JPH09109338A - Protective and decorative colored film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film for forming a protective decorative film on the surface of a molding simultaneously upon injection molding. SOLUTION: A laminated film is formed of a light reflecting layer, a colored transparent layer and a colorless transparent layer. The reflecting layer contains vinyl chloride resin and 2 to 30 pts.wt. of plasticizer and 0.1 to 5 pts.wt. of light reflecting pigment per 100 pts.wt. of the resin and has a thickness of 50 to 300μm. The colored transparent layer contains vinyl chloride resin and 2 to 30 pts.wt. of plasticizer per 100 pts.wt. of the resin and has total light ray permeability of 10% or more and a thickness of 50 to 300μm. The colorless transparent layer contains any one or mixture of two or more of fluororesin, acrylic resin and urethane resin and a thickness of 5 to 60μm. The protective and decorative colored film is obtained by sequentially laminating the light reflecting layer, the colored transparent layer and the colorless transparent layer in this order.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored film having excellent appearance and weather resistance, and more specifically, a protective film capable of forming a decorative film simultaneously with injection molding on the surface of a molded article manufactured by an injection molding method. The present invention relates to a colored film for decoration.

[0002]

2. Description of the Related Art Conventionally, a decorative film mainly made of an opaque or transparent vinyl chloride resin film colored with a pigment or the like has been used for improving the surface design of furniture or wall coverings, or as a signboard or a signboard. It is used as a substitute for painting vehicles. Since such a film is usually attached after the production of a molded product, it does not follow the cubic curved surface sufficiently and is difficult to apply to a molded product having a small radius of curvature such as an injection molded product.

As a method for solving such problems and imparting a design to an injection-molded article, for example, Japanese Patent Publication No. 5-4.
In Japanese Patent No. 1089, a coating film (decorative film) obtained by laminating a metallic compound layer on a releasable film via a transparent layer (clear layer) is closely fixed to the mold surface of a mold cavity for injection molding. In Japanese Patent Publication No. 6-26718, a flexible decorative sheet is formed, and a substantially transparent outer layer made of acrylic resin, vinyl chloride or the like is used, and vinyl chloride or the like is used. A method has been proposed in which a colored layer containing reflective flakes is laminated and a sheet having an adhesive film formed thereon is attached at the same time as injection molding. It is said that such a method has an advantage that the process can be rationalized (the coating process is omitted) and the solvent discharge at the time of coating can be suppressed, as compared with the conventional design giving method by coating.

However, although the film used in the above technique has good followability to the cubic curved surface, when the target molded product also includes a deep-drawn shape or a shape with a small radius of curvature, the film has a glossy surface. It is difficult to obtain the same appearance as that by painting.

[0005]

DISCLOSURE OF THE INVENTION The present inventors have found that in a film for forming a protective decorative film on the surface of a molded product at the same time as injection molding, the molded product having a cubic curved surface, particularly this molded product It is an object of the present invention to provide a film having a color tone equivalent to that of metallic coating, in which a change in color tone and a decrease in gloss of these portions are small when including a diaphragm shape and a shape having a small radius of curvature.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made diligent studies on the above-mentioned problems relating to a film for forming a protective decorative film simultaneously with injection molding, and as a result, the film has a specific composition and a thickness of 3%. It was found that these problems can be solved by forming a layered body or a laminated body of four layers, and completed the present invention.

That is, the gist of the present invention is to provide a light reflecting layer (A),
A laminated film comprising a colored transparent layer (B) and a colorless transparent layer (C), wherein the light reflecting layer (A) comprises a vinyl chloride resin and 2 to 30 parts by weight of a plasticizer per 100 parts by weight of the resin, and A thickness of 50 to 30 containing 1 to 5 parts by weight of a light-reflecting pigment
A layer having a thickness of 0 μm and a colored transparent layer (B) containing a vinyl chloride resin and 2 to 30 parts by weight of a plasticizer per 100 parts by weight of the resin and having a total light transmittance of 10% or more and a thickness of 50 to 200 μm.
m is a transparent layer, and the colorless transparent layer (C) is a fluororesin,
A thickness of 5 to 60 μm made of any one of acrylic resin and urethane resin or a mixture of two or more thereof.
A protective decorative colored film, characterized in that it is a layer of m and is laminated in the order of light reflecting layer (A) / colored transparent layer (B) / colorless transparent layer (C).

Another gist of the present invention is the light reflecting layer (A).
Exists in the protective decorative colored film containing 0.01 to 8 parts by weight of the coloring pigment per 100 parts by weight of the vinyl chloride resin, and further contains 2 to 30 parts by weight of the vinyl chloride resin and 100 parts by weight of the resin. The present invention also exists in the above-mentioned protective decorative colored film comprising a light-reflecting layer (A) and a colored hiding layer (D) having a total light transmittance of 10% or less and a thickness of 50 to 300 μm, which is laminated on the light reflecting layer (A).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The vinyl chloride resin used in the present invention includes not only a vinyl chloride homopolymer but also a copolymer of vinyl chloride and another monomer copolymerizable therewith. As the other monomer copolymerizable with the vinyl chloride monomer, those generally used in the related art can be used and are not particularly limited.
Examples of the other monomer include vinyl acetate, vinyl propionate, vinyl stearates, and other vinyl esters, methyl vinyl ether, ethyl vinyl ether,
Alkyl vinyl ethers such as octyl vinyl ether, lauryl vinyl ether and cetyl vinyl ether, α-olefins such as ethylene, monounsaturated acids such as acrylic acid and methacrylic acid, alkyl esters of these monounsaturated acids such as methyl ester and ethyl ester. Esters, divalent unsaturated acids such as maleic acid, fumaric acid, itaconic acid, etc., methyl esters of these divalent unsaturated acids, alkyl esters such as ethyl esters, vinylidene compounds such as vinylidene chloride, and unsaturated compounds such as acrylonitrile. Examples include one kind or a mixture of two or more kinds such as nitrile. These monomers are usually 30% by weight or less based on the vinyl chloride monomer,
It is preferably used in a proportion of 20% by weight or less, but there is no particular limitation.

The vinyl chloride resin used in the present invention has a degree of polymerization of 600 to 1300, preferably 700 to 1
100 is good. If the degree of polymerization is too low, the film will soften in the injection mold and wrinkles easily occur.Conversely, if the degree of polymerization is too high, it will be difficult to mold the film, or the elongation will be insufficient during injection molding. , It is difficult to make deep drawing.

As the plasticizer used in the present invention, any plasticizer usually used for vinyl chloride resins can be used without particular limitation. For example, di-ethylhexyl phthalate, diisononyl phthalate, di-n-phthalate
-Phthalic acid diester plasticizers such as octyl, trimellitic acid tree 2-ethylhexyl, trimellitic acid triester plasticizers such as trimellitic acid triisodecyl,
Dibasic acid diester plasticizers such as di-2-ethylhexyl adipate, diisononyl azelate and di-2-ethylhexyl sebacate, aliphatic dibasic acids such as adipic acid and glycols such as 1,4-butanediol Examples include condensed polyester polyester plasticizers, tricresyl phosphate, phosphate triester plasticizers such as triphenyl phosphate, and epoxidized soybean oil, epoxidized linseed oil, epoxy plasticizers such as epoxy resins. it can.

The plasticizer is used in an amount of 2 to 100 parts by weight of the vinyl chloride resin in both the light reflecting layer (A) and the colored transparent layer (B).
30 parts by weight, preferably 5 to 20 parts by weight, more preferably 10 to 15 parts by weight. If the plasticizer content is less than 2 parts by weight, the processability during film forming becomes insufficient, and if it exceeds 30 parts by weight, the film softens in the mold during injection molding and wrinkles appear on the surface of the molded product. Easy to enter.

The thickness of the light reflecting layer (A) is 50 to 300 μm.
m, preferably 70 to 200 μm. Thickness is 50μ
When it is less than m, color unevenness is likely to occur due to partial expansion and contraction when the molded product is molded according to the curved surface. Further, when the thickness of the light reflection layer (A) exceeds 300 μm, the heat capacity of the film becomes large, which requires long preheating during injection molding and insufficient moldability in the deep-drawn portion. Become. The light-reflecting layer (A) contains a light-reflecting pigment in addition to the vinyl chloride resin and the plasticizer.
0.1-5 parts by weight per 00 parts by weight, preferably 0.3
It is necessary to contain ~ 3 parts by weight. When the content of the pigment is less than 0.1 parts by weight, the design properties such as the desired metallic luster (metallic feeling) and pearl luster (pearl feeling) are insufficient, and when it is used in excess of 5 parts by weight, The pigment appears to float, and the pigment reduces the brightness, so that only dark-colored films and molded products can be obtained.

Examples of the light-reflecting pigment include metal powders such as aluminum and copper, pearl essence, mica flakes or those whose surface is coated with titanium dioxide. Further, a color pigment may be added to the light reflecting layer (A) in order to conceal the color of the resin serving as the base material or depending on the color tone of the target molded article. The amount of the color pigment added is preferably 0.01 to 8 parts by weight per 100 parts by weight of the vinyl chloride resin.

The color pigment may be selected from inorganic pigments and organic pigments, such as carbon black, titanium oxide, kaolin clay, zinc white, red iron oxide, lake red C, permanent red, permanent orange, molybdenum orange, yellow lead, Examples include Hansa Yellow, cobalt green, phthalocyanine green, ultramarine blue, phthalocyanine blue, cobalt blue, manganese violet, cobalt violet, and quinacridone violet. These pigments can be used alone or in combination of two or more kinds. Also, to improve the concealment,
Fillers such as calcium carbonate, magnesium carbonate, talc and silica may be used together.

The colored transparent layer (B) has a total light transmittance of 10% or more, preferably 90% or less, and a thickness of 50 to 200 μm, in addition to the plasticizer content within the above range. It is necessary. When the total light transmittance is less than 10%, the light reflection layer (A) is hidden by the colored transparent layer (B), and when it exceeds 90%, a sufficient gloss feeling cannot be obtained.
The total light transmittance referred to in the present invention means a wavelength of 550 nm.
Is the ratio (percentage) between the intensity of the total transmitted light including the scattered light and the intensity of the incident light when the light rays of (2) pass through the film.

The colored transparent layer (B) is added with a necessary amount of one or a mixture of two or more kinds of organic pigments and inorganic pigments which can be used in the above-mentioned light reflecting layer (A) according to the intended color tone. To do. The amount of the pigment added is adjusted so that the total light transmittance of the colored transparent layer (B) is 10% or more, preferably 90% or less. Further, the thickness of the colored transparent layer (B) is 50
When it is less than μm, it is difficult to process it into a film because the pigment concentration must be remarkably increased in order to reduce the total light transmittance to 10% or less. Even if a film is obtained, the curved surface of the substrate When it is molded in accordance with the above, color unevenness is likely to occur due to partial expansion and contraction. Conversely, 2
If the thickness exceeds 00 μm, the heat capacity of the film becomes large, so that preheating for a long time is required at the time of injection molding, or uneven stretching and uneven coloring are likely to occur.

The colorless transparent layer (C) is made of any one of fluorine resin, acrylic resin and urethane resin, or a mixture of two or more thereof. As the fluororesin, polytetrafluoroethylene, polytrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride or a copolymer resin of a monomer constituting these fluororesins and a monomer copolymerizable therewith Etc. can be illustrated.

Examples of the acrylic resin include polymers of acrylic acid or methacrylic acid or their alkyl esters such as methyl ester and ethyl ester, alkenylbenzenes and α, which are copolymerizable with these monomers. Examples thereof include polymers with comonomers such as β-unsaturated monomers. As the urethane-based resin, a polyol such as polyester or polyether having two or more hydroxyl groups in the molecule is reacted with an aliphatic or aromatic polyisocyanate having two or more isocyanate groups in the molecule. An example of the urethane-based resin thus obtained is

The colorless transparent layer (C) has a thickness of 5 to 60 μm,
It is preferably 10 to 30 μm. If the thickness is less than 5 μm, the gloss of the surface is insufficient, and if the thickness exceeds 60 μm, the followability to the mold during injection molding becomes insufficient.

Further, in the present invention, the colored hiding layer (D) is used for the purpose of hiding the color of the resin as the base material on the surface of the light reflecting layer (A) on which the colored transparent layer (B) is not laminated. May be laminated. The colored hiding layer (D) is preferably a layer having a thickness of 50 to 300 μm and a total light transmittance of 10% or less containing a vinyl chloride resin and 2 to 30 parts by weight of a plasticizer per 100 parts by weight of the resin, Further, it is more preferable that the total light transmittance is 7% or less. If the amount of the plasticizer compounded is less than 2 parts by weight, the processability during film forming becomes insufficient, and 3
If the amount exceeds 0 parts by weight, the film is softened in the mold during injection molding, and wrinkles are easily formed on the surface of the molded product. When the thickness of the colored concealing layer (D) is less than 50 μm, color unevenness is likely to occur due to partial expansion and contraction when molded according to the curved surface of the molded product. Conversely, the thickness is 300 μm
If it exceeds, the heat capacity of the film will increase,
Pre-heating for a long time is required at the time of injection molding, and moldability in the deep-drawn portion becomes insufficient.

In the colored hiding layer (D), one or a mixture of two or more kinds of the organic pigments and the inorganic pigments used in the light reflecting layer (A) described above is provided in a desired color tone and a degree of hiding. Add the required amount accordingly. By setting the total light transmittance to 10% or less, the hiding property is increased, and the surface color tone of the molded product after coating with the protective decorative colored film (hereinafter referred to as "decorative film") becomes the base material of the molded product. It can be made less susceptible to the color tone of the resin.

The light-reflecting layer (A), the colored transparent layer (B) and the colored hiding layer (D) are composed of a vinyl chloride resin containing a predetermined amount of a plasticizer, a coloring agent and / or a light-reflecting pigment, and various vinyl chlorides. A resin composition is obtained by blending an additive for a system resin and mixing with a mixer such as a ribbon blender, a Banbury mixer, or a super mixer, and the resin composition is obtained by an extrusion molding method such as a T-die method or an inflation method, a calendar method, or a casting method. It can be manufactured by forming a film by a method or the like.

When the decorative film and the molded article coated with the film are mainly used outdoors, the light reflecting layer (A), the colored transparent layer (B) and the colored hiding layer (D) are exposed to ultraviolet rays. It is advisable to add light stabilizers such as absorbers and hindered amines. As a method for laminating the light reflection layer (A), the colored transparent layer (B) and, if necessary, the colored hiding layer (D), two or three kinds of the above-mentioned films are prepared in advance and a heating type laminator is used. A method of pressing these films, a method of laminating using an acrylic or urethane adhesive, a two-layer or three-layer T-die, or a two-layer or three-layer inflation to form a laminate simultaneously with film formation. And the like.

Even if the colorless transparent layer (C) is laminated as a film as in the case of the above-mentioned light reflecting layer (A), colored transparent layer (B) and colored hiding layer (D), it is colored as a coating liquid. One surface of transparent layer (B) (surface opposite to light reflection layer (A))
It may be formed by coating. When the colorless transparent layer (C) is applied and formed as a coating liquid, the resin to be used is dissolved in a solvent and formed by an ordinary method using a gravure roll coater, a reverse roll coater, a die coater, a flow coater or the like. Good. The obtained coating film can also be dried by a commonly used hot air drying method, for example, by heating at a temperature of 80 to 150 ° C for 0.5 to 3 minutes.

In order to form a decorative film on the surface of a molded product simultaneously with injection molding using the decorative film of the present invention, a mold capable of in-mold molding is attached to an injection molding machine, and a film feeding device and film are attached. An apparatus equipped with a heating plate and a vacuum pump for sucking the film is adhered to the inner surface of the cavity of the injection mold so that the colorless transparent layer (C) becomes the surface layer of the molded product, and then the injection molding is performed. Just go.

Alternatively, the decorative film may be vacuum-formed by a vacuum forming machine in advance so as to fit the injection-molding die, and then the inner surface of the cavity of the injection-molding die may be closely adhered to the injection-molding die. The decorative film of the present invention has a uniform distribution of the light-reflecting pigment, and since the unevenness of the light-reflecting layer (A) is small, the change in gloss due to the elongation of the film is small, and the colored transparent layer (B) is also small. Is provided between the light-reflecting layer (A) and the colorless transparent layer (C), the glossiness of the light-reflecting pigment is weakened and a deeper glossiness similar to that of coating can be obtained. Furthermore, by providing the colored hiding layer (D) on the light reflection layer (A) for ensuring hiding properties, the surface color tone of the molded article can be made less susceptible to the color tone of the resin as the base material. Further, it has a feature that it is possible to prevent a decrease in the concealing property during injection molding.

[0028]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. Preparation of Film (Examples 1 to 3, Comparative Examples 1 to 6) Vinyl chloride resin compositions having the compositions shown in Table 1 were mixed with a super mixer and then kneaded on a roll heated to 185 ° C. for 5 minutes. Then
Films a to d corresponding to the light reflecting layer (A), films e to g corresponding to the colored transparent layer (B), and a colored hiding layer (D).
A film h, i corresponding to

The films e to g, h, and i corresponding to the colored transparent layer (B) and the colored hiding layer (D) are Hitachi 33
The total light transmittance for the light having a wavelength of 550 nm was measured using a 0 type spectrophotometer. The results are shown in Table 1. Next, the obtained films having various compositions were laminated in order as shown in Table 2 to obtain a decorative film.

The film is laminated at a roll temperature of 18
Roll surface speed of 0.5m / with laminator at 0 ℃
Min, linear pressure was 2.8 Kg / cm. The colorless transparent layer (C) is a colored transparent layer of a laminated film formed by a Nippon Paint Material Co., Ltd. urethane coating (trade name PU-701) with a bar coater to a predetermined coating thickness. After being coated on (B), it was dried at a temperature of 120 ° C. for 3 minutes to form a film.

Evaluation of Film An injection molding die having a fixing frame for a film insert (decrease ratio of 0.
11, the minimum R5mm), injection molding is performed under the conditions of a film preheating temperature of 100 ° C and a resin temperature of 190 ° C.
A decorative film was formed on the surface of the molded product.

This molded product has a small radius of curvature (R5
mm portion), the color difference (ΔE) from the film before injection molding was measured with a COLOR-7e ² type color difference meter manufactured by Kurabo. In addition, the surface gloss (gloss) of this part can be measured with a portable gloss meter (Murakami Color Research Laboratory, G
MX-202 type), both the incident angle and the reflection angle are 60 °
It measured on condition of. A color difference of 0.2 or less and a 60 ° gloss of 80 or more were judged to be good. Further, the metallic feeling of this portion and the presence or absence of wrinkles on the surface were visually evaluated.

<Metallic feeling> Excellent: It is close to metallic coating. Good: Similar to metallic paint, but inferior to excellent. Poor: The metallic pigment appears to float. The results are shown in Table 2.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

EFFECT OF THE INVENTION By using the decorative film of the present invention, a portion having a small radius of curvature in a molded product when a metallic or pearly light-reflecting (glossy) design is imparted to the molded product simultaneously with injection molding The decrease in gloss and the change in color tone are reduced, and the appearance of the molded product is improved.

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Claims (3)

[Claims] 1. A laminated film comprising a light reflection layer (A), a colored transparent layer (B) and a colorless transparent layer (C), wherein the light reflection layer (A) is a vinyl chloride resin and 100 parts by weight of the resin. A layer having a thickness of 50 to 300 μm and containing 2 to 30 parts by weight of a plasticizer and 0.1 to 5 parts by weight of a light-reflecting pigment, wherein the colored transparent layer (B) is a vinyl chloride resin and the resin 100.
A transparent layer having a total light transmittance of 10% or more and a thickness of 50 to 200 μm containing 2 to 30 parts by weight per part by weight of a plasticizer, and the colorless transparent layer (C) is a fluororesin, an acrylic resin or a urethane resin. Which is a layer having a thickness of 5 to 60 μm, which is made of any one of the above or a mixture of two or more thereof, and is a light reflecting layer (A) / colored transparent layer (B) / colorless transparent layer (C).
A colored film for protective decoration, which is laminated in the order of. 2. The light-reflecting layer (A) comprises a vinyl chloride resin 10
The colored film for protective decoration according to claim 1, which comprises 0.01 to 8 parts by weight of a coloring pigment per 0 parts by weight. 3. A total light transmittance of 10 including a vinyl chloride resin and 2 to 30 parts by weight of a plasticizer per 100 parts by weight of the resin.
% Or less, and the colored concealing layer (D) having a thickness of 50 to 300 μm is laminated on the light reflecting layer (A).