JPH0930847A - 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 block terpolymer comprising blocks at both terminals and an intermediate block comprising a conjugated diene-based polymer 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 block 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-mentioned object, the inventors of the present invention have conducted extensive studies and as a result, have found that both end blocks made of a polymer of an aromatic vinyl compound and an intermediate block made of a conjugated diene polymer. A ternary block copolymer composed of an organic peroxide and a silane coupling agent, which is a thermosetting resin intercalated between the glass plates, and integrated, and the resin layer is thermoset to form a composite. The inventors have found that glass improves impact resistance and penetration resistance of laminated glass, and has completed the present invention.

Therefore, in the laminated glass of the present invention, as described in claim 1, a ternary block composed of both end blocks made of a polymer of an aromatic vinyl compound and an intermediate block made of a conjugated diene polymer is used. It is characterized in that a thermosetting resin in which a polymer is mixed with an organic peroxide and a silane coupling agent is interposed between glass plates to be integrated, and the resin layer is thermoset.

Further, in order to enhance the impact resistance and penetration resistance of the laminated glass and the processability of the resin as an intermediate to a desired level, as described in claim 2 and claim 1, The content of the aromatic vinyl compound constituting the ternary block copolymer is determined by the ternary block copolymer 1
It is desirable to set it in the range of 5 to 50% by weight with respect to 00% by weight.

A silane coupling agent blended as an adhesive with the organic peroxide and glass blended as a curing agent in the ternary block copolymer is also disclosed.
Alternatively, in the laminated glass according to claim 2, 0.1 to 10 parts by weight, and 0.01 to 5 parts by weight are added to 100 parts by weight of the ternary block copolymer as described in claim 3. Is desirable.

Further, as described in claim 4, at least one of an acryloxy group-containing compound, a methacryloxy group-containing compound or an allyl group-containing compound is added to the ternary block copolymer as a curing aid. It is desirable to add 0.1 to 50 parts by weight to 100 parts by weight of the ternary block copolymer.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the copolymer of the present invention, a conventional ethylene-vinyl acetate copolymer is replaced by a double-sided block composed of a polymer of an aromatic vinyl compound and an intermediate block composed of a conjugated diene polymer. By adopting a ternary block copolymer composed of them, the impact resistance and penetration resistance of the laminated glass are improved.

Here, the intermediate block copolymer of the ternary block copolymer used in the present invention is polybutadiene,
It is a conjugated diene linear polymer chain such as polyisoprene or polychloroprene, and the both end block copolymer is a polymer of an aromatic vinyl compound such as polystyrene, poly-α-methylstyrene and polychlorostyrene. It And, the content of the both end blocks is preferably 5 to 50% by weight, and when the content is less than 5%, the reinforcing effect by the aromatic vinyl compound polymer is lowered, and the impact resistance and the resistance to resistance of the laminated glass are decreased. Penetration becomes poor. On the other hand, when the content exceeds 50%, the resin becomes too hard and the workability deteriorates, and the resin becomes brittle, and the impact resistance and the penetration resistance decrease.

Further, in the production of the laminated glass according to the present invention, an organic peroxide is blended as a curing agent for the thermosetting resin composed of the above ternary block copolymer. As the organic peroxide, any one can be used as long as it decomposes to produce 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 higher are preferable, for example, 2,5-dimethylhexane-2,5-dihydroperoxide;
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane-3; di-t-butylperoxide; t
-Butyl cumyl peroxide; 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane; dicumyl peroxide; α-α'-bis (t-butylperoxyisopropyl) benzene; n-butyl-4,4-bis (t-butylperoxy) ) Parelate; 2,2-bis (t-butylperoxy) butane; 1,1-bis (t-
Butylperoxy) cyclohexane; 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane; t-butylperoxybenzoate; benzoyl peroxide and the like. As the organic peroxide, at least one of them is adopted, and the blending amount thereof is 0.1 to 10 parts by weight based on 100 parts by weight of the ternary block copolymer. Also, if necessary, hydroquinone for the purpose of improving stability,
Polymerization inhibitors such as hydroquinone monomethyl ether, p-benzoquinone and methylhydroquinone can be added in an amount of 5 parts by weight or less, and in addition to these, colorants, ultraviolet absorbers, antiaging agents, discoloration inhibitors, etc. Can be added.

Further, in the present invention, a silane coupling agent is blended for the purpose of further improving the adhesive force between the thermosetting resin composed of the above ternary block copolymer 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;
Examples thereof include vinyltriacetoxysilane; γ-mercaptopropyltrimethoxysilane; γ-aminopropyltriethoxysilane; N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane. The compounding amount of these silane coupling agents is 0.01 to 5 parts by weight.

Furthermore, in the present invention, a thermosetting compound comprising the above terpolymer block copolymer is obtained by adding an acryloxy group-containing compound, a methacryloxy group-containing compound or an allyl group-containing compound to the above ternary block copolymer. The initial modulus of the resin 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. Further, esters with polyfunctional alcohols such as ethylene glycol, triethylene glycol and polyethylene glycol can be used in the same manner. As the allyl group-containing compound, diallyl phthalate, diallyl fumarate, diallyl maleate, triallyl isocyanurate, triallyl isocyanurate and the like are preferably used. In addition,
One or a mixture of two or more of these compounds is used in an amount of 0.1 to 50 parts by weight, preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the ternary block copolymer. If it is less than 0.1 part by weight, the effect of improving mechanical strength may be deteriorated, and if it exceeds 50 parts by weight, workability at the time of preparation of an adhesive or film-forming property as an intermediate for laminated glass may be deteriorated. There is.

As described above, the laminated glass according to the present invention is mainly composed of a ternary block copolymer composed of both end blocks made of a polymer of an aromatic vinyl compound and an intermediate block made of a conjugated diene polymer. It has excellent impact resistance, penetration resistance and workability because it is a thermosetting resin and the content of both end blocks made of the above-mentioned polymer of aromatic vinyl compound is optimally selected. Further, an organic peroxide, and an acryloxy group-containing compound and a methacryloxy group-containing compound which are further added as necessary,
Since it has a cross-linked structure with an allyl group-containing compound, penetration resistance, moist heat resistance and transparency are improved. Also, the addition of a silane coupling agent improves the adhesiveness associated with heat curing,
Increased initial adhesive strength and adhesive strength with excellent thermal stability are obtained.

[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 1 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 heat obtained by mixing an organic peroxide and a silane coupling agent into a ternary block copolymer composed of both end blocks composed of a polymer of an aromatic vinyl compound and an intermediate block composed of a conjugated diene polymer. A laminated glass characterized in that a curable resin is interposed between glass plates to be integrated, and the resin layer is thermoset. 2. The laminated glass according to claim 1, wherein the content of the aromatic vinyl compound in the ternary block copolymer is 5 to 50% by weight. 3. The laminated glass according to claim 1, wherein 0.1 to 10 parts by weight of an organic peroxide and 100 parts by weight of the ternary block copolymer and a silane coupling agent are used. 0.01-5 weight part is added, The laminated glass characterized by the above-mentioned. 4. The laminated glass according to claim 1, wherein at least one of an acryloxy group-containing compound, a methacryloxy group-containing compound and an allyl group-containing compound is added to 100 parts by weight of the ternary block copolymer. On the other hand, 0.1 to 50 parts by weight of laminated glass is added.