JPH08188453A - Intermediate film for laminated glass - Google Patents

Abstract

PURPOSE: To prepare an intermediate film capable of storing at ordinary temperature and laminating and processing at a low temperature without requiring humidity control or autoclave by forming the film from an ethylene-(meth)acrylic acid ester copolymer, an organic peroxide, a specific (meth)acrylic acid ester, a condensation reaction product and a silane coupling agent. CONSTITUTION: This intermediate film is composed of 100 pts.wt. ethylene-(meth) acrylic acid ester copolymer, 0.01-5 pts.wt. organic peroxide, 0.03-5 pts.wt. (meth) acrylic acid ester which is a reaction product of (meth)acrylic acid with a 3-35C polyhydric alcohol and has >=2 (meth)acryloyl groups, 0.01-4 pts.wt. condensation reaction product obtained by reacting a penta or more polyvalent polyhydric alcohol or its derivative with 1.8-2.8 equivalent of benzaldehyde or its derivative and 0.01-4 pts.wt. silane coupling agent having one or more functional groups selected from amino group, glycidyl group and mercapto group.

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.

Further, 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 Publication 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 the radicals generated by the decomposition of the organic peroxide are used for the thermosetting reaction, the temperature is 140 to 150 ° C.
The processing temperature is required, and when it is used for colored decorative laminated glass, a heat-resistant dye is required, which has a drawback that processing workability is deteriorated and cost is increased. Further, in the case of a combination process with a synthetic resin plate, there is a problem that the synthetic resin plate is 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. (EN) An interlayer film for laminated glass, which can be stored at room temperature without impairing the basic characteristics, and which does not require humidity control and an autoclave in the manufacturing process and which can be laminated at a relatively low temperature.

[0008]

The interlayer film for laminated glass of the present invention comprises an ethylene- (meth) acrylic acid ester copolymer, an organic peroxide (a), a (meth) acrylic acid ester (b), and a poly (meth) acrylic acid ester (b). It is formed from a resin composition comprising a condensation reaction product (c) obtained by reacting a hydric alcohol and its derivative with benzaldehyde or its derivative, and a silane coupling agent (d).

The ethylene- (meth) acrylic acid ester copolymer (hereinafter referred to as EA copolymer) has different transparency and mechanical properties depending on the content of the (meth) acrylic acid ester. When the content of (a) is low, the tensile strength is good but the transparency is low, and when it is high, the transparency is good but the tensile strength is low.
5% by weight is preferred.

The above-mentioned EA copolymer can be produced by a known production method such as a high pressure method and an emulsification method, and its average weight molecular weight is preferably 5,000 to 500,000, more preferably 3,000 to 300, It is 000.

The melt index of the above EA copolymer (value measured according to ASTM D1238)
Is preferably 0.5 to 500 (g / 10 min), more preferably 1 to 200 (g / 10 min).

The above-mentioned organic peroxide (a) has a 30-minute half-life of 9 in consideration of stability at the time of compounding and crosslinking reactivity.
Those having a temperature of 0 ° C. to 130 ° C. are preferable, and examples of such an organic peroxide include 2,5-dimethylhexane-
2,5-dihydroperoxide, 2,5-dimethylhexane-2,5-di (t-butylperoxy) hexane-3-di-t-butylperoxide, t-butylcumylperoxide, 2,5 -Dimethylhexane-2,
5-di (t-butylperoxy) hexane, t-butylperoxyisobutyrate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t -Butylperoxy) cyclohexane, t-butylperoxy (2-ethylhexanoate), m-toluoyl peroxide, etc. may be mentioned, and these may be used alone or in combination of two or more kinds.

In the above resin composition, when the amount of the organic peroxide (a) used is small, it is difficult to improve the transparency, and when the amount is large, the compatibility with the copolymer is deteriorated.
It is 0.01 to 5 parts by weight with respect to 100 parts by weight of the A copolymer.

The (meth) acrylic acid ester (b)
Is a reaction product of (meth) acrylic acid and a polyhydric alcohol having 3 to 35 carbon atoms, and has two or more (meth) acryloyl groups in the molecule. Examples of such (meth) acrylic acid ester (b) include:
1,6-hexanediol diacrylate, 1,10-
Decanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, 1,3
-Butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, etc. are mentioned, and even if they are used alone, two or more kinds are used in combination. May be done.

In the above resin composition, when the amount of the (meth) acrylic acid ester (b) used is small, the effect of improving the transparency is insufficient, and when it is large, the compatibility with the resin is poor and the transparency is low. EA copolymer 100
It is 0.03 to 5 parts by weight with respect to parts by weight.

The above-mentioned condensation reaction product (c) is obtained by subjecting a polyhydric alcohol having a valence of 5 or more or its derivative to a condensation reaction of benzaldehyde or its derivative. When the amount of the derivative is small, a large amount of the monoacetalized product is formed, and when the amount of the derivative is large, a large amount of the hemiacetalized product is generated. It is limited to 1.8 to 2.8 times the equivalent of the hydroxyl group.

The condensation reaction product obtained by subjecting the polyhydric alcohol having 5 or more valences or its derivative to the condensation reaction of benzaldehyde or its derivative is known in the art, for example, JP-B-40-15489 and JP-B-47-. It can be produced by the method described in Japanese Patent No. 7460.

In the above production method, a polyhydric alcohol having a valence of 5 or more or a derivative thereof is put into a reactor equipped with a cooling pipe and a stirrer in the presence of an inert gas, and then 1.
The condensation reaction product (c) can be synthesized by charging 8- to 2.8-fold equivalent amount of benzaldehyde or its derivative, adding sulfuric acid as a condensation acid catalyst, and reacting by heating.

Examples of the above 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,
The transparency of the resulting interlayer film is significantly improved.

Examples of the above-mentioned benzaldehyde or its derivative include a chlorine atom of benzene ring hydrogen of benzaldehyde, a substituted alkyl group, an aryl group and an alkoxy group. 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 (c) include dibenzylidene sorbitol, bis (methylbenzylidene) sorbitol, bis (ethylbenzylidene) sorbitol, bis (propylbenzylidene) sorbitol, bis (butylbenzylidene) sorbitol and bis ( Examples include pentylbenzylidene) sorbitol, bis (hexylbenzylidene) sorbitol, bis (chlorobenzylidene) sorbitol, dibenzylidenexylitol, dibenzylidene mannitol, and these may be used alone or in combination of two or more.

In the above resin composition, when the amount of the condensation reaction product (c) is small, the transparency of the obtained intermediate film is not sufficiently improved, and when the amount is large, the fluidity of the resin composition is lowered and the intermediate film is reduced. Since the tensile strength of the film decreases, it is limited to 0.01 to 4 parts by weight, preferably 0.05 to 1 part by weight, relative to 100 parts by weight of the EA copolymer.

By further adding a nucleating agent such as tribenzylidene sorbitol, sodium bis (4-t-butylphenyl) phosphate, aluminum hydroxy-di (t-butylbenzoate) to the above resin composition, The transparency is further improved.

The silane coupling agent (d) has at least one functional group selected from the group consisting of an amino group, a glycidyl group and a mercapto group,
For example, 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, methylphenyldimethoxysilane, and the like, which are used alone They may be used or two or more may be used in combination.

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 lowered. Therefore, 100 parts by weight of the EA copolymer is used. Is limited to 0.01 to 4 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-butyl hydroxytoluene (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.

When preparing the above resin composition, it is necessary to uniformly mix the EA copolymer and the silane coupling agent. As a mixing method, a method of melting and kneading the EA copolymer and other components using a mixer such as a roll mill;
Dry blending method in which the EA copolymer and the other components are kneaded as they are; a high-concentration master batch in which the master batch pellets containing the components other than the EA copolymer in a high concentration are diluted with the EA copolymer to a predetermined concentration Etc.
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 a laminated glass from the above-mentioned laminated glass intermediate film, a commonly-used method for producing a laminated glass can be adopted. For example, a sheet-like intermediate film having a thickness of 3 mm from both sides thereof can be used. Sandwiched between transparent rigid plates such as glass plate or synthetic resin plate, and put the sandwich structure in the unpressed state in a rubber bag, and 0 to 20To
After degassing for a certain period of time at a vacuum degree of rr, leave the degassing state
Examples include a method of placing in an oven at 0 ° C. or higher and holding at this temperature for a fixed time, or a method of passing the above sandwich structure through a pressure rubber roll heated to 100 ° C. or higher for a fixed time and then heating and holding in the oven. To be

The layer structure of the laminated glass obtained by using the interlayer film for laminated glass of the present invention is basically glass / intermediate film / glass, but the following layer structures are also included.・ Glass / intermediate film / polyester film / 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

[0033]

Embodiments of the present invention will be described below. (Example 1) Synthesis of condensation reaction product (a) 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 concentrated sulfuric acid were added. After adding 2 ml and reacting at 80 ° C. for 3 hours, toluene was distilled off, neutralized with potassium hydroxide, washed with hot water, filtered and dried to obtain 347 g of dibenzylidene sorbitol. Rate 97%).

Preparation of Resin Composition Predetermined amount of ethylene-methyl methacrylate copolymer (“Acryft WH202” manufactured by Sumitomo Chemical Co., acrylic content 20% by weight, MI = 3), organic peroxide Stuff,
1,6-hexanediol methacrylate (HDM
A), the condensation reaction product (a) and the silane coupling agent were kneaded by a Labo Plastomill at 100 ° C. for 5 minutes to obtain a resin composition. Production of Laminated Glass 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 allowing it to reach room temperature, and the obtained interlayer film sheet is sandwiched between two float glass plates having a thickness of 3 mm that have been washed in advance, and the sheet is placed in a rubber bag to
After degassing at a vacuum degree of 0 Torr for 20 minutes, the glass was prepared by placing it in an oven at a predetermined temperature shown in Table 3 for 30 minutes in the degassed state.

(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) A laminated glass was produced in the same manner as in Example 1 except that an acrylic resin plate ("Acrylite HR" manufactured by Mitsubishi Rayon Co., Ltd.) was used instead of the glass plate.

Example 4 Instead of D-sorbitol, D
-After a condensation reaction product (II) was obtained by reacting in the same manner as in Example 1 except that 182 g (1 mol) of mannitol was used (yield: 75%), a predetermined amount shown in Table 1 Ethylene-methyl methacrylate copolymer (“Acryft WH402” manufactured by Sumitomo Chemical Co., acrylic content 25% by weight, MI = 20), organic peroxide, 1,6-hexanediol acrylate (HDA), the above condensation reaction product A laminated glass was produced in the same manner as in Example 1 except that the resin composition containing the substance (b) and the silane coupling agent was used and the temperature was set as shown in Table 3.

(Example 5) D-sorbitol instead of D
Using 152 g (2 mol) of xylitol, Example 1
After performing a condensation reaction in the same manner as above to obtain 320 g (yield 95%) of dibenzylidene xylitol as a condensation reaction product (c), a predetermined amount of ethylene-methyl methacrylate copolymer, organic compound shown in Table 1 was used. Example 1 except that a resin composition containing a peroxide, trimethylolpropane trimethacrylate, the above condensation reaction product (c) and a silane coupling agent was used and the combination temperature shown in Table 3 was used. A laminated glass was prepared in the same manner as in.

Example 6 A predetermined amount of ethylene-methyl methacrylate copolymer (“DPDJ-9169” manufactured by Nippon Unicar Co., Ltd.), an organic peroxide, trimethylolpropane triacrylate, and the above-mentioned condensation are shown in Table 1. A laminated glass was produced in the same manner as in Example 1 except that the resin composition containing the reaction product (a) and the silane coupling agent was used and the temperature was set to the one shown in Table 3.

(Comparative Example 1) Ethylene-vinyl acetate copolymer ("EVAFLEX3 manufactured by Mitsui DuPont Polychemical Co., Ltd."
60 ", vinyl acetate content 25% by weight, MI = 2) 10
0 parts by weight, triallyl isocyanurate (“Taike” manufactured by Nippon Kasei Co., Ltd.) 3 parts by weight, 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 interlayer film. A laminated glass was produced in the same manner as in Example 1 except that this sheet-shaped intermediate film was used.

Comparative Example 2 Instead of the 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 Comparative Example 1 except that 200 U ″) was used and the laminating temperatures shown in Table 3 were used.

Comparative Example 3 A laminated glass was produced in the same manner as in Comparative Example 1 except that the laminating temperature shown in Table 3 was used.

(Comparative Example 4) An ethylene-vinyl acetate copolymer ("Ultracene 750" manufactured by Tosoh Corporation, vinyl acetate content 32% by weight) was hydrolyzed with sodium hydroxide as a catalyst to give a saponification degree of 90 mol%. After the partial saponification of
180 g of this partially saponified product, 104 g of phthalic anhydride and 40 ml of pyridine were mixed in 1.5 liter of xylene and reacted at 110 ° C. for 4 hours. The obtained reaction product was analyzed by infrared analysis and chemical analysis.
It was confirmed that the vinyl acetate component was 3.2% by weight, the vinyl alcohol component was 6.1% by weight, the vinyl phthalate component was 12.7% by weight, and the remaining amount was composed of an ethylene component.
A laminated glass was produced in the same manner as in Example 1 except that the above reaction product was used as the resin composition.

(Comparative Examples 5 to 8) In the predetermined amount shown in Table 1,
Ethylene-methyl methacrylate copolymer, organic peroxide, 1,6-hexanediol methacrylate (HDM
Example 1 except that the resin composition containing A), the condensation reaction product (1) and the silane coupling agent was used.
A laminated glass was prepared in the same manner as in.

[0045]

[Table 1]

[0046]

[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 has 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, then cooled from 70 ° C. to −20 ° C. over 2 hours, left at −20 ° C. for 2 hours, and then from −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 98% relative humidity 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.

[0053]

[Table 3]

[0054]

The structure of the interlayer film for laminated glass of the present invention is as described above, and includes ethylene- (meth) acrylic acid methyl copolymer, (meth) acrylic acid ester, a specific condensation reaction product and silane. By being formed from a resin composition consisting of a coupling agent, it is possible to perform matching processing without the need for humidity control and autoclave in the manufacturing process, without impairing the transparency and impact resistance that are the basic properties of the intermediate film. Further, since it is possible to lower the matching temperature, it is possible to simplify the manufacturing process.

Claims (1)

[Claims] 1. An ethylene- (meth) acrylic acid ester copolymer 100 parts by weight, (a) an organic peroxide 0.01 to 5
Parts by weight, (b) a (meth) acrylic acid ester, which is a reaction product of (meth) acrylic acid and a polyhydric alcohol having 3 to 35 carbon atoms and has two or more (meth) acryloyl groups, 0.03 to 5 parts by weight, (c) a condensation reaction obtained by reacting a polyhydric alcohol having a valence of 5 or more and its derivative with 1.8 to 2.8-fold equivalent of benzaldehyde or its derivative with respect to the polyhydric alcohol and its derivative Product 0.01
To 4 parts by weight and (d) a silane coupling agent 0.01 to 4 having at least one functional group selected from the group consisting of an amino group, a glycidyl group and a mercapto group.
An interlayer film for laminated glass, which is formed from a resin composition consisting of parts by weight.