JP3260805B2 - 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 laminated glass used for windshields and side glasses of automobiles, window glasses of buildings, soundproofing glass, 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 polyvinyl butyral resin is a thermoplastic resin, the following problems are encountered. Had.

(1) Since the softening point is relatively low, the glass plate is displaced or bubbles are generated due to heat after bonding.

[0004] (2) When left in a high-humidity atmosphere for a long period of time because of its susceptibility to moisture, the peripheral portion gradually becomes white and the adhesion to glass is reduced.

(3) Impact resistance is dependent on temperature, and particularly in a temperature range exceeding room temperature, that is, about 30 ° C. or more, the penetration resistance sharply decreases.

In order to solve the problems of the polyvinyl butyral-based resin, the present inventors applied a thermosetting resin obtained by blending an organic peroxide to an ethylene-vinyl acetate copolymer between glass plates. A laminated glass in which a thermosetting resin layer is thermally cured by being interposed and integrated is proposed, and a patent application was previously filed (for example, JP-A-57-196747).

As a method for improving the impact fracture resistance and penetration resistance of a laminated glass, a weight average molecular weight of 200 to 200 is used.
A laminated glass using a thermosetting resin blended with 50,000 hydrocarbon resins has been proposed, and a patent application has already been filed (for example,
JP-A-3-183645.

[0008]

However, the problem of yellowing resistance, which is an important required characteristic of laminated glass, cannot be said to be sufficiently solved. This is a problem of light stability due to the effect of ultraviolet rays when the laminated glass is mounted for a long period of time, which eventually results in a problem of yellowing resistance of the resin layer in the laminated glass, but has a conventionally satisfactory yellowing resistance. Laminated glass is not provided.

The present invention solves the above-mentioned problems, improves light stability without impairing good impact resistance and penetration resistance, has high transparency over a long period of time, and has excellent yellowing resistance. The purpose is to provide laminated glass.

[0010]

The laminated glass according to the present invention is formed by interposing a thermosetting resin obtained by blending a hydrocarbon resin and an organic peroxide with an ethylene-vinyl acetate copolymer between glass plates. And the hydrogenation rate of the hydrocarbon resin is 91% in a laminated glass obtained by thermosetting this resin layer.
It is characterized by the above.

The laminated glass according to the second aspect is the first aspect.
Wherein the proportion of the hydrocarbon resin is 1 to 100 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer.

The laminated glass according to the third aspect is the first aspect of the present invention.
Or in 2, the ratio of the organic peroxide is 0.1 to 5 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer.
It is characterized by parts by weight.

A laminated glass according to a fourth aspect is characterized in that, in the first, second or third aspect, the hydrocarbon resin has a weight average molecular weight of 200 to 50,000.

A laminated glass according to a fifth aspect is characterized in that, in the first, second, third or fourth aspect, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 10 to 50% by weight.

That is, the present inventors have previously applied for a patent (for example,
183645) focused on the hydrocarbon resin which is a component of the resin layer of the laminated glass, and as a result of diligent studies, the objective was achieved by using a hydrocarbon resin having a hydrogenation rate of 91% or more. The present invention has been completed.

Hereinafter, the present invention will be described in detail. An important feature of the present invention is that the hydrocarbon resin has as few double bonds as possible,
It is to use a hydrocarbon resin having a high hydrogenation rate (also referred to as a hydrogenation rate) for a resin layer of laminated glass.

The hydrogenation rate of the hydrocarbon resin used in the present invention is at least 91%, preferably at least 95%.
The term “hydrogenation rate” as used herein refers to the rate at which double bonds before the hydrogenation reaction are saturated after the hydrogenation reaction, and this can be quantified as an iodine value based on the iodine adsorption rate.

The hydrocarbon resin having a high hydrogenation rate may be a natural resin or a synthetic resin. In the case of natural resin, rosin, rosin derivative, terpene resin and the like are preferably used. Among them, as the rosin, a gum-based resin, a tall oil-based resin, a wood-based resin and the like can be used. As the rosin derivative, those obtained by hydrogenating, disproportionating, polymerizing, esterifying or metal salifying the above rosin can be used. Α as terpene resin
In addition to terpene resins such as -pinene and β-pinene, terpenephenol resins and the like can be used. Further, dammar, co-pal, shellac and the like may be used as other natural resins.

On the other hand, petroleum-based resins, phenol-based resins, xylene-based resins and the like are preferably used in the synthetic resin system. Among these, petroleum resins include aliphatic petroleum resins, aromatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, hydrogenated petroleum resins, pure monomeric petroleum resins, and cumarone indene resins. Etc. can be used. Alkyl phenol resins, modified phenol resins, and the like can be used as phenol resins. As the xylene-based resin, a xylene resin, a modified xylene resin, or the like can be used.

The ratio of the hydrocarbon resin of the present invention is 1 to 100 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer.
Parts by weight, preferably 2 to 80 parts by weight, more preferably 10 to 60 parts by weight.

The hydrocarbon resin has a weight average molecular weight of 200 to 50,000, particularly 200 to 1000.
0 is preferred.

The ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content of 10 to 50.
% By weight, especially 15 to 40% by weight.
If the vinyl acetate content is less than 10% by weight, the transparency of the resin obtained when crosslinking and curing at a high temperature is not sufficient. On the other hand, if it exceeds 50% by weight, the impact resistance and resistance to the laminated glass are obtained. Penetration tends to be insufficient.

The organic peroxide of the present invention is used as a curing agent for an ethylene-vinyl acetate copolymer.
Any substance can be used as long as it decomposes at a temperature of 100 ° C. or more to generate radicals. In consideration of the stability at the time of blending, those having a decomposition temperature of 70 ° C. or more with a half-life of 10 hours are preferable. For example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl- 2,5-di (t-butylperoxy) hexane-
3, di-t-butyl peroxide, 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) valerate, 2,2- Bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzue And benzoyl peroxide. These organic peroxides are 1
The species can be used alone or in combination of two or more.

The proportion of the present organic peroxide is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the ethylene-vinyl acetate copolymer.

In the present invention, in order to improve the initial modulus of the resin layer and improve the penetration resistance, the curing aid is selected from the group consisting of acryloxy group-containing compounds, methacryloxy group-containing compounds, and allyl group-containing compounds. At least one compound can be added.

Among these compounds, as the acryloxy group-containing compound and the methacryloxy group-containing compound, an acrylic acid derivative or a methacrylic acid derivative, for example, an ester thereof can be used. In this case, 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, Examples thereof include a hydroxyethyl group, a 3-hydroxypropyl group, and a 3-chloro-2-hydroxypropyl group. Further, ethylene glycol,
Esters with polyfunctional alcohols such as triethylene glycol and polyethylene glycol can also be used.

As the allyl group-containing compound, diallyl phthalate, diallyl fumarate, diallyl maleate, triallyl isocyanurate and triallyl cyanurate are preferably used.

The compounding amount of these compounds is ethylene-
It is preferable that the amount be 50 parts by weight or less based on 100 parts by weight of the vinyl acetate copolymer.

In the present invention, a silane coupling agent can be added as an adhesion improver in order to further increase the adhesion between the ethylene-vinyl acetate copolymer and glass. In this case, known silane coupling agents, for example, γ-chloropropylmethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyl Trimethoxysilane,
β- (3,4-ethoxycyclohexyl) ethyl-trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β -(Aminoethyl) -γ-aminopropyltrimethoxysilane and the like. The amount of these silane coupling agents is ethylene-
5 parts by weight or less is sufficient for 100 parts by weight of the vinyl acetate copolymer.

In the present invention, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone and methylhydroquinone may be used for the purpose of improving the stability of the resin layer. 5 parts by weight or less can be added to 100 parts by weight of the copolymer. In addition to these additives, a colorant, an ultraviolet absorber, an antioxidant, a discoloration inhibitor and the like can be added as required.

In the present invention, an antioxidant can be used for the purpose of further improving light stability and thermal stability. Examples of the antioxidant include phenol-based, sulfur-based, phosphorus-based, amine-based, hindered phenol-based, hindered amine-based and hydrazine-based antioxidants, and particularly preferred are hindered amine-based antioxidants. It is.

The laminated glass of the present invention is excellent in impact resistance, penetration resistance, yellowing resistance and the like, and is used for windshields and side glasses of automobiles, window glasses of buildings, and the like. Since hydrocarbon resin is added to the layer and the loss coefficient of the resin layer can be increased, it is also suitably used for soundproof glass and the like.

[0033]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.

The ethylene-vinyl acetate copolymer and the hydrocarbon resin used are as follows.

Ethylene-vinyl acetate copolymer: "Ultracene 634" (trademark, manufactured by Tosoh Corporation) Vinyl acetate content = 26% by weight Hydrocarbon resin: Example; "Alcon P-100" (Arakawa Alicyclic hydrocarbon resin having a hydrogenation rate of 98% and a weight average molecular weight of 700 Comparative Example; "Alcon M-100" (trademark made by Arakawa Chemical Industry Co., Ltd.) Example: 90%, alicyclic hydrocarbon resin having a weight average molecular weight of 700 [Example] Using Alcon P-100, each component was blended in the ratio shown in Table 1, and mixed with a roll mill heated to 80 ° C. To prepare a thermoplastic resin.

Using the obtained thermoplastic resin, a sheet having a thickness of 0.76 mm was prepared by using a press, and sandwiched between two pieces of 3 mm-thick float glass which had been washed and dried in advance. . After that, it is put in a rubber bag and vacuum degassed.
Pre-compression bonding at a temperature of Next, the pre-press laminated glass was placed in an oven and treated at 130 ° C. for 30 minutes. The obtained laminated glass had high transparency, had no optical distortion, and had excellent impact resistance and penetration resistance.

This laminated glass was treated with a Super UV tester (SUV-F1 type) manufactured by Iwasaki Electric Co., Ltd. for 30 minutes.
As a result of the accelerated exposure test for 0 hours, no change was observed at all as compared with the laminated glass before the test, and it was found that the yellowing resistance of the laminated glass was extremely excellent.

[Comparative Example] The same procedure as in Example was carried out except that Alcon M-100 was used instead of Alcon P-100. The laminated glass after the exposure test showed remarkable yellowing as compared with the laminated glass before the test.

[0039]

[Table 1]

[0040]

As described above, the laminated glass of the present invention has the above-mentioned structure, so that it has improved light stability without impairing good impact resistance and penetration resistance, and has a high transparency for a long period of time, and is resistant to yellowing. Has an excellent effect.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-196747 (JP, A) JP-A-3-183645 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 27/12

Claims (5)

(57) [Claims] 1. A laminated glass comprising a thermosetting resin obtained by blending a hydrocarbon resin and an organic peroxide in an ethylene-vinyl acetate copolymer, interposed between glass plates and integrated, and the resin layer is thermoset. 3. The laminated glass according to claim 1, wherein the hydrogenation rate of the hydrocarbon resin is 91% or more. 2. The method according to claim 1, wherein the proportion of the hydrocarbon resin is
The laminated glass according to claim 1, wherein the amount is 1 to 100 parts by weight based on 100 parts by weight of the vinyl acetate copolymer. 3. The method according to claim 1, wherein the proportion of the organic peroxide is ethylene-
The laminated glass according to claim 1 or 2, wherein the amount is 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl acetate copolymer. 4. The hydrocarbon resin having a weight average molecular weight of 200
The laminated glass according to claim 1, 2 or 3, wherein the number is from 50,000 to 50,000. 5. The laminated glass according to claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 10 to 50% by weight.