JPH11278878A - Rust preventive film and wired glass sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rust preventive film for a wired glass sheet which exhibits sufficient rust preventiveness by a simple method and a wired glass sheet formed by affixing this film to its peripheral end. SOLUTION: This rust preventive film imparts a rust preventive effect to the wired glass sheet by being affixed to the peripheral end of the wired glass sheet. The rust preventive film is formed by providing the one side of a support layer with a tacky adhesive layer. This tacky adhesive layer contains 1 to 50 wt.% rust preventive pigment by a solid content ratio. The wired glass sheet is formed by affixing the rust preventive film to its peripheral end.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rust-preventive film which gives a rust-preventive effect to a glass plate containing a wire by being attached to the peripheral end of a glass plate containing a wire, and to which the film is attached at the peripheral end. It relates to a glass plate with a wire.

[0002]

2. Description of the Related Art A glass plate with a wire has a metal net or a wire interposed between the glass plates so that glass fragments are scattered even when a shock is applied to the glass plate. It is widely used as a safety glass plate in the field of construction.

[0003] Such a glass plate with a wire is used particularly for window glass of office buildings and condominiums, window glass of trains, windows for ceilings of agricultural houses, and glass for ceilings. For example, as shown in FIG. 1, a wire-containing glass plate 1 has a wire 2 sandwiched inside the glass plate. It is devised to be appropriate.

By the way, at the peripheral end portion of the glass plate 1 with a wire, a portion 3 in which the internal wire 2 is exposed occurs. The exposed wire portion 3 rusts when exposed to the outside air, and the rust enters the inside of the glass plate along the wire from the gap between the wire and the glass, and the transparency of the glass plate with the wire is increased. In addition, there is a problem that the aesthetic properties, strength and the like are significantly reduced.

[0005] As a method for solving such a problem, it has been considered to provide a film 4 for covering the peripheral end of a glass plate with a wire. For example, a method of attaching butyl tape to the peripheral end surface of a glass plate with a wire, a method of applying a silicone resin to the peripheral end surface of a glass plate with a wire (Japanese Patent Application Laid-Open No. 60-3381), A method in which a solvent solution comprising an acrylic ester resin and a silicone varnish is applied to the end surface (Japanese Patent Laid-Open No. 1-162424)
No. 3). However, these methods have a drawback that peeling occurs or deteriorates over time, and the effect cannot be stably maintained for a long time.

Japanese Utility Model Application Laid-Open No. 2-94227 discloses a method in which a concave portion is provided on the peripheral end surface of a glass plate containing a wire, and an organic material or glass having an adhesive property such as a silicone sealant, a polysulfide-based sealant, or hot melt butyl is provided in the concave portion. A method of filling an inorganic material such as a frit and water glass is disclosed. However, in this method, the operation becomes complicated and there is a disadvantage in the manufacturing process.

[0007] JP-A-5-221688 discloses that the peripheral end surface of a glass plate containing a wire has plasticity before curing.
A method is disclosed in which after curing, a thermosetting silicone rubber adhesive having elasticity is pressed and heat-cured. However, in this method, although there is no inferiority in exhibiting rust prevention, a heating step is indispensable, so that it was not possible to eliminate the complexity, and there was a disadvantage in the production step.

[0008]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides, by a simple method, a rust-preventive film for a wire-containing glass plate exhibiting a sufficient rust-preventive property, and affixing the same. It is another object of the present invention to provide a wire-containing glass plate.

[0009]

SUMMARY OF THE INVENTION The present invention relates to a rust-preventive film which imparts a rust-preventive effect to a wire-containing glass plate by being attached to a peripheral end of the wire-containing glass plate. The adhesive layer is provided with an adhesive layer on one side of the layer.
It is a rust-preventive film characterized by containing 含有 50% by weight. The present invention is also a wire-containing glass plate obtained by sticking the above rust-preventive film on a peripheral end. Hereinafter, the present invention will be described in detail.

The rust-preventive film of the present invention is obtained by laminating an adhesive layer on one side of a main layer. The main layer physically forms the main component in the rust-preventive film of the present invention. The material of the main layer is not particularly limited as long as it can form a film. For example, polyvinylidene chloride, polyvinyl acetate, polystyrene, poly (meth) acrylate, polyvinyl alcohol, various polyolefins, polyacetal , Polycarbonate, polyamide, acetylcellulose and the like.

In consideration of the fact that the glass plate with a wire of the present invention is used for outdoor use such as window glass, it is preferable to use a material having excellent weather resistance as the material of the main layer. Examples thereof include polyvinyl chloride (PVC), polyethylene (PE), polypropylene (PP), poly (meth) acrylate (AC),
Examples thereof include polyethylene terephthalate (PET), polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), ethylene / tetrafluoroethylene copolymer (ETFE), and perfluoroalkyl ether copolymer (PFA).

The main layer is preferably a film having a thickness of 20 to 200 μm. The main layer may be transparent or colored, and may be appropriately selected depending on the use of the wire-containing glass plate to which the rust-preventive film of the present invention is applied. In order to color the main layer, a coloring pigment or the like is kneaded into a material, and then formed into a film. The color pigment is not particularly limited, and for example, titanium oxide, carbon black, other organic pigments and the like can be appropriately selected and used.

In order to improve the weather resistance of the main layer,
Various UV absorbers, light stabilizers, antioxidants and other additives can be added. These additives are not particularly limited. For example, 2,6-di-tert-butyl-p-
Cresol, 2,2'-methylenebis (4-methyl-6
-Tert-butylphenol), 1,1,3-tris (2-
Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (3,5-di-tert-butyl-4)
-Hydroxybenzyl) isocyanurate, 1,3,5
-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Methane, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy}
Phenolic antioxidants such as ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane;

Trisnonylphenyl phosphite, tris (2,4-ditertbutylphenyl) phosphite, tridecyl phosphite, di (decyl) phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite Phosphite, di (nonylphenyl) pentaerythritol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1-1,1 Phosphite-based antioxidants such as, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butanetriphosphite;

2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,6-di-tert-butyl-4) -Hydroxybenzyl) malonate, tetra (2,
2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-
Pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-
Hindered amine light stabilizers such as 4-piperidyl) di (tridecyl) butanetetracarboxylate and the like can be mentioned.

Examples of additives that can be added to the main layer as additives other than the above additives include a plasticizer, a softener, an antioxidant, a metal deactivator, an ozone deterioration inhibitor, and a tackifier. And the like.

The pressure-sensitive adhesive layer laminated on one side of the main layer for forming the rust-preventive film of the present invention is formed by adding an additive to the pressure-sensitive adhesive. The gist of the present invention lies in that a rust preventive pigment is used as an additive to be added to the pressure-sensitive adhesive.

As the pressure-sensitive adhesive as a main component of the pressure-sensitive adhesive layer, various pressure-sensitive adhesives can be used. Examples thereof include acrylic resin-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. However, acrylic resin-based pressure-sensitive adhesives are preferred because they are inexpensive and have excellent weather resistance.

Various coloring pigments can be appropriately added to the pressure-sensitive adhesive according to the purpose of use of the glass plate with a wire. Examples of such coloring pigments include those exemplified as those added to the main layer.

A tackifier can be added to the pressure-sensitive adhesive for the purpose of improving the tackiness. Such tackifiers are not particularly limited, and include, for example, a coumarone resin-based tackifier such as a mixture of a coumarone-indene resin, a coumarone resin, a naphthenic oil, a phenol resin, and a rosin; pt-butylphenol-acetylene resin Phenol / terpene resins such as phenol / formaldehyde resin, terpene phenol resin, polyterpene resin, xylene / formaldehyde resin; synthetic polyterpene resin; aromatic hydrocarbon resin; aliphatic hydrocarbon resin; aliphatic cyclic hydrocarbon resin; Alicyclic petroleum resin; aliphatic aromatic petroleum resin; unsaturated hydrocarbon polymer; hydrocarbon-based tackifying resin; petroleum-based hydrocarbon resin; rosin derivative; turpentine-based tackifier, synthetic resin and phthalate ester And nonionic activators and the like. It can be used or two or more.

The pressure-sensitive adhesive layer contains a rust preventive pigment. The rust preventive pigment is not particularly limited, and examples thereof include chromic rust preventive pigments, lead rust preventive pigments, zinc rust preventive pigments, and phosphorus / vanadate rust preventive pigments. Among them, chromic acid-based rust-preventive pigments are most effective and are preferred, but phosphorus-vanadate-based rust-proofed pigments are preferred in view of environmental issues and the like.

Examples of the chromic acid-based rust preventive pigment include calcium chromate, zinc chromate, strontium chromate, barium chromate and the like. Examples of the lead-based rust preventive pigment include basic lead sulfate, lead circle, and cyanamide lead. Examples of the zinc-based rust preventive pigment include zinc dust.

In the present invention, the rust preventive pigment is added to the pressure-sensitive adhesive layer in a solid content ratio of 1 to 50% by weight. If the amount is too small, the rust-preventing property cannot be sufficiently exerted. If the amount is too large, the dispersibility deteriorates, and a gap is easily formed between the rust-preventing film and the glass, and the rust-preventing property deteriorates. More preferably, it is 3 to 30% by weight.

The pressure-sensitive adhesive layer preferably has a thickness of 5 to 200 μm. If the thickness of the pressure-sensitive adhesive layer is too large, the adhesiveness of the rust-preventive film to the glass plate with the wire becomes insufficient, and the rust-preventive property deteriorates. If the thickness of the pressure-sensitive adhesive layer is too small, the pressure-sensitive adhesive will protrude to the glass surface, and the aesthetics will deteriorate. More preferably, it is 20 to 150 μm.

In producing the rust preventive film of the present invention, release paper is usually laminated to prevent the surface of the pressure-sensitive adhesive layer from sticking to other parts during the process. Such release paper can be appropriately used as needed in the usual adhesive film, for example,
Film release paper, paper release paper, and the like can be given. The material of the film release paper is not particularly limited, and may be, for example, a polyester film. These may be those obtained by performing a silicone treatment on one surface to improve the performance. Such release paper may be used as needed, and is not essential for the rust preventive film of the present invention.

No special method is required for applying the rust-preventive film of the present invention to the peripheral end surface of the glass plate containing the wire. For example, the present invention is applied by attaching the rust-preventive film of the present invention to a peripheral end surface of a glass plate with a wire. In this case, use a rust-preventive film having a width longer than the thickness of the wire-containing glass plate, and after sticking to the peripheral end surface, attach both ends of the surplus rust-preventive film to the upper and lower surfaces of the wire-containing glass plate. By bending and pasting,
The blocking property can be further improved.

The rust-preventive film of the present invention can block intrusion of oxygen and water by physically covering the peripheral end surface of the glass plate with wire. The rust-preventive film of the present invention, even if the invasion of oxygen or water physically blocked in this way becomes incomplete over time, the action of the rust-preventive pigment contained in the pressure-sensitive adhesive layer causes the wire to enter the wire. The passivation of the wire in the glass plate is performed, whereby the generation of rust in the glass plate with the wire can be suppressed.

Prior to the completion of the present invention, there was no idea to include an anticorrosive pigment in the pressure-sensitive adhesive layer of the anticorrosive film. According to the present invention, the rust-preventing property of a glass plate with a wire can be extremely effectively improved by such a method that overturns the conventional common sense. A glass plate with a wire, characterized in that the rust preventive film of the present invention is adhered to the peripheral edge, is also one of the present invention.

[0029]

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

Example 1 Preparation of Composition for Pressure-Sensitive Adhesive Layer Acrylic ester-based polymer of 75 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid (number average molecular weight: about 500,000)
And zinc chromate (Kinjiro C) 2
0 parts by weight, and dispersed by a roll mill to a particle size of 20 μm or less, into which trioctyl trimellitate 5
Parts by weight and 0.1 parts by weight of trimethylolpropane tolylene diisocyanate were added and stirred to prepare a composition for an adhesive layer.

Preparation of Rust-Preventive Film The pressure-sensitive adhesive layer composition obtained above was treated with an OP coated with a release agent.
Apply on a P film with a reverse coater, 100
After drying at a temperature of 2 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 80 μm, the pressure-sensitive adhesive was transferred to a vinyl chloride resin film (Artit C-200, 150 μm, manufactured by Nippon Paint Co., Ltd.) by a transfer method, and aged at room temperature for 1 week. did. Thereafter, the film was cut into a width of 30 mm to prepare a rustproof film.

Affixing to Wired Glass Plate The release paper of the rust-preventive film obtained above was peeled off and applied to the peripheral end surface of the glass plate with a thickness of 5 mm, which was folded by hand and brought into close contact with and pressed. Affixed.

Rust prevention performance test (1) Salt spray test According to the salt spray test of JIS Z 2371, the specimen was exposed to a tank under the following salt spray conditions to accelerate rust generation.
The length of rust generation (mm) was measured. The test sample was 145
X 145 mm (48 exposed lines). The temperature in the bath is
The temperature was 35 ± 2 ° C., the humidity was 95 to 98% (relative humidity), and the salt concentration was 5 ± 1% (weight ratio). Evaluation was made according to the following criteria. ：: No rust is formed at all. ：: Rust is formed on the peripheral end surface, but there is no progress of rust to the inside. △: Progress of rust to the inside is less than 10 mm from the peripheral end. Progress is more than 10mm from the peripheral edge

(2) Corrosion Cycle Test A salt spray test according to JIS Z 2371 was performed for 2 hours, and then dried in a greenhouse at 60 ° C. for 2 hours. afterwards,
It was left for 4 hours in a 50 ° C., 95% wet box. This series of tests was defined as one cycle, and a cycle test was performed. Evaluation was made according to the following criteria. ：: No rust is formed at all. ：: Rust is formed on the peripheral end surface, but there is no progress of rust to the inside. △: Progress of rust to the inside is less than 10 mm from the peripheral end. Progress is more than 10mm from the peripheral edge

The results are shown in Table 1. Examples 2 to 14, Comparative Examples 1 to 5 Example 1 except that the composition was changed as shown in Table 1.
A rust-preventive film was prepared in the same manner as described above, and evaluated similarly.
The results are shown in Table 1.

COMPARATIVE EXAMPLE 6 A butyl rubber tape (Sekai Chosha) formed by laminating an amylnium foil (0.025 mm thick), butyl rubber (0.65 mm thick), and a polyester film (0.025 mm thick) as release paper (Trade name: Pebsheet) was used as a rust preventive film and tested and evaluated in the same manner as in Example 1.

Comparative Example 7 Synthetic oil (manufactured by Mobil Sekiyu KK, trade name: Metal Guard # 83)
1) was applied to the end face of a glass plate with a wire by brushing and left for 24 hours. This was tested and evaluated in the same manner as in Example 1.

Each symbol in Table 1 has the following meaning. Ac: Acrylic ester polymer used in Example 1 Gu: Rubber-based adhesive Zn: Zinc chromate (Zincro C) Ar: Arterit C-200 CF: Arterit CF-400 (PVdF film) Pd: Basic lead sulfate (Basic lead sulfate ML, manufactured by Sakai Chemical Industry Co., Ltd.) Pv: Phosphorus-vanadic acid (L-vanadic acid F-121.
(Nippon Paint Co., Ltd.) (a): Adhesive strength tends to be slightly lower (b): Adhesive tends to protrude slightly. (c): The dispersibility of the pressure-sensitive adhesive layer is poor. (d): Adhesive strength is insufficient. (e): The adhesive has protruded. (f): The entire film is stiff and has gaps. (g): It takes time to dry the film. (h): Oil is flowing out of the periphery.

The rubber-based pressure-sensitive adhesive represented by "Gu" is 100 parts by weight of natural rubber (trade name: SMR, manufactured by Kashosha) and petroleum resin (trade name: Clayton D-100; manufactured by Zeon Corporation) ) 80 parts by weight, a softener (trade name: Polybutene H)
V-300. 10 parts by weight, manufactured by Nippon Oil Co., Ltd., an antioxidant (trade name: Irganox 1010, manufactured by Ciba Geigy)
It has a composition of 2 parts by weight.

[0040]

[Table 1]

[0041]

The rust-preventive film of the present invention has the above-mentioned structure, and therefore has excellent barrier properties against oxygen and water by the adhesive,
In addition, since the effect of promoting the passivation of the wire by the rust preventive pigment is exhibited, an extremely excellent peripheral end rust preventive function can be exhibited.

[Brief description of the drawings]

FIG. 1 is a schematic perspective view of a glass plate with a wire.

[Explanation of symbols]

 1 Wired glass plate 2 Wire 3 Wire protruding at the peripheral end

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Keikichi Nishimaki 1-3-2 Shibaura, Minato-ku, Tokyo Shimizu Corporation Inside (72) Inventor Koichi Kimura 19-17 Ikedanakacho, Neyagawa-shi, Osaka Nippon Paint Inside the corporation

Claims (4)

[Claims] 1. A rust-preventive film which gives a rust-preventive effect to a wire-containing glass plate by being attached to a peripheral edge of the wire-containing glass plate, wherein the rust-preventive film has an adhesive layer on one surface of a main layer. The rust-preventive film, wherein the pressure-sensitive adhesive layer contains a rust-preventive pigment in a solid content ratio of 1 to 50% by weight. 2. The rust-preventive film according to claim 1, wherein the pressure-sensitive adhesive layer has a thickness of 5 to 200 μm. 3. The rust preventive pigment is at least one selected from the group consisting of chromic rust preventive pigments, phosphorus / vanadate rust preventive pigments, lead rust preventive pigments, and zinc rust preventive pigments. The rust preventive film according to claim 1 or 2. 4. A glass plate with a wire, wherein the rust-preventive film according to claim 1, 2 or 3 is adhered to a peripheral end.