JPH07247140A - Intermediate membrane for laminated glass - Google Patents

Abstract

PURPOSE:To obtain an intermediate membrane for a laminated glass, not causing self adhesion, not requiring a humidity control, and capable of processing a lamination at a low processing temperature and a low processing pressure, by combining EEVA with a product of condensation reaction of a polyhydric alcohol with benzaldehyde, etc., and a silane coupling agent. CONSTITUTION:An intermediate membrane for a laminated glass is composed of 100 pts.wt. of a modified vinyl acetate copolymer containing 4-18wt.% of vinyl alcohol unit, and 5-60wt.% of vinyl alcohol dicarboxylic acid ester unit, 0.01-4.0 pts.wt. of a condensation reaction product of a 5-12OH polyhydric alcohol and benzaldehyde (derivative) or a compound expressed by the formula, and 0.01-4.0 pts.wt. of a silane coupling agent having 1 or more amino group, mercapto group or glycidyl group. In the formula, (n) expresses a natural number of 4-14. This intermediate membrane has an excellent transparency without damaging impact resistance, and adhesiveness to a glass or a transparent synthetic resin sheet, and is capable of simplifying a laminating process since the lamination process can be conducted without using an autoclave.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an interlayer film for laminated glass.

[0002]

2. Description of the Related Art Laminated glass is a safety glass for automobiles,
It is used for glazing materials for public facilities and sports facilities, partitions, and security doors. Its structure is a plurality of inorganic glasses, or part of them as organic glass, that is, transparent synthetic resin plate, and laminated glass interlayer film. It was processed through the process.

As the laminated glass interlayer film, polyvinyl butyral resin plasticized with a plasticizer has excellent adhesion to glass, tough tensile strength, and high transparency, and is the most common one. Has been used as. However, when the laminated glass interlayer film made of the polyvinyl butyral resin is stored in a roll, it has strong self-adhesiveness and therefore is stored at a low temperature, or a release paper is interposed between the laminated glass interlayer films to prevent blocking. Need to take.

Furthermore, it is necessary to adjust the humidity before the glass is combined with the glass, and it is necessary to perform the combination processing under high temperature and high pressure by an autoclave, which complicates the combination processing operation.

Further, when the transparent synthetic resin plate is processed together, the plasticizer bleeds to the interface between the laminated glass intermediate film and the transparent synthetic resin plate to lower the adhesiveness and at the same time corrode the transparent synthetic resin plate to cause whitening. There was a drawback that

In order to make up for the above drawbacks, a resin obtained by acid-modifying a saponified product of ethylene / vinyl acetate copolymer (hereinafter referred to as "EVA") or a mixture of EVA and an organic peroxide is heat-cured at the time of processing. The laminated glass interlayer film thus obtained is disclosed in JP-B-47-2103 and JP-B-2-5.
It is disclosed in Japanese Patent No. 3381.

However, a laminated glass interlayer film using a resin obtained by acid-modifying the saponified product of EVA has a drawback that it has low transparency because of its high crystallinity.

In the laminated glass interlayer film using EVA and organic peroxide, the crystallinity is lowered during processing, the transparency is improved, and since it is not self-adhesive, it can be stored at room temperature. The previous humidity control is not necessary, and it can be processed without an autoclave, but since the radicals generated by the decomposition of organic peroxide are used for thermosetting, the temperature is 130 ° C.
The above processing temperature is required, and when used in a colored decorative laminated glass, a heat resistant dye is required, which leads to a reduction in processing workability and an increase in manufacturing cost.

Further, when a transparent synthetic resin plate is used, it has the drawback of being thermally deformed.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and has transparency, moisture resistance, weather resistance,
It does not impair the basic properties required for laminated glass such as impact resistance and adhesiveness with transparent synthetic resin plates, does not self-adhere, does not require humidity control, does not require autoclave, and is matched at low processing temperature and processing pressure. An object is to provide a laminated glass intermediate film that can be processed.

[0011]

The laminated glass interlayer film of the present invention is a modified ethylene / vinyl acetate copolymer (hereinafter referred to as "EEVA") obtained by esterifying a partially saponified product of EVA.
Say. ) Consists of a condensation reaction product of a polyhydric alcohol having a valence of 5 to 12 or more and benzaldehyde (derivative) or a compound represented by the general formula (1) (hereinafter referred to as "calixarene").

[0012]

[Chemical 2]

The EEVA used in the present invention can be manufactured by a known technique and is disclosed in, for example, Japanese Patent Publication No. 47-2103.

First, EVA is saponified using a base or an acid as a catalyst to synthesize a partially saponified product of EVA, which is mixed with a dicarboxylic acid anhydride in a suitable solvent, and the reaction temperature is 110 to 140.
The partial esterification reaction is carried out in the range of ° C.

In the above reaction, it is preferable to use an arbitrary catalyst such as an organic acid, an inorganic acid or a metal compound for the purpose of promoting the reaction.

Examples of the dicarboxylic acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, and hexahydrophthalic anhydride. These may be used alone or in combination of two or more kinds. Good.

EEVA used in the present invention is ethylene,
A vinyl alcohol ester component of vinyl acetate, vinyl alcohol and dicarboxylic acid anhydride, for example,
It is obtained by partially saponifying an ethylene / vinyl acetate copolymer with an acid or an alkali and then esterifying it with a dicarboxylic acid anhydride. When the content of the vinyl acetate component of the ethylene / vinyl acetate copolymer used at that time becomes small, The transparency of the obtained laminated glass interlayer film is lowered, the fluidity of the obtained EEVA is lowered, and when it is increased, the adhesiveness and the tensile property are lowered, so that it is preferably 0.5 to 35% by weight.

When the amount of the above-mentioned vinyl alcohol component decreases, the tensile properties and adhesiveness of the laminated glass interlayer film obtained deteriorate, and when the amount of the vinyl alcohol component increases, the water resistance decreases.
Limited to wt%.

If the vinyl alcohol ester component of the dicarboxylic acid anhydride is reduced, the transparency of the laminated glass interlayer film obtained will be lowered, and if it is increased, the tensile property will be lowered, so that it is limited to 5 to 60% by weight.

The condensation reaction product used in the present invention is 5
It is a condensation reaction product of a dihydric polyhydric alcohol and a benzaldehyde (derivative). The addition amount of benzaldehyde (derivative) is such that a large amount of monoacetal compound is produced when the aldehyde amount is small relative to the hydroxyl group of the polyhydric alcohol. , When it increases, a large amount of hemiacetal compound is produced as a by-product,
When these by-products form a laminated glass intermediate film, they hinder the improvement of transparency, so the amount is limited to 1.8 to 2.8 times the equivalent amount.

The above condensation reaction product can be produced by a known technique, and is disclosed in, for example, Japanese Patent Publication Nos. 40-15489 and 47-7460.

In the above-mentioned production method, a polyhydric alcohol having a valence of 12 to 12 is put into 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 is added. (Derivative) is charged, sulfuric acid is added as a condensed acid catalyst, and the mixture is heated and reacted to synthesize.

Examples of the condensation acid catalyst for obtaining the condensation reaction product include p-toluenesulfonic acid, phosphoric acid, hydrochloric acid, zinc chloride and the like, in addition to sulfuric acid.

Examples of the polyhydric alcohol having 5 to 12 valences include D, L-sorbitol (D, L-glucitol),
Xylitol, D, L-mannitol, dulcitol,
L-sorbose, D-arabinitol, ribitol, D
-Fructose and the like can be mentioned. These may be used alone or in combination of two or more, and in particular, when a condensation reaction product obtained from D, L-sorbitol, xylitol, D, L-mannitol and dulcitol is used, the obtained combination is The transparency of the glass interlayer film is significantly improved.

Examples of the benzaldehyde (derivative) include benzaldehyde, chlorine atom of benzene ring hydrogen of benzaldehyde, alkyl group, aryl group and alkoxy group substitution product. These may be used alone or in combination of two or more.

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)
Sorbitol and the like can be used, and these may be used alone or in combination of two or more kinds.

When the amount of the condensation reaction product added is small, the transparency of the laminated glass interlayer film obtained is not sufficiently improved, and when it is large, the tensile strength is lowered and the fluidity of the laminated glass interlayer film is lowered. Therefore, it is limited to 0.01 to 4.0 parts by weight, and more preferably 0.05 to 1.0 parts by weight, based on 100 parts by weight of EEVA.

In the laminated glass interlayer film of the present invention, in addition to the above, tribenzylidene sorbitol and bis (4-phosphate)
t-Butylphenyl) sodium, hydroxy-di (t
Transparency is further improved by adding additives such as -butyl benzoic acid aluminum.

The compound represented by the general formula (1) used in the present invention is, for example, 4-t-butyl calix [4].
Allene, 4-t-butylcalix [6] arene, 4-
Examples thereof include t-butylcalix [8] arene, 4-t-butylcalix [12] arene, and 4-t-butylcalix [16] arene, and particularly n in the general formula (1) is 4
A calixarene of 8 is preferable because of good dispersibility in EEVA.

[0030]

[Chemical 3]

[In the general formula (1), n represents a natural number of 4 to 16. ]

The compound represented by the above general formula (1) can be produced by a known technique, for example, Acco
unts of Chemical Research
h, 16, 161 (1983).

When the amount of the compound represented by the above general formula (1) is reduced, the transparency of the laminated glass interlayer film obtained becomes insufficient, and when it is increased, the compatibility with EEVA is lowered and the transparency is lowered. Therefore, it is limited to 0.01 to 4.0 parts by weight, and more preferably 0.02 to 1.0 parts by weight, relative to 100 parts by weight of EEVA.

Examples of the silane coupling agent having an amino group, a glycidyl group or a mercapto group used in the present invention include 3-aminopropyldimethylethoxysilane, 3-aminopropylmethyldiethoxysilane and 3-aminopropyltrisilane. Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyldimethylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, mercaptomethyldimethylethoxysilane, (Mercaptomethyl) methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-
Examples include mercaptopropyltriethoxysilane,
These may be used alone or in combination of two or more.

If the addition amount of the silane coupling agent used in the present invention is small, the adhesiveness of the obtained laminated glass interlayer film to the glass is deteriorated, and if the addition amount is large, the transparency is decreased. Limited to 0 parts by weight.

The laminated glass intermediate film of the present invention further comprises
For the purpose of preventing the deterioration of EEVA, a stabilizer, an antioxidant, an ultraviolet absorber and the like can be appropriately used if necessary.

Examples of the above stabilizers include calcium stearate soap, dialkanol, and aliphatic tertiary amines.

As the above-mentioned antioxidant, for example, t-butylhydroxytoluene (BHT), "Irganox 1010" manufactured by Ciba-Geigy Co., etc. are used.

Examples of the ultraviolet absorber include "Tinuvin p", "Tinuvin 320" manufactured by Ciba-Geigy,
"Tinuvin 326" and "Tinuvin 328"benzotriazole-based; ADEKA ARGUS "LA-57" hindered amine-based; Cypro Kasei "Seesorb 10"
1 "," Seesaw 102 "," Seesaw 103 ",
Examples thereof include benzophenone series such as "Seesaw 104".

The laminated glass intermediate film of the present invention is EEVA.
And a condensation reaction product or the compound represented by the general formula (1) are uniformly mixed and molded. As a mixing method, for example, a method of melt-kneading using a roll mill, a dry blending method of mixing without melting, a condensation reaction product or a master batch of EEVA containing a compound represented by the general formula (1) at a high concentration The high-concentration masterbatch method in which the pellets of (1) are diluted with the pellets of EEVA to obtain a predetermined concentration can be mentioned.

Examples of the above-mentioned molding method include a method of forming a sheet by an extrusion method, a pressing method or a calender method.

As a method for producing a laminated glass from the laminated glass intermediate film of the present invention, for example, a laminated body is prepared by sandwiching the laminated glass intermediate film between two previously washed glass or transparent synthetic resin plates. Then, this laminated body is placed in a rubber bag, deaerated at a vacuum degree of 0 to 20 torr for a certain period of time, then transferred to an oven at 80 ° C. or higher in the deaerated state and kept at this temperature for a certain period of time.

Alternatively, the laminated body is passed through a pressure rubber roll heated to 100 ° C. or higher for a certain period of time, and then heated and held in an oven to produce a laminated glass.

The layer structure of the laminated glass obtained by using the laminated glass interlayer film of the present invention is basically glass / laminated glass interlayer film / glass, but the layer structure shown below can also be used.

The laminated glass has the following layer structure: (1) glass / interlayer glass intermediate film (hereinafter referred to as “intermediate film”) / polyester film / intermediate film / glass (2) glass / intermediate film / metal plate / intermediate film / Glass / intermediate film / polyurethane film (3) glass / intermediate film / paper / intermediate film / glass (4) polycarbonate plate / intermediate film / polyester film / intermediate film / polycarbonate plate (5) acrylic plate / intermediate film / metal plate / Intermediate film / Acrylic plate / Intermediate film / Polyurethane film (6) Acrylic plate / Intermediate film / Paper / Intermediate film / Acrylic plate (7) Polycarbonate / Intermediate film / Polycarbonate.

Examples of the polyester film include polyethylene terephthalate and polybutylene terephthalate films, and examples of the acrylic plate include polymethylmethacrylate plate.

[0047]

EXAMPLES Next, examples of the present invention will be described. In the following, "parts" means "parts by weight".

(Example 1) (Synthesis of EEVA) E containing 40% by weight of vinyl acetate
VA (Mitsui DuPont Polychemical, trade name; EVAF
LEX40Y.W) is hydrolyzed to obtain a partially saponified product with a saponification degree of 50%. 180 g of this partially saponified product, 5 parts of phthalic anhydride
0 g, 40 g of pyridine, 1500 g of xylene were mixed and reacted at 110 ° C. for 4 hours. The composition of the partially esterified product obtained was examined by infrared analysis and chemical analysis. It was confirmed that the vinyl alcohol component was 10% by weight, the phthalate ester component of vinyl alcohol was 10% by weight, and the balance was an ethylene component.

(Synthesis of Condensation Reaction Product) 182 g of D-sorbitol was placed in a flask equipped with a reflux condenser and a stirrer.
(1.00 mol) and benzaldehyde 212 g (2.0
0 mol), toluene 800 g, concentrated sulfuric acid 2.0 g,
After reacting at 80 ° C. for 3 hours, toluene was distilled off, the mixture was neutralized with potassium hydroxide, washed with hot water, filtered and dried to obtain 347 g of dibenzylidene sorbitol. The yield is 97.0
%Met.

(Preparation of Laminated Glass Intermediate Film) EEVA obtained above, dibenzylidene sorbitol obtained above and N- (2-aminoethyl) -3-aminopropyldimethoxysilane in the predetermined amounts shown in Table 1. Mix
Roll kneading, then sandwich the kneaded thing between polyethylene terephthalate film, using a press,
A 400 μm-thick sheet was prepared, left to stand at room temperature, and the polyethylene terephthalate film was peeled off to obtain a laminated glass intermediate film.

(Preparation of Laminated Glass) Next, the laminated glass interlayer film obtained as described above is sandwiched between two float glass plates having a thickness of 3 mm which have been washed and dried in advance and placed in a rubber bag at 10 torr. After degassing at a vacuum degree for 20 minutes, it was transferred to an oven at 100 ° C. in the degassed state and kept at this temperature for 30 minutes to prepare a laminated glass.

(Preparation of laminated glass for adhesive strength test) The laminated glass interlayer film thus obtained was sandwiched between glass and a polyethylene terephthalate film to prepare laminated glass for adhesive strength test.

(Embodiment 2) EEVA similar to that of Embodiment 1,
Condensation reaction product and N- (2-aminoethyl) -3-
Using aminopropyldimethoxysilane, a laminated glass interlayer film was prepared in a predetermined amount shown in Table 1, and one of the glasses was replaced with a polycarbonate plate (trade name; Yupylon sheet NF200U, manufactured by Mitsubishi Gas). A laminated glass and a laminated glass for adhesive strength test were prepared in the same manner as in 1.

(Embodiment 3) EEVA similar to that of Embodiment 1,
Condensation reaction product and N- (2-aminoethyl) -3-
Example 1 was carried out by using aminopropyldimethoxysilane to prepare a laminated glass interlayer film in a predetermined amount shown in Table 1 and replacing the glass with a polymethylmethacrylate plate (Mitsubishi Rayon, trade name; Acrylite HR). A laminated glass and a laminated glass for adhesive strength test were prepared by the same method as described above.

Example 4 (Synthesis of Condensation Product) 152 g (2.00 mol) of xylitol was added in place of D-sorbitol of Example 1,
When reacted in the same manner, dibenzylidene xylitol 32
0 g was obtained. The reaction yield was 95%.

(Preparation of Laminated Glass) Using the same EEVA as in Example 1 and the dibenzylidene xylitol and 3-mercaptopropyltriethoxysilane obtained above, a laminated glass interlayer film was prepared in a predetermined amount shown in Table 1. Then, a laminated glass and a laminated glass for an adhesive strength test were prepared in the same manner as in Example 1.

(Example 5) (Synthesis of EEVA) E containing 43% by weight of vinyl acetate
VA (manufactured by Tosoh: Ultrasen 760) is hydrolyzed,
A partially saponified product having a saponification degree of 81% was obtained.
g, 50 g of maleic anhydride and 40 g of pyridine,
The mixture was mixed in 500 g of xylene and reacted at 110 ° C. for 4 hours. The composition of the partially esterified product thus obtained was examined by infrared ray analysis and chemical analysis.
It was confirmed that the composition consisted of 50% by weight, 10% by weight of vinyl alcohol component, 25% by weight of maleic acid ester component of vinyl alcohol, and the balance of ethylene component.

(Preparation of laminated glass) E obtained above
A laminated glass intermediate film was prepared in the same manner as in Example 1 by using EVA and the condensation reaction product similar to that in Example 1 and 3-glycidoxypropyltrimethoxysilane in the predetermined amounts shown in Table 1, and the laminated glass was prepared. And the laminated glass for adhesive strength test was created.

(Embodiment 6) EEVA similar to that of Embodiment 5,
Using dibenzylidene xylitol and 3-aminopropyltriethoxysilane, a laminated glass intermediate film was prepared in the same manner as in Example 1 except for the predetermined amounts shown in Table 1 and below, and laminated glass and adhesive A laminated glass for strength test was prepared.

(Example 7) (Synthesis of EEVA) EVA containing 43% by weight of vinyl acetate
(Tosoh, trade name; Ultracene 760) is hydrolyzed to obtain a partially saponified product with a saponification degree of 35%. This partially saponified product 1
80 g, 55 g of succinic anhydride and 40 g of pyridine,
It was mixed with 1500 g of xylene and reacted at 110 ° C. for 4 hours. The composition of the obtained partially esterified product was 28% by weight of vinyl acetate component, 5% by weight of vinyl alcohol component, and 10% by weight of succinic acid ester component of vinyl alcohol.

(Preparation of laminated glass) EEVA obtained
And 4-t-butylcalix [4] arene and 3-aminopropyltrimethoxysilane were used to prepare a laminated glass interlayer film in the same manner as in Example 1 except that the predetermined amounts shown in Table 1 were used. , Laminated glass and laminated glass for adhesive strength test were prepared.

(Comparative Example 1) (Preparation of Composition) EVA (Mitsui DuPont Polychemical, trade name; 2 g / 10 min melt index measured according to ASTM 1238-65T, 25% by weight vinyl acetate). EVAFLEX 360) 100 parts, triallyl isocyanurate (manufactured by Nippon Kasei, trade name; Tayk) 3 parts, 1,1-bis (t-butylperoxy) 3,
3,5-Trimethylcyclohexane (Nippon Yushi) 1.
0 part and 0.3 part of γ-methacryloxypropyltrimethoxysilane were mixed and kneaded by a roll mill heated to 100 ° C. to prepare a laminated glass interlayer film in the same manner as in Example 1, and then the laminating temperature was set. A laminated glass and an adhesive strength test laminated glass were prepared in the same manner as in Example 1 except that the temperature was changed to 130 ° C.

Comparative Example 2 EEVA similar to that of Example 1,
Benzylidene sorbitol, N- (2-aminoethyl)
Laminated glass and a laminated glass for adhesive strength test were prepared in the same manner as in Example 1 except that 3-aminopropylmethyldimethoxysilane was used in the predetermined amounts shown in Table 1.

(Comparative Example 3) EEVA similar to that in Example 1,
Using benzylidene sorbitol and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, laminated glass interlayer films were prepared in predetermined amounts shown in Table 1. Then, a laminated glass and a laminated glass for adhesive strength test were prepared in the same manner as in Example 1.

(Comparative Example 4) EEVA similar to that of Example 7,
Using 4-t-butylcalix [4] arene and 3-mercaptopropyltriethoxysilane, a laminated glass interlayer film was prepared in a predetermined amount shown in Table 1. Then, a laminated glass and a laminated glass for adhesive strength test were prepared in the same manner as in Example 1.

(Comparative Example 5) EEVA similar to that of Example 7,
A laminated glass and an adhesive strength test laminated glass were prepared in the same manner as in Example 1 except that 4-t-butylcalix [4] arene and 3-mercaptopropyltriethoxysilane were used in the predetermined amounts shown in Table 1. Created.

Comparative Example 6 (Synthesis of EEVA) EVA containing 15% by weight of vinyl acetate
(Tosoh: Ultracene 625) is hydrolyzed to obtain a partially saponified product having a saponification degree of 73%. 180 g of this partially saponified product,
55 g of phthalic anhydride and 40 g of pyridine are added to 1500
The mixture was mixed with g xylene and reacted at 110 ° C. for 4 hours.
The composition of the obtained partially esterified product is vinyl acetate component 4
% By weight, 8% by weight of vinyl alcohol component, and 3% by weight of phthalate ester component of vinyl alcohol.

(Preparation of laminated glass) Obtained EEV
A, a benzylidene sorbitol and propyltrimethoxysilane were used to prepare a laminated glass interlayer film in a predetermined amount shown in Table 1, and thereby a laminated glass and a laminated glass for adhesive strength test were prepared.

Comparative Example 7 (Synthesis of EEVA) EVA containing 15% by weight of vinyl acetate
(Tosoh; Ultracene 625) is hydrolyzed to obtain a partially saponified product having a saponification degree of 73%. 180 g of this partially saponified product,
65 g of succinic anhydride and 40 g of pyridine were added to 1500
The mixture was mixed with g xylene and reacted at 110 ° C. for 4 hours.
The composition of the obtained partially esterified product is vinyl acetate component 4
% By weight, 3% by weight of vinyl alcohol component, and 8% by weight of succinic acid ester component of vinyl alcohol.

(Preparation of laminated glass) Obtained EEV
Using A, 4-t-butylcalix [4] arene and vinyltriethoxysilane, a laminated glass intermediate film was prepared in the same amount as shown in Table 1 in the same manner as in Example 1.
From this, laminated glass and laminated glass for adhesive strength test were prepared.

With respect to the laminated glass obtained in Examples 1 to 7 and Comparative Examples 1 to 7, transparency test, impact test, cold heat test,
A moisture resistance test and a boiling test were performed, and a peel strength test was performed on the laminated glass for an adhesive strength test. The results are shown in Table 2.

[0072]

[Table 1]

[0073]

[Table 2]

The method of the above test is as follows. (1) Impact resistance test According to JIS-R3205, temperature 23 ° C, humidity 50%
The laminated glass held for 4 hours was held vertically by a support frame, and an attacker having a weight of 45 kg and a maximum diameter of 75 mm was freely dropped from the height of 30 cm to the center of the laminated glass in a pendulum manner. The case where an opening through which a sphere having a diameter of 75 mm can freely pass was formed in the broken portion was indicated by x, and the case where it was not formed was indicated by o. (2) Transparency test The total light transmittance (%) and the haze value at a temperature of 23 ° C and a humidity of 50% were measured using "Integral turbidity meter" manufactured by Tokyo Denshoku. The test was conducted at n = 10. (3) Cold Heat Test After the laminated glass was left at 70 ° C. for 2 hours, it was cooled from 70 ° C. to −20 ° C. over 2 hours, and further left at −20 ° C. for 2 hours, then from −20 ° C. to 70 ° C. After performing 10 cycles of the step of raising the temperature over time as one cycle, the presence or absence of peeling between the glass and the interlayer film was observed. (4) Humidity resistance test After the laminated glass was left at 55 ° C and an environmental humidity of 98% RH for 2 weeks, the presence or absence of peeling between the glass and the laminated glass interlayer film was observed. (5) Boiling test After the laminated glass was left in boiling water for 2 hours, the presence or absence of peeling between the glass and the laminated glass interlayer was observed. (6) Peel strength test In accordance with JIS K6854, a sample piece having a width of 2 cm and a length of 10 cm was cut out from a laminated glass for adhesive strength test, and a tensile tester (manufactured by Orientec; Tensilon UC) was used.
E500) was used to measure the 90-degree peel strength between the glass and the laminated glass interlayer film at a pulling speed of 500 mm / min.

[0075]

Industrial Applicability As described above, the laminated glass interlayer film of the present invention is a condensation reaction product of EEVA and a polyhydric alcohol having a valence of 5 to 12, and a benzaldehyde (derivative) or a compound represented by the general formula (1). And because it consists of a silane coupling agent, it has excellent transparency and adhesiveness with glass and transparent synthetic resin plates without impairing the impact resistance, which is a basic property, and it can be processed without autoclave, so it can be processed. The process can be simplified and it can be used as a laminated glass interlayer film for vehicles and buildings.

Claims (1)

[Claims] 1. A modified ethylene / vinyl acetate copolymer comprising 4 to 18% by weight of a vinyl alcohol component and 5 to 60% by weight of a dicarboxylic acid ester component of vinyl alcohol, a polyhydric alcohol having a valence of 5 to 12 and a benzaldehyde. 0.01 to 4.0 parts by weight of the condensation reaction product of the (derivative) or the compound represented by the general formula (1), and a silane coupling agent having one or more amino groups, mercapto groups or glycidyl groups. A laminated glass interlayer film, which comprises 01 to 4.0 parts by weight. [Chemical 1] [In general formula (1), n represents a natural number of 4 to 16. ]