic acid ester copolymer based on 100 parts by weight of the polyalkenyl ether.

The SP adhesive strength is the same as that in Table 11.

The ball tack is described in J. It is based on the Dow method and represents the adhesive strength.

The holding force was such that the sample was adhered to a stainless steel plate such that the adhesive surface had a width of 25 mm and a length of 25 mm, and further pressed by one reciprocation of a 2 kg roll,
After leaving it for 15 minutes, fix one end of the stainless steel plate and hang 500g (in the case of 80 ° C atmosphere) and 1kg (in the case of 40 ° C atmosphere) weight on the other end of the sample until the weight falls. Is the value indicated by the time of and represents 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 = 24.0)
0, Mw / Mn = 2.80) Example 32 Based on 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) was added in an amount of 200 parts by weight, and dibutyltin maleate was further added in an amount of 2 parts by weight. The resulting mixture was made into a 40% solution of ethyl acetate and then undercoated to a thickness of 35
One side of the μm polyester film has a thickness of 40 μm
To obtain a pressure-sensitive adhesive tape. SP adhesive strength, ball talc and holding power of this tape were measured.

Further, the addition amount of the copolymer A was changed to 800 parts by weight, the other conditions were the same as above, and the above-mentioned measurement was carried out.

Example 33 With respect to 100 parts by weight of the polymer obtained in Example 17, n
-Butyl acrylate / 2-ethylhexyl acrylate / acrylic acid / hydroxypropyl acrylate (5
5/30/10/5) Copolymer B (Mw = 24,000)
0, Mw / Mn = 2.80) was added in an amount of 200 parts by weight, dibutyltin maleate was further added in an amount of 2 parts by weight, and the whole was mixed. Using the obtained 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.

Further, the addition amount of the above-mentioned copolymer B was changed to 800 parts by weight, and the other conditions were the same as above, and the above-mentioned 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 in Example 32 was added,
Further, 2 parts by weight of dibutyl tin maleate was added and the whole was mixed. Using the obtained 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.

Further, the addition amount of the above-mentioned copolymer B was changed to 800 parts by weight, and the others were carried out in the same manner as above, and the above-mentioned 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 in Example 33 was added,
Further, 2 parts by weight of dibutyl tin maleate was added and the whole was mixed. Using the obtained 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.

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

Comparative Example 7 The copolymer A of Example 32 was used alone, 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, 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 amount of copolymer added, 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 Scientific Co., Ltd.) and 2 parts by weight of dibutyltin maleate were added. The obtained mixture was applied to one side of a polyester film having a thickness of 35 μm so that the thickness of the adhesive was 40 μm, and 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. SP adhesive strength, ball talc and holding power of this tape were measured.

Further, the addition amount of the ester gum A is 0,
The above-mentioned measurement was carried out by changing the amounts to 80 and 120 parts by weight in the same manner as above.

Example 37 Y was added to 100 parts by weight of the polymer obtained in Example 13.
30 parts by weight of S resin Px (β-pinene polymer, Yasuhara Yushi) was added, and 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 36. The physical properties of this sheet were measured as in Example 36.

The amount of the YS resin Px added is 80
The above-mentioned measurement was carried out in the same manner as above except that the parts by weight were changed.

Example 38 To 100 parts by weight of the polymer obtained in Example 14, 30 parts of Escoletz 1103U (petroleum type, manufactured by Esso Chemical Co., Ltd.) were added.
2 parts by weight of dibutyl tin maleate was 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 Escolet 1103U added was changed to 0, 80, and 120 parts by weight, and the other operations were carried out in the same manner as above, and the above measurement was carried out.

Example 39 To 100 parts by weight of the polymer obtained in Example 15, Hirez T-100X (petroleum type, manufactured by Mitsui Petrochemical Co., Ltd.) was added, and further 2 parts by weight of dibutyltin maleate was added, and the whole was mixed. 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-mentioned measurement was carried out by changing the addition amount of the above-mentioned Hiletz T-100X to 80 parts by weight and carrying out the other things in the same manner as above.

Comparative Example 9 Polymerization was carried out in the same manner as in Example 12, then 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 triple-chain star-shaped polyisobutyl vinyl ether having a methoxy group at each end (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 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 36. The physical properties of this sheet were measured as in Example 36.

Further, the amount of the YS resin Px added is 80
The above-mentioned measurement was carried out in the same manner as above except that the parts by weight were changed.

Table 15 shows the results of these measurements.

[0280]

[Table 15]

In Table 15, the amount of copolymer added, SP adhesive strength,
The ball tack and holding power 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 tackifying resin, manufactured by Arakawa Chemical Co., Ltd. YS resin Px: β-pinene polymer tackifying resin, Yasuhara Yushi Escoretz 1103U: Petroleum-based tackifying resin, Hiretsu T-100X manufactured by Esso Chemical Co., Ltd .: 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-based, manufactured by Arakawa Chemical Co., Ltd.) was added, and further dibutyl tin maleate was added. 2 parts by weight was added. The obtained mixture was applied to one side of a polyester film having a thickness of 35 μm so that the thickness of the adhesive was 40 μm, and 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. SP adhesive strength, ball talc and holding power of this tape were measured.

The amount of ester gum A added was 0,
The above-mentioned measurement was carried out by changing the amounts to 80 and 120 parts by weight in the same manner as above.

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

The amount of the YS resin Px added is 80
The above-mentioned measurement was carried out in the same manner as above except that the parts were changed to parts by weight.

Example 42 To 100 parts by weight of the polymer obtained in Example 18, 30 parts of Escoletz 1103U (petroleum type, manufactured by Esso Chemical Co., Ltd.) was added.
2 parts by weight of dibutyl tin maleate was added, and the whole was mixed. An adhesive tape was produced using the obtained mixture by the same operation as in Example 40. The physical properties of this sheet were measured as in Example 40.

The amount of Escolet 1103U added was changed to 0, 80, and 120 parts by weight, and the other operations were carried out in the same manner as described above, and the above measurement was carried out.

Example 43 To 100 parts by weight of the polymer obtained in Example 19, Hiletz T-100X (petroleum, manufactured by Mitsui Petrochemical Co., Ltd.) was added, and further 2 parts by weight of dibutyltin maleate was added, and the whole was mixed. did. An adhesive tape was produced using the obtained mixture by the same operation as in Example 40. The physical properties of this sheet were measured as in Example 40.

The above-mentioned measurement was carried out by changing the addition amount of the above-mentioned Hiletz T-100X to 80 parts by weight and carrying out the other operations in the same manner as above.

Example 44 To 100 parts by weight of the polymer obtained in Example 11, 30 parts by weight of ester gum A (rosin-based, manufactured by Arakawa Chemical Co., Ltd.) was added, and further 2 parts by weight of dibutyltin maleate was added, and the whole was added. Were mixed. An adhesive tape was produced using the obtained mixture by the same operation as in Example 40. The physical properties of this sheet were measured as in Example 40.

The amount of the ester gum A added was 80
The above-mentioned measurement was carried out in the same manner as above except that the parts were changed to parts by weight.

Comparative Example 10 Polymerization was carried out in the same manner as in Example 16, then 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-shaped polyisobutyl vinyl ether having a methoxy group at each end (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 further 2 parts by weight of dibutyltin maleate was added, and the whole was mixed. An adhesive tape was produced using the obtained mixture by the same operation as in Example 40. The physical properties of this sheet were measured as in Example 40.

Further, the amount of the YS resin Px added is 80
The above-mentioned measurement was carried out in the same manner as above except that the parts were changed to parts by weight.

Table 16 shows the results of these measurements.

[0297]

[Table 16]

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

Ester gum A, YS resin Px, Escolet 1103U and Hilet T-100X are shown in Table 15.
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 (40% chlorine content), 20 parts by weight of titanium dioxide and 50 parts by weight of calcium carbonate were added to prepare a blend. Were mixed with three rolls.

To this mixture was added 2 parts by weight of dibutyl tin maleate and the mixture was further mixed.
The cured product sheet having a thickness of 2 mm was prepared by curing at a temperature of 7% for 7 days.

A tensile test was conducted on this sheet in accordance with JIS6301, and the strength at break was 15.2 kg.
The result was / cm ² and elongation at break 450%. Furthermore, an exposure test was performed for 500 hours, but no whitening or cracking occurred.

Example 46 To 100 parts by weight of the polymer obtained in Example 13, 20 parts by weight of tricresyl phosphate, 20 parts by weight of carbon black and 50 parts by weight of silicic acid anhydride were added, and the mixture was rolled on a three-roll roll. Mixed. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 45 and subjected to a tensile test, which revealed a strength at break of 13.1 kg / cm ² and an elongation at break of 4
A result of 80% was obtained. An exposure test was further conducted for 500 hours, but 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 to obtain 3 parts of a mixture.
Mixed with this roll. Example 4 using the resulting mixture
A cured product sheet was prepared in the same manner as in Example 5 and subjected to a tensile test. As a result, strength at break 11.2 kg / cm ² and elongation at break 600% were obtained. An exposure test was further conducted for 500 hours, but 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 to prepare a blend. Were mixed with three rolls. Using the obtained mixture, a cured product sheet was prepared in the same manner as in Example 45, and a tensile test was conducted to find that the strength at break was 12.
The results were 4 kg / cm ² and elongation at break of 550%. An exposure test was further conducted for 500 hours, but no whitening or cracking occurred.

Comparative Example 11 As a resin, polypropylene oxide having a methyldimethoxysilyl group at both ends (Mn = 7.400, Mw /
(Mn = 1.03), the same additive material as in Example 48 was added to 100 parts by weight of the polymer, and the mixture was mixed with a three-roll mill. Example 45 using the resulting mixture
A cured product sheet was prepared in the same manner as above and subjected to a tensile test. As a result, a strength at break 11.3 kg / cm ² and an elongation at break 480% were obtained. When the exposure test was further conducted for 500 hours, cracks up to a length of 5 mm were 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 (40% chlorine content), 20 parts by weight of titanium dioxide, and 50 parts by weight of calcium carbonate were added to prepare a blend. Were mixed with three rolls.

To this mixture was added 2 parts by weight of dibutyltin maleate and the mixture was further mixed.
The cured product sheet having a thickness of 2 mm was prepared by curing at a temperature of 7% for 7 days.

A tensile test was conducted on this sheet in accordance with JIS6301, and the strength at break was 20.2 kg.
The result was / cm ² and elongation at break of 280%. Furthermore, an exposure test was performed for 500 hours, but no whitening or cracking occurred.

Example 50 To 100 parts by weight of the polymer obtained in Example 17, 20 parts by weight of tricresyl phosphate, 20 parts by weight of carbon black and 50 parts by weight of silicic acid anhydride were added, and the mixture was rolled on a three-roll roll. Mixed. 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 strength at break was 21.3 kg / cm ² , the elongation at break was 2
A result of 60% was obtained. An exposure test was further conducted for 500 hours, but 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 to prepare a mixture of 3 parts.
Mixed with this roll. Example 4 using the resulting mixture
A cured product sheet was prepared in the same manner as in Example 9 and subjected to a tensile test. As a result, a strength at break of 26.5 kg / cm ² and an elongation at break of 210% were obtained. An exposure test was further conducted for 500 hours, but no whitening or cracking occurred.

Example 52 To 100 parts by weight of the polymer obtained in Example 19 were added 20 parts by weight of triethylene glycol di-2-ethylbutyrate, 20 parts by weight of carbon black and 50 parts by weight of talc to prepare a blend. Were mixed with three rolls. A cured product sheet was prepared using the obtained mixture by the same operation as in Example 49, and a tensile test was conducted. The strength at break was 24.
The results were 3 kg / cm ² and elongation at break 240%. An exposure test was further conducted for 500 hours, but 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 (40% chlorine content), 20 parts by weight of titanium dioxide, and 50 parts by weight of calcium carbonate were added to prepare a blend. Were mixed with three rolls. A cured product sheet is prepared by the same operation as in Example 49 using the obtained mixture,
A tensile test showed that the strength at break was 19.1 kg /
The results were cm ² and elongation at break 320%. An exposure test was further conducted for 500 hours, but no whitening or cracking occurred.

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

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C09K 3/10 G 9159-4H Z 9159-4H

Claims (5)

[Claims] 1. A general formula: (In the formula, 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, and n is 3
Is a trivalent organic group, 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, R ⁶ , R ⁷ and R ⁸ are the same or different and each is an alkyl group, an aryl group or an alkoxy group, at least one of which is an alkoxy group, and x is 1 to
Alkyl ether compound represented by 10000). 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) acrylic acid ester copolymer. 4. A pressure-sensitive adhesive composition comprising the alkenyl ether compound according to claim 1 and a tackifying substance. 5. A room temperature curable resin composition comprising the alkenyl ether compound according to claim 1.