JPH0825564A - Glass laminate - Google Patents

Abstract

PURPOSE:To obtain a glass laminate having superior heat-insulating properties, a sufficient strength, and such a high safety as it does not splashes even in case of breakage. CONSTITUTION:A glass laminate 10 is provided with a honeycomb structure 14, that is obtained by continuously forming wall bodies of a stainless steel into a honeycomb shape with a height of 3mm and a maximum diameter of 30mm, between glass plates 12. Between the glass plates 12 and the honeycomb structure 14, adhesive layers 16 are provided. The adhesive layer 16 is made of an ethylene-vinyl acetate copolymer. The glass plates 12 are bonded to the wall parts 13 of the honeycomb structure 14 through the adhesive layers 16.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a glass laminate,
More specifically, the present invention relates to a glass laminate excellent in heat insulating property and safety used for a window glass of a building.

[0002]

2. Description of the Related Art Conventionally, as a heat insulating glass used for a window glass or the like of a building, a double glazing in which two glass plates are fixed in parallel via a layer of dry air has been widely used. Although this double glazing has a heat insulating property, it has a drawback that it has a low strength and is easily broken because the total thickness is limited. Further, broken glass is scattered and there is a problem in safety. In order to improve the strength of the glass and prevent the scattering of glass fragments when broken, it is conceivable to fill the space with a resin or the like instead of dry air, but the strength is improved, but the heat insulating property is reduced, It wasn't practical.

[0003]

Therefore, a glass laminate having excellent heat insulating properties and high safety has been demanded.

[0004] That is, an object of the present invention is to provide a glass laminate which has excellent heat insulating properties, has sufficient strength, and has high safety in which glass fragments do not scatter even when broken.

[0005]

The present invention has been made in view of the above problems, and the glass laminate of the present invention is
A honeycomb structure is provided between the glass plate bodies, and an adhesive layer is provided between the glass plate body and the honeycomb structure. Further, the glass laminate according to claim 2 of the present invention is the glass laminate, wherein the adhesive layer is made of an ethylene-vinyl acetate copolymer. Furthermore, the glass laminate according to claim 3 of the present invention is the glass laminate, wherein the adhesive layer contains ethylene-containing an organic peroxide and a silane coupling agent.
It is characterized by comprising a vinyl acetate copolymer.

In the present invention, the honeycomb structure means the same as the honeycomb core in the sandwich structure, and not only the so-called honeycomb (honeycomb) shape but also 2
Includes all structures in which cells (small chambers) each having a maximum diameter of 5 to 300 mm and formed by walls of a metal thin plate having a width of about 50 mm, a synthetic resin, paper, and the like are continuously formed. .

[0007]

The glass laminate of the present invention has a honeycomb structure between two glass plates and an adhesive layer between the glass plates and the honeycomb structure. Since the structure is adhered, an air layer is secured between the two glass plates, and the thermal convection phenomenon, which is a problem with general double glazing, is unlikely to occur and the heat insulation is excellent. Further, by inserting the honeycomb structure, the space between the glass plate bodies is reinforced, the strength is improved, and moreover, the upper and lower ends of the wall portion forming the honeycomb structure are respectively formed by the glass plate body and the adhesive layer. Since it is adhered, even if the glass breaks, the glass pieces do not scatter and the safety is high.

[0008]

EXAMPLES The glass laminate of the present invention will be described in detail below with reference to examples. (Example 1) FIG. 1 is a perspective view showing a part of a glass laminate of Example 1, and FIG. 2 is a sectional view of the glass laminate. The glass laminated body 10 is made of stainless steel and has a honeycomb structure 14 in which a honeycomb-shaped wall portion 13 having a height of 3 mm and a maximum diameter of 30 mm is continuously formed between glass plate bodies 12.
Is inserted. An adhesive layer 16 which is a sheet body made of an ethylene-vinyl acetate copolymer is formed on the inner surface of the glass plate body 12.
Thus, the glass plate 12 and the end of the wall portion 13 of the honeycomb structure 14 are bonded together.

The method for producing the glass laminate of the present invention is not particularly limited. For example, the glass laminate 1 of Example 1 is used.
0 is manufactured as follows.

Each component was blended in the ratio shown in Table 1, and 8
A thermosetting resin containing an ethylene-vinyl acetate copolymer that forms an adhesive layer by mixing with a roll mill heated to 0 ° C. was prepared. This resin composition was molded into a sheet body having a thickness of 0.4 mm using a press to form an adhesive layer 16.

[0011]

[Table 1]

Next, two 3 m sheets which have been washed and dried in advance
The honeycomb structure 14 was sandwiched between glass plates 12 made of m-thick float glass with an adhesive layer 16 interposed therebetween. Thus
An adhesive layer 16 is formed on the inner surface of the glass plate 12 as shown in FIG.
Was formed, and a glass laminated body was formed in which the honeycomb structure 14 was interposed between the glass plate bodies 12 having the pair of adhesive layers 16 formed on the inner surface thereof. Then, this was put in a rubber bag, deaerated under vacuum, and pre-bonded at a temperature of 80 ° C. Next, this pre-compression-bonded glass laminate is put in an oven and treated at 130 ° C. for 30 minutes to interpose the honeycomb structure 14 between the glass plate bodies 12 and fix them by the adhesive layer 16. The glass laminated body 10 thus obtained was obtained.

In the honeycomb structure 14 of this embodiment, a thin aluminum plate is used as the wall portion 13, and honeycomb type cells (small chambers) as shown in FIG. 1 are continuously formed by the wall portion 13. The honeycomb structure used in the invention is not particularly limited in the constitutional unit formed by the wall portion 13, that is, the shape of the cell, and the maximum diameter of the cell in plan view is 5 to 30.
Any shape can be taken within the range of 0 mm.
An example of the shape of the cell is shown in plan view in FIG. For example, the shape of the cell is not only a hexagon forming a so-called honeycomb, but also a circle (FIG. 3 (B)), an ellipse (FIG. 3 (C)), and a triangle (FIG. 3).
(D)) and other polygons, a rectangle having an overall lattice shape, a square (FIG. 3 (E)), a rhombus (FIG. 3 (F)), and the like.
These may have the same shape continuously, as shown in FIG.
It may be configured by a combination of two or more kinds as shown in FIG. The maximum diameter (the maximum diagonal length in the case of a polygon such as a quadrangle) when the cell is viewed in plan is preferably in the range of 5 to 300 mm, more preferably 5 to 200 mm, and particularly 5 to 5.
A range of 100 mm is preferable from the viewpoint of strength and safety.

Further, the thickness of the honeycomb structure, that is, the height of the wall portion 13 forming the honeycomb structure is preferably 3 mm or more from the viewpoint of heat insulation, while the glass laminated body is fitted into the sash. Since it is generally used in, the thickness of the entire glass laminate is preferably 50 mm or less. From the viewpoint of heat insulation and safety, it is more preferably 5 to 20 mm. However, depending on the portion where the glass laminate is used, it may have a thickness of more than 50 mm in order to form a sufficient air layer without limitation of the thickness.

The material of the wall portion forming the honeycomb structure is
Metal plates such as aluminum, iron, stainless steel, copper, polyethylene, polyacrylic, polycarbonate, polyvinyl chloride, polypropylene, polyethylene terephthalate,
A resin plate made of polybutylene terephthalate, polyamide, polyethylene-vinyl acetate or the like, a paper-based plate or the like can be used according to the purpose.

Next, the adhesive layer of the first embodiment will be described. In Example 1, the adhesion is performed using the adhesive layer 16 which is a sheet body formed of resin. The material of the adhesive layer of the sheet, for example, thermosetting ethylene-vinyl acetate resin-based adhesive layer, polyvinyl butyral-based adhesive layer, saponified ethylene-vinyl acetate resin-based adhesive layer,
A polyvinyl chloride adhesive layer is preferably used, and an ethylene-vinyl acetate resin adhesive layer is particularly preferable from the viewpoint of adhesive strength. Here, the thermosetting ethylene-vinyl acetate resin capable of forming a preferable adhesive layer sheet body will be described in detail. The thermosetting resin is a mixture of an ethylene-vinyl acetate copolymer with an organic peroxide.

The ethylene-vinyl acetate copolymer that can be used in the adhesive layer of the glass laminate of the present invention has a vinyl acetate content of 10 to 50% by weight, preferably 15 to 40% by weight. When the vinyl acetate content is less than 10% by weight, the transparency of the resin obtained when it is crosslinked and cured at a high temperature is not sufficient. On the contrary, when it exceeds 50% by weight, the glass plate and the honeycomb are formed into a glass laminate. The adhesive strength with the structure tends to be insufficient, and the strength such as impact resistance tends to be insufficient.

As the organic peroxide used as a curing agent for the ethylene-vinyl acetate copolymer in the production of the glass laminate of the present invention, any organic peroxide which decomposes at a temperature of 100 ° C. or higher to generate radicals can be used. Can also be used. In consideration of stability at the time of compounding, those having a decomposition temperature with a half-life of 10 hours of 70 ° C. or higher are preferable, and examples thereof include 2,5-dimethylhexane-2,5-dihydroperoxide and 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,
Examples thereof include 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, t-butylperoxybenzate, and benzoyl peroxide. At least one of these is used as the organic peroxide.
A seed is selected, and its blending amount is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer.

In order to improve the initial modulus of the ethylene-vinyl acetate resin and the strength,
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, its ester 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.

Further, a silane coupling agent may be added to the thermosetting resin as an adhesive strength improver for the purpose of further improving the adhesive strength between the ethylene-vinyl acetate resin and the glass plate or honeycomb structure. . Known silane coupling agents provided for this purpose, 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 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.

Further, if necessary, for the purpose of improving the stability of the adhesive layer, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-benzoquinone or methylhydroquinone is added to the ethylene-vinyl acetate copolymer 100. It can be added in an amount of 5 parts by weight or less based on parts by weight. In addition to these additives, a colorant, an ultraviolet absorber, a discoloration inhibitor, etc. can be added as necessary, and an antioxidant is further added for the purpose of further improving light stability and heat stability. Can be used. Examples of this antioxidant include a phenol type, a sulfur type, a phosphorus type, an amine type, a hindered phenol type, a hindered amine type, and a hydrazine type, but a hindered amine type is particularly preferable. (Example 2) In Example 2, the glass plate body 12 and the honeycomb structure 14 were bonded together by using an adhesive layer 18 formed by applying an adhesive instead of the adhesive layer 16 of the sheet body. There is. FIG. 4 shows a cross-sectional view of a glass laminated body 20 in which the glass plate body 12 and the honeycomb structure 14 are adhered by an adhesive layer 18 formed of an adhesive. In this case, for example,
Adhesive layer 1 by applying an adhesive agent on both sides of the honeycomb structure 14
After forming 8, the glass plate 12 is inserted between the glass plates 12 and bonded via the adhesive layer 18. The adhesive that can be used is the wall portion 13 that constitutes the glass plate body 12 and the honeycomb structure 14.
There is no particular limitation as long as it can bond with the material of
For example, one-component heat-curable and two-component curable epoxy adhesives, urethane-based, silicon-based, modified silicon-based, polysulfide-based adhesives, acrylic-based, rubber-based, resin-based solvent-based adhesives and acrylic-based adhesives, A rubber-based hot melt type pressure-sensitive adhesive or the like is preferably used. Of these, an adhesive that is transparent after curing and adhesion is preferable in terms of appearance. These adhesives are used by forming the adhesive layer 18 by applying the adhesive to the end portion of the wall portion 13 of the honeycomb structure 14 by a known means such as a roller coater or a brush. When an adhesive having good transparency is used, it is applied to the surface of the glass plate 12 on the side in contact with the honeycomb structure 14, and the adhesive layer is applied to the entire surface of the glass plate 12 in contact with the honeycomb structure 14. 18 may be formed and used.

Further, of the two glass plate members, one glass plate member and the honeycomb structure are bonded to each other via the adhesive layer of the sheet member as described in Example 1, and the other glass plate member is bonded. It is also possible to adhere the honeycomb structure through an adhesive layer formed by applying an adhesive. in this case,
For example, the adhesive layer of the sheet body can be provided only on the surface that is easily damaged, such as the outside of the glass window.

In most cases, the glass laminate of each of the above-mentioned embodiments is used by being fitted in a sash. However, since the glass plate body 12 is bonded to the honeycomb structure 14, a normal hollow glass is used. The strength of the entire glass laminated body is higher than that of the laminated body, and even when the glass plate body 12 is damaged, the honeycomb structure 14 is formed in many portions of the glass pieces.
Since it is adhered to, it will not scatter. Further, even if an opening is formed in the glass plate body 12, it is difficult to form a through hole in the glass laminate itself due to the presence of the honeycomb structure 14 which is an intermediate layer, and therefore it is used as a window glass. It is also preferable for crime prevention. (Example 3) In the glass structure of the present invention, it is not necessary that the glass plate 12 and the honeycomb structure 14 have the same size. FIG. 5 shows a cross-sectional view of a glass laminate 22 in which a honeycomb structure 14 smaller than the glass plate body 12 is inserted between the glass plate bodies 12. In the glass laminated body 22 of Example 3, as shown in FIG.
A honeycomb structure 14 smaller than 2 is inserted between the glass plate bodies 12 and bonded with an adhesive layer 16 of the sheet body interposed therebetween.
A seal portion 24 made of a hydrophilic resin is formed in a space between the glass plate bodies 12 where the honeycomb structure 14 at the end portions does not exist. As described above, since the airtightness of the space between the glass plate bodies 12 can be ensured by providing the seal portion 24 at the end portion of the glass laminate 22, it is preferable from the viewpoint of improving heat insulation and moisture resistance.

In the glass structure 22 of Example 3, the resin used for the seal portion 24 provided at the end of the laminated glass is preferably a resin having a water absorption rate of 0.1% or more. A resin having a water absorption rate of 0.1% or more means a JIS plastic water absorption rate and boiling water water absorption rate test method K7209.
(1984) refers to a resin having a water absorption rate of 0.1% or more when measured, and preferably a water absorption rate of 0.5%.
% Or more, more preferably 1.0% or more. The resin preferably used 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. it can. As the hydrophilic group, a hydroxyl group,
Examples thereof include 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). Therefore, it can be preferably used. The width of the sealing portion 24 is not particularly limited, but it is preferable that the laminated glass is used in combination with the sash and is 30 mm or less in view of appearance. 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.

Moreover, the humidity is maintained by sealing with the hydrophilic resin.
After preventing the invasion of moisture, by combining a seal portion made of a hydrophobic resin (resin having a water absorption rate of less than 0.1%) on the outer periphery of the seal portion 24, it is possible to more effectively prevent the invasion of humidity and moisture. It can be carried out. Examples of the hydrophobic resin include polyethylene and polypropylene.
Further, examples thereof include ethylene-vinyl acetate copolymers and the like, which have a water absorption rate of less than 0.1%.

As described above, the glass laminate 22 in which the sealing portion 24 prevents the intrusion of humidity and moisture from the surroundings.
In addition to the effects of Examples 1 and 2, the honeycomb structure can be preferably used in a high humidity environment, and the honeycomb structure 14 is made of a material having low moisture resistance, such as paper. Even if the durability is not reduced, it has an advantage.

In each of the glass laminates of the above-mentioned examples, one obtained by inserting one layer of a honeycomb structure between two glass plate bodies and adhering it is used. Depending on the purpose of use of the glass laminate, May be formed by using a plurality of honeycomb structures. That is, two glass plates and one
A plurality of glass laminates such as the above-mentioned example comprising a honeycomb structure of layers may be bonded via an adhesive layer to form a multilayer honeycomb structure glass laminate, and a glass plate body and a honeycomb structure. May be alternately laminated via an adhesive layer and adhered to form a multilayer honeycomb structure glass laminate.

[0033]

Since the glass laminate of the present invention has the above-mentioned constitution, it is excellent in heat insulating property, has sufficient strength, and has high safety because the glass pieces do not scatter even when broken. Show the effect.

[Brief description of drawings]

FIG. 1 is a perspective view showing a part of a glass laminate of Example 1.

2 is a cross-sectional view showing a glass laminate of Example 1. FIG.

FIG. 3 is a plan view showing an example of the shape of cells of a honeycomb structure.

FIG. 4 is a cross-sectional view showing a glass laminate of Example 2 in which a glass plate body and a honeycomb structure are bonded together with an adhesive.

FIG. 5 is a cross-sectional view showing a glass laminate of Example 3 in which a seal portion is formed on the periphery.

[Explanation of symbols]

 10, 20, 22 Glass laminated body 12 Glass plate body 14 Honeycomb structure 16 Adhesive layer 18 Adhesive

Claims (3)

[Claims] 1. A glass laminate having a honeycomb structure between two glass plates and an adhesive layer between the glass plates and the honeycomb structure. 2. The glass laminate according to claim 1, wherein the adhesive layer is made of an ethylene-vinyl acetate copolymer. 3. The glass laminate according to claim 1, wherein the adhesive layer is made of an ethylene-vinyl acetate copolymer containing an organic peroxide and a silane coupling agent.