JP7155858B2 - Gas barrier film for resin spacer for double glazing, resin spacer for double glazing, and double glazing - Google Patents

Description

TECHNICAL FIELD The present disclosure relates to a spacer barrier film used for resin spacers of double glazing intended for heat insulation.

Double glazing generally refers to a plurality of glass single plates arranged in parallel at predetermined intervals, and the periphery of the above glass is fixed, adhered, sealed, or the like.
The purpose of using such double glazing is generally to give the entire window a so-called heat insulation effect, which is to suppress heat in and out from the window glass itself. It is necessary to form an internal gas layer, which is a hollow layer isolated from the outside, between a plurality of glass plates by fixing, adhering and sealing.

As described above, the double glazing needs to form a hollow layer isolated from the outside between a plurality of glass plates, so spacers are arranged around the glass to form this hollow layer. There is a need.

Conventional spacers are made of metal such as aluminum, as described in Japanese Patent Application Laid-Open No. 2002-200010, due to strength and other factors. However, when such a metal such as aluminum is used for the spacer, heat conduction occurs in the spacer portion. I had a problem with it getting stuck.

On the other hand, Patent Literature 1 discloses that a spacer made of resin (made of hard resin) with high heat insulation performance is used instead of a conventional metal spacer mainly made of aluminum as a spacer material. It is Moreover, Patent Document 1 discloses the use of an organic multi-layered film having a metal film or a metal-deposited film as a moisture-proof layer. According to the spacer of Patent Document 1, the moisture-proof layer is arranged so as to cover the spacer, that is, the portion facing the outside of the hollow space holding member, and prevents moisture from entering the hollow layer from the outside.

On the other hand, Patent Document 2 also discloses a spacer made of resin (a polymer base body reinforced with glass fibers), an insulating film is arranged on the outer surface of the spacer, and a hollow layer (plate inner chamber) is formed from the spacer. The insulation film reduces the heat transfer to the

JP 2007-277052 A Japanese Patent Publication No. 2015-509900

As described in Patent Documents 1 and 2 above, resin spacers have come to be used from the viewpoint of heat insulation. There was a problem of high volatility. In addition, the hollow layer of the double glazing is filled with an inert gas having heat insulating performance such as argon, krypton, helium, neon or xenon instead of dry air, so-called gas-filled double glazing. In the case of such double glazing, resin spacers have a low gas barrier property, so there is also a problem that inert gas leaks from the resin spacers.

Therefore, it is necessary to provide the resin spacer with a gas barrier layer (moisture-proof layer) in order to impart gas barrier properties. The adhesion of the gas barrier layer to such resin spacers is accomplished by preparing a gas barrier layer, applying an adhesive layer to a portion of the gas barrier layer, and then adhering the gas barrier layer to the resin spacers, as described in Patent Document 1 above. Attachment methods have been adopted. However, the method of applying an adhesive to the gas barrier layer and then affixing it to the resin spacer requires time and effort in the process and is disadvantageous in terms of cost.

The present disclosure has been made in view of the above circumstances, and a main object of the present disclosure is to provide a gas barrier film for a resin spacer that enables easy production of a resin spacer having a gas barrier layer.

The present inventors investigated a method of forming a resin spacer having a gas barrier layer. As a result, the resin spacer is usually formed by extrusion molding. An attempt was made to bond the gas barrier layer by pressure bonding. However, the inventors have found that there is a serious problem in adhesiveness with mere pressure bonding. The present disclosure has been made to solve such new problems.

That is, in the present disclosure, a resin spacer interposed to form a hollow layer between at least two glass plates constituting double glazing is arranged on the side opposite to the hollow layer. Provided is a gas barrier film for resin spacers, the gas barrier film for resin spacers having a gas barrier layer and an adhesive layer disposed on the entire surface of one main surface of the gas barrier layer.

The present disclosure also provides a resin spacer for double glazing interposed to form a hollow layer between at least two glass plates constituting a double glazing, wherein the resin spacer for double glazing is The spacer has a spacer main body and the gas barrier film for resin spacers, and the gas barrier film for resin spacers is arranged in a state in which the resin spacers for double glazing are interposed in the double glazing. Provided is a resin spacer for double glazing arranged on the surface of the spacer main body opposite to the surface on the hollow layer side.

Further, the present disclosure includes at least two glass plates and the resin spacer for double glazing, wherein the resin spacer for double glazing includes a hollow layer between the at least two glass plates. and the resin spacer for double glazing is arranged so that the gas barrier film for the resin spacer is on the opposite side of the hollow layer. do.

According to the gas barrier film for resin spacers of the present disclosure, since the adhesive layer is disposed on the entire surface of one main surface of the gas barrier layer, for example, immediately after the resin spacers are extruded, the gas barrier film is formed. By laminating with the adhesive layer side facing the resin spacer side, there is an effect that the resin spacer gas barrier film can be easily adhered to the resin spacer.

1 is a schematic cross-sectional view showing an example of a gas barrier film for a resin spacer of the present disclosure; FIG. FIG. 4 is a schematic cross-sectional view showing another example of the gas barrier film for resin spacers of the present disclosure. 1 is a schematic cross-sectional view showing an example of a resin spacer for double glazing of the present disclosure; FIG. 1 is a partial cross-sectional view showing an example of double glazing of the present disclosure; FIG.

Hereinafter, embodiments of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be embodied in many different modes and should not be construed as limited to the description of the embodiments exemplified below. In addition, in order to make the description clearer, the drawings may schematically represent the width, thickness, shape, etc. of each part compared to the embodiment, but this is only an example and limits the interpretation of the present disclosure. not something to do. In addition, in this specification and each figure, the same reference numerals may be given to the same elements as those described above with respect to the existing figures, and detailed description thereof may be omitted as appropriate. Also, for convenience of explanation, the terms "upper" and "lower" may be used, but the up-down direction may be reversed.

Also, in this specification, there is no particular limitation when a configuration such as a member or a region is “above (or below)” another configuration such as another member or another region. So far, this includes not only when directly above (or directly below) other structures, but also when above (or below) other structures, i.e. above (or below) other structures and between other structures. Including cases where the constituent elements of are included.

A. Gas Barrier Film for Resin Spacers of Multi-Layer Glass The gas barrier film for resin spacers of multi-layer glass of the present disclosure (hereinafter sometimes simply referred to as a barrier film) comprises at least two glass plates constituting a multi-layer glass. a gas barrier layer and one main surface of the gas barrier layer, the barrier film being disposed on the side opposite to the hollow layer of the resin spacer interposed to form a hollow layer between the gas barrier layer and the gas barrier layer and an adhesive layer disposed over the entire surface of the side.

FIG. 1 shows an example of a barrier film of the present disclosure. As shown in FIG. 1 , the barrier film 15 of the present disclosure has a gas barrier layer 1 and an adhesive layer 2 formed on the entire surface of one surface of the gas barrier layer 1 .
Such a barrier film of the present disclosure is used for resin spacers for double glazing used for double glazing. A double glazing for which the barrier film of the present disclosure is used will be briefly described below with reference to the drawings.

FIG. 4 is a schematic cross-sectional view showing an example of double glazing using a resin spacer for double glazing according to the present disclosure. The multi-layered glass 10 shown in this example is composed of two glass plates 11, 11 arranged with a resin spacer 13 interposed therebetween so as to form a hollow layer 12 having a width t therebetween. The resin spacer 13 has a spacer main body 14 and a barrier film 15 of the present disclosure arranged on the surface of the spacer main body 14 opposite to the surface on the hollow layer 12 side.
The spacer main body 14 is made of, for example, a hollow pipe material having a hexagonal cross section, and a hollow portion 14A of the spacer main body 14 is filled with a desiccant 16 such as zeolite. A through-hole 14C communicating between the hollow portion 14A and the hollow layer 12 is formed in the inner surface 14B of the spacer main body 14 on the hollow layer 12 side. ) are dried by the desiccant 16 .

Between the resin spacer 13 and the glass plates 11, 11, and on the surface (outer surface) of the resin spacer opposite to the hollow layer 14A, a sealing material 17 made of butyl rubber or the like is arranged.
By arranging the barrier film 15 of the present disclosure at the position described above, it is possible to prevent water vapor from entering the hollow layer 12 from the outside air through the spacer body 14 made of resin and to fill the hollow layer 12 with an inert gas. In this case, the inert gas is prevented from leaking from the hollow layer 12 to the outside air through the spacer body 14 made of resin.

The barrier film of the present disclosure is used by arranging it on the spacer main body as described above. Gas barrier properties can be easily imparted to resin-made spacers simply by attaching the barrier film of the present disclosure to the resin-made spacers.
In particular, by pressing the adhesive layer 2 of the barrier film of the present disclosure to the resin spacer in a heated state after extrusion molding with a roll or the like, the gas barrier layer is adhered to the resin spacer in a state having good adhesive strength. can be made possible.

Hereinafter, each configuration of the barrier film of the present disclosure will be described in detail.

1. Adhesive Layer The adhesive layer in the present disclosure is arranged on the entire surface of one side of the gas barrier layer.
Such an adhesive layer in the present disclosure may have a tacky surface, but preferably has a low surface tackiness. This is because it facilitates handling during storage and manufacturing.

The film thickness of such an adhesive layer is preferably in the range of 50 nm to 1000 μm, more preferably in the range of 100 nm to 500 μm.

Although the material constituting the adhesive layer used in the present disclosure is not particularly limited, it is preferably a material that can be adhered simply by being pressed against the resin spacer in a heated state. By using such a material, as described above, good adhesion can be obtained between the barrier film and the resin spacer simply by pressing the adhesive layer side of the barrier film against the resin spacer immediately after extrusion using a roll or the like. This is because power can be imparted.
Preferred embodiments of the material constituting the adhesive layer used in the present disclosure are described below.

(1) Resin having a molecular weight within a predetermined range The material constituting the adhesive layer in the present disclosure is preferably a resin having a weight average molecular weight (Mw) in the range of 60000 to 600000, particularly in the range of 80000 to 550000. Of these, resins with a molecular weight in the range of 100,000 to 500,000 are preferred.

This is because using a resin having a weight-average molecular weight (Mw) within this range makes it possible to adhere the barrier film to the resin spacer by pressing the adhesive layer onto the heated resin spacer.

By pressing the adhesive layer to the resin spacer in a heated state in this manner, the adhesive layer adheres to the resin spacer because the surface portion of the adhesive layer is melted and the heated resin spacer is melted. It is presumed to be welded to the surface.

The weight average molecular weight (Mw) is a polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC). and filtered under pressure through a membrane filter with a pore size of 0.5 μm and a membrane filter with a pore size of 1.0 μm, and then measured under the following conditions.

(conditions)
・Apparatus: Senshu Kagaku SSC-7120 HT-GPC System
・ Sample volume: around 3 mg of polyethylene film sample for 3 mL of solvent ・ Injection volume: 300 μL
・Guard column: HT-G
・Column: 2 HT-806M ・Column temperature: 145°C
- Mobile phase: o-dichlorobenzene (containing 0.025 wt% BHT)
・Flow rate: 1.0 mL/min
・Detector: Differential refractometer
・Molecular weight calibration: polystyrene conversion

In the adhesive layer used in the present disclosure, the type of resin is not particularly limited as long as it is a resin material having the above weight average molecular weight (Mw). More preferably, it contains an acid-modified polyolefin.

Acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of polyolefin with an acid component such as carboxylic acid. Acid components used for modification include, for example, carboxylic acids such as maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride and itaconic anhydride, and anhydrides thereof. Polyolefins to be modified include polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; polypropylene, such as random copolymers (eg, random copolymers of propylene and ethylene); terpolymers of ethylene-butene-propylene, and the like. Among these polyolefins, polyethylene and polypropylene are preferred. Among these acid-modified polyolefins, maleic anhydride-modified polyolefin, and maleic anhydride-modified polypropylene are particularly preferable.

(2) Resin having a predetermined melting point As a material constituting the adhesive layer in the present disclosure, a resin having a melting point in the range of 50 ° C. to 300 ° C. is preferable, particularly in the range of 60 ° C. to 280 ° C., especially 70 ° C. to 250 ° C. It is preferable that the resin is within the range of °C.
By using a resin having a melting point within this range, the barrier film can be adhered to the resin spacer by pressing the adhesive layer against the heated resin spacer in the same manner as in the case of the weight average molecular weight (Mw). This is because

The melting point of the resin used for the material forming the adhesive layer is measured using a differential scanning calorimeter according to JIS K7121. Specifically, a sample of the resin used in the adhesive layer is collected, about 5 mg of the sample is placed in an aluminum cell, and the temperature is raised from -50 ° C. to 200 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere. After holding at 200°C for 5 minutes, the temperature was lowered to -50°C at a cooling rate of 10°C/min, held at -50°C for 10 minutes, and then again heated to 200°C at a heating rate of 10°C/min. The crystal melting peak temperature is determined from the thermogram measured at 100° C. and taken as the melting point. The differential scanning calorimeter can be selected from commercially available ones, and for example, "DSC204" manufactured by NETZSCH can be used.

In the adhesive layer used in the present disclosure, the type of resin is not particularly limited as long as it is a resin material having a melting point within the above range. can be used.

(3) Same Kind of Resin as Resin Constituting Resin Spacer The resin constituting the adhesive layer of the present disclosure is preferably the same kind of resin as the resin constituting the resin spacer. By using such a resin, as in the case of the weight average molecular weight (Mw), the barrier film can be adhered to the resin spacer by pressing the adhesive layer to the heated resin spacer. Because it becomes
Here, the same type of resin in the present disclosure may be a resin in which the type of the structural unit having the highest molar ratio among the structural units constituting the resin is the same, or the type of the structural unit constituting the resin is the same. Resin may be used.

A resin spacer may be reinforced with an inorganic filler such as glass fiber, but the resin constituting the resin spacer does not contain such an inorganic filler.
In the present disclosure, a resin of the same kind as the resin constituting the resin spacer and having the weight-average molecular weight described in the section “(1) Resin having a molecular weight within a predetermined range”, or “(2 ) A resin having a predetermined melting point” is preferable.

(4) Modified Polyolefin Resin Examples of the resin constituting the adhesive layer of the present disclosure include modified polyolefin resins. This is because it has excellent adhesiveness to the resin spacer in a heated state.
Examples of such modified polyolefin resins include acid-modified polyolefins such as acid-modified polypropylene. As such an acid-modified polyolefin, it is preferable to use a polyolefin modified with an unsaturated carboxylic acid or its acid anhydride. Furthermore, the acid-modified polyolefin may be further modified with a (meth)acrylate. The modified polyolefin further modified with a (meth)acrylic acid ester is obtained by acid-modifying a polyolefin using a combination of an unsaturated carboxylic acid or its acid anhydride and a (meth)acrylic acid ester. be. In the present disclosure, "(meth)acrylic acid ester" means "acrylic acid ester" or "methacrylic acid ester".

Acid-modified polyolefin may be used individually by 1 type, and may be used in combination of 2 or more types. The acid-modified polyolefin is not particularly limited as long as it is a resin containing at least an olefin as a monomer unit.
Polyolefin can be composed of, for example, at least one of polyethylene and polypropylene, and is preferably composed of polypropylene. Polyethylene can be composed of, for example, homopolyethylene and/or ethylene copolymers. Polypropylene may be composed of, for example, homopolypropylene and/or propylene copolymers. Propylene copolymers include copolymers of propylene with other olefins such as ethylene-propylene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, and the like.

The proportion of propylene units contained in polypropylene is preferably 50 mol% or more and 100 mol% or less, and preferably 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the outer packaging material. more preferred. In addition, the ratio of ethylene units contained in polyethylene is preferably 50 mol% or more and 100 mol% or less, and 80 mol% or more and 100 mol% or less, from the viewpoint of further improving the insulation and durability of the outer packaging material. is more preferable.

Ethylene copolymers and propylene copolymers can be either random copolymers or block copolymers, respectively. Also, the ethylene copolymer and propylene copolymer may be either crystalline or amorphous, and may be copolymers or mixtures thereof.
Polyolefin may be formed from one type of homopolymer or copolymer, or may be formed from two or more types of homopolymers or copolymers.
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and crotonic acid. As the acid anhydride, the acid anhydrides of the unsaturated carboxylic acids exemplified above are preferable, and maleic anhydride and itaconic anhydride are more preferable.

The acid-modified polyolefin may be modified with one type of unsaturated carboxylic acid or its acid anhydride, or modified with two or more types of unsaturated carboxylic acids or their acid anhydrides. good too.
Examples of (meth)acrylic acid esters include esters of (meth)acrylic acid and alcohols having 1 to 30 carbon atoms, preferably (meth)acrylic acid and alcohols having 1 to 20 carbon atoms. Esterified products can be mentioned. Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, and (meth)acrylate. octyl acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, octyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate and the like. Modification of polyolefin WHEREIN: Only one type of (meth)acrylic acid ester may be used, or two or more types may be used.
The modified polyolefin resin also has the weight average molecular weight described in the section "(1) Resin having a molecular weight within a predetermined range", or the resin described in the section "(2) Resin having a predetermined melting point". Those having a melting point are preferred.

(5) Resin Containing Vinyl Alcohol as a Constituent Unit As the resin constituting the adhesive layer of the present disclosure, a resin containing vinyl alcohol as a constituent unit can be further mentioned. This is because this resin also has excellent adhesiveness to the resin spacers in a heated state. In addition, since the resin containing vinyl alcohol as a structural unit has low oxygen permeability, it is also useful as a complementary layer for the gas barrier layer.

Polyvinyl alcohol, ethylene-vinyl alcohol copolymers, and the like can be given as resins containing such vinyl alcohol as a structural unit.
It is also possible to use the above-mentioned resin in which an inorganic stratiform compound is dispersed.
Any inorganic layered compound may be used as long as it has a layered structure, and examples thereof include graphite; phosphate-based derivative-type compounds (zirconium phosphate-based compounds); chalcogenides; and clay minerals. Among them, clay minerals are preferred.

Specific examples of clay minerals include phyllosilicate minerals such as hydrous silicates; kaolinite group clay minerals such as halloysite, kaolinite, endellite, dickite and nacrite; antigorite group clays such as antigorite and chrysotile. Minerals; smectite group clay minerals such as montmorillonite, iron montmorillonite, beidellite, nontronite, saponite, hectorite, sauconite, and stevensite; vermiculite group clay minerals such as vermiculite; mica such as muscovite and phlogopite; mica or mica group clay minerals such as lyric mica and teniolite; chlorite group clay minerals such as cookeite, pseudoite, clinochlore, chamosite, and nimite; and substitutions and derivatives thereof. These clay minerals may be natural clay minerals or synthetic clay minerals, and may be contained in combination of two or more.

In the present disclosure, among others, phyllosilicate minerals and smectite clay minerals are preferred, and montmorillonite and hectorite contained in smectite clay minerals are particularly preferred.

Further, among resins containing vinyl alcohol as a structural unit, there is a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² are organic groups having 1 to 8 carbon atoms). M represents Si or a metal atom, n represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.). and polyvinyl alcohol, and further includes a sol-gel compound obtained from a raw material liquid obtained by polycondensation by a sol-gel method.
Such a sol-gel compound has a function as the adhesive layer and a function as an overcoat layer. Here, the function as an overcoat layer means that in a gas barrier layer having a resin base material and a gas barrier film comprising a thin film of a metal or an inorganic compound formed on the resin base material, the resin base material of the gas barrier film When the sol-gel compound is formed on the surface opposite to the surface of the gas barrier layer, the gas barrier property of the gas barrier layer is improved.
Therefore, when a gas barrier layer having the gas barrier film is used as the gas barrier layer to be described later, the sol-gel compound is formed on the surface of the gas barrier film opposite to the substrate, and this is used as the adhesive layer in the present disclosure. is preferred.

It should be noted that the function as the above-mentioned overcoat layer is also possessed by the above-mentioned other resins containing vinyl alcohol as a structural unit. It is preferred to use the layer in the manner described above.

2. Gas Barrier Layer The gas barrier layer used in the present disclosure is not particularly limited as long as desired gas barrier properties can be obtained. For example, a metal foil may be used as the gas barrier layer (first aspect), and has a resin substrate and a gas barrier film containing a metal or an inorganic compound disposed on one or both sides of the resin substrate. A laminate may be used as a gas barrier layer (second aspect).
Each aspect of the gas barrier layer will be described below.

(1) First Aspect A first aspect of the present disclosure is an aspect in which the gas barrier layer is a metal foil. Examples of such metal foils include metal foils of aluminum, nickel, stainless steel, iron, copper, titanium, etc. Among them, aluminum foil is preferably used. Since metal foil has good gas barrier properties and excellent flex resistance, the gas barrier properties can be enhanced by using metal foil as the gas barrier layer.

The metal foil may be a single layer, or a laminate in which layers made of the same material or layers made of different materials are laminated. In addition, the thickness of the metal foil (total thickness in the case of a laminate) is not particularly limited as long as the strength of the barrier film can be kept within a predetermined range. Preferably. Also, the lower limit of the thickness is not particularly limited, but can be, for example, 5 μm or more. If the thickness of the metal foil is less than 5 μm, pinholes and the like are likely to occur in the metal foil, and the gas barrier properties may deteriorate. This is because it may become difficult. The thickness of the metal foil may be 7 μm or less, or 6.5 μm or less.

(2) Second aspect The gas barrier layer of the second aspect of the present disclosure is a laminate having a resin base material and a gas barrier film containing a metal or an inorganic compound disposed on one or both sides of the resin base material. It contains the body. In the present disclosure, it is preferred that the gas barrier layer is of the second aspect. This is because the metal foil of the first aspect has high thermal conductivity and may adversely affect the heat insulating properties of double glazing for which the barrier film of the present disclosure is used.

(a) Gas Barrier Film The gas barrier film in the present disclosure is arranged on one or both sides of the resin substrate, contains a metal or an inorganic compound, and mainly contributes to the gas barrier properties of the gas barrier layer. The gas barrier film is not particularly limited as long as it can exhibit desired gas barrier properties. As a film having such a gas barrier property, for example, a metal layer, a layer containing an inorganic compound as a main component, or the like can be used.
Examples of the metal layer include those composed of metals such as aluminum, stainless steel, titanium, nickel, iron and copper, or alloys containing these.

The inorganic compound of the layer containing an inorganic compound as a main component may be any material as long as it can exhibit the desired gas barrier properties. and one or more inorganic compounds selected from silicon zinc oxide and the like. Specific examples include inorganic compounds containing one or more elements selected from silicon, aluminum, magnesium, calcium, potassium, tin, sodium, titanium, boron, yttrium, zirconium, cerium, and zinc. can be done. More specifically, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, tin oxide, silicon-zinc alloy oxide, indium alloy oxide, silicon nitride, aluminum nitride, titanium nitride, oxide Silicon nitride etc. can be mentioned. The inorganic compound may be used alone, or may be used by mixing the above materials in an arbitrary ratio.

The thickness of the gas barrier film is not particularly limited as long as it can exhibit the desired gas barrier properties. Although it depends on the type of the gas barrier film, it is, for example, within the range of 5 nm or more and 800 nm or less. is preferred. This is because if the thickness of the gas barrier film is less than the above range, the film may not be formed sufficiently to exhibit the desired gas barrier properties, and the gas barrier film may deteriorate over time. This is because, if the above range is exceeded, cracks are likely to occur and the flexibility may decrease, and if the gas barrier film contains a metal or an alloy, the heat insulating properties may be adversely affected.

By combining the resin base material and the gas barrier film to obtain the desired strength of the gas barrier layer as a whole, damage or the like can be suppressed even if the gas barrier layer is thin as described above.
The gas barrier film may be a single layer or a laminate of two or more layers. When two or more gas barrier films are used, gas barrier films having the same composition may be combined, or gas barrier films having different compositions may be combined.

(b) Resin substrate The resin substrate is not particularly limited as long as it can support the gas barrier film. Such a resin substrate is usually in the form of a film and may be unstretched or uniaxially or biaxially stretched.
The resin used for the resin substrate is not particularly limited. Polyolefin, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), (meth) acrylic, polycarbonate, polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer (EVOH) ), saponified ethylene-vinyl ester copolymer, polyamide such as nylon, polyimide, polyurethane, polyacetal, and cellulose. In the present disclosure, among the above resins, polyamide, PET, polypropylene, etc. are preferably used, and from the viewpoints of toughness, oil resistance, chemical resistance, availability, etc., polyamide and PET are more preferably used. be done.

(c) Overcoat layer The gas barrier layer of this aspect may have an overcoat layer on the side of the gas barrier film opposite to the resin substrate. This is because the gas barrier properties of the gas barrier film can be improved. Such an overcoat layer is not particularly limited, and those commonly used as overcoat agents can be used.
The thickness of the overcoat layer is not particularly limited, but can be, for example, within the range of 50 nm or more and 500 nm or less.
There are various types of overcoat layers, for example, phosphoric acid alumina-based mixed compounds such as Claristar CF (registered trademark) manufactured by Kuraray Co., Ltd., acrylics such as Becera (registered trademark) manufactured by Toppan Printing Co., Ltd. Acid zinc-based mixed compounds and the like can be mentioned.

Further, the general formula R ¹ _n M (OR ² ) _m (wherein, R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, n is represents an integer of 0 or more, m represents an integer of 1 or more, and n+m represents the valence of M.) and a water-soluble polymer, and further, A sol-gel compound obtained from a raw material liquid obtained by polycondensation by a sol-gel method can be used.
Examples of the water-soluble polymer include polyvinyl alcohol-based resins, ethylene-vinyl alcohol copolymers, acrylic acid-based resins, natural polymer-based methylcellulose, carboxymethylcellulose, cellulose nanofibers, and polysaccharides.

A sol-gel compound using a resin having vinyl alcohol as a structural unit as a water-soluble polymer can be used as an adhesive layer, as described in the above section "1. Adhesive layer (5) Resin containing vinyl alcohol as a structural unit". This is a preferred embodiment in the present disclosure because it is also possible to exhibit the function of

(d) Others When using the gas barrier layer of this embodiment, it is preferable to use a gas barrier layer formed by laminating a plurality of layers of the laminate in consideration of gas barrier properties. Specifically, lamination of 2 to 4 layers is preferred, and lamination of 3 layers is particularly preferred.

FIG. 2 shows an example of the gas barrier layer of this embodiment, which is a gas barrier formed by laminating three layers of laminates 5a, 5b, and 5c each having a gas barrier film 4 laminated on one surface of a resin substrate 3. The overcoat layer 6 is arranged on the surface of the gas barrier film 4 opposite to the resin base material 3 of the laminate 5a in which the gas barrier film 4 is arranged on the outside of the gas barrier layer 1. there is The overcoat layer 6 has the function of the adhesive layer 2 as described above, and the gas barrier film 15 of the present disclosure is composed of the gas barrier layer 1 and the adhesive layer 2 .

As in this example, a gas barrier layer formed by laminating three layers of the above-described laminate can exhibit gas barrier properties equivalent to those of metal foil and have superior heat insulating properties compared to metal foil. can. Moreover, by using an overcoat layer that functions as an adhesive layer, there is no need to form a separate adhesive layer, and there is an advantage that manufacturing can be performed in a small number of steps.

3. Others The barrier film of the present disclosure does not include a state in which it is adhered to a resin spacer, but indicates a state in which it exists as a single body.
Examples of the state in which such a single substance exists include a long shape, specifically a length of 10 m or more, particularly a length of 50 m to 4000 m. Alternatively, it may be wound into a roll.

The width of the barrier film of the present disclosure is appropriately determined depending on the application, but is usually about 6 mm to 150 mm.
When the adhesive layer in the barrier film of the present disclosure has adhesiveness, a release sheet may be arranged on the adhesive layer side surface.
The barrier film of the present disclosure is used for resin spacers for double glazing used for double glazing to be described later.

B. Resin spacer for double glazing The resin spacer for double glazing of the present disclosure is a resin spacer for double glazing interposed to form a hollow layer between at least two glass plates constituting double glazing. The resin spacer for double glazing comprises a spacer body and the barrier film described in the section "A. Gas barrier film for resin spacer for double glazing" (hereinafter referred to as a barrier film provided with an adhesive layer). and the adhesive layer-equipped barrier film is provided on the hollow layer side of the spacer main body in a state in which the resin spacer for double glazing is interposed in the double glazing. It is arranged on the surface opposite to the surface.

FIG. 3 exemplifies the resin spacer 13 for double glazing of the present disclosure. and a barrier film 15 .
The spacer main body 14 is made of, for example, a hollow pipe material having a hexagonal cross section, and has a hollow portion 14A inside. The spacer main body 14 has an inner surface 14B, which is the side of the hollow layer when the double-glazed glass is formed, and an outer surface 14D, which is a portion of the spacer main body 14 facing the side opposite to the hollow layer. 11 and a facing surface 14E that is a surface that faces. A through hole 14C is formed in the inner surface 14B so as to communicate with the hollow layer when the double glazing is formed. A barrier film 15 with an adhesive layer is arranged to cover the outer surface 14D and the facing surface 14E.

The resin spacer for double glazing of the present disclosure includes the adhesive layer on the surface opposite to the hollow layer side in a state in which the resin spacer for double glazing is interposed in the double glazing. By arranging the barrier film, it is possible to prevent the permeation of water vapor from the outside to the hollow layer when the multi-layer glass is formed, and when the inside is filled with an inert gas, such inert gas can be prevented. This has the effect of preventing leakage of active gas.
A resin spacer for double glazing according to the present disclosure has at least a spacer body and an adhesive layer-equipped barrier film.

1. Spacer main body The spacer main body in the present disclosure has an inner surface that will be the hollow layer side when used for double glazing, an outer surface that is a portion facing the opposite side of the hollow layer when used for double glazing, and a double glazing When used in the double glazing, it has two glass plates and a facing surface facing each other.
Since the spacer body needs to contain a desiccant inside, a hollow spacer body is preferably used. In the case of the hollow spacer main body, since it is necessary to communicate the desiccant contained therein with the hollow layer of the multi-layer glass, it is preferable that through holes are formed in the inner surface.

The two opposing surfaces are generally arranged in parallel, and the distance between the two surfaces determines the width of the hollow layer of the double glazing.
Although the outer surface may be flat, it is usually shaped like a trapezoid with the central portion protruding outward, that is, to the side opposite to the hollow layer side. It has a hexagonal shape with two right angles.
Such a spacer main body may be composed only of resin, but is preferably filled with a reinforcing agent such as glass fiber in terms of strength. The content of the reinforcing material such as glass fiber is preferably 20% by mass to 50% by mass, more preferably 30% by mass to 40% by mass.

Resins constituting the spacer body in the present disclosure include polyethylene (PE), polycarbonate (PC), polypropylene (PP), polystyrene, polyester, polyurethane, polymethyl methacrylate, polyacrylate, polyamide, polyethylene terephthalate (PET), and polybutylene. Terephthalate (PBT), polyvinyl chloride (PVC), butyl rubber, preferably acrylonitrile-butadiene-styrene (ABS), acrylic ester-styrene-acrylonitrile (ASA), acrylonitrile-butadiene-styrene-polycarbonate (ABS/PC), styrene - Acrylonitrile (SAN), PET/PC, PBT/PC and/or copolymers or mixtures thereof and the like.
In the present disclosure, it can be said that the use of ABS, polyvinyl chloride, and butyl rubber is preferable for exhibiting the effects of the present disclosure.

2. Adhesive Layer-Equipped Barrier Film The adhesive layer-equipped barrier film used in the present disclosure has been described in the section "A. Gas barrier film for resin spacers of multi-layer glass", and thus description thereof will be omitted here.
The adhesive layer-equipped barrier film may be arranged at least on the outer surface of the spacer main body, but may be arranged on the opposite surface.

C. Double glazing The double glazing of the present disclosure has at least two glass plates and the resin spacer for double glazing described in the above section "B. Resin spacer for double glazing", The resin spacer for double glazing is interposed to form a hollow layer between the at least two glass plates, and the resin spacer for double glazing comprises: It is arranged so as to be opposite to the hollow layer.
FIG. 4 shows an example of double glazing of the present disclosure. Since the description of FIG. 4 has been described in the above section "A. Gas barrier film for resin spacer of multi-layer glass", the description will be omitted here.

The two glass plates are not particularly limited as long as they have a predetermined light transmittance, and are usually made of glass, but may be made of polymer. A functional film such as an infrared protection film or an ultraviolet protection film may be adhered to the glass plate. The shape of the glass plate is usually rectangular, but is not limited to this, and may be circular, polygonal, trapezoidal, rounded geometric shapes, and the like.
A hollow layer is formed between the two glass plates by the resin spacer for double glazing, and the hollow layer contains dry air or a heat insulating material such as argon, krypton, helium, neon, or xenon. is filled with an inert gas having

When the resin spacer for double glazing used in the double glazing of the present disclosure is hollow, a desiccant may be contained therein.
Such desiccants include silica gel, CaCl ₂ , Na ₂ SO ₄ , activated carbon, silicates, bentonite, zeolites, and the like.
In addition, on the opposite side of the hollow layer of the resin spacer for multi-layer glass, a sealing material for sealing the edges of the two sheets of glass and bonding the two sheets of glass is arranged. . Polysulfide, silicone, room-temperature-curing silicone rubber, high-temperature-curing silicone rubber, peroxide-curing silicone rubber, addition-curing silicone rubber, polyurethane, butyl rubber, polyacrylate, or the like is preferably used as such a sealing material. can be done.

Note that the present disclosure is not limited to the above embodiments. The above embodiment is an example, and any device that has substantially the same configuration as the technical idea described in the claims of the present disclosure and achieves the same effect is the present invention. It is included in the technical scope of the disclosure.

EXAMPLES The present disclosure will be described more specifically below with reference to examples and comparative examples.

1. Preparation of film The details of the film used for producing the gas barrier film for resin spacers are shown below.

(1) TEOS-PVA/Al ₂ O ₃ deposited film/PET12
A film in which an aluminum oxide deposition film (Al ₂ O ₃ film) is directly formed on one side of PET12 (12 μm thick polyethylene terephthalate film (“E5120” manufactured by Toyobo Co., Ltd.)) is prepared.

Then, liquid A (mixture of polyvinyl alcohol, isopropyl alcohol and water) prepared according to the composition shown below is added to liquid B (tetraethoxysilane (TEOS), isopropyl alcohol, hydrochloric acid and ion A hydrolyzate consisting of exchanged water) was added and stirred, and a colorless and transparent overcoat layer composition was obtained by a sol-gel method.

The overcoat layer composition was coated on the Al ₂ O ₃ deposited film of PET 12 on which the Al ₂ O ₃ was deposited by gravure coating, and then heated at 120° C., 140° C. and 150° C. for 20 seconds each. An overcoat layer having a required thickness is formed by heat treatment and aged at 55°C for 1 week to form an overcoat layer which is a mixed compound layer containing silicon element, oxygen element and polyvinyl alcohol resin. Then, TEOS-PVA/Al ₂ O ₃ deposition film/PET12 was obtained.

<Composition of composition for overcoat layer>
(A liquid)
・Polyvinyl alcohol: 1.81% by mass
・Isopropyl alcohol: 39.80% by mass
・Water: 2.09% by mass
(B liquid)
・ Tetraethoxysilane: 21.49% by mass
・Isopropyl alcohol: 5.03% by mass
· 0.5N hydrochloric acid aqueous solution: 0.69% by mass
・Ion-exchanged water: 29.10% by mass
(* A liquid and B liquid were combined and set to 100% by mass)

(2) Inorganic layer compound + PVA/PET12
PVA (polyvinyl alcohol) granules (manufactured by Japan Vinyl Acetate & Poval Co., Ltd.: JF-04, saponification degree 98-99%, average polymerization degree 400) are dissolved in ion-exchanged water, and a 20% by mass polyvinyl alcohol aqueous solution is prepared. got Montmorillonite (manufactured by Kunimine Industries Co., Ltd.: Kunipia F) was added to this aqueous solution so as to be 10% by mass of the solid mass, and the mixture was stirred to prepare an inorganic layered compound-containing coating solution.
Next, the inorganic layered compound-containing coating solution is coated on the PET 12 by gravure coating, and then heat-treated at 120° C., 140° C. and 150° C. for 20 seconds each to form an inorganic layered compound film on the PET 12. was directly formed to obtain inorganic layer compound + PVA/PET12.

(3) ABS150
A film made by Okamoto Co., Ltd. and having a thickness of 150 μm was used.

(4) ALM6
Thickness 6 μm, product name: 8021, manufactured by UACJ Foil Manufacturing Co., Ltd. was used.

(5) Acid-modified PP/ALM6
An aluminum foil having a thickness of 6 μm was extrusion-laminated with acid-modified polypropylene (unsaturated carboxylic acid-grafted polypropylene, 30 μm) on one surface.

(6) Corona-treated PET12
PET12 (polyethylene terephthalate film with a thickness of 12 μm (“E5200” manufactured by Toyobo Co., Ltd.)) having both sides subjected to corona treatment was used.

2. Preparation of Gas Barrier Films for Resin Spacers The films described above were laminated as shown in Table 1 below to prepare gas barrier films for resin spacers of Examples 1 to 4 and Comparative Examples 1 and 2.
In the following description, the order of description of each film indicates the order of the layer structure, and // indicates that each film was adhered with an adhesive.

Each film was joined with an adhesive layer. The adhesive is a main agent mainly composed of polyester polyol (product name: RU-77T manufactured by Rock Paint Co., Ltd.), a curing agent containing aliphatic polyisocyanate (product name manufactured by Rock Paint Co., Ltd.: H-7), and ethyl acetate was mixed so that the weight compounding ratio of main agent:curing agent:solvent=10:1:14 was used. This adhesive is applied to one surface of one of the films constituting the outer wrapping material so that the coating amount is 3.5 g/m ² to form an adhesive layer, and the one film with the adhesive layer formed and the other The film was pressurized with an adhesive layer interposed therebetween.

3. Evaluation The gas barrier films for resin spacers of Examples 1 to 4 and Comparative Examples 1 and 2 were evaluated for water vapor permeability, water vapor permeability after bending, durability, and adhesion to the spacer main body. Table 2 shows the results.

As shown in Table 2, those provided with an adhesive layer were excellent in durability and adhesiveness to the spacer main body.
The evaluation method for each evaluation item is as follows.

(water vapor permeability)
The water vapor transmission rate of the gas barrier film for resin spacers was determined in accordance with ISO 15106-5:2015, with a permeation area of about 50 cm ² (permeation area: a circle with a diameter of 8 cm), a temperature of 40° C., and a relative humidity difference of 90% RH. Measure under conditions. For example, "DELTAPERM" manufactured by Technolox, UK can be used as the water vapor transmission rate measuring device. At least three samples were measured for each film, and the average of these measurements was taken as the water vapor transmission rate for that film.

(Water vapor permeability after bending)
From the gas barrier films obtained in Examples 1 to 4 and Comparative Examples 1 and 2, rectangular samples each having a width of 210 mm and a length of 297 mm (A4 size) were cut out, and both ends in the width direction were adhered together and rolled into a cylindrical shape. A shaped test piece was prepared. Both ends of this test piece are held by a fixed head and a driving head of a gelboflex tester (manufactured by Tester Sangyo Co., Ltd., model name BE1006), and are twisted at an angle of 440 degrees in accordance with ASTM F392. The drive head spacing was reduced from 7 inches to 3.5 inches, then the head spacing was reduced to 1 inch while maintaining the twist, then the head spacing was increased to 3.5 inches, and further. Reciprocating motion was performed three times at a speed of 40 times/min at a temperature of 25° C. while untwisting and widening the spacing of the heads to 7 inches.
The water vapor permeability of the gas barrier film obtained by the bending treatment was measured in the same manner as described above, and the average of these measured values was taken as the value of the water vapor permeability of the film.

(durability)
The water vapor transmission rate of the gas barrier film after storage for three weeks in an atmosphere of 50° C. and 95% RH was measured, and the durability was evaluated by comparing with the water vapor transmission rate before the durability test.
[Evaluation criteria]
◎: No change in water vapor permeability before and after the test ○: The difference in water vapor permeability before and after the test is less than 0.5 g / (m ² day) ×: The difference in water vapor permeability before and after the test is 0.5 g / (m ² days) or more

(Adhesion to housing)
After extrusion molding, the resin spacer and the gas barrier film were adhered by pressing the gas barrier film to the heated ABS resin spacer with a roll, and after cooling, the adhesion to the housing was evaluated.
[Evaluation criteria]
○: The housing and the gas barrier film are in close contact ×: The housing and the gas barrier film are not in close contact

DESCRIPTION OF SYMBOLS 1... Gas barrier layer 2... Adhesive layer 3... Resin substrate 4... Gas barrier film 5... Laminate 6... Overcoat layer 11... Glass plate 12... Hollow layer 13... Resin spacer for multi-layer glass 14... Spacer body 15... Resin Spacer Gas Barrier Film 16... Drying Agent 17... Sealing Material

Claims (11)

A gas barrier film for a resin spacer disposed on the side opposite to the hollow layer of a resin spacer interposed to form a hollow layer between at least two glass plates constituting double glazing. and
having a gas barrier layer and an adhesive layer disposed on the entire surface of one main surface of the gas barrier layer,
The gas barrier film for a resin spacer , wherein the adhesive layer is composed of a resin containing vinyl alcohol as a structural unit . 2. The gas barrier film for a resin spacer according to claim 1, wherein said adhesive layer is composed of a resin having a weight average molecular weight in the range of 60,000 to 600,000. 3. The gas barrier film for a resin spacer according to claim 1, wherein the adhesive layer is composed of a resin having a melting point within the range of 50.degree. C. to 300.degree. 4. The gas barrier film for a resin spacer according to any one of claims 1 to 3, wherein an inorganic stratiform compound is dispersed in the resin constituting the adhesive layer. The gas barrier layer has a base material and a gas barrier film made of a metal or an inorganic compound and formed on one main surface of the base material,
The gas barrier film for a resin spacer according to any one of claims 1 to 4 , wherein the adhesive layer is formed on the main surface of the gas barrier film opposite to the base material. A resin spacer for double glazing interposed to form a hollow layer between at least two glass plates constituting a double glazing,
The resin spacer for double glazing has a spacer body and the resin spacer gas barrier film according to any one of claims 1 to 5 ,
The resin spacer gas barrier film is disposed on the surface of the spacer main body opposite to the hollow layer side in a state in which the resin spacer for double glazing is interposed in the double glazing. A resin spacer for double glazing. A resin spacer for double glazing interposed to form a hollow layer between at least two glass plates constituting a double glazing,
The resin spacer for double glazing has a spacer body and a resin spacer gas barrier film,
The resin spacer gas barrier film has a gas barrier layer and an adhesive layer disposed on the entire surface of one main surface of the gas barrier layer,
The adhesive layer is made of the same type of resin as the resin forming the spacer main body,
The resin spacer gas barrier film is disposed on the surface of the spacer main body opposite to the hollow layer side in a state in which the resin spacer for double glazing is interposed in the double glazing. A resin spacer for double glazing. 8. The resin spacer for double glazing according to claim 7, wherein said adhesive layer is composed of a resin having a weight average molecular weight in the range of 60,000 to 600,000. 9. The resin spacer for double glazing according to claim 7, wherein the adhesive layer is made of a resin having a melting point within the range of 50.degree. C. to 300.degree. 10. The resin spacer for double glazing according to any one of claims 7 to 9, wherein the adhesive layer is made of modified polyolefin resin . Having at least two glass plates and the resin spacer for double glazing according to any one of claims 6 to 10 ,
The resin spacer for double glazing is interposed to form a hollow layer between the at least two glass plates,
The resin spacer for double glazing is a double glazing in which the resin spacer gas barrier film is disposed on the side opposite to the hollow layer.

Images