JPS60226436A - Laminated glass - Google Patents

Abstract

PURPOSE:To obtain a laminate glass having high transparency and excellent pierce resistance and durability, by inserting an organic resin film between two or more specific intermediate layers, sandwiching the resultant laminate with a pair of glass plates, and integrating the components. CONSTITUTION:An organic resin film (e.g. polyester film) optionally applied with a thin film of metal (oxide) to impart the heat reflection effect or electrical conductivity, is inserted between two or more intermediate layers obtained by compounding 100pts.(wt.) of an ethylene-vinyl acetate copolymer (e.g. a copolymer of ethylene and vinyl acetate) with <=5pts. of an organic peroxide (e.g. benzoyl peroxide) and if necessary a (meth)acryloxycontaining compound and a silane coupling agent. The obtained laminate is sandwiched with a pair of glass plates, and heated to harden the intermediate layer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a laminated glass with excellent penetration resistance used for automobile windshields, building window glasses, etc.
Specifically, a laminate consisting of at least two layers of ethylene-vinyl acetate copolymer mixed with or impregnated with an organic peroxide and a film made of an organic resin interposed between each intermediate layer is interposed between two glass plates. This relates to a laminated glass made by integrating the above films and thermosetting the intermediate layer.Furthermore, the above-mentioned film is designed to give saturation properties, or the film is colored to enable heat ray absorption. This invention relates to laminated glass in which a thin film of metal or its oxide is attached to a film by vapor deposition or the like to give it a heat ray reflecting effect or conductivity.In the present invention, the glass plate itself can be used as heat ray reflecting/absorbing glass. The invention relates to laminated glass that can also reflect or absorb heat rays.

The applicant filed a patent application for laminated glass by interposing and integrating a resin intermediate layer made of ethylene-vinyl acetate copolymer with an organic peroxide, and by thermosetting this resin layer. No.-80915 (Unexamined Japanese Patent Publication No. 57-196747)
However, in such laminated glass, ethylene
The vinyl acetate content of the vinyl acetate copolymer is 15 to 50
If the vinyl acetate content is less than 15%, the transparency will not be sufficient when crosslinking and curing at high temperatures, while if it is more than 50% by weight, the transparency will be good, but the modulus will decrease, Good penetration resistance cannot be obtained.

The present invention eliminates the above-mentioned drawbacks and provides a hanging laminated glass that is transparent and exhibits sufficient penetration resistance.
The gist is that at least two
A laminated glass according to the present invention is obtained by interposing a laminate in which a film made of an organic resin is interposed between each intermediate layer of the layers and integrating the laminated body between two glass plates, and by thermosetting the intermediate layer. As will be described later, the laminated glass can be provided with extremely excellent penetration resistance without limiting the amount of vinyl acetate in the ethylene-vinyl acetate copolymer.

-r Since the ethylene-vinyl acetate copolymer adheres extremely well to the organic resin constituting the film during thermal crosslinking and hardly impairs transparency, the vinyl acetate content of the ethylene-vinyl acetate copolymer is increased. Also, since the organic resin is interposed as a film between the intermediate layers, it exhibits excellent penetration resistance. That is, even if the vinyl acetate content exceeds 50% by weight, it can still exhibit excellent penetration resistance.

Materials for the organic resin film used in the present invention include polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-vinyl acetate copolymer, saponified ethylene vinyl acetate copolymer, polymethyl methacrylate, and polyvinyl Petitral, ethylene-
These include ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, metal ion crosslinked ethylene-methacrylic acid copolymer, polystyrene, polyurethane, polycarbonate, heptalophan, etc. Polyester film is most preferred from the viewpoints of strength, workability, etc. required for forming a thin film.

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 that decomposes to produce radicals at a temperature of 100°C or higher can be used. In Although,
Taking into account the stability at the time of formulation, the half-life is 10 hours! I temperature is preferably 70'C or higher, for example, 2,5-dimethylhexane-2,5-sibide lobar.
oxide; 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(1-butylperoxy)valley);
2,2-bis(t-butylperoxy)butane; 1,1
-bis(t-butylperoxy)cyclohexane; 1.
1-bis(t-butylperoxy)-3,3,5-)dimethylcyclohexane; t-butylperoxybenzoate; benzoyl peroxide and the like. As the organic peroxide, at least one of these
The species is selected and the amount thereof is 5 parts by weight or less per 100 parts by weight of the ethylene-vinyl acetate copolymer.

The present invention further relates to heat-reflecting/absorbing glass that is extremely safe.

- Conventionally, heat-reflecting/absorbing glass itself has been widely used, but it is extremely easy to break and once broken, the glass will scatter, so especially when used for architectural window glass, if the glass breaks for some reason, the pieces will scatter. It is extremely dangerous to scatter and fall.

In contrast, the laminated glass of the present invention is firmly bonded as described above. Therefore, even if glass breaks, the pieces will not scatter.

In addition, conventionally, when reflecting or absorbing heat rays, a heat ray reflecting/absorbing film was attached to the surface of the glass, but in the case of such glass, attaching the film itself is relatively easy;
Although it is possible to prevent scattering due to broken glass, there are problems with the durability of the film itself, and it is easy to peel off and has low scratch resistance. In addition, there are also products on the market that have a reflective film attached to the glass surface by vapor deposition to give the glass itself a heat ray reflection/absorption effect, and products that have the glass itself colored to give it a heat ray absorption effect, but these are extremely difficult to use. Although it is expensive, the strength of the glass itself is different from that of regular glass, and it does not have the function of safety glass.

On the other hand, since the laminated glass of the present invention has heat ray reflection/absorption ability in itself, the above-mentioned drawbacks can be completely eliminated.

In addition, glass whose surface is decorated with various designs, pictures, photographs, letters, etc. on the entire surface or partially has been used in various fields, but in such cases, There are problems with durability, and discoloration or peeling is particularly likely to occur in humid areas.

On the other hand, in the laminated glass according to the present invention, the above-mentioned design is applied to the film between the cured resins, which is completely isolated from the outside, so that the above-mentioned drawbacks are completely eliminated.

Furthermore, the laminated glass according to the present invention can be produced by applying a coloring method to the film adhesively interposed between the two to absorb heat rays, or by vapor-depositing a metal or metal oxide to impart a heat ray reflecting effect or conductivity. This is possible and, as mentioned above, because of the presence of the film in the middle, a very durable product is obtained.

In the present invention, methods for depositing and forming a thin film of a metal oxide on the film include vapor deposition, sintering, ivy, ion blating, etc., and the main component of the metal or metal oxide is Examples include indium oxide, chromium oxide, gold, nogradium, tin, and in order to improve the initial modulus of the ethylene-vinyl acetate resin that is the intermediate layer in the laminated glass according to the present invention and to enhance the penetration resistance, acryloxy groups or methacryloxy Group-containing compounds can be added. Commonly used compounds for this purpose include acrylic acid or methacrylic acid derivatives, such as their esters and amides, and the alcohol residues of the esters include methyl, ethyl, dodecyl,
In addition to alkyl groups such as stearyl and lauryl groups,
Examples include cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, and 3-chloro-2-hydroxypropyl group. Furthermore, esters with polyfunctional alcohols such as ethylene glycol, triethylene glycol, and polyethylene glycol can also be used.
A typical example of the amide is diacetone acrylamide.

A silane coupling agent may be added for the purpose of further improving the adhesive strength between the ethylene-vinyl acetate resin and glass. Known silane coupling agents used for this purpose include γ-chloropropylmethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxynidoxine silane, γ-methacryloxyglobin trisilane), Methoxysilane, β-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriaheptoxysilane, γ-mercaptoglobiltrimethoxysilane, r-aminopropyltriethoxysilane , N-β-(aminoethyl)-γ
-aminopropyltrimethoxysilane and the like.

EXAMPLES The present invention will be explained in more detail by showing Examples and Comparative Examples below.

Example 1 The adhesion between an ethylene-vinyl acetate copolymer and a polyester resin film was determined as follows.

That is, to 100 parts by weight of a commercially available ethylene-vinyl acetate copolymer (hereinafter abbreviated as FiVA) (vinyl acetate content 26%), 1 part by weight of dicumyl peroxide as an organic peroxide and γ as a silane fogging agent were added.
- After blending 0.3 parts by weight of methacryloxypropyltrimethoxysilane and uniformly dispersing the blend in a V-type mixer, the mixture was prepared for extrusion of plastics with a cylinder diameter of 40 cm (
T with lip width 4QQm at set temperature 80~100℃)
A 117A sheet with a thickness Q of 4 m was extruded from the die.

A commercially available polyester resin film with a thickness of 50 μm was inserted between the two sheets, and the laminate was placed in a rubber bag, degassed, and heat-treated in an oven at 150°C for 40 minutes. Samples for adhesion testing were obtained.

This sample was cut into a 1-inch width, and the adhesive strength was measured by peeling at 180°C using Shimadzu Autograph S-5ooo, and an adhesive strength value of 6 kg/1 nch was obtained.

It was confirmed that the ethylene-vinyl acetate copolymer and the polyester resin film adhered extremely well.

Example 2 In the same manner as in Example 1, ICVA sheets with a thickness of 6.2 t+a were extruded from two extruders, and a thin aluminum film was deposited on one side between the two HVA sheets to a thickness of 50 mm.
A polyester resin film of μ is inserted, this laminated sheet is cut into a rectangular size (305 x 305 ms), and the cut laminated sheet is sandwiched between rectangular size float glass plates with a thickness of 3 cm. After placing the body in a rubber bag and evacuating the inside of the bag, the body was kept at 150°C.
The glass was left in an oven for 40 minutes to obtain a laminated glass.

No air was observed to be mixed into the resulting laminated glass, and the glass had a heat-reflecting effect equivalent to that of heat-reflecting glass in which metal was directly deposited on the glass surface.

The present inventors dropped a 2.25 kg steel ball on the surface of this heat-reflecting safety laminated glass from heights of 2+++, 1, and 5ffl based on J-Technology S R3025, respectively, and observed the fracture state.

The steel ball does not penetrate the laminated glass in both cases of 2f11 and 1.5 m fall, and 79IIIll in the case of 2 m fall.
cracks were formed in the membrane, but no cracks were formed at all in the case of a fall of 1.5 m.

Comparative Example 1 Two EVA sheets each having a thickness of 0.21111 mm were stacked and sandwiched between two 70-glass plates having a thickness of 3111 sl+ to obtain a laminated glass in the same manner as in Example 2.

When a 2.25 kg steel ball was dropped from a height of 1.5 m on this laminated glass based on J-Technology S R3025, the steel ball penetrated in both of the two repeated tests.

Example 3 A 0.4w EVA sheet was extruded in the same manner as in Example,
Appropriate embossing treatment was performed on both sides by cooling the sheet by passing it between an embossing roll and a rubber roll.

This EVA sheet is cut into square pieces, a colored heat-absorbing film made of polyester resin with a thickness of 50μ is sandwiched between two layers, and the laminate is placed between two square float glass plates with a thickness of 3mm. After clamping it, it was placed in a rubber bag, the inside of the bag was evacuated, and the bag was placed in an oven at 150°C for 40 minutes to obtain an air-free laminated glass.

The laminated glass according to the present invention obtained in this way has no air mixed in, no wrinkles in the film, no distortion in the perspective image, and has a heat ray absorption effect equivalent to that of glass with a colored sheet attached. there were.

Penetration resistance was measured by dropping a 2.25 kg steel ball onto each of the six sets of laminated glasses obtained from a height of 4W+, but no penetration occurred in all but one set.

Comparative Example 2 Two KVA sheets obtained in the same manner as in Example 1 were sandwiched between float glasses in the same manner as in Example 3 to obtain a laminated glass.

A steel ball weighing 2.25 kg was dropped onto each of the six sets of laminated glass from a height of 4 m to measure the penetration resistance.
All 6 groups passed through.

Example 4 One EV'A sheet extruded in Example 1 was placed on top and bottom of a polyester film with color gravure printing, and this laminate was sandwiched between two glass plates. A decorative laminated glass similar to that without any defects such as air inclusions was obtained.

A part of this laminated glass is used as a sunshine weather meter (
Accelerated exposure was performed for 500 hours in a test tube (manufactured by Suga Test Instruments).

Conditions: Ducycle Black Panel Temperature: 63°C, Inside Temperature: 40°C, Using Sunshine Carbon On the other hand, another part of this decorative laminated glass was exposed outdoors for one year.

Both accelerated exposure and outdoor exposure will cause foaming, fading,
No signs of discoloration were observed, and the color tone remained the same as the original sample.

Example 5 A commercially available polyester film (thickness: 50 μm) was prepared by vapor-depositing a thin layer of indium oxide (110 g) on one side and cut to a size slightly larger than the size of the glass to which it was to be attached.

Examples above and below this film! The extruded EVA sheets were stacked one on top of the other, the resulting laminate was sandwiched between two glass plates, and the same operation as in Example 1 was carried out to obtain an air-free conductive laminated glass (A ) was obtained.

Separately, a laminated glass (B) was obtained which was obtained in the same manner except that indium oxide vapor deposition was not performed on one side of the polyester film.

Both were stored in a refrigerator at O''C, and after 30 minutes they were taken out.
．． Using the vapor-deposited polyester parts, electrodes were quickly set on the two corresponding sides, and current was continued to flow under constant voltage (24 volts) conditions.

Immediately after taking them out of the refrigerator, the glass surfaces of both (A) and (B) were completely clouded with water droplets, but the fogging quickly began to disappear on the laminated glass (A), and the laminated glass (B) All the cloudiness disappeared overwhelmingly quickly.

From the above results, it is clear that the laminated glass according to the present invention is suitable as a safety glass for preventing movement.

Patent applicant: Brideston Co., Ltd. Representative Patent Attorney 1) Osamu Kuro

Claims (7)

[Claims] (1) A laminate consisting of at least two layers of ethylene-vinyl acetate copolymer blended with an organic peroxide and a film made of an organic resin interposed between each intermediate layer is interposed between two glass plates. A laminated glass characterized by being made of a single piece and a heat-hardened intermediate layer. (2) The laminated glass according to claim (1), wherein the two glass plates are heat ray reflecting/absorbing glasses. (3) The laminated glass according to claim (1), wherein the film made of organic resin is transparent and has various designs applied to the entire surface or a part of the film. (4) The laminated glass according to claim (1), wherein the entire or part of the film made of organic resin is colored to absorb heat rays. (5) The laminated glass according to claim (1), wherein a thin film of metal or metal oxide is adhered and formed on the surface of the film made of organic resin to impart a heat ray reflection effect or conductivity. (6) The laminated glass according to claim (5), in which the thin film of metal or metal oxide is deposited and formed by a method such as vapor deposition, sputtering, or ion blasting. (7) The main components of metals or metal oxides formed to impart conductivity or heat ray reflection effects are indium oxide, chromium oxide, gold, palladium, tin, and lath.