JPH06219792A - Laminated glass - Google Patents

Abstract

PURPOSE:To provide laminated glass excellent in water and moisture resistance. CONSTITUTION:This laminated glass 10 is obtained by inserting a film 14 made of an organic resin between two interlayers 12 composed of a thermosetting resin containing an ethylene-vinyl acetate copolymer blended therein, interposing and integrating the resultant laminate between panes of glass plates 16. A sealing part 18 composed of a resin having >=0.1% water absorptivity is present in the ends between the panes of the glass plates 16. The film 14 made of the organic resin, as desired, is partially or wholly colored. A design is applied to a part or all thereof and/or a thin-film layer is formed by the metallic vapor deposition.

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 glass for buildings, soundproof glass and the like.

[0002]

2. Description of the Related Art Conventionally, in order to enhance the durability of an intermediate layer or an organic resin film interposed between glass plates by sealing the edges of the laminated glass, a sealant is applied to the edges of the laminated glass. The most commonly used method is to apply or tape. As a sealant,
Silicon-based, sulfide-based, oil, etc. are mainly used. As the tape, aluminum tape, polyethylene terephthalate tape, butyl rubber tape, chloroprene rubber tape, ethylene-propylene rubber (EPDM) that has been subjected to an adhesive treatment is mainly used. Came.

[0003]

However, no matter which of the above methods is used, an organic resin film interposed between glass plates, a design formed on the organic resin film, and a thin film layer formed by metal deposition are used. It could not be said to be sufficient when the water was easily eroded by water and humidity.

An object of the present invention is to seal an edge portion of a laminated glass with a hydrophilic resin to use an organic resin film, which is easily deteriorated by humidity, as an intermediate layer, or to design the organic resin film. It is intended to provide a laminated glass excellent in moisture resistance, which does not deteriorate even when used in a high humidity environment.

[0005]

In the laminated glass of the present invention, a laminate having an organic resin film interposed between at least two intermediate layers made of a thermosetting resin is interposed between glass plates, and the intermediate layer is formed. In a laminated glass obtained by curing and integrating layers, the edge of the laminated glass has a water absorption rate of 0.1.
% Or more of resin is used for sealing.

Further, the laminated glass according to claim 2 of the present invention is the laminated glass according to claim 1, wherein the organic resin film is partially or wholly colored. Part or all of the design is applied, and / or a thin film of metal or metal oxide is formed on part or all of the surface of the organic resin film.

That is, the present inventors achieved the object by completing the present invention by sealing the edge of the laminated glass with a specific resin in order to improve the water resistance and moisture resistance of the laminated glass. I arrived.

The present invention will be described in detail below. In the present invention, the water absorption rate for sealing the edge of the laminated glass is 0.1
% Or more resin means a resin having a water absorption rate of 0.1% or more when the water absorption rate is measured by JIS Plastic Water Absorption Rate and Boiling Water Water Absorption Rate Test Method K7209 (1984), and preferably 0% or more. The resin is 0.5% or more, and more preferably 1.0% or more. The resin preferably used in the present invention is a so-called hydrophilic resin having a hydrophilic group in the molecule, but any other resin may be used as long as it exhibits a water absorption rate of 0.1% or more in the test method. Can be used. Examples of the hydrophilic group include a hydroxyl group, an acrylamide group, a carboxyl group, an amino group, a carbonyl group, an ether group and a sulfo group.

Resins derived from natural polymers such as wool, silk and cotton can be generally called hydrophilic resins.
The hydrophilic synthetic resin and the hydrophilic natural resin may be used alone or in combination of two or more kinds.

Suitable hydrophilic resins include polyacrylic acid, sodium polyacrylate, polyvinylamine, polyvinylpyrrolidone, sodium poly-L-glutamate, polyvinyl alcohol, polyacrylamide, viscose, hemoglobin, polypyrrolidone, poly Glycine, polymethacrylic acid, polyurethane, cellulose diacetate, polymethylallyl alcohol, cellulose triacetate, nylon 6, nylon 66, polyvinyl acetate, polymethyl vinyl ketone, cellulose nitrate, ethyl cellulose, nylon 610, polyacrylonitrile, polymethyl methacrylate, Polyvinyl chloride, polyethylene terephthalate, polyvinyl isobutyl ether, polyvinyl butyral, ethylene-vinyl acetate copolymer, phenol resin , Urea resins, melamine resins, allyl resins, unsaturated polyethylene terephthalate, alkyd resins, epoxy resins, silicone resins, polyimides,
Acrylic resins, polystyrene resins, ABS resins, polyvinylidene chloride, styrene-butadiene copolymers, polycarbonates, polyacetals, etc. may be mentioned, but these resins may be used alone or in combination of two or more. Also, whether the resin obtained by modification or the copolymerization of two or more kinds, the finally obtained resin may be a resin having a water absorption rate of 0.1% or more (hereinafter referred to as a hydrophilic resin). For example, it can be used in the present invention.

FIG. 1A is a front view showing one embodiment of the laminated glass of the present invention, and FIG. 1B is a sectional view of the same laminated glass 10.

In the laminated glass 10 of this embodiment, an organic resin film 14 is interposed between two intermediate layers 12 made of a thermosetting resin, and the laminated body is interposed between glass plates 16 to be integrated. At the ends between the glass plates 16, a seal portion 18 made of a hydrophilic resin having a water absorption rate of 0.1% or more is formed.
Exists, and the intermediate layer 12 and the organic resin film 14 are sealed to prevent invasion of humidity and moisture. The width of the sealing portion 18 is not particularly limited, but is 3 in view of the fact that laminated glass is used in combination with the sash and the appearance thereof.
It is preferably 0 mm or less. Further, it is preferable that the thickness is 0.1 mm or more, and if it is less than 0.1 mm, the sealing performance is insufficient.

FIG. 2A is a front view showing a second embodiment of the laminated glass of the present invention, and FIG. 2B is the same laminated glass 20.
FIG.

The laminated glass 20 of this embodiment has a sealing portion 1 made of a hydrophilic resin at the end between the glass plates 16.
The laminated glass 10 is the same as the laminated glass 10 in FIG. 1 except that a sealing portion 22 made of a hydrophobic resin (a resin having a water absorption rate of less than 0.1%) is present on the outer periphery of the laminated glass 8. By combining the seal portion 22 made of a hydrophobic resin, the entry of humidity and moisture can be prevented more effectively. Examples of the hydrophobic resin include polyethylene, polypropylene, and ethylene-vinyl acetate copolymers having a water absorption rate of less than 0.1%.

FIG. 3A is a front view showing a third embodiment of the laminated glass of the present invention, and FIG. 3B is the same laminated glass 30.
FIG.

In the laminated glass 30 of this embodiment, the sealing portion at the end between the glass plates 16 is composed of a sealing portion 22 made of a hydrophobic resin on the inner circumference and a sealing portion 18 made of a hydrophilic resin on the outer circumference. Except for this, it is the same as the laminated glass 20 in FIG. By combining the seal portion 22 made of a hydrophobic resin (a resin having a water absorption rate of less than 0.1%) with the seal portion 18 made of a hydrophilic resin (a resin having a water absorption rate of 0.1% or more), the intrusion of humidity and moisture can be prevented. The prevention is more effective.

The material of the organic resin film used in the present invention is polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polyethylene, ethylene-
Vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, polymethyl methacrylate, polyvinyl butyral, ethylene-ethyl acrylate copolymer,
Examples include ethylene-methyl acrylate copolymer, metal ion cross-linked ethylene-methacrylic acid copolymer, polystyrene, polyurethane, polycarbonate, cellophane, etc., but film smoothness, surface gloss (to form a metal thin film by vapor deposition etc. Is required), strength, workability, etc., and the most preferable is a polyethylene terephthalate film.

In the present invention, a part or the whole of the organic resin film is colored for heat ray reflection and absorption, and various patterns, pictures, photographs, for improving the decorative property.
It is possible to apply a design such as characters and symbols, or to apply a thin film of metal or metal oxide by means such as vapor deposition in order to impart a heat-reflecting effect or conductivity. In the present invention, as a method for forming a metal or metal oxide thin film on an organic resin film, there are methods such as vapor deposition, sputtering, and ion plating, and as a main component of the metal or metal oxide of the thin film to be formed. Are indium oxide, chromium oxide, gold, palladium, tin, cadmium oxide, silver, platinum, aluminum, copper, copper iodide, tin oxide, antimony tin oxide, titanium oxide, etc., which are used in combination of two or more kinds. It doesn't matter.

By coloring, giving a design, or forming a thin film of a metal or a metal oxide, a new function or added value can be added to the laminated glass, and a coloring agent used for coloring or giving a design. In addition, thin films of metals or metal oxides are often deteriorated or deteriorated by humidity, and in particular, discoloration of metal thin films due to humidity significantly reduces the commercial value of laminated glass, which has been a problem.

Next, the thermosetting resin forming the intermediate layer will be described. The thermosetting resin according to the present invention comprises an ethylene-vinyl acetate copolymer and an organic peroxide.

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 of the resin obtained when it is crosslinked and cured at high temperature is not sufficient,
On the other hand, if it exceeds 50% by weight, 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 of 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. It can be used.
In consideration of stability during blending, it is preferable that the decomposition temperature with a half-life of 10 hours is 70 ° C. or higher.
5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane-3, di-t-butylperoxide, t-butylcumylperoxide , 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 Examples thereof include benzate and benzoyl peroxide. As the organic peroxide, at least one of them is selected, and the blending amount thereof is ethylene-vinyl acetate copolymer 1
It is preferably 0.1 to 5 parts by weight with respect to 00 parts by weight.

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

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 alkyl groups such as methyl group, ethyl group, dodecyl group, stearyl group and lauryl group, cyclohexyl group, tetrahydrofurfuryl group, aminoethyl group, 2-hydroxyethyl group Group, 3-hydroxypropyl group, 3-chloro-2-hydroxypropyl group and the like. In addition, ethylene glycol,
Esters with polyfunctional alcohols such as triethylene glycol and polyethylene glycol can also be used in the same manner.

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 preferably 50 parts by weight or less with respect to 100 parts by weight of the vinyl acetate copolymer.

In the present invention, a silane coupling agent may be added as an adhesive strength improver for the purpose of further improving the adhesive strength between the ethylene-vinyl acetate resin and the glass or organic resin film. Known silane coupling agents provided for this purpose, for example, γ-chloropropylmethoxysilane, vinyltrichlorosilane,
Vinyltriethoxysilane, vinyl-tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, 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 blending amount of these silane coupling agents is 5 parts by weight or less with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer.

In the present invention, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone or methylhydroquinone may be added to ethylene-vinyl acetate copolymer for the purpose of improving the stability of the resin layer, if necessary. It can be added in an amount of 5 parts by weight or less based on 100 parts by weight of the coalescence. In addition to these additives, a colorant, an ultraviolet absorber, a discoloration preventing agent and the like can be added as required.

Further, in the present invention, an antioxidant can be used for the purpose of further improving light stability and heat stability. Examples of this antioxidant include phenols, sulfur, phosphorus, amines, hindered phenols, hindered amines, and hydrazines, with hindered amines being particularly preferred.

[0030]

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

Example (Preparation and Evaluation of Sample) Each component was blended in a ratio shown in Table 1 and mixed by a roll mill heated to 80 ° C. to prepare a thermosetting resin forming an intermediate layer. This resin composition was made into a sheet having a thickness of 0.4 mm by using a press. An organic resin film [trade name: Heat Mirror XIR70 manufactured by Southwall (sauthwall)] was sandwiched between the two intermediate layers to prepare a laminate. The organic resin film,
A film of metal and metal oxide is formed on a polyethylene terephthalate film.

[0032]

[Table 1]

As a method for producing a laminated glass, the above-mentioned laminate comprising an intermediate layer and an organic resin film between two 3 mm-thick float glasses which have been washed and dried in advance, and further, the constitution shown in Table 2 is used. After sandwiching the resin in which a predetermined sealing resin was arranged, the resin was put in a rubber bag, deaerated in vacuum, and pre-bonded at a temperature of 80 ° C. Next, this pre-bonded laminated glass was placed in an oven and treated at 130 ° C. for 30 minutes.

In Examples 1 and 2, as in the laminated glass 10 shown in FIG. 1, an organic resin film 14 is interposed between two intermediate layers 12 made of a thermosetting resin, and the laminate is made into a glass plate. 16 and the glass plate 16
A seal portion 18 made of a hydrophilic resin is provided at the end between
Is formed.

In the third embodiment, like the laminated glass 20 shown in FIG. 2, a seal portion 22 made of a hydrophobic resin is formed on the outer periphery of the seal portion 18 made of a hydrophilic resin at the ends between the glass plates 16. Was produced in the same manner as the laminated glass of Examples 1 and 2.

In the fourth embodiment, like the laminated glass 30 shown in FIG. 3, the sealing portions at the ends between the glass plates 16 are made of a hydrophobic resin on the inner circumference and a hydrophilic resin on the outer circumference. The laminated glass was produced in the same manner as the laminated glass of Example 3 except that the laminated glass was used.

(Water and Moisture Resistance Measurement Method) Laminated glass for measuring water resistance and moisture resistance was subjected to an accelerated test at 60 ° C. and 95%.
The state of the laminated glass was visually confirmed by continuously standing in a thermo-hygrostat at a relative humidity for 500 hours.

The results are shown in Table 2.

[0039]

[Table 2]

As shown in Table 2, the laminated glasses of Examples 1 to 4 were found to be abnormal in comparison with Comparative Example 1 and Comparative Product 2 in which the end portions were not sealed at all. It was confirmed that the film showed excellent moisture resistance.

[0041]

Since the laminated glass of the present invention has the above-mentioned constitution, it has an effect of excellent water resistance and moisture resistance even when used under high humidity conditions.

[Brief description of drawings]

1A is a front view showing one embodiment of a laminated glass of the present invention, and FIG. 1B is a sectional view of the same laminated glass 10.

2A is a front view showing a second embodiment of the laminated glass of the present invention, and FIG. 2B is a sectional view of the same laminated glass 20.

FIG. 3A is a front view showing a third embodiment of the laminated glass of the present invention, and FIG. 3B is a sectional view of the same laminated glass 30.

[Explanation of symbols]

 10, 20, 30 Laminated glass 12 Intermediate layer 14 Organic resin film 16 Glass 18 Hydrophilic seal part 22 Hydrophobic seal part

Claims (2)

[Claims] 1. A laminated glass in which a laminate comprising an organic resin film interposed between at least two intermediate layers made of a thermosetting resin is interposed between glass plates, and the intermediate layers are cured and integrated. A laminated glass, characterized in that an end portion of the laminated glass is sealed with a resin having a water absorption rate of 0.1% or more. 2. A part or all of the organic resin film is colored, a part or all of the organic resin film is designed, and / or the surface of the organic resin film. The laminated glass according to claim 1, wherein a thin film of metal or metal oxide is formed on a part or all of the above.