JP3103162B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a linear, triple-stranded or quadruple star such as linear polyalkenyl ether, triple-stranded star polyalkenyl ether and quadruple-star polyalkenyl ether. More specifically, the present invention relates to an epoxy adhesive composition containing an alkenyl compound, which is applied to a substrate without a solvent, has excellent tackiness before curing, and becomes a strong adhesive after curing. About things.

[0002]

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

[0003] Many solvent-free adhesives have been developed to meet these needs. For example, hot-melt adhesives of polyolefin resins and non-solvent reactive adhesives mainly composed of epoxy resins and urethane resins have been proposed (“11691 Chemical Products”, 11).
03-1106, published by The Chemical Daily).

[0004]

However, the former has a problem that it cannot be temporarily bonded by using the former, and the latter has a two-pack type of a main agent and a curing agent, which is poor in workability. In addition, there is a drawback that temporary bonding cannot be performed.

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to use a non-solvent type in which the adhesive strength and the adhesive strength are balanced before curing, the peeling adhesive strength after curing is large, and therefore the workability is good. Another object of the present invention is to provide an adhesive composition capable of temporary bonding.

[0006]

According to the present invention, there is provided an adhesive composition which achieves the above object by combining an alkenyl ether compound having a specific structure with an epoxy resin.

That is, the adhesive composition according to the present invention has a general formula

[0008]

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(Wherein, n is an integer 2, 3 or 4, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic group when n is 2, a trivalent organic group when n is 3, when n is 4, a tetravalent organic group, R ³ is a hydrogen atom or a methyl group, R ⁴ is a monovalent organic group, and x represents 1 to 10,000, respectively) and an epoxy resin. It consists of

First, the linear, three-chain star or four-chain star alkenyl ether compound represented by the above general formula will be described.

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

N is an integer 2, 3 or 4.

R ¹ is a hydrogen atom or a methyl group.

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

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

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

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

[0023]

[Table 7]

[0024]

[Table 8]

[0025]

[Table 9]

[0026]

[Table 10]

R ³ is a hydrogen atom or a methyl group.

R ⁴ is a monovalent organic group.

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

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

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

Next, a method for producing an alkenyl ether compound will be described.

The alkenyl ether compound has the general formula

[0034]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
n is an integer 2, 3 or 4, R ² is a divalent organic group when n is 2, a trivalent organic group when n is 3, and a tetravalent organic group when n is 4) Using an adduct of a polyfunctional alkenyl ether and a cation-providing compound as an initiator,

[0036]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a monovalent organic group), and polymerizes an olefin compound represented by the following general formula:

[0038]

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Wherein M is an alkali metal, R ⁵ and R
⁶ represents an alkyl or aralkyl group, respectively)
The polymerization reaction is stopped by using a metal salt of a malonic ester represented by the formula (1) to obtain an alkenyl ether having a malonic ester at a terminal, and the ester is further alkali-hydrolyzed.

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

General formula CHR ¹ ＣＨCH—O—R ² —O—CH ＝ CHR ¹ (Ia) wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a divalent organic group. Using an adduct of a bifunctional alkenyl ether represented by the formula

[0042]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a monovalent organic group), and an alkenyl ether represented by the following formula:

[0044]

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Wherein M is an alkali metal, R ⁵ and R
⁶ represents an alkyl or aralkyl group, respectively)
By terminating the polymerization reaction using a malonate metal salt represented by to obtain an alkenyl ether having a malonic ester at the terminal, further alkali hydrolysis of the ester,

[0046]

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(Where x is 1 to 10000, R ¹ ,
R ² , R ³ and R ⁴ have the same meanings as described above).

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

General formula

[0050]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² represents a trivalent organic group), and an adduct of a trifunctional alkenyl ether represented by the formula:

[0052]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a monovalent organic group), and alkenyl ether represented by the following general formula:

[0054]

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Wherein M is an alkali metal, R ⁵ and R
⁶ represents an alkyl or aralkyl group, respectively)
By terminating the polymerization reaction using a metal salt of a malonic ester represented by the following formula to obtain an alkenyl ether having a malonic ester at the terminal, and further alkali-hydrolyzing the ester, the general formula

[0056]

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

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

General formula

[0060]

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(Wherein R ¹ is a hydrogen atom or a methyl group,
R ² represents a tetravalent organic group), using an adduct of a tetrafunctional alkenyl ether represented by the formula (I) and a cation-providing compound as an initiator and a Lewis acid as an activator;

[0062]

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(Wherein R ³ is a hydrogen atom or a methyl group,
R ⁴ represents a monovalent organic group), and an alkenyl ether represented by the following formula:

[0064]

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Wherein M is an alkali metal, R ⁵ and R
⁶ represents an alkyl or aralkyl group, respectively)
By terminating the polymerization reaction using a metal salt of a malonic ester represented by the following formula to obtain an alkenyl ether having a malonic ester at the terminal, and further alkali-hydrolyzing the ester, the general formula

[0066]

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(Where x is 1 to 10000, R ¹ ,
R ² , R ³ and R ⁴ have the same meanings as described above).

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

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

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

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

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

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

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

In 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 of a compound or an adduct of a tetrafunctional alkenyl ether [Ic] and a cation-providing compound is used as an initiator. When the cation-providing compound is represented by HA, this adduct has the general formula

[0076]

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

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

Since the degree of polymerization of the polymer is determined by the molar ratio (100% polymerization rate) of the alkenyl ether [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 between the alkenyl ether [II] and the adduct [IV] according to the desired degree of polymerization. The molar ratio is 2 or more when a double-stranded star compound is obtained, 3 or more when a triple-stranded star compound is obtained, and 4 or more when a four-stranded star compound is obtained. Is appropriately determined according to the conditions.

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

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

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

These methods will be described in more detail.

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

R ⁷ _r AlX _s [V] (wherein R ⁷ represents a monovalent organic group, X represents a halogen atom, r and s are integers, r + s = 3, and 0 ≦ r
<3, 0 ≦ s <3. Examples of the organic aluminum compound [V] include, for example, trichloroaluminum, tribromoaluminum, ethylaluminum dichloride, ethylaluminum dibromide, diethylaluminum chloride, diethylaluminum bromide, ethylaluminum diiodo, ethylaluminum difluoride, methyl Aluminum dichloride, methylaluminum dibromide, dimethylaluminum chloride, dimethylaluminum bromide and the like can be mentioned. These organoaluminum compounds may be used alone or in combination of two or more. The amount of the organoaluminum compound used is generally in the range of alkenyl ether [II] / organoaluminum compound [V] = 2 to 10,000 in molar ratio. , Preferably in the range of 10 to 5000.

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

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

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

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

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

To introduce malonic acid to the polymer end,
The following method is performed.

Since the above polymerization reaction is living polymerization,
In order to terminate the polymerization and to introduce a desired functional group into the terminal of the polymer, a general-purpose polymerization terminator is used.

[0093]

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Wherein M is an alkali metal, R ⁵ and R
⁶ represents an alkyl or aralkyl group, respectively)
The polymerization reaction is stopped using a metal salt of a malonic ester represented by

Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the alkyl group for R ⁵ and R ⁶ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. R ⁵ and R
Examples of the aralkyl group ⁶ include benzyl, phenethyl and the like.

The molar ratio of the polymerization terminator, ie, the malonate metal salt, to the cation-providing compound HA is from 1 to 10
000, preferably 1 to 1000.

The alkenyl ether having a malonic ester at the terminal obtained by terminating the polymerization is then subjected to alkaline hydrolysis of the ester. For example, the obtained polymer is dissolved in 1,4-dioxane, and sodium hydroxide or potassium hydroxide is added in a molar ratio of 1 to 100 times, preferably 1 to 5 times with respect to the polymerization terminator, and mixed. After the solution is stirred at room temperature for 1 to 2 days, the solution is neutralized by adding an acid equivalent to the alkali, for example, hydrochloric acid. Thus,
An alkenyl ether having a dicarboxylic acid at the terminal is obtained.

The degree of polymerization x of the alkenyl ether compound is in the range of 1 to 10000, preferably 4 to 5000, more preferably 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 is preferably 1
１1.3.

Since the alkenyl ether compound is crosslinked and cured by moisture in the atmosphere, it is preferable that the alkenyl ether compound be stored in a moisture-free state until it is used.

Next, an epoxy resin which is another component of the adhesive composition according to the present invention will be described.

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

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

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

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

The adhesive composition according to the present invention comprises a filler,
It is also possible to optionally add additives such as tackifiers, plasticizers and antioxidants.

[0107]

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

Further, since the degree of polymerization of the alkenyl ether compound can be adjusted to a desired value or a functional group can be introduced into the desired value, hydrophilicity, hydrophobicity, tackiness, adhesive strength, etc. can be freely controlled, and high Functional adhesives can be prepared.

[0109]

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

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

[0111]Reference Example 1(Tri-functional alkenyl ether
Glass three-necked flask equipped with a condenser and stirrer
In a nitrogen atmosphere, 2-hydroxyl was added to 50 ml of toluene.
9.96 g of siethyl vinyl ether (113 mmol)
Was dissolved, and 2.71 g of sodium hydride powder was added to the solution.
(113 mmol) and the solution was stirred at room temperature for 1 hour.
Was. Then, 10.0 g of trimesic acid chloride was added to this solution.
(33.7 mmol) and tetra-n-butylammonium
Add 0.5 g of muchloride and react at 80 ° C for 4 hours
Was. After extracting the reaction mixture with diethyl ether,
The extract was dried to obtain crude crystals. This is toluene / hex
Recrystallized from sun (1: 1), 1,3,5-benzenetri
Tri (2-vinyloxy) ethyl carboxylate (No. 1 in Table 3)
Eye compound) was obtained. Yield: 70%, melting point: 32-34
° C (light yellow crystal), infrared absorption spectrum (Nujol): ν
_{C = O}= 1740cm^-1, Ν _{C = C}= 1620cm^-1, Ν_Ph=
830cm^-1.

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

[0113]

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Δ (ppm): peak c 4.00 (t, 6
H, -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 Group 2 ) Reference Example 2 (Preparation of trifunctional alkenyl ether) 75 ml of dimethyl sulfoxide in a three-neck glass flask equipped with a condenser and a stirrer under a nitrogen atmosphere.
Was dissolved in 10.0 g (32.6 mmol) of 1,1,1-tris (4-hydroxyphenyl) ethane, and 23.5 g (587 mmol) of sodium hydroxide powder was added to the solution. Stir for 3 hours. Then, 59.7 ml of 2-chloroethyl vinyl ether (58
7 mmol) and reacted at 80 ° C. for 5 hours. The reaction mixture was purified in the same manner as in Reference Example 1 to give 1,1,1-
Tris [4- (2-vinyloxy) ethoxyphenyl] ethane (second compound in Table 4) was obtained. Yield: 62%,
Melting point: 92-93 ° C. (pale yellow crystal), infrared absorption spectrum (Nujol): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm
^-1 .

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

[0116]

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Δ (ppm): peak a 2.05 (s, 3
_{H, 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) Nitrogen atmosphere in a glass three-necked flask equipped with a condenser and a stirrer 75 ml of dimethyl sulfoxide below
Was dissolved in 10.0 g (22.1 mmol) of 1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane, and 21.2 g of sodium hydroxide powder was added to the solution.
(30 mmol) was added and the solution was stirred at 75 ° C. for 3 hours. Next, 53.9 ml (530 mmol) of 2-chloroethyl vinyl ether was added to this solution, and the mixture was reacted at 80 ° C. for 5 hours. The reaction mixture was purified in the same manner as in Reference Example 1 to obtain 1,1,4,4-tetrakis [4- (2-vinyloxy) ethoxyphenyl] cyclohexane (first compound in Table 9). Yield: 48%, melting point: 137.5
139 ° C (light yellow crystal), infrared absorption spectrum (Nujo
l): ν _{C = C} = 1620 cm ⁻¹ , ν _Ph = 830 cm ⁻¹ .

[0118]

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¹ H NMR spectrum (270 MHz, C
Measured value of DCl ₃ ): δ (ppm): peak a 2.25 (m, 8H, cyclohexane ring) d 4.00 (t, 8H, —CH ₂ −) e 4.15 (t, 8H, —CH ₂ −) g 4.00 4.25 (dd, 8H, = CH ₂ ) f 6.50 (dd, 4H, = CH) b 6.80 (d, 8H, aromatic) c 7.00 (d, 8H, aromatic) Example 1 Purification sufficiently under nitrogen atmosphere 50 ml (2.8 mol / l) of isobutyl vinyl ether was dissolved in 50 ml of dried toluene, and 25 ml of 1,4-dioxane was added thereto, and the temperature of the solution was kept at 0 ° C. 5 ml of an adduct of 1,1,1-tris [4- (2-vinyloxy) ethoxyphenyl] ethane (compound of Reference Example 2) diluted with toluene and trifluoroacetic acid (CF ₃ COOH) was added thereto.
(37 mmol / l) and 5 ml (37 mmol / l) of a hexane solution of ethylaluminum dichloride were added in this order to start polymerization, and the polymerization was continued at 0 ° C. for 30 minutes.

Thereafter, a solution of sodium salt of diethyl malonate in 10 ml of 1,4-dioxane (74 mmol / mol
l) was added to terminate the polymerization. After distilling off the solvent and the like from the polymerization reaction liquid, 1,4-dioxane solution 100
and then add 20 ml of aqueous sodium hydroxide solution.
(150 mmol / l) and the mixture was stirred at room temperature for 1 day. Then, 10 ml of hydrochloric acid (150 mmol / l)
Was added to neutralize the mixture.

The solvent and the like were distilled off from the reaction mixture, and the polymer was recovered and dried.

As a result, a three-chain star-shaped polyisobutyl vinyl ether having a dicarboxylic acid at each terminal (Mn = 7,
800, Mw / Mn = 1.05).

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

[0124]

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

[0126]

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Δ (ppm): peak k 0.90 (18 ×
_{H, CH 3) f 1.20 (} 9H, CH 3) g + j 1.40~2.00 (9xH, -CH 2 -, CH) a 2.10 (3H, CH 3) d, e, h, i, m 3.00~4.00 c 4.10 ( 6H, —CH ₂ —) b 6.75 to 7.00 (12H, aromatic) n 6.20 to 7.20 (6H, COOH) The bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.)
200 parts by weight of trade name “Epicoat 828”) and 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol were further added and the whole was mixed. The resulting mixture was applied to a sheet substrate to a thickness of 100 μm, and then cured at 100 ° C. for 30 minutes to prepare an adhesive sheet. This sheet was measured for SP adhesive strength, T peel adhesive strength, and shear adhesive strength.

The above measurement was carried out by changing the addition amount of the bisphenol A type epoxy resin to 400 parts by weight and performing the other operations in the same manner as described above.

Example 2 The measured value of the ¹ H NMR spectrum (270 MHz, CDCl ₃ ) of this three-chain star block copolymer is shown in Example 2.
Was the same as the measured value.

The same operation as in Example 1 was carried out except that potassium salt of dibenzyl malonate was used as a polymerization terminator.

As a result, a three-chain star-shaped polyisobutyl vinyl ether having a dicarboxylic acid at each terminal (Mn = 8,
200, Mw / Mn = 1.04).

The ¹ H NMR spectrum (270 MHz, CDCl
The measured value of ₃ ) was the same as the corresponding measured value of the polymer of Example 1.

To 100 parts by weight of the polymer thus obtained, 20 parts of phenol novolak type epoxy resin (trade name “Epicoat 152” manufactured by Yuka Shell Epoxy Co., Ltd.) was added.
0 parts by weight and further 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol were added and the whole was mixed. The obtained mixture was applied to a sheet substrate so as to have a thickness of 100 μm, and then cured at 120 ° C. for 30 minutes to prepare an adhesive sheet. About this sheet SP
The adhesive strength, T peel adhesive strength and shear adhesive strength were measured.

The above measurement was carried out by changing the amount of the phenol novolak type epoxy resin to 400 parts by weight and performing the other operations in the same manner as described above.

Example 3 50 ml (3.9 mol / l) of ethyl vinyl ether was added to 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere.
l) Dissolved, 25 ml of 1,4-dioxane was added thereto, and the temperature of the solution was kept at 0 ° C. There, 1,4-
5 ml (37 mmol / l) of a toluene solution of an adduct of divinyloxyethoxybenzene (third compound in Table 1) and trifluoroacetic acid (CF ₃ COOH), and 5 ml of a hexane solution of ethyl aluminum dichloride (3
7 mmol / l) were added in this order to initiate the polymerization.
The polymerization was continued at 3 ° C. for 3 hours.

Thereafter, a solution of sodium salt of diethyl malonate in 10 ml of 1,4-dioxane (74 mmol / mol
l) was added to terminate the polymerization. After distilling off the solvent and the like from the polymerization reaction liquid, 1,4-dioxane solution 100
and then add 20 ml of aqueous sodium hydroxide solution.
(150 mmol / l) and the mixture was stirred at room temperature for 1 day. Then, 10 ml of hydrochloric acid (150 mmol / l)
Was added to neutralize the mixture.

The solvent and the like were distilled off from the reaction mixture, and the polymer was recovered and dried.

As a result, a linear polyethyl vinyl ether having a dicarboxylic acid at both terminals (Mn = 8,000, M
w / Mn = 1.05) was obtained.

The ¹ H NMR spectrum (270 MHz, C
Measurement value of DCl ₃ ): <Linear polyethyl vinyl ether>

[0140]

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Δ (ppm): peak e 1.20 (6H,
CH ₃ ) i 1.20 (6 × H, CH ₃ ) f 1.40 to 2.00 (4 × H, —CH ₂ —) c, d, g, h, j 3.00 to 4.00 b 4.10 (4H, —CH ₂ —) a 8.00 (4H, (Aromatic) k 6.20 to 7.20 (4H, COOH) Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) was used for 100 parts by weight of the polymer thus obtained.
200 parts by weight of trade name “Epicoat 828”) and 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol were further added and the whole was mixed. The resulting mixture was applied to a sheet substrate to a thickness of 100 μm, and then cured at 100 ° C. for 30 minutes to prepare an adhesive sheet. This sheet was measured for SP adhesive strength, T peel adhesive strength, and shear adhesive strength.

The above measurement was carried out by changing the addition amount of the bisphenol A type epoxy resin to 400 parts by weight and performing the other operations in the same manner as described above.

Example 4 The same operation as in Example 3 was performed, except that potassium salt of dibenzyl malonate was used as a polymerization terminator.

As a result, a linear polyethyl vinyl ether having a dicarboxylic acid at both terminals (Mn = 8,300, M
w / Mn = 1.04) was obtained.

[0145: ¹ H of the linear poly vinyl ether
The measured value of the NMR spectrum (270 MHz, CDCl ₃ ) was the same as the corresponding value of the measured value of the polymer of Example 3.

To 100 parts by weight of the polymer thus obtained, 20 parts of a phenol novolak type epoxy resin (trade name “Epicoat 152” manufactured by Yuka Shell Epoxy) was added.
0 parts by weight and further 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol were added and the whole was mixed. After applying the obtained mixture to a sheet substrate to a thickness of 100 μm, the mixture was heated at 120 ° C. for 30 minutes and at 180 ° C. for 2 minutes.
It was cured over time to form an adhesive sheet. This sheet was measured for SP adhesive strength, T peel adhesive strength, and shear adhesive strength.

The above measurement was carried out by changing the addition amount of the phenol novolak type epoxy resin to 400 parts by weight and performing the other operations in the same manner as described above.

Example 5 50 ml (2.8 mol / l) of isobutyl vinyl ether was dissolved in 50 ml of toluene which had been sufficiently purified and dried under a nitrogen atmosphere, and 25 ml of 1,4-dioxane was added thereto. The temperature was kept at 0 ° C. There, 1,1,4,4-tetrakis [4- (2-
Vinyloxy) ethoxyphenyl] cyclohexane (compound of Reference Example 3) and trifluoroacetic acid (CF ₃ COOH)
5 ml of a 1 mol / l toluene solution of the adduct (37 mmol / l) and 5 ml of a hexane solution of ethylaluminum dichloride (37 mmol / l) were added in this order to initiate polymerization. The polymerization was continued.

Thereafter, 10 ml of a 1,4-dioxane solution of sodium salt of diethyl malonate (148 mmol / mol
l) was added to terminate the polymerization. After distilling off the solvent and the like from the polymerization reaction liquid, 1,4-dioxane solution 100
and then add 40 ml of aqueous sodium hydroxide solution.
(300 mmol / l) and the mixture was stirred at room temperature for 1 day. Then, 20 ml of hydrochloric acid (300 mmol / l)
Was added to neutralize the mixture.

The solvent and the like were distilled off from the reaction mixture, and the polymer was recovered and dried.

As a result, a four-chain star-shaped polyisobutyl vinyl ether having a dicarboxylic acid at each terminal (Mn = 7,
800, Mw / Mn = 1.05).

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

[0153]

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Δ (ppm): peak g 1.50 (s, 1
_{2H, 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) <Four-chain star-shaped polyisobutyl vinyl ether>

[0155]

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Δ (ppm): peak k 1.20 (24 ×
_{H, CH 3) g 1.40~2.00 (} 8xH, -CH 2 -) a 2.10~2.40 (8H, cyclohexane ring) d, e, h, i 3.00~4.00 c 4.10 (8H, -CH 2 -) m 4.65 ( 4H, CH) n 6.20 to 7.20 (6H, COOH) b 6.75 to 7.00 (16H, aromatic) Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd.) was used for 100 parts by weight of the polymer thus obtained.
200 parts by weight of trade name “Epicoat 828”) and 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol were further added and the whole was mixed. The resulting mixture was applied to a sheet substrate to a thickness of 100 μm, and then cured at 100 ° C. for 30 minutes to prepare an adhesive sheet. This sheet was measured for SP adhesive strength, T peel adhesive strength, and shear adhesive strength.

The above measurement was carried out by changing the addition amount of the bisphenol A type epoxy resin to 400 parts by weight and the other conditions were the same as above.

Example 6 In place of isobutyl vinyl ether in Example 5, 50 ml (3.9 mol / l) of ethyl vinyl ether was used, the polymerization reaction time was set to 3 hours, and the potassium salt of dibenzyl malonate was used as a polymerization terminator. Except for this, the same operation as in Example 1 was performed.

As a result, a four-chain star polyethyl vinyl ether having a dicarboxylic acid at each terminal (Mn = 8, 20
0, Mw / Mn = 1.05).

The ¹ H NMR spectrum (270 MHz, CDCl
The measured value of ₃ ) was the same as the corresponding measured value of the polymer of Example 5.

A phenol novolak type epoxy resin (trade name “Epicoat 152” manufactured by Yuka Shell Epoxy Co., Ltd.) was added to 100 parts by weight of the polymer thus obtained.
0 parts by weight and further 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol were added and the whole was mixed. The obtained mixture was applied to a sheet substrate so as to have a thickness of 100 μm, and then cured at 120 ° C. for 30 minutes to prepare an adhesive sheet. About this sheet SP
The adhesive strength, T peel adhesive strength and shear adhesive strength were measured.

The above measurement was carried out by changing the amount of the phenol novolak type epoxy resin to 400 parts by weight and performing the other operations in the same manner as described above.

Comparative Example 1 After the polymerization was carried out in the same manner as in Example 1, the polymerization was stopped by adding 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 terminal (Mn = 7.6)
00, Mw / Mn = 1.04) was obtained.

The bisphenol A type epoxy resin “Epicoat 828” was added to 2 parts by weight of 100 parts by weight of the polymer.
Then, 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol was added, and the whole was mixed. Using the obtained mixture, an adhesive sheet was prepared in the same manner as in Example 1, and the physical properties of this sheet were measured.

Comparative Example 2 After polymerization was carried out in the same manner as in Example 3, the polymerization was stopped by adding methanol, and the solvent and the like were distilled off from the reaction mixture to recover a viscous liquid.

As a result, a linear polyethyl vinyl ether having methoxy groups at both ends (Mn = 7,700, Mw
/Mn=1.04) was obtained.

With respect to 100 parts by weight of the polymer, the above bis
Phenol A type epoxy resin "Epicoat 828"
00 parts by weight and 2,4,6-tris (dimethyl
Add 5 parts by weight of aminomethyl) phenol and mix the whole
did. Using the obtained mixture, an adhesive was used in the same manner as in Example 3.
A sheet was prepared and the physical properties of the sheet were measured. Comparative Example 3 After polymerization was performed in the same manner as in Example 5, methanol was added.
The polymerization is stopped by the addition, and the solvent etc. is distilled from the reaction mixture.
On leaving, the viscous liquid was collected.

As a result, a quadruple star polyisobutyl vinyl ether having a methoxy group at each terminal (Mn = 7.6)
00, Mw / Mn = 1.04) was obtained.

The above bisphenol A type epoxy resin “Epicoat 828” was added to 2 parts by weight of 100 parts by weight of the polymer.
Then, 5 parts by weight of 2,4,6-tris (dimethylaminomethyl) phenol was added, and the whole was mixed. Using the obtained mixture, an adhesive sheet was prepared in the same manner as in Example 5, and the physical properties of this sheet were measured.

Comparative Example 4 After the polymerization was carried out in the same manner as in Example 6, the polymerization was stopped by adding 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 polyethyl vinyl ether having a methoxy group at each terminal (Mn = 8,000, M
w / Mn = 1.04) was obtained.

To 100 parts by weight of the polymer, 200 parts by weight of a phenol novolak type epoxy resin (trade name “Epicoat 152” manufactured by Yuka Shell Epoxy Co., Ltd.) was added, and further 2,4,6-tris (dimethylaminomethyl) 5 parts by weight of phenol was added and the whole was mixed. Using the obtained mixture, an adhesive sheet was prepared in the same manner as in Example 6, and the physical properties of this sheet were measured.

Table 11 shows the results of these measurements.

[0175]

[Table 11]

In Table 11, the SP adhesive strength was determined by adhering a sample having a width of 15 mm to a stainless steel plate, pressing the sample with five reciprocations of a 2 kg roll, leaving it to stand for 15 minutes, and turning it over at a folding angle of 180 degrees at 300 mm / min. It shows the strength when peeled off from the stainless steel plate at a speed, and indicates the adhesive force and the condensing force.

[0177] The T-peeling adhesive strength was measured by applying an adhesive composition to one side of a release-treated double-sided release paper, and having a thickness of 0.6 mm and a width of 25 mm.
The above adhesive sheet is stuck on an aluminum plate of mm, the release paper is peeled off and another aluminum plate is stuck, and the pressure is 2 kg /
pressurized 2 min cm ² and temporarily bonded, to prepare a test piece subjected to heat curing under conditions of 30 minutes at 110 ° C., a value measured in compliance with ASTMD-1876 This test piece.

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

Epicoat 828: bisphenol A type epoxy resin Epicoat 152: phenol novolak type epoxy resin

Continuation of the front page (56) References JP-A-49-26349 (JP, A) JP-A-51-116844 (JP, A) JP-A-52-121644 (JP, A) JP-A-54-14440 (JP) JP-A-50-51598 (JP, A) JP-A-6-239944 (JP, A) JP-A-5-117340 (JP, A) JP-A-5-43615 (JP, A) 5-310836 (JP, A) JP-A-5-247121 (JP, A) JP-A-5-279414 (JP, A) JP-B-49-49199 (JP, B1) (58) Fields investigated (Int. Cl ^7, DB name) C09J 1/00 -. 201/10 C08G 59/00 - 59/72 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A compound of the general formula (In the formula, n is an integer 2, 3 or 4, R ¹ is a hydrogen atom or a methyl group, R ² is a divalent organic group when n is 2, n is 3
Is a trivalent organic group, when n is 4, a tetravalent organic group, R ³
Is a hydrogen atom or a methyl group, R ⁴ is a monovalent organic group, and x represents 1 to 10000), respectively, and an epoxy resin.