JP2002001877A - Colored film for in-molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored film for in-molding formed by laminating a color base coating film and a clear coating film having a specific composition on a plastic film, excellent in hardness and molding processability and used for being bonded to a plastic molded object to impart aesthetic properties and durability. SOLUTION: The colored film used for being bonded to the plastic molded object is formed by coating the surface of the color base coating film on the plastic film with clear paint containing (a) a hydroxyl group-containing resin with a glass transition temperature of 10-60 deg.C, a weight average mol.wt. of 30,000-150,000 and a hydroxyl number of 5-55, (b) an alicyclic polyisocyanate compound and (c) cellulose acetate butyrate. A plastic molded product of which the surface is colored is obtained by integrally bonding the color film to be surface of the plastic molded object.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored film obtained by laminating a colored base coating film and a clear coating film of a specific composition on a plastic film, which is hard and has excellent moldability. It is useful for applying to cosmetics and durability by sticking to plastic molded articles.

[0002]

2. Description of the Related Art Plastics, particularly polypropylene resin molded products, are widely used as members of automobiles, home electric appliances and the like. The surface is usually coated with a colored paint in order to impart aesthetics and durability. However, there is a defect that the coating cost is increased due to insufficient coating efficiency of the coating material, and that it is difficult to uniformly coat the curved surface and the corner of the molded product.

As a method of solving these defects, for example, it has been proposed that a laminated colored film composed of a plastic film, a colored base coating film, an adhesive layer and a clear film is adhered to a plastic molded body and integrally molded. Have been. According to this method, the above-mentioned defects are eliminated, but for the production of a laminated colored film, an adhesive is applied to a clear film, a colored base paint is applied to a plastic film, and a heat lamination of both films is performed. Is necessary, the operation for that is extremely complicated,
In addition, there are defects such as air bubbles being easily mixed between these layers and insufficient adhesion between the clear film and the colored base coating film.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned defects particularly in a laminated colored film. As a result of intensive studies, a glass transition temperature of 10 to 60.degree. Average molecular weight 30,000-
150,000, a hydroxyl group-containing resin having a hydroxyl value of 5 to 55, an alicyclic polyisocyanate compound, and a clear paint containing cellulose acetate butyrate were found to achieve the object, and the present invention was completed. .

According to the present invention, (a) a glass transition temperature of 10 to 60 ° C. and a weight average molecular weight of 30,000 to 15,000
0. A color for sticking on a plastic molded body, which is obtained by applying a clear paint containing 0, a hydroxyl group-containing resin having a hydroxyl value of 5 to 55, (b) an alicyclic polyisocyanate compound and (c) cellulose acetate butyrate. A film is provided.

The colored film of the present invention is mainly composed of three layers: a plastic film (A), a colored base coating film (B) and a clear coating film (C). It is preferable that the colored film and the molded body are integrally molded so that the colored film is adhered so as to be in contact with the body surface.

It is preferable that the plastic film (A) has excellent adhesiveness to a resin molded body and workability. Specifically, ABS resin, styrene resin,
A film known per se such as an acrylic resin, a vinyl chloride resin, polyethylene, polypropylene, and polycarbonate can be suitably used. These films have a thickness of about 20 to about 1000 μm, especially about 100 to about 500 μm.
m, elongation (20 ° C.) is 10% or more, especially 20 to 500
%. In addition, this film itself,
It can be colorless, transparent, colored or opaque.

[0008] The colored base coating film (B) imparts a color design to the plastic molded article, and includes, for example, a solid color coating film, a metallic coating film, a light interference coating film and a multi-colored coating film. Can be Specifically, it can be formed by applying a liquid color paint obtained by mixing a base resin and a color pigment with an organic solvent and / or water.

The base resin is dried in an atmosphere at a temperature not higher than the temperature at which the plastic film (A) is not deformed and deteriorated (for example, 140 ° C. or lower, preferably 100 ° C. or lower).
Alternatively, a component that forms a three-dimensionally cross-linked and cured coating film can be used, for example, an acrylic resin, a polyester resin, an alkyd resin, a urethane resin, and the like. These may have a cross-linkable functional group such as a hydroxyl group. No problem. Further, a crosslinking agent such as a melamine resin or a (block) polyisocyanate compound which reacts with these functional groups can be used in combination. The ratio of the base resin to the crosslinking agent is 50 to 90% by weight, preferably 65 to 80% by weight, the latter is 50 to 10% by weight, particularly 3
A range of 5 to 20% by weight is suitable.

As coloring pigments, titanium oxide, carbon black, graphite, loess, yellow iron oxide, Hansa yellow, pigment yellow, chrome orange, chrome vermilion,
Solid color pigments such as permanent orange, amber, permanent red, brilliant carmine, fast violet, methyl violet lake, ultramarine, navy blue, cobalt blue, phthalocyanine blue, pigment green, naphthol green; aluminum powder, evaporated aluminum, aluminum oxide, bronze powder Metallic pigments, such as copper powder, tin powder, mica-like iron oxide;
Examples include, but are not limited to, light interference pigments such as mica flakes and mica flakes coated with titanium oxide or iron oxide. One or more of these can be used.

The compounding amount of the color pigment is suitably 0.5 to 200 parts by weight per 100 parts by weight of the base resin (including the cross-linking agent). Metallic coatings, light interference coatings, multi-colored coatings, etc. can be formed. The coloring paint for forming the coloring base coating film (B) can be prepared by mixing the above-mentioned base resin and coloring pigment with an organic solvent and / or water.

The clear coating film (C) has a glass transition temperature of 10
６０60 ° C., weight average molecular weight 30,000-150,000,
It can be formed by applying a clear paint containing a hydroxyl group-containing resin (a) having a hydroxyl value of 5 to 55, an alicyclic polyisocyanate compound (b) and a cellulose acetate butyrate (c).

The hydroxyl group-containing resin (a) has a glass transition temperature of from 10 to 60 ° C., preferably from 20 to 40 ° C., and a weight average molecular weight of from 30,000 to 150,000, preferably from 60,000 to 60,000.
120,000, hydroxyl value 5-55, preferably 30-5
Any resin may be used as long as it falls within the range of 5, and a vinyl resin is particularly preferable. Such a vinyl resin can be prepared, for example, by copolymerizing a hydroxyl group-containing unsaturated monomer with another unsaturated monomer.

The hydroxyl group-containing unsaturated monomer is a compound having at least one hydroxyl group and at least one polymerizable unsaturated double bond in one molecule. Examples thereof include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. And an equimolar addition product of an alkylene glycol having 2 to 10 carbon atoms such as hydroxybutyl (meth) acrylate and (meth) acrylic acid.

Other unsaturated monomers are compounds having one or more polymerizable unsaturated double bonds in one molecule, and do not include the above-mentioned hydroxyl group-containing unsaturated monomers. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate,
Propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate,
1-20 carbon atoms such as stearyl (meth) acrylate
Monoester of monoalcohol with (meth) acrylic acid; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate And carboxyl group-containing unsaturated compounds such as carboxypentyl (meth) acrylate; glycidyl (meth) acrylate and glycidyl group-containing unsaturated compounds such as allyl glycidyl ether; perfluorobutylethyl (meth) acrylate;
Perfluoroisononylethyl (meth) acrylate,
Perfluoroalkyl (meth) acrylates such as perfluorooctylethyl (meth) acrylate; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and α-chlorostyrene; N, N-dimethylaminoethyl (meth) acrylate , N, N-diethylaminoethyl (meth) acrylate, nitrogen-containing alkyl (meth) acrylates such as Nt-butylaminoethyl (meth) acrylate; acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl ( (Meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N,
Polymerizable amides such as N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide; 2-vinylpyridine, 1-vinyl-2-pyrrolidone And aromatic vinyl-containing monomers such as 4-vinylpyridine, and polymerizable nitriles such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more.

The vinyl resin as the hydroxyl group-containing resin (a) is prepared by copolymerizing the above-mentioned hydroxyl group-containing unsaturated monomer and other unsaturated monomers by a known method such as solution polymerization. Can be. The glass transition temperature can be easily adjusted by the unsaturated monomer components and the ratio thereof. With respect to the hydroxyl group-containing resin (a), if the glass transition temperature, the weight average molecular weight and the hydroxyl value deviate from the above ranges, the object of the present invention cannot be achieved, which is not preferred.

Alicyclic polyisocyanate compound (b)
Is a compound in which two or more isocyanate groups are directly bonded to a carbon atom of an alicyclic hydrocarbon, for example, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (Or -2,6-) diisocyanate, 1,
3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane diisocyanate,
Examples thereof include 1,3-cyclopentane diisocyanate and 1,2-cyclohexane diisocyanate. Further, these alicyclic polyisocyanate compounds and an isocyanate group in an excess amount with respect to the hydroxyl groups of polyols such as ethylene glycol, propylene glycol, 1,4-butylene glycol, polyalkylene glycol, trimethylolpropane, and hexanetriol. Products obtained by reacting at a certain ratio, burette type adducts, isocyanuric ring type adducts, and the like can also be used as the alicyclic polyisocyanate compound.

Cellulose acetate butyrate (c)
Is a product obtained by further butyl esterifying an acetylated product of cellulose (CAB).
-30% by weight, preferably 1-14% by weight, a butyl group content of 16-60% by weight, preferably 35-60% by weight, and ASTM-D1343-54T (Formul
Those having a viscosity of 0.05 to 5 seconds, preferably 0.005 to 1 second, as measured by the viscosity measurement method described in A). Specifically, the United States
Trade name [manufactured by Stoman Kodak Co.] [The first two digits indicate the butyl group content (% by weight), the third digit indicates the hydroxyl group content, and the second digit indicates the viscosity (seconds). ], CAB-171-2, CAB-381-0.
5, CAB-381-2, CAB-531-1, CAB
-551-0.2, CAB-551-0.01 and the like are advantageously used. Among them, CAB-551-0.2, CAB-551-, and the like in view of compatibility, solubility, viscosity and the like.
0.01 is preferred. The clear paint for forming the clear coating film (C) contains the above-mentioned components (a), (b) and (c), and further, if necessary, makes the above-mentioned coloring pigment transparent. It can be contained to such an extent that it does not hinder, and is obtained by mixing these with an organic solvent, and the coating film is colorless and transparent or colored and transparent.

The ratio of each component in the clear paint can be arbitrarily selected according to the purpose.
Component (c) is 20 to 6 per 100 parts by weight of component (a).
0 parts by weight, especially 30 to 50 parts by weight, is preferred. Also,
The equivalent ratio of the hydroxyl group of the component (a) to the isocyanate group of the component (b) is 0.2 to 0.8, based on OH / NCO,
Particularly, it is preferably in the range of 0.4 to 0.6.

The colored film of the present invention comprises three layers: a plastic film (A), a colored base coating film (B) and a clear coating film (C). For example, one surface of the plastic film (A) is colored. It is obtained by applying a paint to form a colored base coating film (B), and then applying a clear paint on the coated surface to form a clear coating film (C).

Specifically, the plastic film (A)
Is coated on one side by a spray, roll coater, knife coater, agar flow coater, silk screen, gravure printing, etc. to give a colored base coating film (B)
Is formed. Its film thickness is based on the dried and cured coating,
A range of 5 to 50 μm, especially 10 to 25 μm is suitable. The colored base coating film (B) can be dried or cured within a temperature range from room temperature to 100 ° C., depending on the composition of the base resin. Then, after or before drying or curing the colored base coating film (B), the clear coating is applied to the coated surface by spraying, roll coater, knife coater, agar flow coater, silk screen, gravure printing, or the like. To form a clear coating film (C). The film thickness is 10 to 1 based on the dried and cured coating film.
00 μm, especially in the range of 30 to 50 μm is suitable,
By drying and curing this coating film, the colored film of the present invention is obtained.

The colored film of the present invention is adhered to a plastic molded product such that the clear coating film (C) is on the outside and the plastic film (A) surface is in contact with the surface of the plastic molded product, and injection molding is performed. By doing so, both can be molded integrally.

Injection molding is carried out by injecting and filling the above-mentioned colored film provided in a mold (unevenness) with a plastic material which has been heated and melted, cooling it, and then taking out the plastic material from the mold as a molded product. . The colored film provided in the mold is preferably provided so that the plastic film (A) surface of the film is in contact with the surface of the plastic molded body.

The heated and melted plastic material is injected into a colored film provided in a mold. At this time, the molten plastic material is not filled between the mold surface and the colored film. The plastic film (A) is filled in the plane direction. Further, the size of the colored film may be a part of the inner surface of the mold or the whole. That is, by changing the size of the colored film, it can be formed on part or all of the surface of the plastic molded product.

Prior to injection molding, the colored film is preliminarily processed so as to be in contact with the inner surface (concave surface) of the mold, and then the inner surface (concave surface) of the mold and the surface of the plastic film (A) of the colored film. Are placed in contact with each other, and then the plastic material that has been heated and melted is injection-filled into a mold,
By molding, a colored film melt-bonded to the surface of the plastic molded product can be formed. This preliminary processing can be performed, for example, by softening the colored film and warming it to such an extent that the colored film can be processed, and pressing the colored film against the concave or convex surface of the mold. The molding temperature can be arbitrarily selected according to the composition of the colored film and the plastic material,
Usually, the melting temperature of the plastic, e.g.
C., especially 180-230.degree. C., and 30-70.degree. C., especially 40-50.degree.

[0026]

The plastic film (A) of the present invention,
A colored film composed of three layers of a colored base coating film (B) and a clear coating film (C) can be prepared by a so-called two-coat method in which a colored base coating material and a clear coating material are applied to a plastic film. The manufacturing process can be greatly simplified as compared with a conventional laminated film composed of a plastic film, a colored base coating film, an adhesive layer and a clear film, and air bubbles are hardly mixed between these layers. The adhesion between the film and the colored base coating is also good.

[0027]

EXAMPLES Examples and comparative examples according to the present invention will be described below. All parts and percentages are based on weight, and the thickness of the coating is based on the cured coating.

1. Production example of clear paint a): Hydroxyl group-containing acrylic resin (glass transition temperature 31.
4 ° C., hydroxyl value 53.1, weight average molecular weight 90000)
100 copies, "CAB551-0.2" (Eastman
Chemical Co., trade name, cellulose acetate butyrate (40 parts) and Desmodur Z4470 (Sumitomo Bayer Urethane Co., trade name, isocyanuric ring type of isophorone diisocyanate) are 0 based on hydroxyl group-containing acrylic resin and OH / NCO. These were used in a ratio of 0.5 equivalent and dissolved in toluene.

2. Examples 1 to 4 and Comparative Examples 1 and 2 Example 1 One side of “A-404” (trade name, ABS sheet, 230 μm thick, manufactured by Sanbo Plastics Co., Ltd.) was provided with “SOFLEX 420”
T "(manufactured by Kansai Paint Co., Ltd., trade name, metallic paint for isocyanate-curable acrylic resin-based plastic) is spray-coated with a dry coating film to a film thickness of 25 μm, and left at room temperature for 5 minutes. On the uncured coated surface, the above clear paint a) is dried with a knife coater to a thickness of 40 μm.
And dried at 80 ° C. for 30 minutes to obtain a colored film for sticking a plastic molded product.

Example 2 One side of "A-404" was spray-coated with "SOFLEX 420T" as a dry coating to a thickness of 25 μm, left at room temperature for 5 minutes, and then uncured. On the side, "Desmodur Z447" in the above clear paint a) is used.
0 0.5 eq. "To" isophorone diisocyanate
A colored film for sticking a plastic molded product was obtained in the same manner as in Example 1 except that the clear paint b) was changed to "0.5 equivalent".

Example 3 One side of "A-404" was spray-coated with "SOFLEX 420T" as a dry film to a thickness of 25 μm, left at room temperature for 5 minutes, and then uncured. On the surface, “CAB551-0.2” in the above clear paint a) was used.
40 parts "as" CAB531-1 (manufactured by Eastman Chemical Company, trade name, cellulose acetate butyrate) "
The same procedure as in Example 1 was carried out except that the clear paint c) was changed to "40 parts" to obtain a colored film for sticking a plastic molded product.

Example 4 On one side of "A-404", "SOFLEX 420T" was spray-coated with a dry coating to a thickness of 25 μm, left at room temperature for 5 minutes, and then uncured. On the surface, “CAB551-0.2” in the above clear paint a) was used.
Example 1 except that "40 parts" was replaced by "CAB531-1 40 parts" and "clear paint d) obtained by changing" Desmodur Z4470 0.5 equivalent "to" isophorone diisocyanate 0.5 equivalent ", respectively. 1 In the same manner, a colored film for sticking a plastic molded product was obtained.

Comparative Example 1 On one side of "A-404", "SOFLEX 420T" was spray-coated with a dry coating to a thickness of 25 μm, left at room temperature for 5 minutes, and then uncured. On the surface, "Desmodur Z4470" in the above clear paint a) is used.
0.5 equivalent "was replaced with" Sumidur N3300 "(manufactured by Sumitomo Bayer Urethane Co., Ltd., trade name, hexamethylene diisocyanate isocyanuric ring type) 0.5 equivalent". In the same manner as in Example 1, a colored film for sticking a plastic molded product was obtained.

COMPARATIVE EXAMPLE 2 One side of "A-404" was spray-coated with "SOFLEX 420T" to a thickness of 25 .mu.m with a dry coating film, allowed to stand at room temperature for 5 minutes, and then uncured. On the surface, “CAB551-0.2” in the above clear paint a) was used.
40 parts "except that the clear paint f) was replaced,
In the same manner as in Example 1, a colored film for sticking a plastic molded product was obtained.

3. Examples 5 to 8, Comparative Examples 3 and 4 The colored films obtained in the above Examples and Comparative Examples were coated on the inner surface of an injection mold capable of being molded into a cup mold (maximum deformation rate: 2). Installed so that it contacts the inner surface of the mold,
Next, after the ABS heated and melted at about 180 ° C. is injected under pressure by an injection molding machine into the ABS sheet surface of the colored film, the mold is cooled, taken out of the mold, and an ABS molded product decorated with the colored film is obtained. Was. A performance test of this molded product was performed. The results are shown in Table 1.

The performance test method is as follows. Moldability: The molded product has no abnormalities on both the curved surface and the flat surface and shows a good appearance. ○, wrinkles, blisters, cracks, peeling, etc., when slight abnormalities occur, △, wrinkles, blisters, cracks, peeling Those with a large number of abnormalities such as were indicated by x. Hardness: Pencil hardness of the surface (clear layer) of the molded product (20
° C). B or more is indicated by ○, 2B to 5B is indicated by Δ, and 6B or less is indicated by ×. Adhesion: Cut the surface of the molded product (clear layer) with a cutter knife so as to reach the substrate, and measure 2 mm x 2 m
100 m-thick meshes were prepared, an adhesive cellophane tape was stuck on the surface thereof, and the number of the remaining sticky meshes after abrupt peeling was measured. ○, 99 to 100
95 is indicated by Δ, and 94 or less is indicated by ×. Water resistance: The result of observing the clear coated surface after being immersed in warm water of 40 ° C. for 10 days. If no abnormality such as blisters or gloss on the painted surface is observed at all,
も の 少 し 少 し 少 し 少 し 少 し 少 し 少 し 少 し 少 し
Those with many occurrences of gloss were indicated by x.

[0037]

[Table 1]

[0038]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 101/14 C09D 101/14 175/04 175/04 // B29L 9:00 B29L 9:00 (72) Inventor Naoya Haruta 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term (reference) in Kansai Paint Co., Ltd. GB32 GB48 HB00B JA05B JA07B JA20B JB09B JL00 JL01 JL10 JL10B JN01B 4F206 AA13 AD08 AD20 AG03 JA07 JB13 JF05 4J038 BA062 DG191 DG271 GA03 MA13 MA14 NA23 PA07 PB07 PB09 PC08

Claims (3)

[Claims] 1. A colored base coating surface of a plastic film, wherein (a) a hydroxyl group-containing resin having a glass transition temperature of 10 to 60 ° C., a weight average molecular weight of 30,000 to 150,000 and a hydroxyl value of 5 to 55; A colored film for attaching a plastic molded product, which is obtained by applying a clear paint containing an isocyanate compound and (c) cellulose acetate butyrate. 2. The ratio of each component in the clear paint is a solid content ratio per 100 parts by weight of the component (a), the component (c) is 20 to 60 parts by weight, and the hydroxyl group of the component (a) and ( b) The equivalent ratio of the component to the isocyanate group is OH / N
The colored film for sticking a plastic molded product according to claim 1, which is 0.2 to 0.8 based on CO. 3. A plastic molded product in which the colored film is adhered to the surface of a plastic molded body and the surface is colored.