JP2001226500A - Glossy synthetic film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glossy synthetic resin film free of foreign body feeling and dullness, having excellent brightness with three-dimensional feeling and excellent transparency. SOLUTION: This glossy synthetic resin film has a glossy synthetic resin layer containing glossy pigment. Scaly particles obtained by coating the surface of flake-like glass with a metal oxide having higher refractive index than a refractive index of the flake-like glass is used as the glossy pigment. A film- forming raw material obtained by compounding a liquid synthetic resin composition containing a solvent with the glossy pigment is applied onto a substrate and the solvent is volatilized to provide a synthetic resin coating film and then, the coated film is released from the substrate to produce the objective glossy synthetic resin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly decorative glossy synthetic resin film suitable as a marking film and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Heretofore, as a synthetic resin film used for a marking film and the like, a film formed by forming a film of a vinyl chloride resin or the like by calendaring or casting has been proposed.

[0003] Such a synthetic resin film is colored by blending an appropriate pigment or the like. In order to enhance the decorativeness, a gloss pigment such as a metal foil or pearl mica is blended with the resin of the film forming material to increase the gloss. Grants have also been made. In this case, practically, an aluminum foil is often used as the metal foil.

[0004]

A synthetic resin film containing an aluminum foil as a luster pigment has the following drawbacks. The aluminum foil has a weak brilliant feeling, and the brilliant feeling is flat, so that the decorative effect is not sufficient. In the process of kneading the aluminum foil in addition to the resin,
The foil surface is shaved to produce fine particles, which cause darkening. When the reflected light from the aluminum foil does not reach sight,
The foil appears as a black dot and is visually recognized as a foreign substance (hereinafter, this phenomenon is referred to as “foreign substance feeling”).

[0005] On the other hand, pearl mica generally refers to mica coated with titanium dioxide, but mica as a base material originally has cleavage properties, so that a step is formed on the surface and surface smoothness is poor. Therefore, the glitter is weak. When pearl mica is added to a resin and kneaded, it is easily damaged, peels or cracks due to the cleavage property, and as a result, the glossiness is remarkably lost and the transparency of the synthetic resin film is lowered. Pearl mica using natural mica causes dullness because mica contains colored impurities such as iron. There are drawbacks.

The present invention relates to a glossy synthetic resin film having excellent three-dimensional appearance, excellent brilliancy, and excellent transparency without the foreign substance feeling and dullness of the above-mentioned conventional glossy synthetic resin film. It is intended to provide a manufacturing method.

[0007]

The glossy synthetic resin film of the present invention comprises a glossy synthetic resin film having a glossy synthetic resin layer containing a glossy pigment, wherein the glossy pigment covers the surface of the flaky glass with the flakes. It is characterized by being flaky particles coated with a metal oxide having a higher refractive index than that of the glass.

The glossy synthetic resin film of the present invention using flake-like particles obtained by coating the surface of a flake-like glass with a metal oxide having a higher refractive index than this glass as the glossy pigment, The feeling is remarkably superior to the glitter of a synthetic resin film using a conventional glossy pigment. A glossy, high-grade, beautiful film can be formed in which a group of glossy pigment particles composed of individual particles dispersed in the layer is observed three-dimensionally.

In addition, a metal oxide coating such as titanium dioxide can obtain various brilliant interference colors by changing the thickness of the layer. A glossy synthetic resin film having various glittering to chromatic colors without foreign-body sensation and excellent in glitter can be obtained.

The glossy synthetic resin film of the present invention may have a single-layer structure composed of such a glossy synthetic resin layer, and a colored synthetic resin layer is laminated on the back side of the glossy synthetic resin layer. It may have a laminated structure.

The scaly particles of the gloss pigment used in the present invention are:
Average thickness 0.05-7 μm, average particle size 10-300 μm
It is preferable that a coating layer of the metal oxide having a thickness of 0.02 to 0.8 μm is formed on the surface of the glass flake.

The content of the glossy pigment in the glossy synthetic resin layer is preferably 1 to 40% by weight.

The thickness of such a glossy synthetic resin layer is 10
It is preferably 0 μm or less.

According to the method of the present invention, such a glossy synthetic resin film of the present invention is formed by coating a film-forming raw material obtained by blending the above-mentioned glossy pigment with a liquid synthetic resin composition containing a solvent on a substrate. After that, the solvent can be volatilized to obtain a synthetic resin coating film, and then the coating film can be easily manufactured by peeling the coating film from the substrate. Cracks can be prevented and the orientation thereof can be facilitated, and a glossy synthetic resin film having extremely excellent glitter can be produced.

[0015]

Embodiments of the present invention will be described below in detail.

First, the gloss pigment according to the present invention will be described.

The gloss pigment used in the present invention is a flaky particle obtained by coating the surface of a flake glass with a metal oxide having a higher refractive index than glass (hereinafter referred to as "high refractive index metal oxide"). In other words, it is a flaky particle in which flake glass is used as a base material (core portion) and the surface thereof is provided with a coating layer of a high refractive index metal oxide.

Here, examples of the high refractive index metal oxide include anatase type titanium dioxide, rutile type titanium dioxide, zirconium dioxide and iron oxide.
In particular, because it is practical in terms of cost, quality, etc., anatase type titanium dioxide or rutile type titanium dioxide,
Particularly, rutile type titanium dioxide is preferable.

The glass flakes at the core are flaky glass particles, the size of which is the average particle diameter (longitudinal dimension).
Is preferably in the range of 10 to 300 μm and the average thickness is in the range of 0.05 to 7 μm. When the average thickness of the flake glass is 0.05 to 7 μm and the average particle diameter is 10 to 300 μm, not only is the compounding with the synthetic resin composition easy, but also the orientation in the film (resin layer) is high. Excellent and particularly beautiful gloss is exhibited. The glass composition of the glass flakes is not particularly limited, and examples thereof include those having SiO ₂ as a main component and a small amount of Al ₂ O ₃ , CaO, B ₂ O ₃ and other components.

The refractive index of such a glass flake is usually about 1.5 to 1.6, and the high refractive index metal oxide coating the surface of the glass flake has a refractive index of 2.0.
A range of about to 3.0 is preferable. The refractive index of anatase type titanium dioxide is about 2.5, and the refractive index of rutile type titanium dioxide is about 2.7.

As a method of coating the surface of such a flake glass with a metal oxide having a high refractive index, for example, anatase or rutile type titanium dioxide, a sol-gel method and a liquid phase method are known. For example, Japanese Patent Application Laid-Open No. 9-176515 describes that a metal oxide-coated flake glass having an average shape ratio (average thickness / average particle size) of 1/9 to 1 and an average particle size of 25 to 500 μm can be obtained by a sol-gel method. Have been.
U.S. Pat. No. 5,753,371 discloses that, as an example of the liquid phase method, flake glass having a C glass composition is dispersed in an acidic aqueous solution, and ferric chloride and zinc chloride or tin chloride are added thereto, followed by stirring. While adjusting the pH, a titanium tetrachloride (TiCl ₄ ) aqueous solution is poured, and when a predetermined interference color is reached, the reaction is terminated, and the mixture is filtered, washed with water, and then heated and calcined at a predetermined temperature to coat the metal oxide. A method for obtaining flaked glass is described.

The present inventors have disclosed in US Pat.
By further developing the method described in Japanese Patent Laid-Open No. 1-2005, the following method capable of uniformly and stably coating a high refractive index metal hydroxide film without unevenness has been developed.

First, as a pretreatment, a flaky glass is surface-treated with tin chloride in an aqueous hydrochloric acid solution.
Treat with hexachloroplatinic acid. Next, this flaky glass is added to a hydrochloric acid aqueous solution adjusted to a pH of 1.3 or less, for example, about 1.0, and the temperature of the slurry liquid is reduced to 55-8.
The temperature is raised to 5 ° C., for example, 75 ° C., to adjust the pH to 0.5 to 1.3.
While adjusting the pH, an aqueous solution of TiCl ₄ is added and reacted until a predetermined interference color is reached. Then, the reaction product is filtered, washed with water, and then heated and calcined at a predetermined temperature, for example, 600 ° C. According to this method, US Pat.
The rutile-type titanium dioxide coating can be formed more uniformly and more stably without unevenness than the method described in JP-A-53371. Although the details of the reason why such an excellent rutile-type titanium dioxide film is formed by this method are not clear, in this method, platinum adheres to the surface of the flake glass, and the action of this platinum causes It is considered that the adhesion of the metal oxide is promoted and a uniform high-refractive-index metal oxide film without spots is formed.

The coating amount of the high-refractive-index metal oxide varies depending on the type of the high-refractive-index metal oxide, the required degree of glitter, the desired interference color, and the like.
Preferably, the thickness is 0.8 μm. If the thickness is excessively small, sufficient gloss cannot be obtained, and if the thickness is excessively large, economic efficiency is impaired.

The purity of the high refractive index metal oxide such as titanium dioxide to be coated is preferably higher, but is preferably 96 to 99%.
To the extent, impurities containing impurities such as SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , and moisture may be used.

The gloss pigment according to the present invention preferably further has a protective film formed on the surface of a high refractive index metal oxide layer such as titanium dioxide in order to improve weather resistance. Specifically, a material containing silicon dioxide as a main component is used. As the protective film, specifically, JP-A-62
Known protective films such as those used for mica pearl luster pigments described in JP-A-91567, JP-A-1-292607 and JP-A-7-268241 can be employed.

The glossy synthetic resin film of the present invention has a single-layer structure composed of a glossy synthetic resin layer containing such a gloss pigment (hereinafter, may be referred to as a "single-layer film"). Alternatively, a layered structure in which a colored synthetic resin layer is laminated on the back side of the glossy synthetic resin layer (hereinafter, sometimes referred to as a “laminated film”) may be used.

The glossy synthetic resin layer containing the glossy pigment is
The most beautiful glossiness is exhibited when the resin layer itself is colorless and transparent, but the glossy synthetic resin layer may be appropriately colored with a dye or a pigment. However, when imparting coloring to the glossy synthetic resin film, in particular, a colorless and transparent glossy synthetic resin layer containing a glossy pigment, on a transparent or opaque colored synthetic resin layer colored with a dye or pigment. It is preferable to have a laminated structure in which the layers are laminated. With such a laminated film, a vivid color tone and a beautiful glossiness are simultaneously expressed, and a glossy synthetic resin film having extremely high decorativeness can be obtained. .

Regardless of the single-layer film or the laminated film, the content of the gloss pigment in the glossy synthetic resin layer is 1 to the total weight of the glossy synthetic resin layer.
It is preferably set to 40% by weight. If the content is excessively small, sufficient gloss cannot be obtained. If the content is excessively large, economic efficiency is impaired, and further, film formation becomes difficult and film performance may be deteriorated.

The liquid synthetic resin composition used for producing the synthetic resin film according to the method of the present invention is preferably selected from, for example, a synthetic resin solution and an organosol, and contains a solvent. Is required. Such a solvent is effective for keeping the viscosity of the synthetic resin composition low, thereby preventing breakage of the flake-like glass of the gloss pigment at the time of film formation, facilitating the orientation of the flaky particles, and enhancing the glitter.

The kind of resin component contained in such a synthetic resin composition is not particularly limited, but it is colorless, transparent, flexible, and has practical physical strength characteristics as a film. It is desirable that it has. Examples of such synthetic resins include vinyl chloride resin, EVA
(Ethylene-vinyl acetate copolymer) resins, acrylic resins, urethane resins and the like.

As the solvent, tetrahydrofuran, cyclohexanone, ethyl methyl ketone, methyl isobutyl ketone and the like can be used.

The liquid synthetic resin composition as a film-forming raw material contains, in addition to the resin, gloss pigment, and solvent, a plasticizer, a heat stabilizer, an ultraviolet absorber, a surfactant, and other properties as required. An enhancer may be blended.

If necessary, one or more selected from color pigments, other metallic pigments (eg, aluminum pigments, iron oxide pigments, etc.), and interference color pigments (eg, mica coated with metal oxides) or Two or more kinds may be blended so as not to impair the glitteriness based on the gloss pigment.

In order to produce a single-layer glossy synthetic resin film according to the method of the present invention, such a liquid synthetic resin composition is coated on a substrate having excellent releasability and then coated with 50 to 50%. Preliminary drying is performed at 80 ° C. to evaporate the solvent to solidify, and further main drying is performed at 140 to 160 ° C. to form a glossy synthetic resin coating film.

When a glossy synthetic resin film of a laminated film is produced, a colored liquid synthetic resin composition is further coated on the glossy synthetic resin coating film formed on the substrate by the above-mentioned method. After the application, the coating may be dried in the same manner to form a colored synthetic resin coating film, and the laminated film may be separated from the substrate.

In forming the film, the liquid synthetic resin composition used for forming the film is formed in order to prevent the gloss pigment from cracking and to improve the compoundability without impairing the film forming property. The solvent content is preferably 360 to 440 parts by weight with respect to 100 parts by weight of the resin component,
The gloss pigment is preferably contained in an amount of 1 to 40 parts by weight based on 100 parts by weight of such a resin component.

The glossy synthetic resin film produced as described above has a thickness of 100 μm or less, particularly 40 to 80 μm if it is a single-layer film, and a thickness of 60 μm or less if it is a laminated film. Especially 20-40μ
m glossy synthetic resin layer and a thickness of 90 μm or less, especially 40 to
It is preferable that a colored synthetic resin layer of 70 μm is laminated.

The glossy synthetic resin film of the present invention thus produced is a film having a beautiful glossiness and a remarkably excellent decorative property, and also excellent in weather resistance.
By providing an adhesive layer or the like on one side, it can be suitably used in a wide range of fields as a used marking film, poster, wall material for decoration, etc. instead of paint.

[0040]

The present invention will be described more specifically below with reference to examples and comparative examples. In the following, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively.

In the following Examples and Comparative Examples, a base synthetic resin composition was first prepared by the following method in order to prepare a liquid synthetic resin composition as a film forming raw material. [Method of Preparing Base Synthetic Resin Composition] Polyvinyl chloride resin: 100 parts, polyester plasticizer: 20 parts, heat stabilizer: 4 parts, ultraviolet absorber: 0.8
Part and cationic surfactant (polyoxyethylene alkylamine): 0.1 part is mixed and dissolved in a mixed solvent of 80 parts of tetrahydrofuran and 320 parts of cyclohexanone using a Hobart mixer to prepare a base resin composition (I). did.

2. Polyvinyl chloride resin for paste: 10
0 parts, polyester plasticizer: 35 parts, heat stabilizer: 4
Part, ultraviolet absorber: 0.8 part, cationic surfactant (polyoxyethylene alkylamine): 0.1 part, methyl isobutyl ketone 26 parts, mineral spirit 13
Parts and 13 parts of toluene were kneaded using a crusher to prepare a base resin composition (II).

The specifications of the gloss pigment used in Examples and Comparative Examples are as follows.

[0044]

[Table 1]

Example 1 Metashine RCFSX-5090RS (8078) was mixed with 7 parts of the base synthetic resin composition (I) and mixed gently to prepare a glossy synthetic resin composition A. This glossy synthetic resin composition A is applied on a substrate made of a polyester film so as to have a thickness of 250 μm,
After predrying at 150 ° C. to solidify and further drying at 150 ° C., the film was peeled off from the substrate to obtain a single-layer film of the present invention.

The monolayer film thus obtained has a thickness of about 50 μm, and the gloss pigment is oriented almost parallel to the film surface. It was excellent in transparency, and had a deep glittering property without a feeling of foreign matter or dullness.

Example 2 The glossy synthetic resin composition A prepared in Example 1 was applied on a substrate made of silicone resin-treated release paper so as to have a thickness of 150 μm, and preliminarily dried at 50 to 80 ° C. It was solidified and further dried at 150 ° C.

Next, a colored synthetic resin composition B was prepared by adding 0.07 parts of a green pigment to the base synthetic resin composition (II).
It was applied so as to have a thickness of 0 μm, preliminarily dried at 120 to 150 ° C. to solidify, and further completely gelled at 200 to 220 ° C., and then peeled from the substrate to obtain a laminated film of the present invention.

The laminated film thus obtained is
The thickness is about 90μm, and the gloss pigment is oriented almost parallel to the upper layer of the film surface. As a result of visual inspection with natural light, it has excellent glittering properties against a green background, and feels foreign matter and dullness. It was a very beautiful thing with a three-dimensional feeling that could not be done.

Example 3 In the preparation of the glossy synthetic resin composition A in Example 1, Metashine RCFSX-509 was used as a gloss pigment.
A glossy synthetic resin composition C was prepared in the same manner except that 0RC (8052) was used, and a single-layer film of the present invention was obtained using this glossy synthetic resin composition C in the same manner as in Example 1. Was.

The film thus obtained had a thickness of about 50 μm and, like the monolayer film of Example 1, had gloss pigments oriented substantially parallel to the film surface and was visually observed under natural light. As a result of the examination, excellent gloss and transparency,
Moreover, it had a deep glittering property without a feeling of foreign matter or dullness.

Example 4 The multilayer film of the present invention was prepared in the same manner as in Example 2 except that the glossy synthetic resin composition C prepared in Example 3 was used instead of the glossy synthetic resin composition A. Obtained.

The laminated film thus obtained is
The thickness is about 90 μm, and as in the multilayer film of Example 2, the gloss pigment is oriented almost parallel to the upper layer of the film surface. It was excellent in brilliantness and was very beautiful with a three-dimensional effect without a feeling of foreign matter or dullness.

The evaluation results of Examples 1 to 4 are summarized in Table 2.

Comparative Examples 1 to 3 In the preparation of the glossy synthetic resin composition A in Example 1, Astroflake No. 1 was used as a glossy pigment. 10 (Comparative Example 1), Glossy Synthetic Resin Composition D, and Glossy Synthetic Resin Composition, respectively, except that Metashine RCFS5090PS02 (Comparative Example 2) or Pearl Glaze MS-100R (Comparative Example 3) were used. E, a glossy synthetic resin composition F was prepared, and each of the glossy synthetic resin compositions D, E,
Using F, single-layer films were obtained in the same manner as in Example 1, and the same evaluation was performed. The results are shown in Table 2.

Comparative Examples 4 to 6 In Example 2, the glossy synthetic resin composition D prepared in Comparative Examples 1 to 3 was used instead of the glossy synthetic resin composition A.
(Comparative Example 4), glossy synthetic resin composition E (Comparative Example 5),
A multilayer film was obtained in the same manner except that the glossy synthetic resin composition F (Comparative Example 6) was used.
The results are shown in Table 2.

[0057]

[Table 2]

As is clear from Table 2, according to the present invention, there is no foreign substance sensation or dullness, excellent brilliancy with a three-dimensional effect, extremely good transparency, and beautiful gloss with excellent decorativeness. It can be seen that a hydrophilic synthetic resin film can be obtained.

[0059]

As described in detail above, according to the glossy synthetic resin film of the present invention and the method for producing the same, there is no foreign substance or dullness, excellent three-dimensional brilliancy and extremely good transparency. In addition, a beautiful glossy synthetic resin film having excellent decorativeness is provided. The glossy synthetic resin film of the present invention is a film having such a beautiful glossiness and a remarkably excellent decorative property, and also having excellent weather resistance. It can be suitably used in a wide range of fields as a marking film, a poster, a wall material for decoration, etc. used instead.

Claims (7)

[Claims] 1. A glossy synthetic resin film comprising a glossy synthetic resin layer containing a glossy pigment, wherein the glossy pigment has a surface of a flake-like glass having a higher refractive index than that of the glass of the flake-like glass. A glossy synthetic resin film, which is a flake-like particle coated with: 2. The glossy synthetic resin film according to claim 1, comprising the glossy synthetic resin layer. 3. A glossy synthetic resin film according to claim 1, wherein said glossy synthetic resin layer and a colored synthetic resin layer are laminated. 4. The flake-like particle according to claim 1, wherein the flake-like particles have an average thickness of 0.05 to 7 μm and an average particle size of 10 to 300 μm, A glossy synthetic resin film comprising a coating layer having a thickness of 0.02 to 0.8 μm. 5. The glossy synthetic resin layer according to claim 1, wherein the content of the glossy pigment in the glossy synthetic resin layer is 1%.
A glossy synthetic resin film characterized in that the content is from 40 to 40% by weight. 6. The glossy synthetic resin film according to claim 1, wherein the thickness of the glossy synthetic resin layer is 100 μm or less. 7. A coating material obtained by blending a gloss pigment with a liquid synthetic resin composition containing a solvent is applied on a substrate, and the solvent is volatilized to obtain a synthetic resin coating film.
Next, a method for producing a glossy synthetic resin film in which this coating film is peeled from a substrate, wherein the surface of the flake glass is a metal oxide having a higher refractive index than the glass of the flake glass as the gloss pigment. The method for producing a glossy synthetic resin film according to any one of claims 1 to 6, wherein scale-like particles coated are used.