KR100334551B1 - glass anti-scattering film - Google Patents

Abstract

An object of the present invention is to provide a glass shatterproof film which is excellent in scattering prevention effect of weather resistant glass and which can prevent looseness of the glass plate surface when detached from the glass plate surface after sticking to the surface of the glass plate for a long time. As a solution, an acid component and a diol component composed of aliphatic dicarboxylic acid and aromatic dicarboxylic acid on one side of a base film made of a plastic film selected from the group consisting of polyolefin resin, polyester resin, acetate resin, polystyrene resin and vinyl chloride resin. It is characterized by forming a polyester pressure-sensitive adhesive layer prepared from a polyester resin obtained by polycondensation.

Description

Glass anti-scattering film

The present invention is excellent in weather resistance and anti-scattering effect of the glass, and prevents the glass surface from loosening when detached from the glass surface by re-sticking or the like after sticking to the glass surface for a long time. It is about a film.

Glass plates, such as window glass of buildings, are provided with shatterproof films on the surface of glass plates for the purpose of preventing the shattering of broken glass in the event of an earthquake or preventing the shattering of glass when an object collides. Work is being done.

Conventionally, as a glass scattering prevention film, what formed the acryl-type pressure sensitive adhesive layer in the single side | surface of a base film is known.

However, this glass scattering prevention film has a problem that an acrylic pressure-sensitive adhesive remains after the acrylic pressure-sensitive adhesive layer is formed, and the glass scattering prevention film adhered to the glass plate surface is removed. In this way, if the solution is present on the surface of the glass plate, there is a drawback that if another glass shatterproof film is attached to the place, the glue cannot be pasted cleanly. In addition, when it sticks neatly, the operation | work which removes the acryl-type pressure sensitive adhesive which remained on the glass plate surface is needed, and it is inefficient in the reattachment of a glass shatterproof film. In addition, in order to remove the acrylic pressure-sensitive adhesive remaining on the surface of the glass plate, it is efficient to wash with a solvent, but since the solvent adversely affects the rubber of the window frame, it is difficult to clean the surface of the worker. I have a request.

This invention is made in view of the said prior art situation, and is excellent in weather resistance and the scattering prevention effect of glass, and when sticking to the surface of a glass plate for a long time, when peeling from a glass plate surface, it can prevent the looseness of the glass plate surface. An object of the present invention is to provide a glass scattering prevention film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the said subject can be achieved by the glass shatterproof film which provided the polyester-type pressure-sensitive adhesive layer on the single side | surface of a base film, and this knowledge. Based on this, the present invention has been completed.

That is, the present invention, the acid component and diol component consisting of aliphatic dicarboxylic acid and aromatic dicarboxylic acid on one side of the base film consisting of a plastic film selected from the group consisting of polyolefin resin, polyester resin, acetate resin, polystyrene resin and vinyl chloride resin A polyester-based pressure-sensitive adhesive layer prepared from a polyester resin obtained by polycondensation is to provide a glass scattering prevention film.

Moreover, this invention provides the glass shatterproof film whose adhesive force of the polyester-type pressure-sensitive adhesive layer in the said glass shatterproof film is 500-3000g / 25mm.

The present invention also provides a glass scattering prevention film having a dynamic storage modulus at 23 ° C. of a polyester-based pressure-sensitive adhesive layer in a vapor glass scattering prevention film at 5 × 10 ⁶ to 3 × 10 ⁷ dyne / cm 2. It is.

Hereinafter, the present invention will be described in detail.

In the present invention, the base film is, for example, a polyolefin resin such as polyethylene resin, polypropylene resin, polybutylene terephthalate resin, polyester resin such as polyethylene terephthalate resin, acetate resin, polystyrene resin, vinyl chloride resin, or the like. The plastic film etc. are mentioned. Among these, polyester resin films are preferable, and polyethylene terephthalate resin films are particularly preferable. The base film may be comprised only by one layer, and may be a multilayered structure of two or more layers. Moreover, unstretched may be sufficient as a base film, and it may be extended | stretched to the uniaxial direction or biaxial direction, such as a longitudinal or a horizontal.

Although the thickness of a base film is not specifically limited, Usually, it is 30-200 micrometers, Preferably it is 50-100 micrometers.

The base film may be colored or may be colorless and transparent. Moreover, a base film may be a thing with high light transmittance, and a thing with low light transmittance may be sufficient as it.

In the present invention, a polyester pressure-sensitive adhesive layer is formed on one side of the base film, but a metal thin film such as a metal sputter layer may be formed between one side of the base film and the polyester pressure-sensitive adhesive layer.

It is preferable that adhesive force is 500 g / 25 mm or more, and, as for the adhesive force with respect to the glass of the polyester-type pressure-sensitive adhesive bond layer in this invention, it is 1000 g / 25 mm or more especially. The upper limit of the adhesive force of the polyester-based pressure-sensitive adhesive layer is not particularly limited as long as it can be removed from the glass surface, but is preferably 3000 g / 25 mm or less, and particularly preferably 2500 g / 25 mm or less.

It is preferable that the holding force with respect to the glass of the polyester-type pressure sensitive adhesive bond layer in this invention is 70000 second or more.

Moreover, it is preferable that balltack of this polyester-type pressure-sensitive adhesive layer is 5 or less.

Immediately after attaching this polyester pressure-sensitive adhesive layer to the glass plate surface, it is easy to remove from the glass plate, and strongly adheres after 1 to 2 minutes.

Moreover, in this invention, it is preferable that the dynamic storage elastic modulus in 23 degreeC of a polyester-type pressure-sensitive adhesive layer is 5x10 <^6> dyne / cm <2> or more, Especially preferably, it is 1x10 <^7> -3 * 10 <^7> dyne / Cm 2. If the dynamic storage modulus at 23 ° C. of the polyester-based pressure-sensitive adhesive layer is less than 5 × 10 ⁶ dyne / cm 2, the polyester-based pressure-sensitive adhesive may remain on the glass when the glass scattering prevention film is peeled from the glass. .

The polyester pressure-sensitive adhesive used in the polyester pressure-sensitive adhesive layer has a polyester resin as the resin component.

The polyester resin of a polyester pressure sensitive adhesive is manufactured by polycondensation of an acid component and a diol component. As an acid component, although aliphatic dicarboxylic acid and aromatic dicarboxylic acid are mentioned, the combination of aliphatic dicarboxylic acid and aromatic dicarboxylic acid is preferable. When combining aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the ratio of aliphatic dicarboxylic acid and aromatic dicarboxylic acid has the preferable weight ratio of the range of 5: 95-50: 50. As aliphatic dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, decane-1, 10 dicarboxylic acid, etc. are mentioned, for example. As aromatic dicarboxylic acid, For example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, diphenyl ether-4,4'- dicarboxylic acid, diphenyl dicarboxylic acid Etc. can be mentioned. As a diol component, although an aliphatic diol and an aromatic diol are mentioned, an aliphatic diol is preferable, for example. Although an aliphatic diol may be 1 type, 2 or more types are preferable and 2-4 types of combination is especially preferable. Examples of the aliphatic diols include ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hexamethylene glycol, dodecamethylene glycol and neopentyl glycol. Etc. can be mentioned.

You may add a crosslinking agent to the polyester resin as a resin component to a polyester pressure-sensitive adhesive agent. As a crosslinking agent, an isocyanate type crosslinking agent is preferable. Isocyanate type crosslinking agent is a polyisocyanate compound which has 2 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-isocyanate ethyl-2,6- diisocyanate hexanoate, etc. are mentioned. Moreover, modified | denatured products of these isocyanates, for example, an isocyanurate type, a urethane type, etc. can also use a trifunctional or more than trifunctional isocyanate compound. 1-20 weight part is preferable with respect to 100 weight part of polyester resins, and, as for the quantity of a crosslinking agent, 2-10 weight part is especially preferable.

In addition, the polyester-based pressure-sensitive adhesive can be contained one or more of various additives. As an additive, dye, a pigment, a filler, antioxidant, a ultraviolet absorber, etc. are mentioned, for example. Examples of the filler include zinc oxide, titanium oxide, silica, calcium carbonate and barium sulfate. Examples of the antioxidants include anilide series, phenol series, phosphite series, thioester series, and the like. As a ultraviolet absorber, a benzophenone series, a benzotriazole system, etc. are mentioned.

The thickness of the polyester-based pressure-sensitive adhesive layer is not particularly limited, but is usually 5 to 40 µm, and preferably 10 to 30 µm.

The surface of the polyester pressure sensitive adhesive layer of the glass scattering prevention film of this invention can be coat | covered with a peeling sheet.

At least one surface of the release sheet is made of a support substrate having peelability, and is usually treated with a release treatment agent on the support substrate.

As a base material, paper, synthetic paper, a plastic film, etc. are mentioned, for example. Examples of the paper include glassine paper and polyethylene laminate paper. Examples of the plastic film include polyolefin resins such as polyethylene resin and polypropylene resin, polybutylene terephthalate resin, and polyethylene terephthalate resin. Plastic films such as ester resins, acetate resins, polystyrene resins, vinyl chloride resins, and the like, but are not limited thereto.

As a peeling treatment agent used for a peeling sheet, a silicone resin, an alkyd resin, a fluororesin, a long chain alkyl containing resin, etc. are mentioned.

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 suitable example, the polyester-based pressure-sensitive adhesive is dissolved in a solvent such as ethyl acetate, toluene, methyl ethyl ketone, and applied on a base sheet. And drying to form a polyester pressure-sensitive adhesive layer, and a method of laminating a release sheet on the polyester pressure-sensitive adhesive layer.

Although the glass shatterproof film of this invention can be used for various uses, the use for the window glass of a building is especially useful.

Next, an Example demonstrates this invention further more concretely. In addition, this invention is not restrict | limited at all by these.

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 test measurement and the dynamic viscoelasticity test of the Examples and Comparative Examples were carried out in accordance with the following methods.

(1) Adhesive force measurement test: The adhesive force of the glass shatterproof film was measured in accordance with JIS Z0237.8.3.1. However, the test plate used the glass plate.

(2) Holding force measurement test: The holding force of the glass shatterproof film was performed in accordance with JIS Z0237.11.

(3) Weather resistance test: The glass shatterproof film was stuck to the glass plate, and the accelerated weather test was done by the sunshine carbon accelerated weather resistance tester. The test conditions were 63 degreeC of temperature, 50 relative humidity, and 1000 hours of continuous irradiation. After the test, the adhesive force of the glass shatterproof film was measured, and the presence or absence of pooling was visually observed.

(4) Glass scattering prevention performance test: It was carried out in accordance with JIS A5759 (1996) 6.6.2.

A glass shatterproof film with a glass shatterproof film is prepared by attaching a glass shatterproof film 910 mm wide and 1215 mm long to the plate glass having a width of 914 mm, a length of 1219 mm, and a thickness of 5 mm with a gap of about 2 mm from the edge of the plate glass. Left at room temperature for 4 days.

Next, the glass plate with a glass shatterproof film was attached to the tester, and the in-plane shearing change was applied.

At the end of performing the method, the amount of glass scattered from the test piece is measured. The percentage of the glass amount scattered with respect to the total glass amount of the test piece before a test was computed by following Formula, and the glass scattering prevention rate (A) was calculated | required. In addition, the test was done 4 times and the average value was calculated | required.

A = (1-W / W _O ) × 100

Where A is the glass scattering prevention rate (%), W _O is the mass of the test piece before the test (g), and W is the weight of the test piece after the glass plate is broken and the scattered glass is removed after the test. .)

(5) Balltack measurement test: The balltack of the glass shatterproof film was measured in accordance with JIS Z0237.12. The inclination angle of the inclined plate is 30 °, the measurement temperature is 23 ° C, and the unit is 1/32 inches.

(6) Dynamic viscoelasticity measurement test: The temperature dependence (measurement frequency: 1 Hz) is measured by a torsional shear method using a measuring device of a dynamic spectrum meter RDS (II) (manufactured by Leo Matrix). The dynamic storage modulus at 23 ° C. was obtained.

(Example 1)

Isocyanate type crosslinking agent (Dainichi Seika Co., Ltd. product) with respect to 100 weight part (solid content) of a phthalic-acid polyester resin (made by Daiichi Seika Co., Ltd., Seikabond E-295, non volatile matter 60 weight), Seika Bond C-75 N, non-volatile content 75 weight) On the one side of the base film made of a transparent polyethylene terephthalate resin film having a thickness of 50㎛ polyester-based pressure-sensitive adhesive mixed with 5 parts by weight, the thickness of the adhesive layer after drying The coatings were dried to a thickness of 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 scattering prevention film. The initial adhesive force of the polyester pressure-sensitive adhesive layer was 1500 g / 25 mm.

(Example 2)

Isocyanate type crosslinking agent (Dainichi Seika Co., Ltd. product) with respect to 100 weight part (solid content) of a phthalic-acid polyester resin (made by Daiichi Seika Co., Ltd., Seikabond E-263, non-volatile content 60 weight), Seika Bond C-75N, non-volatile content 75 weight) The base film consisting of a transparent polyethylene terephthalate resin film having a thickness of 50㎛ thick polyester-based pressure-sensitive adhesive is mixed with 5 parts by weight, the thickness of the adhesive layer after drying is 20㎛ It applied and dried so that it might become. Next, the adhesive layer was covered with a release sheet made of polyethylene terephthalate having a thickness of 38 µm to prepare a glass scattering prevention film. The initial adhesive force of the polyester type pressure-sensitive adhesive layer was 550 g / 25 mm.

(Comparative Example 1)

In Example 1, it carried out similarly to Example 1 except having used the base film (Lintec Co., Ltd. make, Lumikul 1501UH) which apply | coated acrylic pressure sensitive adhesive instead of the base film which apply | coated polyester pressure sensitive adhesive. A glass shatterproof film was made.

About the glass scattering prevention film of the said Example and the comparative example, said test was done and the result was shown in Table 1.

Example 1 Example 2 Comparative Example 1 Initial adhesive force (g / 25㎜) 1500 550 1800 Holding force (seconds) 70000 No deviation 70000 No deviation 70000 No deviation Weather resistance Adhesion after weather resistance test (g / 25㎜) 2800 1000 2900 Solving condition after tearing off none none none Glass shatterproof rate (%) 98 98 97 Balltack Less than 2 Less than 2 9 Dynamic storage modulus (dyne / ㎠) 1.0 × 10 ⁷ 2.4 × 10 ⁷ 1.0 × 10 ⁶

The glass shatterproof film of the present invention is excellent in weather resistance and the shatterproofing effect of glass, and can be prevented from loosening of the glass plate surface when peeling from the glass plate surface after sticking to the surface of the glass plate for a long time.

Claims (3)

Obtained by polycondensation of acid and diol components consisting of aliphatic dicarboxylic acids and aromatic dicarboxylic acids on one side of a base film composed of a plastic film selected from the group consisting of polyolefin resins, polyester resins, acetate resins, polystyrene resins and vinyl chloride resins. A glass scattering prevention film, comprising forming a polyester pressure-sensitive adhesive layer prepared from a polyester resin. The glass shatterproof film according to claim 1, wherein the polyester-based pressure-sensitive adhesive layer has an adhesive strength of 500 to 3000 g / 25 mm. The glass scattering prevention film according to claim 1 or 2, wherein the dynamic storage modulus at 23 ° C. of the polyester-based pressure-sensitive adhesive layer is 5 × 10 ⁶ to 3 × 10 ⁷ dyne / cm 2.