JPH05339036A - Laminated glass - Google Patents

Abstract

PURPOSE:To obtain a laminated glass resistant to impact and penetration and maintaining high transparency over a long period by interposing a thermosetting resin obtained by incorporating an org. peroxide and a specified (meth) acryloyloxy group-contg. compd. into an ethylene-vinyl acetate copolymer between glass sheets and thermally curing the resin. CONSTITUTION:An org, peroxide, 50 pts.wt. of a (meth)acryloyloxy group-contg. compd. (e.g. 1-methyl-1,3-dimethacryloyloxypropane) shown by the formula (R<1> and R<2> are alkyl, X is O or NH, P is -(CH2)- and -CR<4>R<4>- the number of the bonded P units is 1 to 20, and R<3> and R<4> are H, alkyl and hydroxyl where R<3> does not contain H) and 5 pts.wt. of a silane coupling agent, as required, are incorporated into 100 pts.wt. of an ethylene-vinyl acetate copolymer contg. 10-50wt.% vinyl acetate and mixed by a roll mill heated at about 80 deg.C to prepare a thermoplastic resin. The resin is formed into a sheet, interposed between glass sheets, the sheets are preliminarily press-bonded, and then the laminate is heat-treated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated glass having excellent impact resistance, penetration resistance and transparency, which is used for windshields of automobiles, side windows, 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. Since the polyvinyl butyral resin is a thermoplastic resin, it has the following problems. (1) Since the softening point is relatively low, the glass plate may be displaced or bubbles may be generated due to heat after bonding. (2) Since it is easily affected by moisture, when left in a high-humidity atmosphere for a long period of time, whitening gradually occurs from the peripheral portion and a decrease in adhesive strength with glass is observed. (3) The impact fracture resistance depends on the temperature, and especially in the temperature range exceeding room temperature, that is, at about 30 ° C. or more, the penetration resistance is sharply reduced.

In order to solve the above problems of the polyvinyl butyral resin, the present inventors have prepared a thermosetting resin in which an ethylene-vinyl acetate copolymer is blended with an organic peroxide and a compound containing an acryloxy group or a methacryloxy group. A patent application was previously filed for a laminated glass in which the resin layer is integrated by interposing it between glass plates, and the resin layer is thermoset. (For example, Japanese Patent Publication No. 2-53381)

[0004]

However, in consideration of safety, which is one of the major purposes of laminated glass, impact resistance, penetration resistance and transparency are still obtained by the inventors of the present invention. It was not sufficient over a wide range of conditions.

Therefore, the present invention solves the above problems,
It is an object of the present invention to provide a laminated glass which has excellent impact resistance and penetration resistance and has a high transparency for a long period of time.

[0006]

The laminated glass according to claim 1 comprises a thermosetting resin prepared by blending an ethylene-vinyl acetate copolymer with an organic peroxide and a compound containing an acryloxy group or a methacryloxy group between glass plates. In the laminated glass formed by interposing by interposing and thermosetting this resin layer, the acryloxy group- or methacryloxy group-containing compound is at least one compound represented by the general formula (A), and its compounding amount. There ethylene - formula, wherein the vinyl acetate copolymer in an amount of 50 parts by weight or less ^{_{(a) CH 2 = CR 1}} -CO-X-P-X-CO-R 2 C = CH ₂ (R ¹ and R ² in the general formula (A) represent a hydrogen atom or an alkyl group and may be the same or different. X represents an —O— bond or —NH— bond. P represents -(CH ₂ ) -bonding unit And / or -C (R ³ ) (R ⁴ )-bond unit, the number of bond units in P is 1 to 20, R ³ and R ⁴ represent a hydrogen atom, an alkyl group or a hydroxyl group, and are the same. Or may be different, provided that R ³
Does not include a hydrogen atom. The laminated glass according to claim 2 is characterized in that, in claim 1, the ethylene-vinyl acetate copolymer has a vinyl acetate content of 10 to 50% by weight.

The laminated glass according to claim 3 is the same as claim 1.
Or 2, a silane coupling agent is blended in the thermosetting resin, and the blending amount is ethylene-
The amount is 5 parts by weight or less based on the vinyl acetate copolymer.

That is, in order to improve the impact resistance, penetration resistance and transparency of the laminated glass, the present inventors have included an acryloxy group or a methacryloxy group which is a constituent of the thermosetting resin of the laminated glass previously applied. Focus on the compound,
As a result of intensive studies, the object was achieved and the present invention was completed by using an acryloxy group- or methacryloxy group-containing compound having a specific molecular structure.

The present invention will be described in detail below. In the present invention, at least one kind of the acryloxy group- or methacryloxy group-containing compound represented by the general formula (A) is used.

R ¹ and R ² in the general formula (A) represent a hydrogen atom or an alkyl group and may be the same or different. Further, the alkyl group is a methyl group, an ethyl group,
Examples thereof include a propyl group and a butyl group. A hydrogen atom or a methyl group is preferably used for R ¹ and R ² .
X represents an -O- bond or an -NH- bond, and has the general formula (A).
In consideration of the above, the former represents an ester bond and the latter represents an amide bond, but an -O- bond, that is, an ester bond is usually preferable.

P in the general formula (A) consists of-(CH ₂ ) -bonding unit and / or -C (R ³ ) (R ⁴ ) -bonding unit,
The number of this bond unit in P is 1 to 20,
0 is preferable, 1 to 5 is more preferable, and 3 to 5 is the most preferable. When the number of the bonding units is more than 20, the reactivity with the ethylene-vinyl acetate copolymer becomes weak, which is not preferable. When P is composed of both a-(CH ₂ ) -bonding unit and a -C (R ³ ) (R ⁴ ) -bonding unit, the ratio of both units is not limited, but-(C
H ₂ ) -bond units are usually 50% or more. R
³ and R ⁴ represent a hydrogen atom, an alkyl group or a hydroxyl group, and may be the same or different, provided that R ³ does not contain a hydrogen atom. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and the like. R ³ is preferably a methyl group or a hydroxyl group, and R ⁴ is preferably a hydrogen atom, a methyl group or a hydroxyl group.

Examples of the compound represented by the general formula (A) include diacryloxymethane, dimethacryloxymethane, dimethyldiacryloxymethane, dimethyldimethacryloxymethane, hydroxymethyldiacryloxymethane and hydroxyethyl. Dimethacryloxymethane, 1,2
-Diacryloxyethane, 1,2-dimethacryloxyethane, 1-methyl-1,2-diacryloxyethane, 1
-Methyl-1,2-dimethacryloxyethane, 1-methyl-2-hydroxy-1,2-diacryloxyethane,
1-methyl-2-hydroxy-1,2-dimethacryloxyethane, 1-methyl-2-hydroxy-1-acryloxy-2-methacryloxyethane, 1-methyl-1,3
-Dimethacryloxypropane, 2-methyl-1,3-dimethacryloxypropane, 1-methyl-1,3-diacryloxypropane, 2-methyl-1,3-diacryloxypropane, 1,1-dimethyl -1,3-Diacryloxypropane, 1,1-Dimethyl-1,3-dimethacryloxypropane, 1,1-Dimethyl-1-acryloxy-
3-methacryloxypropane, 1,2-dimethyl-1,
3-diacryloxypropane, 1,2-dimethyl-1,
3-dimethacryloxypropane, 1,2-dimethyl-1
-Acryloxy-3-methacryloxypropane, 2,2
-Dimethyl-1,3-diacryloxypropane, 2,2
-Dimethyl-1,3-dimethacryloxypropane, 2,
2-dimethyl-1-acryloxy-3-methacryloxypropane, 2-hydroxy-1,3-diacryloxypropane, 2-hydroxy-1,3-dimethacryloxypropane, 2-hydroxy-1-acryloxy-3- Methacryloxypropane, 1,2-dihydroxy-1,3-
Diacryloxypropane, 1,2-dihydroxy-1,
3-dimethacryloxypropane, 1,2-dihydroxy-1-acryloxy-3-methacryloxypropane,
1,2-dihydroxy-1-methacryloxy-3-acryloxypropane, 2,2-dihydroxy-1,3-diacryloxypropane, 2,2-dihydroxy-1,3
-Dimethacryloxypropane, 1,3-dihydroxy-
1,3-Diacryloxypropane, 1,3-Dihydroxy-1,3-dimethacryloxypropane, 1,2,3-
Trihydroxy-1,3-diacryloxypropane,
1,2,3-trihydroxy-1,3-dimethacryloxypropane, 1-hydroxy-2-methyl-1,3-diacryloxypropane, 1-hydroxy-2-methyl-
1,3-dimethacryloxypropane, 1,2-dihydroxy-3-methyl-1,3-diacryloxypropane,
1,2-dihydroxy-3-methyl-1,3-dimethacryloxypropane, 1-hydroxy-2,3-dimethyl-1,3-diacryloxypropane, 1-hydroxy-
2,3-dimethyl-1,3-dimethacryloxypropane, 2-hydroxy-1,3-dimethyl-1,3-diacryloxypropane, 2-hydroxy-1,3-dimethyl-1,3-dimethacryl Roxypropane, 1,2,3-
Trimethyl-1,3-diacryloxypropane, 1,
2,3-trimethyl-1,3-dimethacryloxypropane, 1-methyl-1,4-diacryloxybutane, 1-
Methyl-1,4-dimethacryloxybutane, 2-methyl-1,4-diacryloxybutane, 2-methyl-1,4
-Dimethacryloxybutane, 1,3-dimethyl-1,4
-Diacryloxybutane, 1,3-dimethyl-1,4-
Dimethacryloxybutane, 2,3-dimethyl-1,4-
Diacryloxybutane, 2,3-dimethyl-1,4-dimethacryloxybutane, 2,2-dimethyl-1,4-diacryloxybutane, 2,2-dimethyl-1,4-dimethacryloxybutane, 1,1-dimethyl-1,4-diacryloxybutane, 1,1-dimethyl-1,4-dimethacryloxybutane, 1-hydroxy-1,4-diacryloxybutane, 1-hydroxy-1,4 -Dimethacryloxybutane, 2-hydroxy-1,4-diacryloxybutane, 2-hydroxy-1,4-dimethacryloxybutane, 1,3-dihydroxy-1,4-diacryloxybutane, 1,3 -Dihydroxy-1,4-dimethacryloxybutane, 2,3-dihydroxy-1,4-diacryloxybutane, 2,3-dihydroxy-1,4-dimethacryloxybutane 2,2-dihydroxy-1,4-diacrylate Loki Sibu Tan, 2,2-dihydroxy-1,4
Dimethacryloxybutane, 1,1-dihydroxy-1,
4-diacryloxybutane, 1,1-dihydroxy-
1,4-dimethacryloxybutane, 1-hydroxy-2
-Methyl-1,4-diacryloxybutane, 1-hydroxy-2-methyl-1,4-dimethacryloxybutane,
2-hydroxy-3-methyl-1,4-diacryloxybutane, 2-hydroxy-3-methyl-1,4-dimethacryloxybutane, 1-hydroxy-3-methyl-1,
4-diacryloxybutane, 1-hydroxy-3-methyl-1,4-dimethacryloxybutane, 1-hydroxy-2,2-dimethyl-1,4-diacryloxybutane,
1-hydroxy-2,2-dimethyl-1,4-dimethacryloxybutane, 1-hydroxy-2,3-dimethyl-
1,4-diacryloxybutane, 1-hydroxy-2,
3-dimethyl-1,4-dimethacryloxybutane, 1-
Methyl-2-hydroxy-1,4-diacryloxybutane, 1-methyl-2-hydroxy-1,4-dimethacryloxybutane, 1-methyl-2,3-dihydroxy-
1,4-diacryloxybutane, 1-methyl-2,3-
Di-hydroxy-1,4-dimethacryloxybutane,
2,2-dimethyl-1,5-diacryloxypentane,
2,2-Dimethyl-1,5-dimethacryloxypentane, 3,3-dimethyl-1,5-diacryloxypentane, 3,3-dimethyl-1,5-dimethacryloxypentane, 2-hydroxy-1 , 5-diacryloxypentane, 2-hydroxy-1,5-dimethacryloxypentane and the like. Among these, 1-methyl-1,3-dimethacryloxypropane,
2,2-dimethyl-1,3-diacryloxypropane,
2,2-dimethyl-1,3-dimethacryloxypropane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, 2-hydroxy-1,3-dimethacryloxypropane, 1-hydroxy-2-methyl- 1,3
-Diacryloxypropane, 1-hydroxy-2-methyl-1,3-dimethacryloxypropane.

The compounding amount of the compound represented by the general formula (A) of the present invention is preferably 50 parts by weight or less with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer.

The ethylene-vinyl acetate copolymer used in the present invention has a vinyl acetate content of 10 to 50.
% By weight, preferably 15-40% by weight. If the vinyl acetate content is less than 10% by weight, the transparency is not sufficient when crosslinked and cured at a high temperature, while it is 50% by weight.
If it exceeds, the impact resistance and penetration resistance of the laminated glass tend to be insufficient.

As the organic peroxide used as a curing agent for the ethylene-vinyl acetate copolymer in the production of the laminated glass according to the present invention, any organic peroxide can be used as long as it decomposes at a temperature of 100 ° C. or higher to generate radicals. Although it is also possible to use, it is preferable that the decomposition temperature with a half-life of 10 hours is 70 ° C. or higher in consideration of the stability at the time of compounding, for example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane-3, di-t-butylperoxide, t-butylcumyl 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-butylper Examples thereof include oxybenzate and benzoyl peroxide. These organic peroxides can be used alone or in combination of two or more. The blending amount thereof is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate polymer.

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 resin and glass. In this case, known silane coupling agents are used, such as 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, N-β- (aminoethyl) -γ -Aminopropyltrimethoxysilane and the like can be mentioned. The compounding amount of these silane coupling agents is preferably 5 parts by weight or less.

In the present invention, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone or methylhydroquinone may be added to 100 parts by weight of ethylene-vinyl acetate copolymer for the purpose of improving the stability of the resin layer. It can be added in an amount of 5 parts by weight or less based on parts.

In the present invention, an ultraviolet absorber, a discoloration preventing agent, a coloring agent and the like can be further used if necessary. As the ultraviolet absorber used for imparting the ultraviolet absorbing performance, known ones can be used, but the adhesiveness with the glass of the obtained resin is not hindered, and the yellowing degeneration is extremely small. UV absorbers of benzophenone type and benzotriazole type are suitable. As the ultraviolet absorber, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, Benzophenone compounds such as 2,2'-dihydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octoxybenzophenone, and 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6) "-Tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3 ', 5'-
Particularly preferred are benzotriazole compounds such as di-t-amylphenyl) benzotriazole and hydroxyphenylbenzotriazole derivatives. The amount of such an ultraviolet absorber added is ethylene-vinyl acetate copolymer 10
It is preferably 5 parts by weight or less with respect to 0 parts by weight. If the amount added exceeds 5 parts by weight, surface bleeding may occur in the resin, resulting in poor adhesion to glass.

In the present invention, an antioxidant can be used for the purpose of further improving light stability and heat stability. Examples of the antioxidants include phenol-based, sulfur-based, phosphorus-based, amine-based, hindered phenol-based, hindered amine-based, and hydrazine-based antioxidants, with hindered amine-based antioxidants being preferred.

According to the present invention, when it is used for windshields and side windows of automobiles, window glass of buildings, etc., it has excellent impact resistance and penetration resistance, and it is a safe laminate even if it is damaged by the action of external force. Glass can be provided.

[0021]

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

The ethylene-vinyl acetate copolymer used, the shot bag test method, and the transparency test method are as follows.

Ethylene-vinyl acetate copolymer: "Ultrasen 635" (trademark of Tosoh Corporation) Vinyl acetate content = 25% by weight Shot bag test method: JIS R3025 (198)
In accordance with 3), the state of cracking by impact (index of impact resistance) was measured with the falling height of the steel balls set to 120 cm.

Transparency test method: The haze value (cloudiness value) (index of transparency) was measured using a haze meter manufactured by Suga Test Instruments Co., Ltd.

Example 1 Using 1-methyl-1,3-dimethacryloxypropane, the components were blended in the proportions shown in Table 1 and mixed by a roll mill heated to 80 ° C. to prepare a resin. .. A sheet having a thickness of 0.76 mm was prepared from the obtained thermoplastic resin by using a press, and the sheet was sandwiched between two float glass sheets having a thickness of 3 mm and washed and dried in advance. After that, put this in a rubber bag and vacuum degas,
Pre-compression bonding was performed at a temperature of 0 ° C. Next, this pre-bonded laminated glass was placed in an oven and treated at 130 ° C. for 30 minutes.

As shown by the results in Table 1, all of the obtained laminated glasses were excellent in impact resistance according to the shot bag test, and had a high transparency based on the haze value and were optically free from distortion. I knew it was.

[0027]

[Table 1]

[Examples 2 to 4] According to Table 1, 20 parts by weight of 1-methyl-1,3-dimethacryloxypropane in Example 2 and 1-methyl-1,3 in Examples 3 and 4 were used.
-Except that 5 parts by weight of 2,2-dimethyl-1,3-dimethacryloxypropane and 5 parts by weight of 2-hydroxy-1,3-dimethacryloxypropane were added instead of dimethacryloxypropane. It carried out like Example 1. As shown in Table 1, in the laminated glass of this example, no crack was observed in any of the four test pieces in the shot bag test, and the haze value was 0.8. That is, it was found that both impact resistance and transparency were excellent.

Comparative Example 1 1-methyl-according to Table 1
Example 1 except that 5 parts by weight of triallyl isocyanurate was blended instead of 1,3-dimethacryloxypropane.
It carried out similarly to. As can be seen from the results in Table 1, in the laminated glass, in the shot bag test, the average length of the crack openings of the four test pieces was 80 mm, and the haze value was 0.
It was 6. This result shows that the laminated glass of this comparative example has a poor impact resistance as compared with the examples. This means that it has a functional group at both ends, such as 1-methyl-1,3-dimethacryloxypropane of the present invention.
It is shown that when a trifunctional compound such as triallyl isocyanurate of this comparative example is used for the functional compound, the laminated glass is inferior in impact resistance.

[0030]

The laminated glass of the present invention, having the above-mentioned constitution, has a well-balanced and excellent effect that it is excellent in impact resistance and penetration resistance and exhibits good transparency for a long period of time.

 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kiyomi Sasaki 156-19 Kamiyamaguchi, Tokorozawa, Saitama Prefecture (72) Inoue Tanuma 3405-181 Kashihara, Sayama City, Saitama Prefecture

Claims (3)

[Claims] 1. A thermosetting resin prepared by mixing an ethylene-vinyl acetate copolymer with an organic peroxide and a compound containing an acryloxy group or a methacryloxy group is interposed between glass plates to be integrated, and the resin layer is thermoset. In the laminated glass obtained by the above, the acryloxy group- or methacryloxy group-containing compound is at least one kind of the compounds represented by the general formula (A), and the compounding amount thereof is 50% by weight with respect to the ethylene-vinyl acetate copolymer. A laminated glass characterized in that the amount is not more than a part. Formula ^{_{(A) CH 2 = CR 1}} -CO-X-P-X-CO-R 2 C = CH 2 (R 1 and R ² in the general formula (A) represents a hydrogen atom or an alkyl group, the same a .P representing the or different may .X also be the -O- bond or -NH- bond than - (CH ₂₎ - linking units and / or ^{- C (R 3) (R} 4) - bond unit And the number of bond units in P is 1 to 20, R ³ and R ⁴ represent a hydrogen atom, an alkyl group or a hydroxyl group, and may be the same or different, provided that R ³
Does not include a hydrogen atom. ) 2. The laminated glass according to claim 1, wherein the ethylene-vinyl acetate copolymer has a vinyl acetate content of 10 to 50% by weight. 3. The thermosetting resin, wherein a silane coupling agent is blended, and the blending amount is 5 parts by weight or less based on the ethylene-vinyl acetate copolymer. The laminated glass according to 1 or 2.