JPH10130596A - Peelable window film for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a peelable window film for automobile, easily passable to a window, peelable without damaging or staining the window glass, reflecting ultraviolet rays and cutting visible light by forming a specific tacky adhesive layer on a surface of a substrate film. SOLUTION: This peelable film is produced by forming a peelable pasting layer 2 having low tackiness and composed of an adhesive having low tackiness such as a polyurethane-based adhesive on one surface of a substrate film 1 such as a polyester film. Preferably, an evaporated metal layer 4 is formed between the substrate film 1 and the pasting layer 2, a transparent releasing film 3 is pasted on the surface of the pasting layer 2 and a colorant and an ultraviolet absorber are preferably included in the adhesive having low tackiness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be applied to a window glass of an automobile having a smooth surface, and after being attached, is sufficiently held on the window glass of the automobile and damages the window glass. The present invention relates to a removable window film for automobiles which can be easily peeled off without being contaminated, and which can cut off ultraviolet light and visible light depending on the application.

[0002]

2. Description of the Related Art Conventionally, a window film adhered to a window glass of an automobile is a base film suitable for purposes such as fashionability, design, privacy protection, etc., and an adhesive similar to a glass shatterproof film for building materials. Was applied, and a silicone-based polyester release film was adhered thereto.

[0003]

However, since the above-mentioned window film for automobiles uses a strong adhesive, there are many failures due to sticking between the adhesive surfaces when attaching to a window. It was difficult to attach the window film to the window. In addition, once an automotive window film is adhered to a window, it is attached with a strong adhesive, and when peeled off, the automotive window film may be damaged, or the window may have adhesive residue, leaving There is a disadvantage that the window film cannot be easily replaced. Further, thinners and solvents are used to remove the adhesive residue remaining on the windows, but these may damage polyurethane leather and polyvinyl chloride leather of automobile interiors. The present invention
When affixing to the window of an automobile, even if the adhesive surfaces are adhered to each other, it can be peeled off, and it is easy to attach the automotive window film to the window. It is an object of the present invention to provide a removable window film for automobiles, which can maintain the adhesion to the window glass and can be easily removed without damaging or contaminating the window glass.
Another object of the present invention is to provide a method for attaching an automobile window film to an automobile window easily.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, by forming an adhesive layer comprising a low-adhesive agent on one surface of a substrate film, Finding that the above tasks can be achieved,
Based on this finding, the present invention has been completed.

[0005] That is, the present invention provides a removable window film for automobiles, characterized in that a releasable and low-adhesive adhesive layer comprising a low-adhesive agent is formed on one surface of a substrate film. Is provided. Hereinafter, the present invention will be described in detail.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive layer in the automotive removable window film of the present invention comprises a low tackiness agent.
Examples of the low tackiness agent include polyurethane-based low tackiness agents. As a polyurethane-based low tack agent,
An example is a polyurethane elastomer. The polyurethane elastomer is composed of a soft segment having a long-chain polyol as a main component, and a hard segment composed of a diisocyanate and a chain extender.As the long-chain polyol, polyester polyol and polyether polyol are mainly used, As diisocyanates, TDI (tolylene diisocyanate), Pure M
DI (diphenylmethane diisocyanate), HDI
(Hexamethylene diisocyanate) and the like. As the chain extender, a low molecular weight polyhydric alcohol, an aromatic diamine, or the like is used. Examples of the polyurethane elastomer include a one-pack type obtained by diluting a long-chain polyol and a thermoplastic polyurethane elastomer obtained by polymerizing a diisocyanate such as TDI or MDI with an organic solvent, or a polyurethane elastomer or its prepolymer and a polyisocyanate. For example, a two-pack type one in which a crosslinking agent such as the above is added and cured later. The polyisocyanate used for the crosslinking agent is, in terms of weather resistance,
Aliphatic or cycloaliphatic polyisocyanates are preferred. It is preferable to add a crosslinking accelerator to the two-pack type. In addition, a moisture-curable or hot-melt extrusion-type hot-melt polyurethane elastomer which reacts isocyanate with moisture in the air may be used.

Other polyurethane-based low tackifiers include terminal isocyanate groups obtained by reacting one or more polyol mixtures having an average functional group number of 2 to 2.6 with an excess of organic diisocyanate. A prepolymer having an average number of functional groups of 2 or more, and a polyol mixture of one or more polyols whose sum with the average number of functional groups of the polyol mixture as a component of the prepolymer is not more than 4 and not more than 5 and NCO / OH equivalent ratio of 0.65
Polyurethane obtained by reacting at 1.15. In this polyurethane, as the polyol of the polyol mixture, propylene glycol, ethylene glycol or those obtained by addition polymerization of propylene oxide or ethylene oxide or both thereof, polyether diols such as polytetramethylene ether glycol, ethylene glycol, propylene Glycol, polyester glycol, glycerin, trimethylolpropane, pentaerythritol obtained by dehydration condensation from a low molecular weight glycol such as 1,4-butanediol and an organic acid such as adipic acid and phthalic acid;
Examples thereof include arabitol, sorbitol, and those obtained by subjecting propylene oxide or ethylene oxide or both to addition polymerization using these as an initiator.
Polymer polyols obtained by polymerizing olefin monomers such as acrylonitrile and styrene in these polyols can also be used. Examples of the organic diisocyanate include 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate or a mixture thereof, crude toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and polymethylene polyisocyanate. Fatty acids such as aromatic diisocyanates such as phenyl polyisocyanate and 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene bis (cyclohexyl isocyanate) and xylylene diisocyanate Group or alicyclic diisocyanates and dimers, trimers, modified carbodiimides thereof, and the like.
From the viewpoint of weather resistance, an aliphatic or alicyclic diisocyanate is preferred.

Further, other polyurethane-based low tackifiers do not contain a polar group in the skeleton, have a hydroxyl group at a molecular terminal, and have a number average molecular weight of 500 to 5
Examples of the polyurethane include a low-molecular-weight polyolefin-based polyol having 1.5 to 8 hydroxyl groups per 000 molecule and a polyurethane containing a polyisocyanate compound as an essential component.
As the polyisocyanate compound used here,
The same as the above-mentioned thing is mentioned. The low viscosity agent is
One type or a combination of two or more types can be used. In the present invention, the low tackiness is preferably 1 to 5
It means a peeling force of 0 g / 25 mm.

In the present invention, a coloring agent may be contained in the low tackiness agent. As the colorant, a known colorant such as a dye or a pigment is used. Specifically, phthalocyanine type, azo type, condensed azo type, azo lake type, Hansa type, benzimidazolone type, anthraquinone type, diallylide type, perylene type, perinone type, indigo type,
Thioindigo-based, isoindolinone-based, azomethineazo-based, dioxazine-based, quinacridone-based, aniline black-based, triphenylmethane-based, carbon black-based, methine-based, quinophthalone-based, organic pigments or dyes such as anthrapyridone-based zinc, lead, Titanium, antimony, cadmium, iron, arsenic, magnesium, aluminum, cobalt, chromium and other oxides, sulfides and sulfates, and inorganic pigments such as metal powders. Specific examples of the inorganic pigments include titanium oxide. System, iron oxide system, iron hydroxide system,
Examples thereof include a chromium oxide type, a spinel type firing type, a chromic acid type, a chromium vermilion type, a navy blue type, an aluminum powder type, and a bronze powder type. In particular, when a clear color tone and high transparency are required, anthraquinone-based, indigoid-based, and diazo-based dyes and pigments are used. When weather resistance is required, oxides such as zinc, lead, titanium, antimony, cadmium, iron, arsenic, magnesium, aluminum, cobalt and chromium, sulfides and sulfates are used. The colorant preferably allows only an arbitrary color to pass therethrough, and particularly preferably allows the colorant to pass only blue, brown and gold colors. The content of the coloring agent may be appropriately selected depending on the required degree of coloring.

In the present invention, the low tackiness agent may contain an ultraviolet absorber. As an ultraviolet absorber,
For example, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone,
Benzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane, phenyl salicylate, p-tert-butylphenyl salicylate, p- Salicylic acid-based ultraviolet absorbers such as octylphenyl salicylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole, 2- ( 2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-3-tert)
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-
Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole,
-{2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″,
6 "-tetrahydrophthalimidomethyl) -5'-methylphenyl {benzotriazole, 2,2-methylenebis} 4- (1,1,3,3-tetramethylbutyl) -6
Benzotriazole-based ultraviolet absorbers such as-(2H-benzotriazol-2-yl) phenol}, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3 ' -Cyanoacrylate-based ultraviolet absorbers such as diphenylacrylate. The content of the ultraviolet absorber is preferably in the range of 0.2 to 5 parts by weight based on 100 parts by weight of the low tackiness agent. In the present invention, the thickness of the adhesive layer is not particularly limited, and may be generally in the range of 5 to 100 μm, preferably in the range of 10 to 50 μm.

In the removable window film for an automobile of the present invention, a metal deposition layer may be provided between the base film and the adhesive layer. Examples of the type of metal used for the metal deposition layer include, for example, aluminum, gold, silver, copper, nickel, cobalt, chromium, tin, indium and the like, preferably aluminum, gold, silver, tin,
Particularly preferred is aluminum. The thickness of the metal deposition layer is preferably in the range of 50 to 300 °.

The base film of the present invention is preferably transparent. Specific examples of the base film include, for example, polyethylene, polyolefin resin such as polypropylene, vinyl chloride resin, styrene resin, ABS resin,
Polyvinyl alcohol, acrylic resin, acrylonitrile-styrene resin, vinylidene chloride resin, AAS resin, AES resin, polyurethane resin, polyvinyl butyral resin, poly-4-methylpentene-1 resin, polybutene-1 resin, vinylidene fluoride resin, fluorine resin Polyvinyl resin, fluorine resin, polycarbonate resin, polyamide resin, acetal resin, polyester resin such as polyphenylene oxide resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide resin, polyimide resin, polysulfone resin, polyether sulfone resin, aromatic polyester resin , A film of various resins such as polyarylate resin, or a laminated film thereof, preferably a polyester resin film, vinyl chloride Fat film, include polyolefin resin film, particularly preferably a polyester resin film. These base films may be uniaxially or biaxially stretched.

The thickness of the base film may be appropriately selected, but is usually in the range of 5 to 200 μm, preferably 1 to 200 μm.
The range is from 0 to 100 μm. In the automotive removable window film of the present invention, a release film layer may be provided in order to protect the surface of the adhesive layer. The release film layer is preferably transparent. As the release film layer, a non-silicone polyester release film is preferable.

The method of providing the adhesive layer on one side of the substrate film can be carried out by various methods. For example, a method of dissolving the above low tackiness agent in an appropriate solvent and applying the solution.
Method of applying by hot melt extrusion method, method of applying by dispersing or emulsifying in a suitable medium, method of applying without solvent, method of applying by casting method or method of applying by calender roll or knife, on release paper An adhesive layer is applied and formed in advance, and a method of attaching the adhesive layer, a double-sided tape coated with an adhesive and a low-adhesive agent on one side, respectively, are laminated so that the adhesive layer is in contact with the surface of the base film. And the like.

When the anchoring property between the base film and the adhesive layer is insufficient, the surface of the base film on which the adhesive layer is to be formed may be subjected to a corona discharge treatment or a polyester resin, a urethane resin, a chlorinated polyolefin or the like as a main component. It is preferable to provide a primer layer by applying a primer containing a filler as necessary. As fillers, silica, calcium carbonate, magnesium carbonate, kaolin, calcined clay,
Various fillers such as bentonite, zeolite, talc, diatomaceous earth and the like can be used.

Since the automotive removable window film of the present invention uses a low-adhesive agent having removability, it can be attached to glass having a smooth surface, and can be applied after being attached. Is well held on the car window glass,
Further, the glass can be easily peeled without being damaged or contaminated at the time of peeling. In addition, a coloring agent and an ultraviolet absorber can be mixed with the low tackiness agent, and visible light and ultraviolet light can be efficiently cut according to the application. Furthermore, when a metal vapor deposition layer is provided between the base film and the adhesive layer, it can reflect ultraviolet light and cut visible light.

[0017]

Next, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples.

Embodiment 1 FIG. 1 is a cross-sectional view of an embodiment of an automotive removable window film of the present invention. Transparent substrate film 1 (polyester resin film, thickness: 25 μm)
Is coated on one side with a polyether-based polyurethane elastomer (Crisbon NT-165, manufactured by Dainippon Ink and Chemicals, Inc.)
EL, concentration 65%), 20 parts by weight of an aliphatic isocyanate-based cross-linking agent (manufactured by Dainippon Ink and Chemicals, Inc., Vernock DN-950, concentration 75%) and 100 parts by weight of a crosslinking accelerator (Dainippon Ink and Chemicals, Inc.) Adhesive layer 2 made of polyurethane elastomer having a thickness of 20 μm by applying 3 parts by weight of Chrisbon, Axel T, manufactured by Co., Ltd. and uniformly mixing and applying the mixture by a casting method and heating at 100 ° C. for 12 minutes. A non-silicone polyester transparent release film 3 (thickness: 25 μm) was provided on the surface of the adhesive layer 2 to obtain a removable window film for automobiles.

Example 2 Polyester polyurethane elastomer (Chrisbon 5150S, manufactured by Dainippon Ink and Chemicals, Inc., concentration: 50%)
100 parts by weight of an aromatic isocyanate-based crosslinking agent (Chrisbon NX, manufactured by Dainippon Ink and Chemicals, Inc., concentration 7
5%) and 3 parts by weight of a cross-linking accelerator (Chrisbon Accel HM, manufactured by Dainippon Ink and Chemicals, Inc.) were mixed and uniformly mixed. A peelable window film was obtained.

Example 3 10 parts by weight of a blue dye (Neo Super Liquid Blue) was added to the polyurethane elastomer of Example 1 based on 100 parts by weight of the polyurethane elastomer.
Except for mixing C531-L, manufactured by Chuo Synthetic Chemical Co., Ltd., 1: 2 type metal complex dye, a car removable window film was obtained in the same manner as in Example 1.

Example 4 Except that the polyurethane elastomer of Example 2 was mixed with 10 parts by weight of a blue dye (MICROLITH Blue KP, an anthraquinone type manufactured by Ciba Geigy K.K.) based on 100 parts by weight of the polyurethane elastomer. In the same manner as in Example 2, an automotive re-peelable window film was obtained.

Example 5 1.5 parts by weight of a benzophenone ultraviolet absorber and 2,4-dihydroxybenzophenone (Biosorb 100, Kyodo Yakuhin Co., Ltd.) were added to the polyurethane elastomer of Example 1 in an amount of 1.5 parts by weight based on 100 parts by weight of the polyurethane elastomer.
Ex.) Was mixed in the same manner as in Example 1 to obtain an automotive removable window film.

Example 6 To the polyurethane elastomer of Example 2, 1.5 parts by weight of a benzophenone-based ultraviolet absorber and 2,4-dihydroxybenzophenone (Biosorb 100, Kyodo Yakuhin Co., Ltd.) were added in an amount of 1.5 parts by weight based on 100 parts by weight of the polyurethane elastomer.
Ex.) Was obtained in the same manner as in Example 2 except that the resin was mixed.

Example 7 As shown in FIG. 2, on one side of a transparent substrate film 1 (polyester resin film, thickness: 25 μm), aluminum was vapor-deposited to form a metal vapor-deposited layer 4 (thickness of aluminum vapor-deposited layer: 100 °). A polyurethane elastomer (manufactured by Dainippon Ink and Chemicals, Inc., Chris Bon 551)
6S, concentration 30%) by the casting method.
By heating at 00 ° C. for 12 minutes to form a sticking layer 2 made of a polyurethane elastomer having a thickness of 20 μm, a non-silicone-based polyester release film 3 (thickness: 25 μm) is provided on the surface of the sticking layer 2, and is used for automobiles. A peelable window film was obtained.

Example 8 Polyester-based polyurethane elastomer (Chrisbon 5150S, manufactured by Dainippon Ink and Chemicals, Inc., concentration: 50%)
100 parts by weight of an aromatic isocyanate-based crosslinking agent (Chrisbon NX, manufactured by Dainippon Ink and Chemicals, Inc., concentration 7
5%) and 3 parts by weight of a cross-linking accelerator (Chrisbon Accel HM, manufactured by Dainippon Ink and Chemicals, Inc.) were mixed and uniformly mixed. A peelable window film was obtained.

The removable window film for automobiles obtained in Examples 1 to 8 was adhered to a transparent window glass of automobile. These removable window films for automobiles were sufficiently held on the transparent window glass of the automobile after being adhered. After that, when the automotive removable window film was peeled off from the transparent window glass of the automobile, the automotive removable window film was easily peeled without damage, and the window glass was not damaged and had a low tackiness agent. There was no rest. In addition, a test piece produced from the automotive re-peelable window film obtained in each of Examples 1 to 8 was attached to a smooth glass plate, and the peeling force, pole tack, and holding force were measured. Table 1 shows the results.

[0027]

[Table 1]

When measuring the holding force shown in Table 1, there was no displacement of the test piece on the test plate in any of Examples 1 to 8. The peel force, pole tack and holding force were measured by the following methods. (1) Peeling force The peeling force was measured based on the 180-degree peeling method specified in JIS Z 0237 (1991) 8.3.1. (2) Hole tack Based on a test method of a tilted ball tack specified in JIS Z 0237 (1991) 12, the hole tack was measured using a tilt plate having a tilt angle of 30 degrees. (3) Holding force The holding force was measured based on the holding force test method specified in JIS Z 0237 (1991) 11. The holding force is a test for the cohesive force or shear resistance of the pressure-sensitive adhesive, and the longer the fall time, the greater the shear resistance.

[0029]

The removable window film for automobiles of the present invention uses a low-adhesive agent having removability, so that it can be adhered to a window glass of an automobile having a smooth surface. After being attached, it is sufficiently held on the window glass of the car, and when peeling, it can be easily peeled without damaging and contaminating the glass. Even if it is adhered, it can be peeled off and can be easily constructed. In addition, a coloring agent,
When an ultraviolet absorber is mixed, visible light and ultraviolet light can be efficiently cut. Furthermore, when a metal vapor deposition layer is provided between the base film and the adhesive layer, it can reflect ultraviolet light and cut visible light.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of one embodiment of the automotive removable window film of the present invention.

FIG. 2 is a cross-sectional view of one embodiment of the automotive removable window film of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent base material film layer 2 Adhesive layer 3 Non-silicone polyester transparent release film 4 Metal deposition layer

Claims (5)

[Claims] 1. A removable window film for automobiles, comprising a substrate film having a removable and low-adhesive adhesive layer formed of a low-adhesive agent on one surface. 2. The removable window film for an automobile according to claim 1, wherein a metal deposition layer is provided between the base film and the adhesive layer. 3. The removable window film for automobiles according to claim 1, wherein a colorant is contained in the low tackiness agent. 4. The removable window film for an automobile according to claim 1, further comprising an ultraviolet absorber in the low tackiness agent. 5. The removable window film for an automobile according to claim 1, wherein a transparent release film is adhered to the surface of the adhesive layer.