JPH11263953A - Colored film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored film colored with a pigment and having excellent visibility, transparency, light resistance, stability, etc. SOLUTION: This colored film is obtained by disposing at least one colored adhesive layer colored with a colorant on at least one surface of a transparent film. Therein, the colored adhesive layer contains a polyester-based resin as an adhesive, and the colorant comprises a pigment and a polyester dispersant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored film, and more particularly to a colored film having excellent clarity, transparency, light resistance, stability and the like.

[0002]

2. Description of the Related Art Colored films have been widely used in vehicles, buildings, packaging materials, display materials and the like. When these colored films are used for decoration, selection of incident light wavelength, prevention of external see-through, and the like, for example, for solar control, the colored films have excellent clarity, transparency, and light resistance. , Stability, etc. are required. In addition, these colored films are required to be easily adhered and peeled off. For this purpose, a layer made of a pressure-sensitive adhesive or a heat-sensitive adhesive is provided on one surface of the transparent film. Note that the pressure-sensitive adhesive referred to herein is a self-adhesive (has no surface tackiness, but has an airtightness between mirror surfaces between a smooth surface such as a glass plate, a metal plate, a painted surface, and a plastic plate and the self-adhesive surface). (Hereinafter, simply referred to as a self-adhesive). In addition, since coloring is required to be transparent, a dye that is soluble in an adhesive has been conventionally used. It is difficult, if not impossible, to color the transparent film itself with a dye, and therefore, coloring is mainly performed on the pressure-sensitive adhesive and the heat-sensitive adhesive as described above.

[0003]

In the above-mentioned prior art, the coloring of the adhesive with a dye is easy, and a colored film having excellent clarity and transparency can be obtained. When used under conditions of exposure to external light, such as a control film, there are problems such as the light resistance of the dye being poor and fading or discoloring after a certain period of time. As a method for solving these problems, various proposals have been made to use a pigment instead of a dye.However, in the prior art, although a colored film excellent in light resistance can be obtained, the pigment in the adhesive is not used. Fine dispersion was difficult, and even if dispersed, the pigment particles were strongly agglomerated, and a colored film satisfying sharpness and transparency could not be obtained. Accordingly, an object of the present invention is to provide a colored film which is colored by a pigment and which is excellent in clarity, transparency, light resistance, stability and the like.

[0004]

The above object is achieved by the present invention described below. That is, the present invention provides a colored film comprising at least one colored adhesive layer colored with a coloring agent on at least one surface of a transparent film, wherein the colored adhesive layer contains a polyester resin as an adhesive. And a coloring film comprising a pigment and a polyester-based dispersant.

According to the present invention, by forming a colored adhesive layer from a specific adhesive and coloring with a specific colorant, excellent sharpness and transparency are obtained which cannot be obtained by the prior art. , A colored film having light resistance, stability and the like can be provided.

[0006]

Next, the present invention will be described in more detail with reference to preferred embodiments. The colored film of the present invention is a colored film comprising at least one colored adhesive layer colored by a coloring agent on at least one surface of a transparent film, wherein the colored adhesive layer comprises a polyester resin as an adhesive. And a colorant comprising a pigment and a polyester-based dispersant.

The transparent film used in the present invention includes, for example, those used for conventional colored films such as polyethylene film, polypropylene film, polyester film, polycarbonate film, polyvinyl chloride film, polyvinylidene chloride film, polystyrene film and polyamide film. Any of the known transparent films can be used. The size of these films is not particularly limited, and the thickness varies depending on the application, but is usually a film or sheet of about 6 to 200 μm.

The adhesive used in the present invention is a polyester-based adhesive. The polyester-based adhesive is conventionally known as an adhesive, and any of the conventionally known polyester-based adhesives used in the present invention is used. Yes, it is not particularly limited. Specific examples of the polyester-based heat-sensitive adhesive, for example, terephthalic acid, isophthalic acid, succinic acid,
Dibasic acids such as adipic acid, sebacic acid and dodecanoic acid;
Ethylene glycol, propylene glycol, 1,4-
Polymers and copolymers obtained from glycols such as butanediol, 1,6-hexanediol, cyclohexanediol, and polyoxylene glycol are exemplified. Generally, polyester-based adhesives include polyethylene terephthalate, polybutylene terephthalate, etc., dibasic acids such as isophthalic acid, adipic acid and sebacic acid, side-chain glycols such as neopentyl glycol, and long-chain polyoxyalkylene glycols. Those obtained by copolymerizing the above are used. The degree of polymerization of these polyester-based adhesives is about 3,000 to 20,000, and those having a glass transition temperature of 20 ° C. or less are used. In addition, conventionally known polyester-based pressure-sensitive adhesives and polyester-based curable adhesives can also be used.

In the present invention, the above-mentioned adhesive is previously colored with a pigment colorant described below, and the colored adhesive is applied to a transparent film to a predetermined thickness by an appropriate application method. Is obtained. As the dispersant for the pigment composed of the polyester resin used in the present invention, the same dispersant as the above-mentioned polyester adhesive can be used. By kneading the polyester-based adhesive and the pigment in such a ratio that the pigment becomes highly concentrated, a master batch-like colorant can be obtained.
The polyester-based dispersant to be used may be the same as the polyester-based adhesive, but in consideration of the dispersibility of the pigment and the viscosity when used as a colorant, the molecular weight is about 1,000.
~ 100,000, even 3,000 ~ 50,000.
Preferably, the polyester resin is in the range of 00.

The pigment used in the present invention is a pigment conventionally used in various fields, and any known pigment can be used. Specifically, phthalocyanine, azo, condensed azo, azo lake, anthraquinone, perylene / perinone, indigo / thioindigo, isoindolinone, azomethineazo, dioxazine, quinacridone, aniline black, Organic pigments such as triphenylmethane and carbon black;
And inorganic pigments such as titanium oxide, iron oxide, iron hydroxide, chromium oxide, spinel type calcination, chromate, chromium vermillion, navy blue, aluminum powder, and bronze powder. . These pigments may be in any form, and these pigments may have been subjected to various dispersion treatments by various known methods.

The colorant used in the present invention is obtained by kneading the dispersant and the pigment with a kneader such as a sand grind mill, a ball mill, an attritor mill, or a three-roll mill. At this time, the dispersant is pigment 10
It is used in the range of about 10 to 500 parts by weight per 0 parts by weight. When kneading the dispersant and the pigment, for example, by mixing the dispersant (with an appropriate amount of an organic solvent if necessary) to the powdered pigment, for example, by mixing and kneading with a three-roll mill, It is possible to obtain a colorant having excellent transparency with very few aggregated particles of the pigment. The resulting colorant is
It may be in the form of a powder, a chip, a paste containing an organic solvent, or a liquid in which an organic solvent is used as a medium.
The colorant may be added with various additives, for example, an organic solvent, a film-forming resin, a flame retardant, an antioxidant, an ultraviolet absorber, a plasticizer, a surfactant, and the like, depending on the target coloring material. Can be.

The coloring of the adhesive with the coloring agent is carried out by mixing the two in the presence of water or an organic solvent, if necessary, and thoroughly stirring and mixing. The colorant has a property of easily and stably dispersing in an adhesive (or a solution thereof), and does not require any special treatment. Kneading using a kneader such as a lighter mill or a three-roll mill makes it possible to completely disperse the pigment. The amount of the colorant used is preferably in the range of 0.1 to 10 parts by weight of the colorant or 0.1 to 5 parts by weight in terms of pigment per 100 parts by weight of the adhesive. If no power is obtained, on the other hand, if the pigment concentration is too high, the transparency and light transmittance may be insufficient.

Next, a colored film according to a preferred embodiment of the present invention will be described with reference to the accompanying drawings. The example shown in FIG. 1 is an example in which a colored adhesive (heat-sensitive adhesive, pressure-sensitive adhesive, curable adhesive, etc.) layer 2 is interposed between two transparent films 1A and 1B. When the colored adhesive layer 2 is formed of a heat-sensitive adhesive, one of the transparent films 1, ie,
A solution or dispersion of the heat-sensitive adhesive is applied to one surface of the transparent film 1A and dried. Thereafter, the other transparent film 1B is bonded by a laminator such as a hot roll or a hot plate. When sticking the colored film of this example to another article, it is necessary to use an appropriate adhesive (which may be colorless or colored) on the transparent film 1A or 1B side or on the article to be stuck.

The example shown in FIG. 2 differs from the example shown in FIG. 1 in that a pressure-sensitive adhesive layer 3 is formed on the outward surface of the transparent film 1A. In this state, since the pressure-sensitive adhesive has tackiness at room temperature, a release paper or a release sheet 4 is attached to the outer surface of the adhesive layer 3 for the purpose of solving the inconvenience.
This is an example of bonding. The method for forming the colored film in this example is the same as that in the example shown in FIG. In addition, at least one of the adhesive layer 2 and the pressure-sensitive adhesive layer 3 in this example may be colored. As a method of using the colored film, for example, when the colored film is pasted to a glass window of an automobile, the release paper 4 on the surface is peeled off, or laminating while peeling. In the example shown in FIG. 3, two colored adhesive layers 2A, 2A, 3B are interposed between three transparent films 1A, 1B, 1C.
Although this is an example in which 2B is formed, it is not essential to color both adhesive layers 2A and 2B, and only one of the adhesive layers may be colored. The method of using the colored film of this example is the same as the example shown in FIG.

In each of the above embodiments, the density and light transmittance of the obtained colored film can be freely adjusted. For example, the color density can be freely adjusted by preparing a colored adhesive having a high pigment concentration first and diluting it with a similar colorless adhesive. Also, a required amount of the above-mentioned coloring agent may be added to a colorless adhesive to form a colored adhesive having a required concentration, and this may be used to form a colored film having a desired concentration.

The light transmittance can be adjusted by changing the pigment concentration of the colored adhesive layer. For example, in order to obtain a light-colored film having a low light-transmitting property, a transparent film is required. Is subjected to thin metal deposition or the like on at least one surface of the substrate.
Further, when an infrared reflection effect is required together with coloring regardless of the coloring concentration, metal deposition can be performed in the same manner as described above. At this time, it is preferable to use a metal-deposited film as a transparent film as a raw material, but it is also possible to apply a metal deposition after forming a colored film. As described above, it is natural that the colored film of the present invention can be provided with other required performance by combining known techniques.

The above-mentioned colored adhesive is applied to the transparent film by applying an organic solvent solution or an aqueous dispersion of the colored adhesive to a suitable coating means, for example, a knife over roll coater, a roll coater, a reverse coater, The coating is performed by using a known coating machine such as a gravure coater and, if necessary, drying. Alternatively, a coextrusion method of simultaneously extruding a transparent film base material and a colored adhesive can be used.Furthermore, a colored adhesive is formed into a film, and the adhesive film is laminated on a transparent base film. Is also effective. The coating amount (or thickness) of the coloring adhesive is generally about 1 to 50 g / m ² on a solid basis, and the coating amount is such that the desired coloring concentration and transparency can be obtained. It is selected and determined in consideration of the pigment concentration in the medium. When the adhesive is a pressure-sensitive adhesive,
In consideration of handling properties, it is preferable that a release sheet such as a resin film or paper coated with release silicone is adhered to the surface of the adhesive layer.

[0018]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following description, “parts” or “%” is based on the weight of solid content unless otherwise specified. (Preparation of Colorant 1) 10 parts of a pigment (phthalocyanine green pigment) was mixed with 10 parts of a dispersant (polyester resin; Byron 300, manufactured by Toyobo Co., Ltd.), and after premixing with a dissolver, 3 The dispersion was carried out with this roll to obtain Colorant 1.

(Preparation of Colorant 2) 10 parts of a pigment (phthalocyanine blue pigment) was mixed with 10 parts of a dispersant (polyester resin; Pesresin S310, manufactured by Takamatsu Yushi Co., Ltd.), and premixed with a dissolver. Thereafter, the mixture was dispersed with three rolls to obtain Colorant 2. (Preparation of Colorant 3) In the preparation method of Colorant 1, the dispersant was replaced with a vinyl chloride-based dispersant (a copolymer consisting of 90 parts of vinyl chloride, 5 parts of vinyl alcohol and 5 parts of vinyl acetate). Colorant 3 was obtained in the same manner as in the production of Colorant 1. (Preparation of Colorant 4) In the method of preparing Colorant 2, Colorant 4 was obtained in the same manner as in Preparation of Colorant 2, except that the dispersant was replaced with a vinyl chloride-based dispersant (the same as Colorant 3). Was.

Example 1 100 parts of a polyester resin (Vylon 100; manufactured by Toyobo Co., Ltd.), 10 parts of a crosslinking agent (Coronate L; manufactured by Nippon Polyurethane Co., Ltd.) and 2 parts of a coloring agent 1 were mixed and applied. A working solution was prepared. This coating liquid was applied to one surface of a 25 μm-thick polyester film so as to have a dry film thickness of 3 g / m ² and dried to form a colored adhesive layer. Further, a polyester film having a thickness of 12 μm was laminated on the surface of the colored adhesive layer of the above film with a hot lami roll (100 ° C.) to obtain a colored film of the present invention.

Example 2 A pressure-sensitive adhesive (PA-TI; manufactured by Lintec Co., Ltd.) was applied to the side of a 12 μm-thick polyester film of the colored film obtained in Example 1 so that the film thickness when dried was 15 g / The colored film of the present invention was obtained by coating and drying to obtain m ² .

Example 3 50 parts of a two-part polyurethane resin (Resamine UND-8380; manufactured by Dainichi Seika Kogyo Co., Ltd.) and polymerization were applied to the side of a 12 μm-thick polyester film of the colored film obtained in Example 1. Accelerator (Rezamine HI
-215; a coating solution of a self-adhesive adhesive composed of 0.5 parts (manufactured by Dainichi Seika Kogyo Co., Ltd.) so as to have a film thickness of 10 g / m ² when dried, and then dried. A colored film was obtained.

Example 4 Example 1 was the same as Example 1 except that the polyester resin as the adhesive was changed to Pesresin S310 (manufactured by Takamatsu Yushi Co., Ltd.) and the colorant 1 was changed to the colorant 2. A colored film of the present invention was obtained in the same manner as in the above.

[Comparative Example 1]
Was replaced with Coloring Agent 3, except that a colored film of Comparative Example was obtained in the same manner as in Example 1.

Comparative Example 2 In Example 2, the colorant 1
Was replaced with Coloring Agent 3, except that a colored film of Comparative Example was obtained in the same manner as in Example 2.

[Comparative Example 3] In Example 4, the colorant 2
Was replaced with Coloring Agent 4, except that a colored film of Comparative Example was obtained in the same manner as in Example 4.

Each of the colored films of the above Examples and Comparative Examples was evaluated according to the following items and criteria.
Table 1 shows the evaluation results. 1. Transparency A: good B: somewhat good C: bad Haze 3. Light resistance The colored film sample was irradiated with a sunshine type fade meter, and the color difference ΔE after 500 hours of irradiation was measured.
Those having a value of 2.0 or less were determined to be acceptable. A: Acceptable lightfastness B: Unacceptable lightfastness

Table 1: Evaluation results

[0029]

As can be seen from the above results, the colored film according to the present invention is excellent in transparency, light resistance and the like.

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating a cross section of a colored film of one example of the present invention.

FIG. 2 is a diagram schematically illustrating a cross section of a colored film of another example of the present invention.

FIG. 3 is a diagram schematically illustrating a cross section of a colored film of another example of the present invention.

[Explanation of symbols]

 1: transparent film 2: colored adhesive (heat-sensitive adhesive, pressure-sensitive adhesive, etc.) 3: pressure-sensitive adhesive 4: release paper

Continued on the front page (72) Inventor Garcia, M., Leonardo Wharf Industrial Parkway, Massachusetts, USA 45 Inside Lintec Research Boston, Inc. (72) Inventor Patel, Cee, Chandrakant Wharf Industrial, Mass., USA Parkway 45 Inside Lintec Research Boston, Inc.

Claims (7)

[Claims] 1. A colored film having at least one colored adhesive layer colored by a coloring agent on at least one surface of a transparent film, wherein the colored adhesive layer contains a polyester resin as an adhesive, And a colorant comprising a pigment and a polyester-based dispersant. 2. The colored film according to claim 1, wherein another transparent film is further laminated on the outer surface of the colored adhesive layer. 3. The colored film according to claim 1, wherein a pressure-sensitive adhesive layer is formed on another surface of the transparent film. 4. The colored film according to claim 2, wherein a pressure-sensitive adhesive layer is formed on an outer surface of any one of the transparent films. 5. The colored film according to claim 1, wherein the colorant comprises 10 to 500 parts by weight of the dispersant per 100 parts by weight of the pigment. 6. The colored film according to claim 1, wherein the colored adhesive layer comprises 0.1 to 10 parts by weight of the coloring agent per 100 parts by weight of the adhesive. 7. The colored film according to claim 1, which is attached to a window.