JP3276671B2 - 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 a laminated glass excellent in impact resistance, penetration resistance and transparency, used for windshields and side glasses of automobiles and window glasses of buildings.

[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-based resin is a thermoplastic resin, it has the following problems. (1) Since the softening point is relatively low, the glass plate is displaced or bubbles are generated by heat after lamination. (2) Since it is easily affected by moisture, if left in a high-humidity atmosphere for a long period of time, the peripheral portion gradually becomes white and a decrease in the adhesive strength with glass is recognized. (3) The impact fracture resistance depends on the 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 above problems of the polyvinyl butyral resin, the present inventors have developed a thermosetting resin obtained by blending an organic peroxide and a compound containing an acryloxy or methacryloxy group with an ethylene-vinyl acetate copolymer. Was interposed between glass plates and integrated, and the resin layer was thermally cured. (For example, Japanese Patent Publication 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 not improved even in the past inventions of the present inventors. It was not enough over a wide range of conditions.

Accordingly, the present invention solves the above problems,
An object of the present invention is to provide a laminated glass having excellent impact resistance and penetration resistance and having a high transparency over a long period of time.

[0006]

The laminated glass according to the present invention is characterized in that a thermosetting resin obtained by mixing an organic peroxide and a compound containing an acryloxy group or a methacryloxy group with an ethylene-vinyl acetate copolymer is interposed between glass plates. In the laminated glass obtained by intervening and integrating and thermally curing the resin layer, the acryloxy group or methacryloxy group-containing compound is at least one of the compounds represented by the general formula (A), and Is an amount of 50 parts by weight or less based on the ethylene-vinyl acetate copolymer. CH ₂ CR ¹ -CO-XPXCO-R ² CＣＯCH 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 an —NH— bond. -(CH ₂ ) -linking unit And / or ^{- C (R 3) (R} 4) - consists binding units, the number of binding units in P is 1 to 20, R ³ and R ⁴ represents a hydrogen atom, an alkyl group or a hydroxyl group, the same Or different, provided that R ³
Does not contain a hydrogen atom. 2) The laminated glass according to claim 2 is characterized in that, in claim 1, the vinyl acetate content of the ethylene-vinyl acetate copolymer is 10 to 50% by weight.

[0007] The laminated glass according to the third aspect is the first aspect.
Or 2, in the thermosetting resin, a silane coupling agent is compounded, and the compounding amount is ethylene-
The amount is 5 parts by weight or less based on the vinyl acetate copolymer.

[0008] That is, the present inventors, in order to improve the impact resistance, penetration resistance and transparency of a laminated glass, containing an acryloxy group or a methacryloxy group, which is a component of the thermosetting resin of the laminated glass previously filed. Focusing on compounds,
As a result of intensive studies, the use of an acryloxy or methacryloxy group-containing compound having a specific molecular structure has achieved the object and completed the present invention.

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

In the general formula (A), R ¹ and R ² represent a hydrogen atom or an alkyl group, which 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. R ¹ and R ² are preferably a hydrogen atom or a methyl group.
X represents an —O— bond or an —NH— bond;
In the above, the former represents an ester bond, and the latter represents an amide bond, and an —O— bond, that is, an ester bond is usually preferred.

P in the general formula (A) comprises a — (CH ₂ ) -linking unit and / or —C (R ³ ) (R ⁴ ) -linking unit;
The number of this linking unit in P is from 1 to 20;
0 is preferable, 1 to 5 is more preferable, and 3 to 5 is most preferable. If the number of the bonding units is larger than 20, the reactivity to the ethylene-vinyl acetate copolymer becomes weak, which is not preferable. When P is composed of both a-(CH ₂ ) -linking unit and a -C (R ³ ) (R ⁴ ) -linking unit, the ratio of both units is not limited, but-(C
Usually, the content of H ₂ ) -linked units is 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group. 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,
-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-1,1,
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. Preferred examples thereof include 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 formula (A) of the present invention is preferably 50 parts by weight or less based on 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.
%, Preferably 15 to 40% by weight. When the vinyl acetate content is less than 10% by weight, the transparency is insufficient when cross-linking and curing at a high temperature.
When the ratio exceeds the above, 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 which decomposes at a temperature of 100 ° C. or more to generate radicals can be used. However, in consideration of the stability at the time of blending, those having a decomposition temperature of 70 ° C. or higher with a half-life of 10 hours are preferable, and for example, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, di-t-butyl peroxide, 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-butylperoxy Oxybenzate, benzoyl peroxide and the like can be mentioned. These organic peroxides can be used alone or in combination of two or more. The compounding amount is preferably 0.1 to 5 parts by weight based on 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 the glass. In this case, known silane coupling agents, 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, N-β- (aminoethyl) -γ -Aminopropyltrimethoxysilane and the like. The amount of these silane coupling agents is preferably 5 parts by weight or less.

In the present invention, if necessary, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone, methylhydroquinone, etc. may be added to 100% by weight of ethylene-vinyl acetate copolymer in order to improve the stability of the resin layer. 5 parts by weight or less can be added per part.

In the present invention, if necessary, an ultraviolet absorber, a discoloration inhibitor, a colorant and the like can be used. Known UV absorbers can be used as the UV absorber used to impart UV absorption performance, but without impairing the adhesiveness of the obtained resin to glass, and because the yellowing over time is extremely small. And benzophenone-based and benzotriazole-based ultraviolet absorbers are preferred. Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, Benzophenones 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'-
Benzotriazole-based compounds such as (di-t-amylphenyl) benzotriazole and hydroxyphenylbenzotriazole derivatives are particularly preferred. The amount of the ultraviolet absorber added is determined by the ethylene-vinyl acetate copolymer 10
It is preferable that the content be 5 parts by weight or less based on 0 parts by weight. If the addition amount exceeds 5 parts by weight, surface bleeding occurs in the resin, which may cause poor adhesion to glass.

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 ones, and preferred are hindered amine-based ones.

According to the present invention, when used for a windshield or a side glass of an automobile, a window glass of a building, etc., it has excellent impact resistance and penetration resistance, and can be safely assembled even if it is damaged by the action of an external force. Glass can be provided.

[0021]

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

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

Ethylene-vinyl acetate copolymer: "Ultracene 635" (trade name, manufactured by Tosoh Corporation) Vinyl acetate content = 25% by weight Shot bag test method: JIS R3025 (198)
According to 3), the state of cracking due to impact (index of impact resistance) was measured with the falling height of the steel ball set to 120 cm.

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

Example 1 Using 1-methyl-1,3-dimethacryloxypropane, the respective components were blended in the proportions shown in Table 1 and mixed with 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 using a press, and this sheet was sandwiched between two float glass sheets having a thickness of 3 mm which had been washed and dried in advance. After that, this was put in a rubber bag and vacuum degassed.
Pre-compression bonding was performed at a temperature of 0 ° C. Next, the pre-press laminated glass was placed in an oven and treated at 130 ° C. for 30 minutes.

As shown in the results of Table 1, the obtained laminated glasses were all excellent in impact resistance according to the shot bag test, had high transparency from the haze value, and had no optical distortion. I found it.

[0027]

[Table 1]

[Examples 2 to 4] According to Table 1, 20 parts by weight of 1-methyl-1,3-dimethacryloxypropane is used in Example 2, and 1-methyl-1,3 is used in Examples 3 and 4.
-Except that dimethacryloxypropane was replaced with 5 parts by weight of 2,2-dimethyl-1,3-dimethacryloxypropane and 5 parts by weight of 2-hydroxy-1,3-dimethacryloxypropane, respectively. Performed as in 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 the impact resistance and the transparency were excellent.

Comparative Example 1 According to Table 1, 1-methyl-
Example 1 was repeated except that 5 parts by weight of triallyl isocyanurate was used instead of 1,3-dimethacryloxypropane.
Was performed in the same manner as described above. As can be seen from the results in Table 1, in the laminated glass, the average length of the crack openings of the four specimens in the shot bag test was 80 mm, and the haze value was 0.1 mm.
It was 6. This result indicates that the laminated glass of this comparative example is poor in impact resistance as compared with the example. This means that a compound having a functional group at both terminals, such as 1-methyl-1,3-dimethacryloxypropane of the present invention, may be used.
The results show that when a trifunctional compound such as triallyl isocyanurate of this comparative example is used with respect to the functional compound, the impact resistance of the laminated glass is inferior.

[0030]

According to the laminated glass of the present invention, the laminated glass of the present invention has a well-balanced and excellent effect of being excellent in impact resistance and penetration resistance and showing good transparency for a long period of time.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Itsuo Tanuma 3405-181 Kashiwara, Sayama City, Saitama Prefecture (56) References JP-A-55-90445 (JP, A) JP-A-61-44741 (JP, A) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) C03C 27/12

Claims (3)

(57) [Claims] 1. A thermosetting resin obtained by blending an organic peroxide and an acryloxy or methacryloxy group-containing compound with an ethylene-vinyl acetate copolymer is interposed between glass plates and integrated, and the resin layer is thermoset. In the laminated glass, the acryloxy or methacryloxy group-containing compound is at least one kind of the compound represented by the general formula (A), and its compounding amount is 50% by weight based on the ethylene-vinyl acetate copolymer. The laminated glass characterized in that the amount is not more than 1 part by weight. General formula (A) CH ₂ ＣＲCR ¹ —CO—X—P—X—CO—R ² CＣＨCH ₂ (R ¹ and R ² in the general formula (A) represent a hydrogen atom or an alkyl group, and are the same. X represents an —O— bond or an —NH— bond, and P represents a — (CH ₂ ) —bond unit and / or a —C (R ³ ) (R ⁴ ) − bond unit. And the number of bonding units in P is from 1 to 20, and 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. ) 2. The laminated glass according to claim 1, wherein the vinyl acetate content of the ethylene-vinyl acetate copolymer is 10 to 50% by weight. 3. The thermosetting resin, wherein a silane coupling agent is compounded, and the compounding amount is 5 parts by weight or less based on the ethylene-vinyl acetate copolymer. 3. The laminated glass according to 1 or 2.