JP3264452B2 - Adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymer of a saponified ethylene-vinyl ester copolymer and at least one selected from the group consisting of (meth) acrylates and vinyl esters with an unsaturated carboxylic acid. A composition comprising a graft copolymer obtained by grafting a polymer to the ethylene-vinyl ester copolymer and / or a saponified product thereof;
Or a composition comprising this composition and a tackifier,
It is characterized by having excellent adhesion to various adherends.

Further, by using this composition as an interlayer film for laminated glass, it is excellent in workability, has a uniform thickness with little gel, and has transparency, penetration resistance, light resistance and water resistance. The present invention relates to a laminated glass having characteristics required for glass.

[0003]

BACKGROUND OF THE INVENTION Ethylene-vinyl ester copolymers are compared with polyethylene,
It has excellent flexibility and tackiness, and is used as a main raw material for hot melt adhesives. Among them, in particular, saponified ethylene-vinyl acetate copolymer (ethylene-vinyl acetate copolymer is referred to as E
VA, which has a hydroxyl group in the side chain, has further excellent adhesive properties and is widely used as an adhesive for metals, plastics, glass, fibers and the like. However, depending on the application, the adhesive properties are not yet sufficient. For example, when an interlayer film of laminated glass is used, there are various problems.

[0004] The properties required for an interlayer film for laminated glass include transparency, adhesion to glass, water resistance, penetration resistance, and the like. Among these properties, plasticized polyvinyl butyral is conventionally used. Is widely used. However, plasticized polyvinyl butyral is expensive, and its film surface is very sticky at room temperature. Spraying an anti-blocking agent such as baking soda to prevent sticking requires washing, removing, and drying. Therefore, there are various problems that the operation is very complicated, and the adhesiveness to glass is reduced due to moisture absorption, and a phenomenon such as cloudiness and opacity is observed.

Further, as a type having improved film surface tackiness, a product obtained by esterifying saponified EVA with a cyclic acid anhydride is used, but even with these, transparency, adhesion and water resistance are not necessarily sufficient. .

Further, a product obtained by directly grafting an unsaturated carboxylic acid or an acid anhydride thereof to a saponified EVA is used. At the time of the graft copolymerization, gelation of the saponified EVA also occurs, and a uniform film thickness is obtained. Not only cannot a film be obtained, but also stable adhesiveness cannot be obtained, and it cannot be said that it is always good. An object of the present invention is to solve such a problem.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies in consideration of the above points, and as a result, have found that a saponified ethylene-vinyl ester copolymer and a group consisting of (meth) acrylic acid ester and vinyl ester are obtained. A composition comprising a graft copolymer obtained by grafting a copolymer of at least one or more selected unsaturated carboxylic acids with the ethylene-vinyl ester copolymer and / or a saponified product thereof, or It has been found that the composition comprising the tackifier has excellent adhesion to various substrates, particularly to glass.
Further, when the composition was used as an interlayer film for laminated glass, it was found that the composition had characteristics that solved the above-mentioned disadvantages, and the present invention was reached.

That is, the present invention relates to (I) 50 to 98% by weight of a saponified ethylene-vinyl ester copolymer, and (II)
5-90% by weight of a copolymer portion of at least one or more selected from the group consisting of (meth) acrylate esters and vinyl esters with unsaturated carboxylic acids, and ethylene-vinyl ester copolymers and / or saponified products thereof Part 95
A graft copolymer having a content of unsaturated carboxylic acid of 0.1 to 10% by weight, or a composition of 2 to 50% by weight; The present invention relates to a composition comprising less than 25 parts by weight of a tackifier per 100 parts by weight of a composition, and relates to an adhesive composition having excellent adhesion to various adherends. Further, the present invention relates to a laminated glass in which the composition is used as an intermediate film and glass is laminated on both sides thereof.

Hereinafter, the present invention will be described in detail. Ethylene which is a base range of the component (I) used in the present invention.
As the vinyl ester copolymer, those obtained by copolymerizing ethylene and ethylene-vinyl ester by a general high-pressure polyethylene plant can be used.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and the like. In the present invention, those using vinyl acetate are preferred. In the present invention, the vinyl ester content in the ethylene-vinyl ester copolymer is preferably 10 to 40% by weight. If the vinyl ester content is less than 10% by weight, the adhesion to glass and the transparency will be poor, and if it exceeds 40% by weight, the tackiness of the film surface may become strong.

Next, the saponification method of the ethylene-vinyl ester copolymer is a method of saponifying pellets or powder of the ethylene-vinyl ester copolymer in a lower alcohol such as methanol using an alkali catalyst, toluene, xylene and the like. And a method of dissolving the ethylene-vinyl ester copolymer in advance using a solvent that dissolves the ethylene-vinyl ester copolymer such as hexane, and then saponifying using a small amount of alcohol and an alkali catalyst.

The saponification degree of the saponified ethylene-vinyl ester copolymer is preferably less than 50%. It has a saponification degree of 50
%, The transparency deteriorates, which is not preferable.

The melt flow rate of the ethylene-vinyl ester copolymer and / or its saponified product (hereinafter referred to as M
FR) is not particularly defined, but is preferably 0.5 to 50 g / 10 minutes in order to obtain good adhesion and workability.

The saponified ethylene-vinyl ester copolymer used for the component (I) and the saponified ethylene-vinyl ester copolymer used for the graft copolymer (II) are the same. Is preferred, but there is no particular limitation.

The graft copolymer (I) used in the present invention
I) is a graft copolymer obtained by grafting at least one or more selected from the group consisting of (meth) acrylates and vinyl esters and an unsaturated carboxylic acid onto an ethylene-vinyl ester copolymer and / or a saponified product thereof. Combine.

(Meth) in the graft copolymer (II)
The copolymer of the unsaturated carboxylic acid and at least one selected from the group consisting of acrylic esters and vinyl esters is a copolymer of both monomers, and the number average degree of polymerization of the copolymer Is preferably in the range of 5 to 10,000, more preferably 10 to 5,000. Here, if the number average polymerization degree is less than 5, the adhesiveness with glass is insufficient,
On the other hand, when the number average polymerization degree exceeds 10,000, the viscosity at the time of melting becomes high, and the transparency is unfavorably reduced.

The acrylate in the graft copolymer (II) is, for example, a mixture of (meth) acrylic acid such as methyl (meth) acrylate and ethyl (meth) acrylate with an alkyl having 1 to 8 carbon atoms. Esters are mentioned.
Examples of the vinyl ester include the same vinyl esters as those used in the component (I).

Examples of the unsaturated carboxylic acids include acrylic acid, fumaric acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, malic anhydride,
Citraconic anhydride, itaconic anhydride, 4-methylcyclohex-4-ene-1,2-dicarboxylic anhydride, bicyclo (2,2,2) oct-5-ene-2,3-dicarboxylic anhydride, etc. These may be used alone or in a composite system.

Preferred examples of the copolymer of the unsaturated carboxylic acid with at least one selected from the group consisting of acrylic esters and vinyl esters in the graft copolymer (II) include methyl methacrylate-methyl methacrylate. Acrylic acid copolymer, methyl methacrylate-methacrylic acid copolymer, butyl acrylate-acrylic acid copolymer, butyl acrylate-methacrylic acid copolymer, vinyl acetate-acrylic acid copolymer, vinyl acetate-methacrylic acid Copolymers, vinyl acetate-maleic anhydride copolymers and the like are mentioned, and more preferred are methyl methacrylate-acrylic acid copolymer and vinyl acetate-acrylic acid copolymer.

The graft copolymer (II) contains 5 to 90% by weight of a copolymer portion of at least one selected from the group consisting of (meth) acrylates and vinyl esters and an unsaturated carboxylic acid. , Preferably 5 to 80% by weight, most preferably 10 to 50% by weight, the ethylene-vinyl ester copolymer and / or
~ 95% by weight, preferably 20-95% by weight, most preferably
It consists of 50-90% by weight.

If the copolymer portion of at least one selected from the group consisting of (meth) acrylic acid esters and vinyl esters with unsaturated carboxylic acids is less than 5% by weight, adhesion to glass is reduced. Is insufficient, and if the copolymer portion of the unsaturated carboxylic acid with at least one selected from the group consisting of (meth) acrylates and vinyl esters exceeds 90% by weight, the amount of the component (I) The compatibility is poor, and the transparency is undesirably reduced.

As a grafting method for producing the graft copolymer (II), any of generally known methods such as a chain transfer method and an ionizing radiation method may be used. Is a method described below.
This is because the grafting efficiency is high and secondary aggregation due to heat does not occur, so that the expression of performance is more effective.

Hereinafter, specific examples of the method for producing the graft copolymer (II) of the present invention will be described. That is, 100 parts by weight of an ethylene-vinyl ester copolymer and / or a saponified product thereof to be grafted are suspended in water, and at least one type of vinyl selected from the group consisting of (meth) acrylates and vinyl esters is separately prepared. 5 to 400 parts by weight of the monomer and the unsaturated carboxylic acid are combined with a polymerization initiator having a decomposition temperature of 40 to 90 ° C. to obtain a half-life of 10 hours by a total of 100 parts by weight of the vinyl monomer and the unsaturated carboxylic acid. And a solution prepared by dissolving 0.01 to 5 parts by weight with respect to parts by weight, and heating under a condition where decomposition of the polymerization initiator does not substantially occur, and converting the vinyl monomer, the unsaturated carboxylic acid, and the polymerization initiator into ethylene. Impregnating the vinyl ester copolymer and / or its saponified product; Next, the temperature of the aqueous suspension is increased, and the vinyl monomer and the unsaturated carboxylic acid are copolymerized in the ethylene-vinyl ester copolymer and / or the saponified product thereof to obtain a grafting precursor. .

The graft precursor does not necessarily have to be melt-kneaded before mixing with the component (I). That is, the grafting precursor may be directly melt-kneaded with the component (I).

The graft copolymer of the present invention can be obtained by melt-kneading the graft precursor at a temperature of 100 to 300 ° C.

Further, the most preferable production method of the present invention is the following method. Namely, an ethylene-vinyl ester copolymer to be grafted and / or a saponified product thereof
100 parts by weight are suspended in water, and at least one vinyl monomer selected from the group consisting of (meth) acrylic acid esters and vinyl esters and unsaturated carboxylic acid
400 parts by weight of a radical polymerizable organic peroxide represented by the following general formula (1) or (2) or a mixture of two or more thereof is added to a vinyl monomer and an unsaturated carboxylic acid in a total amount of 1
A polymerization initiator having a decomposition temperature of 40 to 90 ° C. to obtain a half life of 10 hours or less with respect to 100 parts by weight of a vinyl monomer, an unsaturated carboxylic acid, and a radical polymerizable organic peroxide. And a solution prepared by dissolving 0.01 to 5 parts by weight with respect to 100 parts by weight of the total amount of the monomers, and heating under a condition that decomposition of the polymerization initiator does not substantially occur. ,
A radically polymerizable organic peroxide and a polymerization initiator are impregnated into an ethylene-vinyl ester copolymer and / or a saponified product thereof.

Next, the temperature of the aqueous suspension was increased, and the vinyl monomer, the unsaturated carboxylic acid and the radically polymerizable organic peroxide were mixed in the ethylene-vinyl ester copolymer and / or the saponified product thereof. It is copolymerized to obtain a grafting precursor.

This graft precursor does not necessarily have to be melt-kneaded before being mixed with component (I), as described above. That is, this grafted precursor is directly used as the component (I)
And melt-kneading.

The graft copolymer of the present invention can be obtained by melt-kneading the graft precursor at a temperature of 100 to 300 ° C.

Here, the radically polymerizable organic peroxide of the general formula (1) is (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and R ₄ are alkyl groups having 1 to 4 carbon atoms, and R ₅ is a carbon atom having 1 carbon atom. ~
It represents 12 alkyl groups, phenyl groups, alkyl-substituted phenyl groups or cycloalkyl groups having 3 to 12 carbon atoms. m is 1
Or 2. ).

The radical polymerizable organic peroxide represented by the general formula (2) is (Wherein, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and R ₉ are alkyl groups each having 1 to 4 carbon atoms, and R ₁₀ is a carbon atom having 1 carbon atom. ~ 12
An alkyl group, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0,
1 or 2. ).

As the radical polymerizable organic peroxide represented by the general formula (1), specifically, t-butylperoxyacryloyloxyethyl carbonate; t-amylperoxyacryloyloxyethyl carbonate;
Hexyl peroxyacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutyl peroxyacryloyloxyethyl carbonate; cumyl peroxyacryloyloxyethyl carbonate; p-isopropylcumyl peroxyacryloyloxyethyl carbonate; t-butyl Peroxymethacryloyloxyethyl carbonate; t-amylperoxymethacryloyloxyethyl carbonate; t-hexylperoxymethacryloyloxyethyl carbonate; 1,1,3,3-tetramethylbutyl peroxymethacryloyloxyethyl carbonate; cumylperoxymethacryloy Roxyethyl carbonate; p-isopropylcumyl peroxymethacryloyloxyethyl carbonate; t-butylperoxymethacryloyl Roxyethyl carbonate; t-amyl peroxyacryloyloxyethoxyethyl carbonate; t-hexylperoxyacryloyloxyethoxyethyl carbonate; 1,1,3,3-tetramethylbutyl peroxyacryloyloxyethoxyethyl carbonate; cumylperoxyacryloyl Roxyethoxyethyl carbonate; p-isopropylcumyl peroxyacryloyloxyethoxyethyl carbonate; t
-Butyl peroxymethacryloyloxyethoxyethyl carbonate; t-amyl peroxymethacryloyloxyethoxyethyl carbonate; t-hexylperoxymethacryloyloxyethoxyethoxyethyl carbonate;
1,1,3,3-tetramethylbutyl peroxymethacryloyloxyethoxyethyl carbonate; cumyl peroxymethacryloyloxyethoxyethyl carbonate; p-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate; t-butylperoxyacryloyloxyisopropyl Carbonate; t-amylperoxyacryloyloxyisopropyl carbonate; t-hexylperoxyacryloyloxyisopropylcarbonate; 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropylcarbonate; cumylperoxyacryloyloxyisopropylcarbonate; p -Isopropylcumylperoxyacryloyloxyisopropylcarbonate; t-butylperoxymethacryloyl B carboxymethyl isopropyl carbonate; t-amyl peroxy methacryloyloxy isopropyl carbonate; t-hexyl peroxy methacryloyloxy isopropyl carbonate; 1,1,3,3
Examples thereof include tetramethylbutyl peroxymethacryloyloxyisopropyl carbonate; cumyl peroxymethacryloyloxyisopropyl carbonate; p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate.

Further, the compounds represented by the general formula (2) include t-butyl peroxyallyl carbonate; t-amyl peroxyallyl carbonate; t-hexyl peroxyallyl carbonate; 1,1,3,3
-Tetramethylbutyl peroxyallyl carbonate;
p-menthane peroxy allyl carbonate; cumyl peroxy allyl carbonate; t-butyl peroxy methallyl carbonate; t-amyl peroxy methallyl carbonate; t-hexyl peroxy methallyl carbonate; 1,1,3,3-tetramethyl butyl peroxy meta Ryl carbonate; p-menthane peroxy methallyl carbonate; cumyl peroxy methallyl carbonate; t-butyl peroxy allyloxyethyl carbonate; t-amyl peroxy allyloxy ethyl carbonate; t-hexyl peroxy allyloxy ethyl carbonate; Roxyethyl carbonate; t-amylperoxymetalaryloxyethyl carbonate; t-hexylperoxymetalaryloxyethyl carbonate; t- Chill peroxy allyloxy isopropyl carbonate; t-amyl peroxy allyloxy isopropyl carbonate; t-hexyl peroxy allyloxy isopropyl carbonate; t-butyl peroxy meth Lilo carboxylate isopropyl carbonate; t-amyl peroxy meth Lilo carboxylate isopropyl carbonate over sulfonate;
T-hexyl peroxy metalaryloxy isopropyl carbonate and the like can be exemplified.

Among them, preferred are t-butyl peroxyacryloyloxyethyl carbonate; t-butyl peroxymethacryloyloxyethyl carbonate; t-butyl peroxyallyl carbonate; and t-butyl peroxymethallyl carbonate.

The ratio of the component (I) to the graft copolymer (II) is 2 to 50% by weight of the graft copolymer (II) based on 50 to 98% by weight of the component (I). Is preferred. When the content of the graft copolymer (II) is less than 2% by weight, the adhesion to glass deteriorates. When the content of the graft copolymer (II) exceeds 50% by weight, transparency and water resistance are improved. This is not preferred because it becomes worse.

Further, the component (I) and the graft copolymer (I
The content of unsaturated carboxylic acid in the composition consisting of I)
Preferably it is 0.1 to 10% by weight. Here, when the content of the unsaturated carboxylic acid is less than 0.1% by weight, the adhesion to glass is deteriorated, which is not preferable. When the content of the unsaturated carboxylic acid is more than 10% by weight, the water resistance is deteriorated, which is not preferable.

The tackifier used in the present invention is
Examples thereof include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic hydrocarbon resins, polyterpene resins, rosins, and styrene resins.

Examples of the aliphatic hydrocarbon resin include:
Butene-1, butadiene, isoprene, polymers mainly comprising mono or diolefin C ₄ -C _5, such as 1,3-butadiene, as examples of aliphatic hydrocarbon resins, spent C ₄ -C ₅ fractions Examples of the resin obtained by polymerizing a diene component therein after cyclization dimerization, a resin obtained by polymerizing a cyclic monomer such as cyclopentadiene, and an aromatic hydrocarbon resin include vinyl toluene, indene, α-methyl toluene, and the like. C ₂
Examples of polyterpene-based resins such as a resin containing a vinyl aromatic hydrocarbon resin as a component include α-pinene polymers, β-
Examples of rosins such as pinene polymers, dipentene polymers, terpene-phenol copolymers, etc. include rosin, polymerized rosin, hydrogenated rosin, rosin pentaerythrol, hydrogenated products or polymers thereof, and styrene-based resins. Examples include styrene homopolymers, styrene-olefin copolymers, vinyl toluene-α-methyl toluene copolymers, and the like. Among these tackifiers, aliphatic hydrocarbon resins and alicyclic hydrocarbon resins are preferred from the viewpoint of color tone, compatibility with the composition, and the like.

The amount of the tackifier used in the composition is preferably less than 25% by weight based on 100 parts by weight of the composition. This is because when the amount of the tackifier exceeds 25% by weight, processability and transparency are reduced.

The tackifier may be added at the same time as the component (I) and the graft copolymer (II) are melt-kneaded, or may be added in advance to the component (I) and the graft copolymer. The composition of (II) may be prepared and the tackifier may be melt-kneaded again. Specific examples of the melt kneading method include a hot roll, an extruder, and a Banbury.

The method of using the composition obtained by the present invention as an intermediate film includes inflation, casting, calendering and the like. The thickness of the interlayer is preferably in the range of 0.1 to 2 mm for laminated glass. During processing, a lubricant such as a higher fatty acid amide may be added as required. Further, for the purpose of improving weather resistance, a benzotriazole-based or hindered amine-based ultraviolet absorber or a light-resistant stabilizer may be added. Further, an additive such as silane coupling may be added for the purpose of improving the adhesiveness.

In order to produce a laminated glass using the interlayer film of the present invention, the interlayer film may be laminated between a plurality of glasses and adhered under heating and pressing. The heating temperature can be in a wide temperature range of 80 to 180 ° C., which is also a feature of the present invention.

[0043]

Next, the present invention will be further described with reference to examples. The haze, boiling test, penetration resistance test, and evaluation of the film appearance in Examples and Comparative Examples were performed as follows.

Haze: According to ASTM D1003. 1.0% or less is preferable as the laminated glass.

Boiling test: Based on JIS K 3205. The value obtained by subtracting the haze before boiling from the haze after boiling was displayed. A smaller value is preferred.

[0046] Penetration resistance test: Based on JIS K 3205. ：: No penetration of steel ball. ×: Steel balls penetrated.

Evaluation of film appearance: A film having a thickness of 80 μm was prepared, and the number of gels having a diameter of 0.3 mmφ or more was counted by a gel counter.

Reference Example 1 (Production of graft copolymer (IIA)) Pure water was placed in a 5-liter stainless steel autoclave.
Add 2500g and add polyvinyl alcohol as a suspending agent
2.5 g was dissolved. In this, vinyl acetate content 28% by weight
EVA "Mersen H" obtained by saponifying EVA from 20%
800 g (manufactured by Tosoh Corporation) was stirred and dispersed.

Separately, 1.0 g of benzoyl peroxide "Niper B" (manufactured by NOF Corporation) as a polymerization initiator, 6 g of t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide, and 6 g of unsaturated carboxylic acid 100 g of acrylic acid and 100 g of methyl methacrylate as a (meth) acrylic acid ester were mixed well, and this solution was charged into the autoclave and stirred.

Then, the temperature of the autoclave was raised to 60 ° C.
By stirring for a time, the saponified EVA was impregnated with the polymerization initiator, the radical polymerizable organic peroxide, the (meth) acrylate and the unsaturated carboxylic acid. Then the temperature
The temperature was raised to 80 ° C., polymerization was carried out at that temperature for 2 hours, washed with water and dried to obtain a graft precursor. The copolymer of methyl methacrylate and acrylic acid as the graft precursor was extracted with ethyl acetate, and the number average degree of polymerization was measured by GPC to be 800.

Next, the grafting precursor was kneaded with a single screw extruder at 160 ° C. to carry out a grafting reaction to obtain a graft copolymer (IIA). In this graft copolymer (IIA), the graft efficiency of the methyl methacrylate-acrylic acid copolymer to the saponified EVA was 65% by weight. The content of acrylic acid in the graft copolymer (IIA) was 7% by weight.

Reference Example 2 (Production of graft copolymer (IIB)) In Reference Example 1, 600 g of saponified EVA, 2 g of benzoyl peroxide, 12 g of t-butylperoxymethacryloyloxyethyl carbonate, and 200 g of acrylic acid
g and methyl methacrylate were changed to 200 g to obtain a graft copolymer (IIB) by repeating Reference Example 1.

The methyl methacrylate-acrylic acid copolymer had a number-average degree of polymerization of 780, and the methyl methacrylate-acrylic acid copolymer had a graft efficiency of 55 to the saponified EVA.
% By weight. Further, the content of acrylic acid in the graft copolymer (IIB) was 13% by weight.

Reference Example 3 (Production of Graft Copolymer (IIC)) The procedure of Reference Example 1 was repeated except that t-butylperoxymethacryloyloxyethyl carbonate was not used. I got

The methyl methacrylate-acrylic acid copolymer had a number average degree of polymerization of 800, and the methyl methacrylate-acrylic acid copolymer had a grafting efficiency of 15 to the saponified EVA.
% By weight. Further, the content of acrylic acid in the graft copolymer (IIC) was 6% by weight.

Reference Example 4 (Production of Graft Copolymer (IID)) A graft copolymer (IID) was obtained by repeating Reference Example 1 except that 100 g of methyl methacrylate was changed to 100 g of vinyl acetate. Was.

The vinyl acetate-acrylic acid copolymer had a number average degree of polymerization of 1300, and the graft efficiency of the vinyl acetate-acrylic acid copolymer on saponified EVA was 45% by weight.
Further, the content of acrylic acid in the graft copolymer (IID) was 6% by weight.

Example 1 Saponified EV used in Reference Example 1
A 85% by weight, graft copolymer 5 synthesized in Reference Example 1
10% by weight of an alicyclic petroleum resin “ALCON P-100” (manufactured by Arakawa Chemical Industry Co., Ltd.) as a tackifier and kneading at 160 ° C. with a twin-screw extruder. A composition for a glass interlayer was obtained.

Using a cast molding machine, this composition was
A sheet having a thickness was prepared, sandwiched between glasses having a thickness of 3 mm, and heated and pressed at 110 ° C. for 5 minutes to prepare a laminated glass.

The haze was measured as a measure of transparency of the laminated glass, a penetration resistance test was performed as a measure of adhesiveness, a boiling test was performed as a measure of heat resistance and water resistance, and the appearance of the film was evaluated. The results are shown in Table 1.

Example 2 Saponified EV used in Reference Example 1
A 80% by weight, graft copolymer 10 synthesized in Reference Example 1
A composition was obtained in the same manner as in Example 1 except that the content was changed to% by weight. Using this composition, a laminated glass was prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.

Example 3 A composition was obtained in the same manner as in Example 2 except that the graft copolymer synthesized in Reference Example 2 was used. Using this composition, a laminated glass was prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.

Example 4 A composition was obtained in the same manner as in Example 2 except that the graft copolymer synthesized in Reference Example 3 was used. Using this composition, a laminated glass was prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.

Example 5 A composition was obtained in the same manner as in Example 2 except that the graft copolymer synthesized in Reference Example 4 was used. Using this composition, a laminated glass was prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.

Comparative Example 1 Saponified EV used in Reference Example 1
One part by weight of acrylic acid was grafted to 100 parts by weight of A by a melt extrusion method to obtain an acid-modified saponified EVA. 90 parts by weight of this acid-modified saponified EVA was well mixed with 10 parts by weight of the tackifier used in Example 1, and a composition was obtained in the same manner as in Example 1. Using this composition, a laminated glass was prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.

(Comparative Example 2) Saponified EV used in Reference Example 1
A 99.5% by weight, graft copolymer synthesized in Reference Example 1
A composition was obtained in the same manner as in Example 1 except that the content was 0.5% by weight. Using this composition, a laminated glass was prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Table 1.

[0067]

[Table 1]

[0068]

The present invention relates to a copolymer of a saponified ethylene-vinyl ester copolymer and at least one selected from the group consisting of (meth) acrylates and vinyl esters, and an unsaturated carboxylic acid. It is a composition having excellent adhesive properties, comprising a graft copolymer consisting of about 90% by weight and 95 to 10% by weight of the ethylene-vinyl ester copolymer and / or saponified product thereof, and a tackifier.
In particular, for use as an interlayer film for laminated glass, there is no tackiness on the film surface unlike plasticized polyvinyl butyral, and workability is good.

Further, as compared with the conventional modified ethylene-vinyl ester copolymer and / or saponified product thereof, it is an intermediate film having a less gel and a uniform film thickness, and has a high transparency and
Since it has excellent adhesion to glass and excellent water resistance, it can be used as a laminated glass for a wide range of automobiles, vehicles, buildings and the like.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09J 151/00 C09J 151/00 151/06 151/06 (72) Inventor Motoyuki Sugiura 2 Mt. Reference No. 34 (56) References JP-A-1-138279 (JP, A) JP-A-3-285849 (JP, A) JP-A-57-16082 (JP, A) JP-A-57-70168 (JP, A) JP-A-60-264348 (JP, A) JP-A-63-128032 (JP, A) JP-A-61-189933 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB Name) C09J 123/08 C09J 123/26 C09J 129/04 C09J 151/00 C09J 151/06 C03C 27/12 B32B 17/10

Claims (5)

(57) [Claims] (1) 50 to 98% by weight of a saponified ethylene-vinyl ester copolymer and (II) at least one or more selected from the group consisting of (meth) acrylic acid esters and vinyl esters. A composition comprising 5 to 90% by weight of a copolymer part with a saturated carboxylic acid and 2 to 50% by weight of a graft copolymer comprising 95 to 10% by weight of an ethylene-vinyl ester copolymer and / or a saponified part thereof. Wherein the content of unsaturated carboxylic acid in the composition is 0.1 to 10
An adhesive composition which is wt%. 2. A saponified ethylene-acetic acid obtained by saponifying the ethylene-vinyl ester copolymer according to claim 1, wherein the saponified ethylene-vinyl acetate copolymer having a vinyl acetate content of 10 to 40% by weight is saponified by 5 to 50%. An adhesive composition which is a vinyl copolymer. 3. An adhesive composition obtained by adding less than 25 parts by weight of a tackifier to 100 parts by weight of the composition according to claim 1. 4. A laminating agent for laminated glass comprising the composition according to claim 1, 2 or 3 as a main component. 5. A laminated glass comprising the laminating agent according to claim 4 as an intermediate film and glass bonded on both sides thereof.