JP3204864B2 - Interlayer for laminated glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention 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 sports facilities, partitions, security doors, and the like. Alternatively, a part thereof is replaced with an organic glass, that is, a transparent synthetic resin plate, and processed through an intermediate film.

As the above-mentioned intermediate film, polyvinyl butyral resin plasticized with a plasticizer is most commonly used because it has excellent adhesiveness to glass, tough tensile strength, high transparency and the like. ing. However,
When the intermediate film made of the polyvinyl butyral resin is stored in a roll-wound state, it is stored at a low temperature because of strong self-adhesiveness, or a release paper is interposed between the intermediate films.
Some measures had to be taken to prevent blocking.

[0004] Further, when actually manufacturing a laminated glass, it is necessary to perform a humidity control step of an interlayer before laminating with the glass, and furthermore, it is necessary to perform laminating under high temperature and high pressure by an autoclave. Work is complicated. In addition, when the synthetic resin transparent plate is processed together, the plasticizer bleeds out at the interface between the interlayer and the synthetic resin plate, lowering the adhesiveness, and eroding the synthetic resin plate to cause whitening. there were.

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

However, an intermediate film composed of a partially esterified EVA copolymer has poor adhesion to glass,
There is a drawback that heat resistance and moisture resistance are inferior. Also, EV
The intermediate film comprising the organic peroxide compound of the A copolymer has improved crystallinity at the time of thermal denaturation, thereby improving transparency, and can be stored at room temperature, and does not require humidity control before processing. There is an advantage that the processing can be performed without an autoclave. However, since the radical generated by the decomposition of the organic peroxide is used for the thermosetting reaction,
In the case where it is used for colored decorative laminated glass, a heat-resistant dye is required, and there is a disadvantage that processing workability is deteriorated and cost is increased. In addition, in the case of processing 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 has as its object the purpose of laminated glass such as transparency, moisture resistance, weather resistance, impact resistance and adhesiveness. It is an object of the present invention to provide an interlayer film for laminated glass that can be stored at room temperature without deteriorating its basic characteristics and can be laminated at a relatively low temperature without requiring humidity control and autoclave in a manufacturing process.

[0008]

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

The above ethylene- (meth) acrylate copolymer (hereinafter referred to as EA copolymer) has different transparency and mechanical properties depending on the content of the (meth) acrylate, and the (meth) acrylate When the content is low, the tensile strength is good but the transparency is low. When the content 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, an emulsification method and the like, and its average molecular weight is preferably 5,000 to 500,000, more preferably 3,000 to 300,000. 000.

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

The above organic peroxide (a) has a half-life of 30 minutes in consideration of stability at the time of blending and crosslinking reactivity.
Those having a temperature of 0 ° C. to 130 ° C. are preferred. Such organic peroxides include, for example, 2,5-dimethylhexane-
2,5-dihydroperoxide, 2,5-dimethylhexane-2,5-di (t-butylperoxy) hexane-3-di-t-butyl peroxide, t-butylcumyl peroxide, 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 and the like, and these may be used alone or in combination of two or more.

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

The above (meth) acrylate (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 a (meth) acrylate (b) include, for example,
1,6-hexanediol diacrylate, 1,10-
Decanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol dimethacrylate, tritylene glycol dimethacrylate, 1,3
-Butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, and the like. These may be used alone or in combination of two or more. 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 the amount is large, the compatibility with the resin becomes poor and the transparency becomes poor. EA copolymer 100
It is 0.03 to 5 parts by weight based on parts by weight.

The above condensation reaction product (c) is obtained by subjecting a benzaldehyde or a derivative thereof to a condensation reaction with a pentavalent or higher polyhydric alcohol or a derivative thereof. When the amount of the derivative is small, a large amount of monoacetalized compound is generated, and when the amount is large, a large amount of hemiacetalized compound is generated, and when these by-products are used as an intermediate film, they hinder the improvement in transparency. Is limited to 1.8 to 2.8 equivalents to the hydroxyl group of

Condensation reaction products obtained by subjecting the above pentahydric or higher polyhydric alcohol or its derivative to a condensation reaction with benzaldehyde or its derivative can be obtained by known techniques, for example, Japanese Patent Publication Nos. 40-15489 and 47-47. It can be manufactured by the method described in, for example, US Pat.

In the above production method, a pentavalent or higher polyhydric alcohol or a derivative thereof is charged into a reactor equipped with a cooling pipe and a stirrer in the presence of an inert gas.
The condensation reaction product (c) can be synthesized by charging 8 to 2.8 equivalents of benzaldehyde or a derivative thereof, adding sulfuric acid as a condensation acid catalyst, and causing a heating reaction.

Examples of the above-mentioned pentahydric or higher polyhydric alcohol or a derivative thereof include, for example, D, L-sorbitol (D, L-glucitol), xylitol, D, L-mannitol, dulcitol, L-sorbose, D-arabinitol, Ribitol,
D-fructose and the like, which may be used alone or in combination of two or more. In particular, as a polyhydric alcohol or a derivative thereof, when D, L-sorbitol, xylitol, D, L-mannitol, and dulcitol are used,
The transparency of the resulting interlayer is significantly improved.

Examples of the above benzaldehyde or a derivative thereof include a chlorine atom, an alkyl group, an aryl group and an alkoxy group substituent of benzene ring hydrogen of benzaldehyde. These may be used alone or in combination of two or more. You may.

Examples of the condensed acid catalyst include sulfuric acid,
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 (butylbenzylidene) sorbitol. Pentyl benzylidene) sorbitol, bis (hexyl benzylidene) sorbitol, bis (chlorobenzylidene) sorbitol, dibenzylidene xylitol, dibenzylidene mannitol, etc., may be used alone or in combination of two or more.

In the above resin composition, if the amount of the condensation reaction product (c) is too small, the transparency of the obtained intermediate film is not sufficiently improved, and if the amount is too large, the fluidity of the resin composition is lowered and Since the tensile strength of the membrane decreases, the amount 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 EA copolymer.

The above resin composition is further added with a nucleating agent such as tribenzylidene sorbitol, sodium bis (4-tert-butylphenyl) phosphate, or aluminum hydroxy-di (tert-butylbenzoate). 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-chloropropyl
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, etc., and these may be used alone. They may be used or two or more of them 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. Is restricted to 0.01 to 4 parts by weight.

If necessary, a stabilizer, an antioxidant, an ultraviolet absorber and the like may be added to the resin composition for the purpose of preventing deterioration of the resin.

Examples of the stabilizer include calcium stearate soap and dialkanol aliphatic tertiary amine. 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 Cipro Kasei
04 "and the like.

In 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 melt-kneading the EA copolymer and other components using a mixer such as a roll mill;
A dry blending method in which the EA copolymer and other components are kneaded as they are; a high-concentration master batch in which a master batch pellet containing a high concentration of components other than the EA copolymer is diluted with the EA copolymer to a predetermined concentration. And the like.
Examples of a method of forming an interlayer film for laminated glass from the above resin composition include a method of forming a sheet by an extrusion method, a press method, a calendar method, or the like.

As a method for manufacturing a laminated glass from the above-mentioned interlayer film for a laminated glass, a commonly used method for manufacturing 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 a transparent rigid plate such as a glass plate or a synthetic resin plate, and the sandwich structure in an uncompressed state is placed in a rubber bag.
After degassing at a vacuum of rr for a certain period of time,
A method in which the mixture is placed in an oven at 0 ° C. or more and held at this temperature for a certain time, or a method in which the sandwich structure is passed through a pressurized rubber roll heated to 100 ° C. or more for a certain time and then heated and held in the oven. Can be

The layer structure of the laminated glass obtained by using the interlayer film for a laminated glass of the present invention is basically glass / intermediate film / glass, but other than this, the following layer structure can be mentioned.・ Glass / interlayer / polyester film / interlayer / glass ・ Glass / interlayer / metal plate / interlayer / glass / interlayer /
Polyurethane film ・ Glass / interlayer / paper / interlayer / glass ・ Polycarbonate plate / interlayer / polyester film / interlayer / polycarbonate plate ・ Acrylic resin plate / interlayer / metal plate / interlayer / acrylic resin plate ・ Acrylic resin plate / Interlayer / Paper / Interlayer / 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 equipped with a stirrer, 182 g (1 mol) of D-sorbitol, 212 g (2 mol) of benzaldehyde, 800 ml of toluene and concentrated sulfuric acid 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 A predetermined amount of an ethylene-methyl methacrylate copolymer ("Aklift WH202" manufactured by Sumitomo Chemical Co., Ltd., acrylic content 20% by weight, MI = 3) shown in Table 1 was prepared. object,
1,6-hexanediol methacrylate (HDM
A), the condensation reaction product (a) and the silane coupling agent were kneaded with 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 400 μm thick sheet for an interlayer film. Then, the polyethylene terephthalate film was peeled off by leaving it to reach room temperature, and the obtained intermediate film sheet was sandwiched between two float glass plates having a thickness of 3 mm which had been washed in advance, and placed in a rubber bag.
After degassing for 20 minutes at a vacuum of 0 Torr, the glass was placed in an oven at a predetermined temperature shown in Table 3 and maintained for 30 minutes in a degassed state.

(Example 2) Instead of a glass plate, a polycarbonate plate ("Iupilon sheet NF" manufactured by Mitsubishi Gas Chemical Company, 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
-Reaction was carried out in the same manner as in Example 1 except that 182 g (1 mol) of mannitol was used to obtain a condensation reaction product (b) (yield: 75%). Ethylene-methyl methacrylate copolymer (“Aclift WH402” manufactured by Sumitomo Chemical Co., Ltd., 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 product (b) and the silane coupling agent was used and the laminating temperature was as shown in Table 3.

(Example 5) D-sorbitol was replaced with D
Example 1 using 152 g (2 mol) of xylitol
To obtain 320 g (95% yield) of dibenzylidene xylitol as a condensation reaction product (c), and then a predetermined amount of ethylene-methyl methacrylate copolymer shown in Table 1 Example 1 was repeated except that a resin composition containing a peroxide, tritylolpropane trimethacrylate, the above condensation reaction product (c), and a silane coupling agent was used and the combination temperature was as shown in Table 3. A laminated glass was produced in the same manner as described above.

(Example 6) A predetermined amount of ethylene-methyl methacrylate copolymer ("DPDJ-9169" manufactured by Nippon Unicar), an organic peroxide, tritylolpropane triacrylate, and the above-mentioned condensed amount 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 laminating temperature was as shown in Table 3.

(Comparative Example 1) Ethylene-vinyl acetate copolymer (EVAFLEX3 manufactured by DuPont-Mitsui Polychemicals, Inc.)
60 ", vinyl acetate content 25% by weight, MI = 2) 10
0 parts by weight, 3 parts by weight of triallyl isocyanurate (“Tyke” manufactured by Nippon Kasei Co., Ltd.), 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (“Perhexa 3M” manufactured by NOF CORPORATION) ") A resin composition comprising 1 part by weight and 0.3 part by weight of γ-methacryloxypropyltrimethoxysilane was kneaded by 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-like intermediate film was used.

(Comparative Example 2) Instead of a glass plate, a polycarbonate plate ("Iupilon sheet NF" manufactured by Mitsubishi Gas Chemical Company) was used.
A laminated glass was produced in the same manner as in Comparative Example 1, except that the temperature was changed to the temperature shown in Table 3 using "200 U").

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

Comparative Example 4 An ethylene-vinyl acetate copolymer ("Ultracene 750" manufactured by Tosoh Corporation, vinyl acetate content: 32% by weight) was hydrolyzed using sodium hydroxide as a catalyst to give a saponification degree of 90 mol%. After obtaining partially saponified
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)
Ethylene-methyl methacrylate copolymer, organic peroxide, 1,6-hexanediol methacrylate (HDM
Example 1 except that a resin composition containing A), a condensation reaction product (1) and a silane coupling agent was used.
A laminated glass was produced in the same manner as described above.

[0045]

[Table 1]

[0046]

[Table 2]

Evaluation of Performance of Laminated Glass The laminated glass obtained in the above Examples and Comparative Examples was
The following evaluation was performed, and the results are shown in Table 3. (1) Transparency test Using an “integration turbidity meter” manufactured by Tokyo Denshoku Co.,
The total light transmittance (%) and the haze value at 50 ° C. and a relative humidity of 50% were measured.

(2) Adhesion strength test A laminated glass prepared using a glass plate or a synthetic resin plate on one side and polyethylene terephthalate on the other side was used to measure the width 2
The test piece was cut into 0 mm and 100 mm in length. This test piece was manufactured by Orientec “Tensilon UCE50”.
0 ", the 90-degree peel strength was measured at a tensile speed of 500 mm / min.

(3) Impact test According to JIS R3205, a laminated glass specimen left for 4 hours at a temperature of 23 ° C. and a relative humidity of 50% was vertically held by a support frame, and weighed 45 kg and had a maximum diameter of 75 mm. The striking body was dropped from the height of 30 cm to the center of the laminated glass in a pendulum manner. did.

(4) Cooling 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 stored at −20 ° C. to 70 ° C. The process of raising the temperature over 2 hours until 1 cycle was repeated for 10 cycles, and then the laminated glass was visually observed for delamination.

(5) Moisture Resistance Test The laminated glass was left under an environment of 55 ° C. and a relative humidity of 98% for 2 weeks, and then visually observed for delamination.

(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-methyl (meth) acrylate copolymer, (meth) acrylate, a specific condensation reaction product and silane. By being formed from a resin composition consisting of a coupling agent, it can be processed without the need for humidity control and autoclave in the manufacturing process without impairing the transparency and impact resistance, which are the basic properties of the interlayer. Since the matching temperature can be reduced, the manufacturing process can be simplified.

Claims (1)

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