JPH0930845A - Laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a safe laminated glass, capable of improving impact and penetration resistances of a conventional one and further hardly causing the scattering even if the glass is broken with an external force. SOLUTION: This laminated glass is obtained by blending a terpolymer comprising an ethylene-acrylate-based and/or a methacrylate-based compound- maleic acid and/or maleic anhydride with an organic peroxide and a silane coupling agent, interposing the resultant thermosetting resin between glass plates, integrating the whole and then thermosetting the resin layer. In addition to the organic peroxide, an adequate amount of at least one of a compound containing acryloxy group, a compound containing methacryloxy group and a compound containing allyl group, as necessary, as a curing agent may be added to the terpolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass used for windshields and side windows of automobiles, window glasses of buildings and the like.

[0002]

2. Description of the Related Art Conventionally, polyvinyl butyral resin has been most commonly used as an intermediate layer of laminated glass. However, since the polyvinyl butyral resin is a thermoplastic resin, it has the following problems. That is, (1)
Since the softening point is relatively low, the glass plate may shift due to heat after bonding and bubbles may be generated. (2) Since it is easily affected by moisture, leave it in a high temperature atmosphere for a long period of time. If it is left, whitening will gradually occur from the periphery and the adhesive strength with the glass will decrease, and (3) the impact fracture resistance depends on the temperature, and especially in the temperature range above room temperature, that is, at about 30 ° C or higher. It had defects such as a sharp drop in penetration performance. Therefore, in order to solve the above problems of the polyvinyl butyral resin, the present inventors interpose a thermosetting resin in which an ethylene-vinyl acetate copolymer is blended with an organic peroxide and interpose it between glass plates to integrate them. , A laminated glass in which a thermosetting resin layer is thermoset has been proposed (for example, JP-A-57-196747).

[0003]

However, when considering safety, which is one of the major purposes of laminated glass,
The impact resistance and penetration resistance were not sufficient over a wide range of conditions even with the past inventions of the present inventors.

In view of the above situation, an object of the present invention is to improve the impact resistance and penetration resistance of conventional laminated glass, and further, to provide a safe laminated glass which is unlikely to scatter even if the glass is broken by an external force. Is to provide glass.

[0005]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted extensive studies and found that ethylene, acrylate and / or methacrylate compounds, and maleic acid and / or maleic anhydride are used. A thermosetting resin in which an organic peroxide and a silane coupling agent are mixed in a terpolymer to be integrated by interposing between glass plates, and a laminated glass formed by thermosetting this resin layer,
The inventors have found that the laminated glass has improved impact resistance and penetration resistance, and have completed the present invention.

Therefore, in the laminated glass of the present invention, as described in claim 1, the terpolymer of ethylene-acrylate and / or methacrylate compound-maleic acid and / or maleic anhydride is added to the organic polymer. It is characterized in that a thermosetting resin mixed with an oxide and a silane coupling agent is interposed between glass plates to be integrated, and the resin layer is thermoset.

Further, in order to increase the impact resistance and transparency of the laminated glass to desired levels, as described in claim 2, an acrylate constituting the terpolymer described in claim 1. The content of the maleic acid and / or maleic anhydride with the type and / or methacrylate compound is 5 to
It is preferably in the range of 40% by weight and 0.01 to 10% by weight.

Further, in the laminated glass according to claim 1 or 2, a silane coupling agent blended as an adhesive with an organic peroxide blended with the terpolymer as a curing agent and glass is used. As described in claim 3, 0.1 parts by weight relative to 100 parts by weight of the terpolymer.
It is desirable to add 10 to 10 parts by weight and 0.01 to 5 parts by weight.

Further, as described in claim 4, in the terpolymer, at least one of an acryloxy group-containing compound, a methacryloxy group-containing compound or an allyl group-containing compound is added to the terpolymer as a curing aid. The above terpolymer 1
It is desirable to add 0.1 to 50 parts by weight to 00 parts by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the laminated glass of the present invention, ethylene-vinyl acetate copolymer is used in place of ethylene-vinyl acetate copolymer.
The impact resistance and penetration resistance of laminated glass have been improved by adopting a terpolymer of acrylate and / or methacrylate compound-maleic acid and / or maleic anhydride. The content of maleic acid and / or maleic anhydride in the terpolymer used in the present invention is preferably 0.01 to 10% by weight, particularly preferably 0.05 to 5% by weight. It may be randomly bonded in the main chain, or may be grafted to the side chain. The content of maleic acid and / or maleic anhydride is 0.0
If it is less than 1% by weight, the impact resistance is lowered, and if it exceeds 10% by weight, the transparency of the glass is deteriorated and the impact resistance is also lowered.

In this case, the content of the acrylate-based and / or methacrylate-based compound is preferably 5 to 50% by weight, more preferably 14 to 45% by weight from the viewpoint of the transparency and the physical properties of the laminated glass. %. When the content of the acrylate-based and / or methacrylate-based compound is less than 5% by weight, the transparency is insufficient when cross-linked and cured at a high temperature, while when it exceeds 50% by weight, the impact resistance or the penetration resistance is deteriorated. . Here, the acrylate-based or methacrylate-based monomer is a monomer selected from acrylic acid ester or methacrylic acid ester-based monomers, and examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, and glycidyl methacrylate.

Further, in the production of the laminated glass according to the present invention, an organic peroxide is added as a curing agent for the thermosetting resin composed of the above terpolymer. As the organic peroxide, any one can be used as long as it decomposes to generate radicals at 100 ° C. or higher, but if the stability during compounding is taken into consideration, the decomposition temperature with a half-life of 10 hours is 70%.
Those having a temperature of ℃ or more are preferable, for example, 2,5-dimethylhexane-2,5-dihydroperoxide; 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane-3; Di-t-butylperoxide; t-Butylcumylperoxide; 2,5-Dimethyl-2,5-di (t-butylperoxy) ) Hexane; dicumyl peroxide; α-α'-bis (t-butylperoxyisopropyl) benzene; n-butyl-4,4-bis (t-butylperoxy) parellate; 2,2-bis (t-) Butylperoxy) butane; 1,1-bis (t-butylperoxy) cyclohexane; 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane;
Examples thereof include t-butyl peroxybenzoate; benzoyl peroxide and the like. As the organic peroxide, at least one of them is adopted, and its blending amount is 0.1 to 1 with respect to 100 parts by weight of the terpolymer.
0 parts by weight is sufficient. Further, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone or methylhydroquinone can be added in an amount of 5 parts by weight or less for the purpose of improving stability. Also, a colorant, an ultraviolet absorber, an antiaging agent, a discoloration preventing agent, etc. can be added.

In the present invention, a silane coupling agent is added for the purpose of further improving the adhesive force between the thermosetting resin composed of the above terpolymer and the glass. Known silane coupling agents used for this purpose include, for example, γ-chloropropylmethoxysilane; vinyltrichlorosilane; vinyltriethoxysilane; vinyl-tris (β-methoxyethoxy) silane; γ-methacryloxypropyltrisilane. Methoxysilane; β- (3,4-ethoxycyclohexyl) ethyl-trimethoxysilane; γ
-Glycidoxypropyltrimethoxysilane; vinyltriacetoxysilane; γ-mercaptopropyltrimethoxysilane; γ-aminopropyltriethoxysilane;
Examples thereof include N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. The compounding amount of these silane coupling agents is 0.01 to 5 parts by weight.

Further, in the present invention, an acryloxy group-containing compound, a methacryloxy group-containing compound and an allyl group-containing compound are added to the terpolymer to give an initial thermosetting resin of the terpolymer. The modulus is increased to improve penetration resistance. As a compound provided for this purpose, an acrylic acid or methacrylic acid derivative such as an ester thereof can be used. As the alcohol residue of the ester, in addition to an alkyl group such as a methyl group, an ethyl group, a dodecyl group, a stearyl group and a lauryl group, a cyclohexyl group, a tetrahydrofurfuryl group, an aminoethyl group, a 2-hydroxyethyl group, 3- Examples thereof include a hydroxypropyl group and a 3-chloro-2-hydroxypropyl group. In addition, ethylene glycol,
Esters with polyfunctional alcohols such as triethylene glycol and polyethylene glycol can also be used in the same manner. As the allyl group-containing compound, diallyl phthalate, diallyl fumarate, diallyl maleate,
Triallyl isocyanurate and triallyl isocyanurate are preferably used. One or a mixture of two or more of these compounds is 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the terpolymer.
Used by adding parts by weight. If it is less than 0.1 parts by weight, the effect of improving mechanical strength may be lowered,
When it exceeds the weight part, workability at the time of preparation of the adhesive and film forming property as an intermediate of laminated glass may be deteriorated.

In the laminated glass according to the present invention, as described above, a thermosetting resin containing an ethylene-acrylate and / or methacrylate-maleic acid and / or maleic anhydride terpolymer as a main component. In addition, since the content of the acrylate-based and / or methacrylate-based compound-maleic acid and / or maleic anhydride is optimally selected, the transparency, impact resistance and penetration resistance are excellent. Further, since it has a cross-linked structure of an organic peroxide, and an acryloxy group-containing compound, a methacryloxy group-containing compound, and an allyl group-containing compound, which are added as necessary, penetration resistance, wet heat resistance, and transparency are improved.
In addition, the addition of the silane coupling agent improves the adhesiveness associated with heat curing, and increases the initial adhesive strength and the adhesive strength with excellent thermal stability.

[0016]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples.

Each component was blended as shown in Table 1 and 80
A resin was prepared by mixing with a roll mill heated to ℃. This composition was processed into a 0.76 mm thick resin sheet using a press, and two 3 mm sheets that had been washed and dried in advance were used.
The resin is sandwiched between thick float glasses, put in a rubber bag, vacuum degassed, pre-compressed at a temperature of 80 ° C., and then the pre-compressed laminated glass is put in an oven at a temperature of 130 ° C. for 30 minutes. Processed for minutes. Each of the obtained laminated glasses was highly transparent and optically free from distortion.

[0018]

[Table 1]

Regarding the laminated glass of Examples and Comparative Examples prepared as described above, JIS-R3205 (198)
As a result of performing a shot bag test according to 3), no large cracks were observed in each glass of the example at a drop height of 120 cm. On the other hand, in the laminated glass of Comparative Example, a large crack was generated on the glass surface.

Further, when a transparency test was carried out using a haze meter manufactured by Suga Test Instruments Co., Ltd., the haze value was 2 or less in each of the laminated glasses of Examples and Comparative Examples, showing good transparency. The test results are summarized in Table 2.

[0021]

[Table 2]

[0022]

INDUSTRIAL APPLICABILITY The laminated glass according to the present invention is excellent in impact resistance and penetration resistance when used in windshields and side windows of automobiles, window glass of buildings, etc., and is damaged by the action of external force. Even if it does, flying of glass fragments hardly occurs. Therefore, according to the present invention, a safe laminated glass can be supplied.

Claims (4)

[Claims] 1. A glass plate comprising a thermosetting resin obtained by blending an organic peroxide and a silane coupling agent in a terpolymer of ethylene-acrylate and / or methacrylate compound-maleic acid and / or maleic anhydride. Laminated glass characterized by being formed by interposing between them and integrating them, and thermosetting this resin layer. 2. The laminated glass according to claim 1, wherein the content of the acrylate-based and / or methacrylate-based compound in the terpolymer is 5 to 50% by weight, and the content of maleic acid and / or maleic anhydride is Content rate is 0.01 ~
Laminated glass characterized by being 10% by weight. 3. The laminated glass according to claim 1 or 2, wherein, relative to 100 parts by weight of the terpolymer,
A laminated glass comprising 0.1 to 10 parts by weight of an organic peroxide and 0.01 to 5 parts by weight of a silane coupling agent. 4. The laminated glass according to any one of claims 1 to 3, wherein at least one of an acryloxy group-containing compound, a methacryloxy group-containing compound and an allyl group-containing compound is used with respect to 100 parts by weight of the terpolymer. , 0.1
A laminated glass characterized by being added in an amount of up to 50 parts by weight.