JP2000079660A - Class scatter preventive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent weather resistance and glass scatter preventive effect and to further prevent a paste from remaining on a surface of a glass plate in the case of peeling a glass scatter preventive film from the surface of the plate after the film is adhered for a long period by providing a polyester pressure sensitive adhesive layer on one surface of a base material film. SOLUTION: A base material film made of a polyethylene terephthalate resin film is coated on its one surface with a polyester pressure sensitive adhesive, and dried. Then, a polyester pressure sensitive adhesive layer is coated with a peel sheet made of polyethylene terephthalate. Here, an adhesive force of the adhesive layer to glass is about 500g/25 mm or more, and a holding force of the layer to the glass is about 70,000 sec or more. Thus, excellent weather resistance and glass scatter preventive effect can be provided. In the case of peeling the film from a surface of a glass plate after the film is adhered to the surface of the plate for a long period, a paste can be prevented from remaining on the surface of the plate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in weather resistance and glass scattering prevention effect. Further, after the glass surface is adhered to the glass surface for a long period of time, when the glass surface is peeled off from the glass surface due to a request such as replacement, etc. The present invention relates to a glass shatterproof film capable of preventing adhesive residue.

[0002]

2. Description of the Related Art Glass sheets such as window glass of buildings are designed to prevent broken glass from scattering in order to prevent glass scattering in the event of an earthquake and to prevent glass scattering in the event of an object collision. In addition, a film for preventing scattering is attached to the surface of a glass plate. Conventionally, as a glass shatterproof film, a film in which an acrylic pressure-sensitive adhesive layer is provided on one side of a base film is known. However, since this glass shatterproof film is provided with an acrylic pressure-sensitive adhesive layer, the glass shatterproof film stuck on the surface of the glass plate is peeled off,
There is a problem that the acrylic pressure-sensitive adhesive remains. As described above, when the adhesive residue is present on the surface of the glass plate, there is a disadvantage that when another glass shatterproof film is stuck to that location, it cannot be stuck neatly. In addition, in order to paste the glass sheet neatly, it is necessary to remove the acrylic pressure-sensitive adhesive remaining on the surface of the glass plate, which is inefficient in replacing the glass shatterproof film. Furthermore, in order to remove the acrylic pressure-sensitive adhesive remaining on the surface of the glass plate, it is effective to wash with a solvent.However, since the solvent has a bad effect on the rubber of the window frame, washing with the solvent should be avoided as much as possible. There is a demand of workers who want to.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and has excellent weather resistance and glass scattering prevention effects. It is an object of the present invention to provide a glass scattering prevention film that can prevent adhesive residue on a glass plate surface when peeled from the glass plate surface.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have found that a glass shatterproof film having a polyester-based pressure-sensitive adhesive layer provided on one surface of a base film. The present inventors have found that the above-mentioned object can be achieved, and have completed the present invention based on this finding.

That is, the present invention provides a glass shatterproof film characterized in that a polyester-based pressure-sensitive adhesive layer is provided on one side of a substrate film. Further, the present invention provides the above-mentioned glass shatterproof film, wherein the adhesive force of the polyester-based pressure-sensitive adhesive layer is 500 g.
An object of the present invention is to provide a glass shatterproof film having a thickness of at least / 25 mm and a holding force of at least 70000 seconds. Further, the present invention provides a glass shatterproof film in which the dynamic storage elastic modulus at 23 ° C. of the polyester-based pressure-sensitive adhesive layer in the steam glass shatterproof film is 5 × 10 ⁶ dyne / cm ² or more. . Hereinafter, the present invention will be described in detail.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, examples of the base film include polyolefin resins such as polyethylene resin and polypropylene resin, polyester resins such as polybutylene terephthalate resin and polyethylene terephthalate resin, acetate resins, polystyrene resins, and vinyl chloride resins. And plastic films. Of these, a polyester resin film is preferable, and a polyethylene terephthalate resin film is particularly preferable. The base film may be composed of only one layer, or may have a multilayer structure of two or more layers. Further, the base film may be unstretched, or may be stretched in a uniaxial direction or a biaxial direction such as a vertical or horizontal direction. The thickness of the substrate film is not particularly limited, but is usually 30 to 200 μm, and preferably 50 to 100 μm. The substrate film may be colored or colorless and transparent. Further, the substrate film may have a high light transmittance or a low light transmittance.

In the present invention, a polyester-based pressure-sensitive adhesive layer is provided on one side of a base film, and a metal sputter layer or the like is provided between one side of the base film and the polyester-based pressure-sensitive adhesive layer. A thin film or the like may be provided. The adhesive strength of the polyester-based pressure-sensitive adhesive layer to glass in the present invention is preferably 500 g / 25 mm or more, particularly preferably 1000 g / 25 mm or more in order to prevent the glass from scattering. The upper limit of the adhesive force of the polyester-based pressure-sensitive adhesive layer is
There is no particular limitation as long as it can be removed from the glass surface,
It is preferably at most 3000 g / 25 mm, particularly preferably at most 2500 g / 25 mm. The holding power of the polyester-based pressure-sensitive adhesive layer to glass in the present invention is preferably 70,000 seconds or more. The polyester pressure-sensitive adhesive layer has a ball tack of 5%.
The following is preferred. Immediately after the polyester-based pressure-sensitive adhesive layer is attached to the surface of the glass plate, it is easily peeled off from the glass plate, and after 1-2 minutes, it adheres strongly. Also,
In the present invention, the polyester-based pressure-sensitive adhesive layer 2
Dynamic storage elastic modulus at 3 ° C. is 5 × 10 ⁶ dyne / c
m ² or more, and particularly preferably 1 × 1
0 ⁷ is ^{~3 × 10 7 dyne / cm 2} . When the dynamic storage elastic modulus at 23 ° C. of the polyester pressure-sensitive adhesive layer is less than 5 × 10 ⁶ dyne / cm ² , the polyester pressure-sensitive adhesive may remain on the glass when the glass shatterproof film is peeled off the glass. There is.

The polyester-based pressure-sensitive adhesive used in the polyester-based pressure-sensitive adhesive layer has a polyester resin as a resin component. The polyester resin of the polyester-based pressure-sensitive adhesive is produced by polycondensation of an acid component and a diol component. Examples of the acid component include an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, and a combination of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid is preferable. When the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid are combined, the ratio of the aliphatic dicarboxylic acid to the aromatic dicarboxylic acid is 5:95 to 5 by weight.
A range of 0:50 is preferred. Examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, azelaic acid, decane-1,10 dicarboxylic acid, and the like.
Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, diphenyldicarboxylic acid, and the like. Is mentioned. Examples of the diol component include an aliphatic diol and an aromatic diol, and an aliphatic diol is preferable. One kind of aliphatic diol may be used, but two or more kinds are preferable, and
A combination of species is preferred. Examples of the aliphatic diol include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol,
Hexamethylene glycol, dodecamethylene glycol, neopentyl glycol and the like can be mentioned.

In the polyester-based pressure-sensitive adhesive, a crosslinking agent may be added to a polyester resin as a resin component. As the crosslinking agent, an isocyanate-based crosslinking agent is preferable. The isocyanate-based crosslinking agent is a polyisocyanate compound having two or more isocyanate groups per molecule, for example, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate, Lysine methyl ester diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, biphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, methylene bis (phenyl isocyanate), bis (isocyanate ethyl) fumarate, isophorone diisocyanate, methylcyclohexyl Diisocyanate, 2-isocyanateethyl-
2,6-diisocyanate hexanoate and the like can be mentioned. In addition, modified isocyanates, for example, trifunctional or higher polyfunctional isocyanate compounds such as isocyanurate type and urethane type can also be used. The amount of the crosslinking agent is preferably from 1 to 20 parts by weight, particularly preferably from 2 to 10 parts by weight, based on 100 parts by weight of the polyester resin.

[0010] Further, polyester-based pressure-sensitive adhesives include:
One or more of various additives can be included. Examples of the additives include dyes, pigments, fillers, antioxidants, and ultraviolet absorbers. Examples of the filler include zinc white, titanium oxide, silica, calcium carbonate, barium sulfate, and the like. Examples of the antioxidant include anilide-based, phenol-based, phosphite-based, and thioester-based. Examples of the ultraviolet absorber include a benzophenone type and a benzotriazole type.
The thickness of the polyester-based pressure-sensitive adhesive layer is not particularly limited, but is usually 5 to 40 μm, preferably 10 to 30 μm.
m.

The surface of the polyester-based pressure-sensitive adhesive layer of the glass shatterproof film of the present invention can be covered with a release sheet. The release sheet is made of a support substrate having at least one surface having releasability, and is usually a substrate obtained by treating the support substrate with a release agent. Examples of the support substrate include paper, synthetic paper, and plastic film.
Examples of the paper include glassine paper, polyethylene laminated paper, and the like.As the plastic film,
For example, polyethylene resin, polyolefin resin such as polypropylene resin, polybutylene terephthalate resin,
Polyester resin such as polyethylene terephthalate resin, acetate resin, polystyrene resin, plastic film such as vinyl chloride resin and the like,
It is not limited to these.

Examples of the release treatment agent used for the release sheet include a silicone resin, an alkyd resin, a fluororesin, and a long-chain alkyl-containing resin. The thickness of the release sheet is not particularly limited, and may be appropriately selected. The method for producing the glass shatterproof film of the present invention can be carried out by various methods. As a preferred example, the polyester-based pressure-sensitive adhesive is dissolved in a solvent such as ethyl acetate, toluene, methyl ethyl ketone, and the like. A method in which a polyester-based pressure-sensitive adhesive layer is formed by coating and drying on a material sheet, and a release sheet is laminated on the polyester-based pressure-sensitive adhesive layer. The glass shatterproof film of the present invention can be used for various applications, but it is particularly useful to use it for window glasses of buildings.

[0013]

Next, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples. The adhesive force measurement test, the holding force measurement test, the weather resistance test of the glass shatterproof film, the glass shatterproof performance test, the ball tack measurement test and the dynamic viscoelasticity test of the examples and comparative examples were performed according to the following methods. . (1) Adhesive force measurement test: The adhesive force of the glass shatterproof film was measured according to JIS Z02377.8.3.1. However, a glass plate was used as the test plate. (2) Holding force measurement test: The holding force of the glass shatterproof film was measured according to JIS Z0237.11. (3) Weather resistance test: A glass shatterproof film was affixed to a glass plate, and a sunshine carbon accelerated weather resistance tester was used.
An accelerated weathering test was performed. The test conditions were a temperature of 63 ° C., a relative humidity of 50%, and a continuous irradiation of 1000 hours. After the test,
The adhesive strength of the glass shatterproof film was measured, and the presence or absence of glue residue was visually observed.

(4) Glass scattering prevention performance test: JIS
A5759 (1996) 6.6.2. Width 914mm, length 1219mm, thickness 5mm
A glass shatterproof film having a width of 910 mm and a length of 1215 mm was stuck to the sheet glass at a distance of about 2 mm from the edge of the sheet glass to prepare a sheet glass stuck with the glass shatterproof film, and allowed to stand at room temperature for 4 days.

Next, the glass sheet with the glass shatterproof film attached thereto was attached to a tester, and an in-plane shear change was applied. At the end of the above method, the amount of glass scattered from the test piece is measured. The percentage of the amount of glass scattered with respect to the total amount of glass of the test piece before the test was calculated by the following formula, and the glass scattering prevention ratio (A) was obtained. The test was performed four times, and the average value was obtained. A = (1−W / W ₀ ) × 100 (In the above formula, A is the glass scattering prevention rate (%), W ₀
Represents the mass (g) of the test piece before the test, and W represents the mass (g) of the test piece from which the glass plate was broken after the test and the scattered glass was removed. (5) Ball tack measurement test: The ball tack of the glass shatterproof film was measured according to JIS Z0237.12. The inclination angle of the inclined plate is 30 degrees, and the measurement temperature is 2
3 ° C., the unit is 1/32 inch. (6) Dynamic viscoelasticity measurement test: The temperature dependence (measurement frequency: 1 Hz) was measured by a torsional shear method using a measuring device of a dynamic spectrum meter RDS (II) (manufactured by Rheometrics), and 23 The dynamic storage modulus at ℃ was obtained.

Example 1 A phthalic polyester resin (manufactured by Dainichi Seika Kogyo Co., Ltd.)
Seikabond E-295, nonvolatile content 60% by weight) 100
A polyester-based pressure-sensitive adhesive obtained by mixing 5 parts by weight of an isocyanate-based cross-linking agent (manufactured by Dainichi Seika Kogyo Co., Ltd., Seikabond C-75N, non-volatile content 75% by weight) with respect to parts by weight (solid content) On one side of a base film made of a transparent polyethylene terephthalate resin film of 50 μm,
Coating and drying were performed so that the thickness of the dried adhesive layer was 20 μm. Next, the adhesive layer was covered with a release sheet made of polyethylene terephthalate having a thickness of 38 μm to prepare a glass shatterproof film. The initial adhesive strength of the polyester pressure-sensitive adhesive layer was 1500 g / 25 mm.

Example 2 Phthalic acid-based polyester resin (manufactured by Dainichi Seika Kogyo Co., Ltd.)
Seika Bond E-263, nonvolatile content 60% by weight) 100
A polyester-based pressure-sensitive adhesive obtained by mixing 5 parts by weight of an isocyanate-based cross-linking agent (manufactured by Dainichi Seika Kogyo Co., Ltd., Seika Bond C-75N, non-volatile content 75% by weight) with respect to parts by weight (solid content) It was applied to a base film made of a transparent polyethylene terephthalate resin film having a thickness of 50 μm and dried so that the thickness of the adhesive layer after drying was 20 μm. Next, the adhesive layer was covered with a release sheet made of polyethylene terephthalate having a thickness of 38 μm to prepare a glass shatterproof film. The initial adhesive strength of the polyester-based pressure-sensitive adhesive layer was 550 g / 25 mm.

Comparative Example 1 In Example 1, a substrate film coated with an acrylic pressure-sensitive adhesive (Lumitech Co., Ltd., 1501 UH) was used in place of the substrate film coated with the polyester-based pressure-sensitive adhesive. A glass shatterproof film was prepared in the same manner as in Example 1 except for the above.

The above-mentioned tests were conducted on the glass shatterproof films of the above Examples and Comparative Examples, and the results are shown in Table 1.

[0020]

[Table 1]

[0021]

The glass shatterproof film of the present invention is excellent in weather resistance and glass shatterproof effect. Further, when the glass shatterproof film is peeled off from the glass plate surface after being adhered to the glass plate surface for a long period of time, the adhesive on the glass plate surface is removed. The rest can be prevented.

Claims (3)

[Claims] 1. A glass shatterproof film characterized in that a polyester-based pressure-sensitive adhesive layer is provided on one side of a substrate film. 2. The glass shatterproof film according to claim 1, wherein the polyester-based pressure-sensitive adhesive layer has an adhesion to glass of 500 g / 25 mm or more and a holding force of 70,000 seconds or more. 3. The polyester-based pressure-sensitive adhesive layer has a temperature of 23 ° C.
Has a dynamic storage modulus of 5 × 10 ⁶ dyne / cm ²
The glass shatterproof film according to claim 1 or 2, which is the above.