JPH08175851A - Intermediate film for glass laminate - Google Patents

Abstract

PURPOSE: To provide an intermediate film for glass laminate having excellent autohesion, capable of being laminated at a low temperature under low pressure, by making a resin composition having a specific composition consisting essentially of an ethylene-vinyl acetate-vinyl alcohol terpolymer into a film. CONSTITUTION: (A) An ethylene vinyl acetate-vinyl alcohol terpolymer having 10-35wt.% vinyl acetate content, 1-20wt.% of vinyl alcohol content and the rest of ethylene in an amount of 100 pts.wt. is mixed with (B) 0.01-4 pts.wt. of a condensation reaction product obtained by reacting a pentafunctional or polyfunctional alcohol (e.g. sorbitol) or its derivative with 1.8-2.8 times equivalent of benzaldehyde or its derivative and (C) 0.01-4 pts.wt. of a silane coupling agent (e.g. 3-methacryloxypropyltriethoxysilane) selected from an amino group, a glycidyl group and a mercapto group. Then the prepared resin composition is made into a film by extrusion method to give an intermediate film for glass laminate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an interlayer film for laminated glass.

[0002]

2. Description of the Related Art Conventionally, laminated glass has been widely used for safety glass for automobiles, glazing materials for public facilities and exercise facilities, partitions, crime prevention doors, etc., and its structure is composed of a plurality of inorganic glasses, Alternatively, a part of it is replaced with an organic glass, that is, a transparent synthetic resin plate, and is processed through an intermediate film.

Polyvinyl butyral resin plasticized with a plasticizer is most commonly used as the interlayer film because it has excellent adhesion to glass, tough tensile strength, high transparency, and the like. ing. However,
The intermediate film made of the polyvinyl butyral resin is, when stored in a rolled state, stored at a low temperature because of its strong self-adhesiveness, or a release paper is interposed between the intermediate films.
It was necessary to take some measures to prevent blocking.

However, in the case of actually producing laminated glass, the process of adjusting the humidity of the interlayer film is required before the process of laminating with the glass, and the process of laminating needs to be performed under high temperature and high pressure by an autoclave. Is complicated. Further, when processing a synthetic resin transparent plate together, there is a drawback that the plasticizer bleeds out at the interface between the intermediate film and the synthetic resin plate to reduce the adhesiveness, and also erodes the synthetic resin plate to cause whitening. there were.

As a solution to the above drawbacks, an interlayer film for laminated glass made of a thermoplastic resin obtained by partially esterifying a partially saponified ethylene-vinyl acetate copolymer (hereinafter referred to as "EVA copolymer") with phthalic anhydride. (Japanese Patent Publication 4
No. 7-2103) and an interlayer film for laminated glass made of a thermosetting resin in which an EVA copolymer is mixed with an organic peroxide (Japanese Patent Laid-Open No. 2-53381).

However, the interlayer film made of a partially esterified product of EVA copolymer has poor adhesion to glass,
It has a drawback that it has poor heat resistance and moisture resistance. Also, EV
The interlayer film composed of the organic peroxide compound of the A copolymer has improved crystallinity during thermal denaturation, and thus has improved transparency, and can be stored at room temperature, and does not require humidity control before being combined. It had the advantage that it could be processed without autoclave. However, since radicals generated by the decomposition of the organic peroxide are used for the thermosetting reaction, when used for colored decorative laminated glass, the processing temperature is 130 ° C. or higher, and therefore a heat resistant dye is required, which causes There was a drawback that it caused deterioration and increased costs. Further, when the synthetic resin plates are processed together, there is a problem that they are thermally deformed at a high temperature.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and its purpose is to provide a laminated glass having transparency, moisture resistance, weather resistance, impact resistance, adhesiveness, and the like. Provided is an interlayer film for laminated glass, in which the self-adhesiveness of the film itself is improved without impairing the basic characteristics, and which does not require humidity control and an autoclave in the manufacturing process, and which can be subjected to a laminating process at a low processing temperature and a processing pressure. There are things.

[0008]

The interlayer film for laminated glass of the present invention is formed from a resin composition comprising an ethylene-vinyl acetate-vinyl alcohol terpolymer, a condensation reaction product and a silane coupling agent. .

The above ethylene-vinyl acetate-vinyl alcohol terpolymer (hereinafter referred to as "EVL copolymer")
Is obtained by partially saponifying the EVA copolymer by hydrolysis. That is, as a method of hydrolyzing the EVA copolymer, a method of mixing and reacting with methanol in the presence of a metal alcoholate, a base or an acid catalyst can be mentioned.

The EVA copolymer used in the EVL copolymer has a vinyl acetate content of 20% by weight and a melt index (measured in accordance with ASTM D1238).
It is preferably 0.5 to 500 (g / ml), and such EVA copolymer can be synthesized by a known technique such as an emulsification method or a high pressure method.

In the above EVL copolymer, when the proportion of the vinyl acetate component is small, the transparency and fluidity of the resulting interlayer film is low, and when it is high, the adhesiveness and the tensile strength of the interlayer film are low. It is limited to 10 to 30% by weight.

In the above EVL copolymer, when the proportion of the vinyl alcohol component is small, the adhesiveness and tensile strength of the resulting interlayer film are low, and when it is high, the water resistance of the resulting interlayer film is low, so that it is 1 to 20. Limited to wt%.

The above-mentioned condensation reaction product is obtained by subjecting a polyhydric alcohol having a valence of 5 or more to a benzaldehyde or a derivative thereof to a condensation reaction, wherein the hydroxyl group of the polyhydric alcohol is a benzaldehyde or a derivative thereof. When the amount is small, a large amount of monoacetal compound is generated, and when the amount is large, a large amount of hemiacetal compound is generated,
Since these by-products hinder the improvement of transparency when they are used as an intermediate film, they are limited to 1.8 to 2.8 times equivalents.

A condensation reaction product obtained by subjecting a polyhydric alcohol having a valence of 5 or more or a derivative thereof to a condensation reaction of benzaldehyde or a derivative thereof is known in the art (Japanese Patent Publication No. Sho 40).
-15489, Japanese Patent Publication No. 47-7460, etc.)
Can be manufactured by.

In the above production method, a polyhydric alcohol having a valence of 5 or more or a derivative thereof is put in a reactor equipped with a cooling pipe and a stirrer in the presence of an inert gas, and then 1.
8 to 2.8 times equivalent amount of benzaldehyde or its derivative is charged, and sulfuric acid is added as a condensed acid catalyst to react with heat,
A condensation reaction product can be synthesized.

Examples of the polyhydric alcohol having a valence of 5 or more and derivatives thereof include, for example, D, L-sorbitol (D, L-glucitol), xylitol, D, L-mannitol, dulcitol, L-sorbose, D-arabinitol, Ribitol,
Examples thereof include D-fructose, and these may be used alone or in combination of two or more kinds. In particular, as the polyhydric alcohol or its derivative, when D, L-sorbitol, xylitol, D, L-mannitol, dulcitol is used,
It is preferable because the transparency of the obtained intermediate film is remarkably improved.

Examples of the above-mentioned benzaldehyde and its derivatives include chlorine atom-substituted alkyl group, aryl group and alkoxy group of benzene ring hydrogen of benzaldehyde. These may be used alone or in combination of two or more kinds. May be.

Examples of the condensed acid catalyst include sulfuric acid,
Examples thereof include p-toluenesulfonic acid, phosphoric acid, hydrochloric acid, zinc chloride and the like.

Examples of the condensation reaction product include dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (ethylbenzylidene) sorbitol, bis (propylbenzylidene) sorbitol,
Bis (butylbenzylidene) sorbitol, Bis (pentylbenzylidene) sorbitol, Bis (hexylbenzylidene) sorbitol, Bis (chlorobenzylidene)
Examples thereof include sorbitol, dibenzylidene xylitol, dibenzylidene mannitol, etc. These may be used alone or in combination of two or more kinds.

In the above resin composition, when the amount of the condensation reaction product is small, the transparency of the obtained interlayer film is not sufficiently improved, and when the amount is large, the fluidity of the resin composition is lowered and the tensile strength of the interlayer film is increased. Since the strength decreases, it is limited to 0.01 to 4 parts by weight, preferably 0.05 to 1 part by weight, based on 100 parts by weight of the EVL copolymer.

By adding tribenzylidene sorbitol, bis (4-t-butylphenyl) sodium phosphate, aluminum hydroxy-di (t-butylbenzoate) or the like to the above resin composition, the transparency can be improved. Further improve.

The silane coupling agent has one or more functional groups selected from the group consisting of amino groups, glycidyl groups and mercapto groups.
3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane , N- (2-aminoethyl) -3-aminopropyltrimethoxysilane,
N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane, 3
-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, Propyltrimethoxysilane, propyltriethoxysilane, dodecyltriethoxysilane, hexyltrimethoxysilane, isobutyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, methylphenyldiethoxysilane, methylphenyldimethoxy Examples thereof include silane and the like, and these may be used alone or in combination of two or more kinds.

In the above resin composition, when the amount of the silane coupling agent is small, the effect of improving the adhesiveness of the obtained intermediate film is not recognized, and when the amount is large, the transparency is deteriorated. Therefore, 100 parts by weight of the EVL copolymer is used. For 0.01 to 4
Limited to parts by weight.

For the purpose of preventing the deterioration of the resin, a stabilizer, an antioxidant, an ultraviolet absorber, etc. may be added to the above resin composition, if necessary.

Examples of the stabilizer include calcium stearate soap, dialkanol aliphatic tertiary amine and the like, and examples of the antioxidant include t-butylhydroxytoluene (BHT) and tetrakis [methylene-].
3- (3 ′, 5′-t-butyl-4-hydroxyphenyl) propionate] methane (“Irganox 1010” manufactured by Ciba-Geigy) and the like.

Examples of the ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole ("Tinuvin P" manufactured by Ciba-Geigy), 2- (2'-hydroxy-3 ', 5'-). Di-t-butylphenyl) benzotriazole (“Tinuvin 320” manufactured by Ciba-Geigy), 2
Benzotriazoles such as-(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole ("Tinuvin 326" manufactured by Ciba-Geigy);
Hindered amines such as "LA-57" manufactured by ADEKA ARGUS; "Seesorb 101", "Seesorb 102", "Seesorb 103", and "Seesorb 1" manufactured by Cypro Kasei.
04 "and the like.

In preparing the above resin composition, EVL
It is necessary to uniformly mix the copolymer and the silane coupling agent. As a mixing method, a method of melt kneading the EVL copolymer and other components using a mixer such as a roll mill; a dry blending method of kneading the EVL copolymer and the other components as they are; components other than the EVL copolymer A high-concentration masterbatch in which a masterbatch pellet containing a high concentration of is diluted with an EVL copolymer to a predetermined concentration is used. Moreover, as a method of forming an intermediate film for laminated glass from the above resin composition, for example, a method of forming a sheet by an extrusion method, a pressing method, a calendering method, or the like can be mentioned.

As a method for producing laminated glass from the above-mentioned interlayer film for laminated glass, a method used in the production of ordinary laminated glass can be adopted. For example, a sheet-like intermediate film having a thickness from both sides thereof can be used. It is sandwiched between transparent rigid plates such as a 3 mm glass plate or a synthetic resin plate, and this sandwich structure in a non-compressed state is put in a rubber bag, and 0-20
After degassing at a vacuum of Torr for a certain period of time, put it in an oven at 80 ° C or higher in the degassed state and hold for a certain period of time, or pass the sandwich structure through a pressure rubber roll heated to 100 ° C or higher for a certain period of time. After heating, a method of heating and holding in an oven may be used.

The laminated glass obtained by using the laminated film for laminated glass of the present invention is basically composed of glass / intermediate film / glass, but the following laminated structures are also included.・ Glass / intermediate film / polyester / intermediate film / glass ・ Glass / intermediate film / metal plate / intermediate film / glass / intermediate film /
Polyurethane film ・ Glass / intermediate film / paper / intermediate film / glass ・ Polycarbonate plate / intermediate film / polyester film / intermediate film / polycarbonate plate ・ Acrylic resin plate / intermediate film / metal plate / intermediate film / acrylic resin plate ・ Acrylic resin plate / Interlayer film / Paper / Interlayer film / Acrylic resin plate

[0030]

Embodiments of the present invention will be described below. (Example 1) Preparation of EVL copolymer (1 ) 100 g of an EVA copolymer having a vinyl acetate content of 25% by weight ("Ultracene 765" manufactured by Tosoh Corporation) was hydrolyzed in methanol with sodium hydroxide as a catalyst. Then, an EVL copolymer having a saponification degree of 20 mol% was prepared. This EVL
It was confirmed by infrared analysis and chemical analysis that the copolymer was composed of 20% by weight of vinyl acetate component, 5% by weight of vinyl alcohol component, and the balance of ethylene component.

Synthesis of condensation reaction product (1) In a 3 liter flask equipped with a reflux condenser and a stirrer, 182 g (1 mol) of D-sorbitol, 212 g (2 mol) of benzaldehyde, 800 ml of toluene and 2 ml of concentrated sulfuric acid. Was added, and the mixture was reacted at 80 ° C. for 3 hours, then toluene was distilled off, neutralized with potassium hydroxide, washed with hot water, filtered and dried to obtain 347 g of dibenzylidene sorbitol (yield 97%). .

A resin composition was obtained by blending the predetermined amount shown in Table 1 with the EVL copolymer (1), the condensation reaction product (1) and the silane coupling agent. This resin composition was sandwiched between polyethylene terephthalate films and press-molded to produce a sheet for interlayer film having a thickness of 400 μm.
Then, the polyethylene terephthalate film is peeled off by leaving it to reach room temperature, and the obtained interlayer film sheet is sandwiched between two float glass plates with a thickness of 3 mm that have been washed in advance, placed in a rubber bag, and vacuumed at 10 Torr. After degassing for 20 minutes at a temperature, the laminated glass was prepared by placing the degassed state in an oven at 100 ° C. for 30 minutes.

(Example 2) Instead of a glass plate, a polycarbonate plate ("Iupilon sheet NF" manufactured by Mitsubishi Gas Chemical Co., Inc.) was used.
A laminated glass was produced in the same manner as in Example 1 except that 200 U ″) was used.

Example 3 Instead of D-sorbitol,
Using 152 g (2 mol) of xylitol, a condensation reaction was performed in the same manner as in Example 1 to obtain 320 g of dibenzylidene xylitol (yield 95%) as a condensation reaction product (2). A fixed amount of EVL copolymer (1),
Except that a resin composition was used by blending the condensation reaction product (2) and a silane coupling agent, and an acrylic resin plate (“Acrylite HR” manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the glass plate. A laminated glass was produced in the same manner as in Example 1.

Example 4 Instead of D-sorbitol,
Using 182 g (1 mol) of D-mannitol, a condensation reaction was carried out in the same manner as in Example 1, and 269 g of dibenzylidene mannitol as a condensation reaction product (3) (yield 75%).
Then, from the resin composition containing the EVL copolymer (1), the condensation reaction product (3) and the silane coupling agent in the predetermined amounts shown in Table 1, in the same manner as in Example 1,
A laminated glass was produced.

(Examples 5 and 6) Preparation of EVL copolymer (2) EVA copolymer having a vinyl acetate content of 33% by weight ("EVAFLEX 150" manufactured by DuPont Mitsui Polychemicals) 1
00 g was hydrolyzed in methanol using sodium hydroxide as a catalyst to prepare an EVL copolymer having a saponification degree of 70 mol%. It was confirmed by infrared analysis and chemical analysis that this EVL copolymer was composed of 10% by weight of vinyl acetate component, 23% by weight of vinyl alcohol component, and the balance of ethylene component. The predetermined amount shown in Table 1,
A laminated glass was produced in the same manner as in Example 1 from the resin composition containing the EVL copolymer (2), the condensation reaction product (1) and the silane coupling agent.

Example 7 Preparation of EVL Copolymer (3 ) 100 g of an EVA copolymer having a vinyl acetate content of 43% by weight (“Ultracene 760” manufactured by Tosoh Corporation) was catalyzed with sodium hydroxide. Was hydrolyzed to prepare an EVL copolymer having a saponification degree of 35 mol%. This EVL
By infrared analysis and chemical analysis, it was confirmed that the copolymer was composed of 28% by weight of vinyl acetate component, 15% by weight of vinyl alcohol component and the balance of ethylene component.

The resin composition containing the EVL copolymer (3), the condensation reaction product (1) and the silane coupling agent in the predetermined amounts shown in Table 2 was combined in the same manner as in Example 1. Glass was produced.

(Embodiments 8 and 9) In the predetermined amount shown in Table 2,
A laminated glass was produced in the same manner as in Example 1 from the resin composition containing the EVL copolymer (1), the condensation reaction product (1) and the silane coupling agent.

COMPARATIVE EXAMPLE 1 EVA copolymer having a melt index of 2 and a vinyl acetate content of 25% by weight (“EVAFLEX360” manufactured by DuPont Mitsui Polychemicals) 100
3 parts by weight of triallyl isocyanurate (“Taike” manufactured by Nippon Kasei), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (“Perhexa 3M” manufactured by NOF Corporation) 1 part by weight and 0.3 part by weight of γ-methacryloxypropyltrimethoxysilane were kneaded with a roll mill heated to 100 ° C. to obtain a sheet-like intermediate film. A laminated glass was produced in the same manner as in Example 1 except that this sheet-shaped intermediate film was used and the laminating temperature was 130 ° C.

Comparative Example 2 Vinyl acetate content 32% by weight
EVA copolymer ("Ultrasen 75" manufactured by Tosoh Corporation
0 ") is hydrolyzed and 180 g of a partially saponified product having a saponification degree of 90 mol%, 104 g of phthalic anhydride and 40 ml of pyridine are mixed in 1.5 liter of xylene.
Reaction was carried out at 10 ° C. for 4 hours to prepare an esterified product.
This esterified product is composed of 3.2% by weight of vinyl acetate component, 16.1% by weight of vinyl alcohol component, 12.7% by weight of vinyl phthalate component and the balance of ethylene component by infrared analysis and chemical analysis. I confirmed that. A laminated glass was produced in the same manner as in Example 1 using the above esterified product as a resin composition.

(Comparative Examples 3 and 4) With a predetermined amount shown in Table 1,
A laminated glass was produced in the same manner as in Example 1 from the resin composition containing the EVL copolymer (1), the condensation reaction product (1) and the silane coupling agent.

Comparative Example 5 Preparation of EVL Copolymer (4 ) 100 g of an EVA copolymer having a vinyl acetate content of 25% by weight (“Ultrasen 635” manufactured by Tosoh Corporation) was catalyzed with sodium hydroxide. Was hydrolyzed to prepare an EVL copolymer (4) having a saponification degree of 68 mol%. It was confirmed by infrared analysis and chemical analysis that this EVL copolymer (4) was composed of 8% by weight of vinyl acetate component, 17% by weight of vinyl alcohol component and the balance of ethylene component. The predetermined amount of EV shown in Table 1 above
A laminated glass was produced in the same manner as in Example 1 from the resin composition containing the L copolymer (4), the condensation reaction product (1) and the silane coupling agent.

[0044]

[Table 1]

[0045]

[Table 2]

Performance Evaluation of Laminated Glass With respect to the laminated glass obtained in the above Examples and Comparative Examples,
The following evaluations were performed and the results are shown in Table 3. (1) Transparency test Using an "integral turbidimeter" manufactured by Tokyo Denshoku Co., Ltd., a temperature of 23
The total light transmittance (%) and the haze value at a temperature of 50 ° C. and a relative humidity of 50% were measured.

(2) Adhesive strength test A laminated glass prepared by using a glass plate or a synthetic resin plate on one side and polyethylene terephthalate on the other side, and having a width of 2
A test piece was obtained by cutting it to 0 mm and a length of 100 mm. This test piece was manufactured by Orientec Co., Ltd., "Tensilon UCE50".
"0" was used to measure 90 degree peel strength at a pulling speed of 500 mm / min.

(3) Impact Test According to JIS R3205, a laminated glass test piece left standing for 4 hours at a temperature of 23 ° C. and a relative humidity of 50% is held vertically by a support frame and weighs 45 kg and has a maximum diameter of 75 mm. When the attacking body was dropped from the height of 30 cm to the center of the laminated glass in a pendulum manner, and there was an opening through which a sphere with a diameter of 75 mm could freely pass in the broken part of the test body, it was marked with X, and when it did not, it was marked with ○. did.

(4) Cold Heat Test The laminated glass was left at 70 ° C. for 2 hours, cooled from 70 ° C. to -20 ° C. over 2 hours, left at -20 ° C. for 2 hours, and then -20 ° C. to 70 ° C. The process of raising the temperature for 2 hours was continuously performed for 10 cycles, and the laminated glass was visually observed for delamination.

(5) Moisture resistance test After the laminated glass was left in an environment of 55 ° C. and a relative humidity of 98% for 2 weeks, the presence or absence of delamination was visually observed.

(6) Boiling test After the laminated glass was left in boiling water for 2 hours, the presence or absence of delamination was visually observed.

[0052]

[Table 3]

[0053]

The structure of the interlayer film for laminated glass of the present invention is as described above, and is a resin comprising an ethylene-vinyl acetate-vinyl alcohol terpolymer, a specific condensation reaction product and a silane coupling agent. By being formed from the composition, the manufacturing process can be simplified because it does not impair the transparency and impact resistance, which are the basic properties of the intermediate film, and it can be processed in the manufacturing process without humidity control and autoclave. Can be converted.

Claims (1)

[Claims] 1. An ethylene-vinyl acetate-vinyl alcohol terpolymer having a vinyl acetate content of 10 to 35% by weight, a vinyl alcohol content of 1 to 20% by weight, and the balance of ethylene being 100 parts by weight, pentavalent or more. From 0.01 to 4 parts by weight of a condensation reaction product obtained by reacting 1.8 to 2.8 times the equivalent amount of benzaldehyde or its derivative with the polyhydric alcohol or its derivative, and an amino group, a glycidyl group and a mercapto group. A silane coupling agent having at least one functional group selected from the group consisting of 0.01 to
An interlayer film for laminated glass, which is formed from a resin composition consisting of 4 parts by weight.