JP4627099B2 - Decorative film for molding and method for producing molded product - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative decorative film particularly suitable for outdoor use and a method for producing a molded product using the decorative film.
[0002]
[Prior art and problems]
Currently, products that require a high degree of outdoor durability, such as automobile bodies and exterior parts, are generally coated with a thermosetting paint. However, these paintings take a lot of man-hours, require a large space for installing a booth and baking oven for painting, and require a lot of energy to operate them. In addition, there are various problems such as dust being deposited during the painting operation.
[0003]
As an external decoration alternative to painting, a flexible decorative film is attached, or an outdoor durable decorative film is inserted into the mold, and injection molding is performed by injecting molten resin from the back of the decorative surface. Have proposed methods for producing plastic parts and the like having a cosmetic surface having durability in the outdoors (for example, Japanese Patent Laid-Open Nos. 63-216717, 63-123469, and 2-503077). ).
[0004]
However, the products obtained by these proposed methods are thermoplastic resin film surfaces, so when used outdoors, they are contaminated with dust and dirt flying from the air, scratched by car wash brushes, etc. There is a problem that durability against chemical substances such as rain and gasoline is not sufficient. The durability against chemical substances can be considerably improved by the use of fluorine-containing resin-based films, etc., but the films are expensive, and the scratch resistance and chemical resistance are not as good as those of thermosetting paint films. It is a fact. As a method for obtaining a product with improved scratch resistance, Japanese Utility Model Laid-Open No. 62-128815 discloses a melt-molding material capable of forming a transparent molded article containing rubber in polymethyl methacrylate. Has been proposed in which a printed surface of a polycarbonate film that has been hard-coated and printed on the back surface is bonded to the molding material during injection molding. However, in this method, since the hard coat does not have sufficient flexibility and elongation, if the deformation rate at the time of molding of the polycarbonate film on which the hard coat is applied is large, it breaks or cracks and the cosmetic effect is lost. Therefore, there is a problem that it can be applied only to the production of a molded product with a small deformation rate such as a simple curved surface or a quadratic curved surface at most.
[0005]
In addition, the molded product according to the present proposal has good outdoor durability such as acrylic resin because actinic rays such as ultraviolet rays in sunlight reach the surface of the molded product substrate via the surface layer at least partially. If the base material is not used, the surface of the base material deteriorates due to transmitted light during use, and the film layer on the surface peels off. There is a problem that it is limited to a good base material.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-described problems, the present inventor has completed the present invention.
Thus, according to the present invention,
“1. (A) uncured ultraviolet or electron beam curable hard coat layer, (b) thermoplastic transparent resin layer, and (c) thermoplastic coloring layer, which are sequentially laminated. the film.
2. The decorative film according to claim 1, wherein (d) a thermoplastic sheet layer is laminated on the opposite side of the thermoplastic colored layer (c) to the (b) layer.
3. The decorative film according to claim 1 or 2, wherein the thermoplastic colored layer (c) contains a glittering material.
4). The decorative film according to any one of claims 1 to 3, wherein the thermoplastic colored layer (c) comprises two or more layers.
5. The decorative film according to claim 4, wherein the thermoplastic colored layer (c) comprises two or more layers and has a pattern on the layer (b) of the (c) layer.
6). The decorative film according to any one of claims 1 to 5, wherein at least one of the thermoplastic transparent resin layer (b) and the thermoplastic colored layer (c) is formed by a casting method.
7). The decorative film according to any one of claims 1 to 6, wherein a release film layer (a ') is provided on the opposite side of the ultraviolet or electron beam curable hard coat layer (a) to the thermoplastic transparent resin layer (b).
8). The decorative colored film obtained in any one of claims 1 to 7 is placed on a female mold of an injection mold so that the thermoplastic colored layer (c) or the thermoplastic sheet layer (d) is in contact with the injection molding resin. Pre-molded so that it can be inserted into the female mold in advance or inserted into the female mold by vacuum and / or heating so as to follow the inner wall of the female mold, and then the gold mold is placed in a predetermined position. After closing the mold and pressing the molten resin into the gap between the male mold and the decorative film, the molded product is taken out from the mold, and further from the hard coat layer (a) or the releasable film layer (a ′) side. A method for producing a molded article in which a decorative film layer is formed on a surface by irradiating ultraviolet rays or an electron beam to cure a hard coat layer and then peeling off the release film layer (a ′).
9. The manufacturing method of Claim 8 which peels before the mold release film layer (a ') of the decorating film obtained in Claim 7 is inserted into a metal mold | die, or before preforming or after an ultraviolet-ray irradiation. "
Is provided.
Molded products manufactured using decorative films have sufficient weather resistance, chemical resistance, and scratch resistance for automobile bodies or parts thereof, and an inexpensive resin with low weather resistance is used as a base material. Can also be used, so that it is economically superior to the conventional one.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
For the hard coat layer (a) in the present invention, an ultraviolet ray or electron beam curable hard coat composition is used, and there is no particular limitation as long as the hard coat composition is an ultraviolet ray or electron beam curable type. In the present invention, it is preferable to provide a cured film having a pencil hardness of 6H or more on the glass plate of the coated film after UV curing.
[0008]
As such a hard coat composition, for example, a trivalent or higher valent (meth) acrylate oligomer such as pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, or a mixture thereof, if necessary, physical properties A composition in which a divalent to monovalent (meth) acrylate is mixed for adjustment of the above; a polymer having a glass transition temperature of 70 ° C. or higher such as polymethyl methacrylate, pentaerythritol tri (meth) acrylate, Trivalent or higher (meth) acrylate oligomers such as dipentaerythritol tetra (meth) acrylate alone or a mixture thereof and, if necessary, divalent to monovalent (meth) acrylates are mixed to adjust physical properties. A light that initiates polymerization with UV light on the above composition Ultraviolet-curable composition was blended with initiator; UV-curable organic such as those described in JP-A-3-237113 Patent Publication (Patent No. 2804582) - inorganic composite composition; and the like.
[0009]
In addition, it is possible to improve the light resistance by adding an ultraviolet absorber, HALS or the like to these hard coat compositions, but use it considering the light emission characteristics of the source of actinic rays used for curing. It is necessary to pay close attention to the type and amount of UV absorber.
These hard coat compositions may be diluted with a solvent or the like that can dissolve the composition, if necessary, and a flowability adjusting agent, a colorant, a dispersant, an adhesion-imparting agent, or the like may be added. Good. In particular, the inorganic-organic composite hard coat composition described in JP-A-3-237113 has high scratch resistance, high chemical resistance, small curing shrinkage, excellent adhesion, and the like. This is particularly preferable for the purpose of the present invention.
[0010]
The polymer for forming the thermoplastic transparent resin layer (b) in the present invention is not particularly limited as long as it has transparency. For example, an acrylic resin polymer, a polyurethane polymer, a fluorine-containing polymer, polycarbonate, PVC Examples thereof include a film made of a polymer, ABS, PET, PBT, and the like. For applications to be used outdoors, an acrylic resin polymer, polyurethane polymer, fluorine-containing polymer, or PVC polymer film is preferred. Furthermore, particularly preferred for outdoor use are those in which an acrylic resin such as polymethyl methacrylate is blended with acrylic rubber, a monomer that forms a polymer having a high glass transition temperature such as methyl methacrylate, and methyl acrylate. Copolymers with monomers that give such polymers with low glass transition temperatures, low linear branched polyurethane resins obtained by reaction of aliphatic diisocyanates with polyols based on glycols, (meth) acrylic Examples thereof include a copolymer of a monomer and a fluorine-containing polymerizable monomer such as vinylidene fluoride, soft PVC, and the like, and these resins can be used alone or, if necessary, can be kneaded or alloyed with each other. These are used as films. In these films, various additives usually used for forming a resin film can be used. Moreover, you may mix | blend a coloring material etc. in the range which does not lose transparency.
[0011]
Among the above-mentioned polymers, ABS, PET, PBT, etc. are not inherently light-resistant, but can be used for outdoor use unless a very high light-resistance is required by appropriately blending UV absorbers, etc. It is.
[0012]
The film forming method is performed by a known method such as a calender roll method, a T-die method, or a casting method, and may be combined by lamination of different films or a co-extrusion method. Alternatively, as described later, the (b) layer may be formed by casting a coating solution in which the composition for forming the (b) layer is dissolved or dispersed in a solvent directly on the (a) layer or the (c) layer. Good.
[0013]
The thermoplastic colored layer (c) in the present invention is made of the same transparent resin layer forming material as that used in the layer (b), pigment, metal powder, mica powder, and metal or metal oxide on the surface of these powders. These are formed by dispersing coloring materials such as those formed by vapor deposition or the like. For outdoor use, after the layer (a) is cured, the colorant of the layer (c) is such that the transmittance of light having a wavelength of 190 nm to 400 nm irradiated from the surface of the layer (a) is 10% or less, preferably 5% or less. It is preferable to adjust the amount and the amount of UV absorber. By controlling the light transmittance, a molded product having excellent outdoor weather resistance can be obtained even if a material having low light resistance is used as the layer (d) or the molded resin base material. In addition, the (c) layer may be multilayered, and each layer may be a laminate of different colorants, or (b) a non-continuous pattern printed on the layer in contact with the layer. It may include a typical pattern.
[0014]
The thermoplastic resin sheet layer (d) in the present invention is not particularly limited as long as the adhesion between the (c) layer and the molded resin base material is good, and the above-described material forming the (b) layer is used. it can. In order to supplement the adhesiveness, (d) an adhesive layer or a primer layer for assisting adhesion may be provided on both sides or one side of the layer as necessary. For example, when the molding resin substrate is a polyolefin, a primer A chlorinated polyolefin layer is provided as a layer.
[0015]
In the decorative film according to the present invention having no (d) layer, the above-mentioned adhesive layer or primer layer may be provided on the surface of the (c) layer in order to supplement the adhesion to the molded resin substrate. .
In the present invention, the release film layer (a ′) is a hard coat layer after the molding is completed using the decorative film or after the hard coat layer is cured by irradiating ultraviolet rays or electron beams through (a ′). If it can peel from the layer surface, there will be no restriction | limiting in particular. Moreover, in order to assist peeling, the surface may be treated with a release agent such as silicone.
[0016]
The structure of the decorative film according to the present invention is shown in FIG. The production may be performed by a known method, but a typical method will be described below.
1. (1) A hard coat for forming the layer (a) is applied to the surface of the releasable film layer (a ') or the release-treated (a'), and if necessary, heated to coat the hard coat coating film. (A) Step of forming the layer by removing the solvent contained (2) The transparent film-like (b) layer and the colored layer (c) layer on the surface of the (a) layer (b), (c) layer Laminating step (3) A method comprising a step of laminating a sheet-like (d) layer on the (c) layer surface as required.
[0017]
2. (1) A hard coat for forming the layer (a) is applied to the surface of the releasable film layer (a ') or the release-treated (a'), and if necessary, heated to coat the hard coat coating film. (A) Step of forming the layer by removing the solvent contained (2) Step of laminating the transparent film (b) layer on the surface of the (a) layer (3) Composition for forming the colored layer (c) layer (4) A step of removing the solvent contained in the coated product by casting it on the surface of the layer (b) and heating it, etc. A method comprising a step of forming a sheet-like (d) layer on the (c) layer surface.
[0018]
3. (1) A hard coat for forming the layer (a) is applied to the surface of the releasable film layer (a ') or the release-treated (a'), and if necessary, heated to coat the hard coat coating film. (A) Step of forming layer by removing solvent (2) A coating agent prepared by dissolving or dispersing a composition for forming a transparent film (b) layer in a solvent (a) The step of removing the solvent contained in the coating by casting on the surface of the layer and heating, etc. (3) The composition for forming the colored layer (c) layer was dissolved or dispersed in the solvent to enable coating. (4) A step of removing the solvent contained in the coating by casting the coating agent on the surface of the layer (b) and heating, etc. (4) Further, if necessary, the sheet-like (d) layer is replaced with the (c) layer surface A method comprising the steps of forming a film.
[0019]
4). A hard coat for forming the layer (a) is applied to the surface of the support material made of a releasable film (a ′) or a metal plate, and if necessary, the solvent contained in the hard coat coating film is removed by heating ( a) After forming the layer, the (b) layer, (c) layer, and if necessary, the (d) layer are formed in the same manner as in the methods 1 to 3, and then supported from the surface of the (a) layer. A method comprising a step of peeling and removing a material.
[0020]
5. (1) Step (c) for forming a layer (c) on the surface of a support material made of a releasable film (a ′) or a metal plate in the same manner as in the above methods 1 and 2. (b) A layer in the above 1 or 2 (C) Step of forming on the surface of the layer by the same method as (3) (b) Applying a hard coat to the surface of the layer and removing the solvent contained in the hard coat coating film by heating if necessary. Step (4) for forming the hard coat layer (a) Step (4) for laminating the releasable film layer (a ') on the surface of the layer (a) if necessary (5) Peeling the support material from the surface of the layer (c) , A method comprising a removing step.
[0021]
6). (3) A method of forming the layer (c) on the surface of the layer (b) in a semi-dry state where the solvent is not completely removed.
7). (D) If the layers (c), (b), (a) are further required in the reverse order on the surface of the layer, the (a ′) layer is formed by any one of the methods 1 to 3 above. How to be.
[0022]
In the decorative film of the present invention, when the adhesive layer or the primer layer is provided on the open surface of the (d) layer, the (d) layer or the (d) layer surface is released from the mold. A temporary protective film may be laminated.
The (d) layer can be formed by laminating a film-like material on the (c) layer, or on the support as described above or on the (c) layer by a casting method. The support is peeled off and removed from the surface of the layer (d) after the decorative film is formed.
[0023]
In the decorative film of the present invention, when it is composed of a combination of materials in which the adhesion between the (b) layer and the (c) layer in the dry state is not sufficient, the application of the (b) layer or the (c) layer Immediately or in the semi-dry state, it is particularly preferable to apply the (c) layer or the (b) layer on the surface, because the adhesion is improved by the mutual mixing of the surfaces. In addition, the formation of the (c) layer may be performed by laminating a film-like material containing a coloring material in advance to the (b) layer or the (d) layer in addition to the casting method. In this case, the layers (b) and (c) or the layers (c) and (d) may be combined in advance by coextrusion or an adhesive.
[0024]
In the production of the decorative film of the present invention, when each layer is formed by a casting method, the casting is performed by a known method such as a spray method, a roll coating method, a curtain coater method, a fountain coater method, a gravure printing method, a screen printing method, or the like. It can be carried out. The decorative film according to the present invention may be in the form of a sheet cut into a certain size or a continuous film.
[0025]
A molded product using the decorative film of the present invention thus obtained is produced as follows.
A decorative film is preformed on a female mold of an injection mold so that the thermoplastic coloring layer (c) or the thermoplastic sheet layer (d) is in contact with the injection molding resin so that it can be inserted into the female mold in advance. Or after being molded along the inner wall of the female mold by vacuum and / or heating in the female mold, the mold is closed so that the male mold is in a predetermined position, and the male mold and the decorative film are After the molten resin is press-fitted between the gaps, the molded product is taken out from the mold and further irradiated with ultraviolet rays or electron beams from the hard coat layer (a) or the release film layer (a ′) side to form the hard coat layer. By curing and then peeling off the release film layer (a ′), a molded product having a decorative film layer formed on the surface is obtained. Further, the molded product of the present invention can also be obtained by peeling off the (a ′) layer of the decorative film before being inserted into a mold or before preforming.
[0026]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.
[0027]
Production Example 1 Production of hard coat 1
100 parts of dipentaerythritol tetramethacrylate, 10 parts of methyl methacrylate, 15 parts of an adduct of 1 mole of 1,6-hexamethylene diisocyanate and 2 moles of 2-hydroxyethyl methacrylate, and 8 parts of 2-hydroxy-2-methyl-propiophenone Were mixed to obtain a hard coat 1.
[0028]
Production Example 2 Production of Hard Coat 2
A hard coat having the composition (Note 1) described in Example 2 of JP-A-3-237113 was designated as hard coat 2.
(Note 1) 100 parts of silica sol NBA-ST (Nissan Chemical Co., Ltd., solid content 20%)
50 parts of 3,4-epoxycyclohexylmethyl acrylate
Tetrakis (ethyl acetoacetonato) zirconium 1 part
Hydroquinone 0.01 part
The raw materials were mixed and reacted at 90 ° C. for 8 hours with stirring to obtain a solution having a solid content of 24%.
A composition comprising 1050 parts of the solution, 150 parts of trimethylolpropane triacrylate and 20 parts of benzoin ethyl ether.
[0029]
Production Example 3 Production of hard coat 3
100 parts of paraloid A-21 (acrylic resin from Rohm and Haas), 100 parts of dipentaerythritol pentaacrylate, 40 parts of 1,4-butanediol dimethacrylate, 2-methyl {4- (methylthio)} phenyl 2-morpholino- Hard coat 3 was obtained by mixing 20 parts of 1-propanone, 300 parts of toluene and 100 parts of methyl ethyl ketone.
[0030]
Example 1
(A) A hard coat 1 of Production Example 1 was applied to a release-treated surface of a 120 μm-thick PET film (a ′) treated with a silicone-based release agent with a roll coater so as to have a thickness of 5 μm. A layer was formed. ((1) step). Next, an acrylic resin-based lacquer (Aclick # 2000, manufactured by Kansai Paint Co., Ltd.) in which aluminum powder is blended on one side of the acrylic resin-based transparent film (b) having a thickness of 50 μm is spray-applied to a dry film thickness of 30 μm, After heating at 100 ° C. for 5 minutes, a polyethylene film having a thickness of 30 μm was pressure-bonded to the painted surface to form a (c) layer having a temporary protective film (step (2)). The (b) layer side of the (c) layer obtained in the step (2) was pressure-bonded to the hard coat surface of the (a) layer obtained in the step (1) to obtain a decorative film F1 for molding.
[0031]
F1 from which the temporary protective film has been removed is placed so that the surface of the layer (a ′) faces the mold wall surface of the vacuum forming machine for preforming, and F1 is preformed into a desired shape by vacuum and heating. After the preformed F1 is fitted into a female mold of a desired shape for injection molding, the mold is closed and the molten styrene resin is press-fitted so that the male mold is in a predetermined position, and then the mold is cooled. Was opened and the molded product was taken out, and the surface of the obtained molded product was irradiated with 20,000 J / m 2 (measured at 366 nm) using a high-pressure mercury lamp. Next, the layer (a ′) was peeled off from the surface to obtain a molded product 1 for the purpose.
[0032]
The maximum deformation rate of the molding was about 250%. The surface of the molded product showed a good gloss and appearance, and even when the surface was rubbed with No. 0000 steel wool 30 times, no gloss was formed and the surface was hardly scratched, and a good surface state was maintained.
Furthermore, an abrasion resistance test (Note 2) and a solvent resistance test (Note 3) were performed on the molded product. The change in haze (ΔHaze) before and after the taper wear test was 53% (the lower the value, the better), and the appearance in the MEK wiping test was good.
(Note 2) Test temperature: 25 ° C., Wear condition: Wear wheel CS-10 load 500 g, 500 rotations.
ΔHaze = [(Haze value after test) − (Haze value before test)] ÷ Haze value before test × 100
(Note 3) Methyl ethyl ketone (MEK) was attached to the gauze, and the appearance after wiping with fingers 20 times was observed.
[0033]
Example 2
In Example 1, instead of the temporary protective film (polyethylene film), an ABS film (d) layer having a thickness of 200 μm was pressure-bonded to obtain a decorative film F2 for molding.
The target molded product 2 is the same as in Example 1 except that F2 is directly attached to the preform mold and is fitted to the inner wall of the female mold by vacuum and heating, and ABS resin is used instead of styrene resin at the time of injection molding. Got. The surface of the molded product showed good gloss and appearance, and even when the surface was rubbed with No. 0000 steel wool 30 times, no glossiness was generated and the surface was hardly scratched, and a good surface state was maintained.
Further, the haze% of the abrasion test was 55%, and the MEK wiping test was also good.
[0034]
Example 3
50 parts of paraloid B-44 and 50 parts of paraloid A-21 on one side of an ABS film (d) layer having a thickness of 200 μm (a resin mixture made of acrylic resin from Rohm and Haas is used as a mixed solvent of toluene and isopropanol). (5/1 weight ratio) A coating obtained by dispersing 60 parts of titanium white and 1 part of carbon black in 400 parts of a solution dissolved in 300 parts was applied with a knife coater to a dry film thickness of 30 μm, and then Acrylic # 2000 containing mica powder was spray-coated with a dry film thickness of 10 μm and heated at 80 ° C. for 10 minutes to form a layer (c), and then paraloid A-21 100 thereon. And 1 part of Tinuvin 328 (UV absorber manufactured by Ciba Geigy) were dissolved in 200 parts of a mixed solvent of toluene and methyl ethyl ketone (5/1 weight ratio). The dissolved solution was coated with a knife coater so that the dry film thickness was 50 μm, heated at 80 ° C. for 15 minutes to form the layer (b), and then the hard coat 2 of Production Example 2 was dried to 2 μm. Thus, it was coated with a spin coater and heated at 80 ° C. for 5 minutes to form the layer (a) to obtain a decorative film F3 for molding.
[0035]
A target molded product was obtained in the same manner as in Example 1 except that F3 was placed so that the (a) layer opposed to the wall surface of the preform mold instead of the (a ′) layer. The surface of the molded product showed good gloss and appearance, and even when the surface was rubbed with No. 0000 steel wool 30 times, no glossiness was generated and the surface was hardly scratched, and a good surface state was maintained.
Further, the haze% of the abrasion test was 10%, and the MEK wiping test was also good.
[0036]
Example 4
The treated surface of a 25 μm thick PET film treated with a silicone release agent on the layer (a) of Example 3 was pressure-bonded so as to be in contact with the layer (a) to obtain a decorative film for molding F4.
The target molded product 4 was obtained in the same manner as in Example 1 except that ABS resin was used instead of styrene resin as the resin for injection molding. The surface of the molded product showed good gloss and appearance, and even when the surface was rubbed with No. 0000 steel wool 30 times, no glossiness was generated and the surface was hardly scratched, and a good surface state was maintained.
Further, the haze% of the abrasion test was 5%, and the MEK wiping test was also good.
[0037]
Example 5
A resin mixture comprising 50 parts of paraloid B-44 and 50 parts of paraloid A-21 on one side of a 125 μm thick acrylic resin film (b) layer is a mixed solvent of toluene and n-butanol (5/1 weight ratio). A coating obtained by dispersing 100 parts of titanium white and 2 parts of carbon black in 400 parts of a solution dissolved in 300 parts was applied with a knife coater to a dry film thickness of 50 μm and heated at 120 ° C. for 8 minutes. Thereafter, a solution obtained by dissolving 100 parts of chlorinated polypropylene resin in 400 parts of toluene is further spray-coated to a dry film thickness of 5 μm and heated at 100 ° C. for 2 minutes. The hard coat 3 of Production Example 3 was spray-coated so as to have a dry film thickness of 10 μm, and then heated at 100 ° C. for 3 minutes to obtain a decorative film for molding F5.
[0038]
The target molded product 5 was obtained in the same manner as in Example 3 except that polypropylene resin was used instead of ABS resin as the resin for injection molding. The surface of the molded product showed good gloss and appearance, and even when the surface was rubbed with No. 0000 steel wool 30 times, no glossiness was generated and the surface was hardly scratched, and a good surface state was maintained.
Further, the haze% of the wear test was 62%, and the MEK wiping test was also good.
[0039]
Example 6
In Example 3, the target molded product 6 was obtained in the same manner as in Example 3 except that a paint in which 2 parts of cyanine blue pigment was dispersed instead of mica powder was printed in a predetermined pattern so as to have a dry film thickness of 15 μm by screen printing. Got. The surface of the molded product showed good gloss and appearance, and even when the surface was rubbed with No. 0000 steel wool 30 times, no glossiness was generated and the surface was hardly scratched, and a good surface state was maintained.
[0040]
Comparative Example 1
A film was obtained in the same manner as in Example 3 except that the hard coat 2 was not applied, and a comparative molded product 1 was obtained in the same manner as in Example 3. The surface of this molded product showed good gloss and appearance, but when the surface was rubbed with No. 0000 steel wool 30 times, the gloss of the surface was lost and deep scratches were generated.
In addition, the haze% of the abrasion test was 97%, and the MEK wiping test caused gloss.
[0041]
Comparative Example 2
After obtaining the decorative film for molding of Example 2, it was 20,000 J / m with a high-pressure mercury lamp from the (a) layer side of the film. ² Irradiation gave the film of Comparative Example 2.
Comparative molded product 2 was obtained in the same manner as in Example 2 except that irradiation with a high-pressure mercury lamp was not performed after injection molding.
The obtained molded product has a hard appearance on which the hard coat layer on the surface is cracked and peeled off to form a continuous hard coat film. Did not show.
[0042]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the molded article which requires large and high cosmetics, a weather resistance, and deep drawability, such as a bumper for automobiles and a door panel which have very high damage resistance, can be manufactured easily.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view showing a decorative film of the present invention.
[Explanation of symbols]
(A) UV or electron beam curable hard coat layer
(A ′) Releaseable film layer
(B) Thermoplastic transparent resin layer
(C) Thermoplastic coloring layer
(D) Thermoplastic sheet layer

Claims (9)

(a) An uncured ultraviolet curable hard coat layer, (b) a thermoplastic transparent resin layer, and (c) a thermoplastic colored layer are sequentially laminated, and the hard coat layer (a) is dispersed in an organic solution. Trimethylolpropane triacrylate and a photopolymerization initiator in a solution obtained by reacting the colloidal silica (A) with 3,4-epoxycyclohexylmethyl acrylate (B) in the presence of tetrakis (ethylacetoacetonato) zirconium. A decorative film for molding, which is an uncured coating film of a hard coat composition comprising an ultraviolet curable organic-inorganic composite composition.   The decorative film according to claim 1, wherein (d) a thermoplastic sheet layer is laminated on the opposite side of the thermoplastic colored layer (c) to the (b) layer.   The decorative film according to claim 1 or 2, wherein the thermoplastic colored layer (c) contains a glittering material. The decorative film according to any one of claims 1 to 3, wherein the thermoplastic colored layer (c) comprises two or more layers.   The decorative film according to claim 4, wherein the thermoplastic coloring layer (c) comprises two or more layers and has a pattern on the layer (c) that adheres to the (b) layer. The decorative film according to any one of claims 1 to 5, wherein at least one of the thermoplastic transparent resin layer (b) and the thermoplastic colored layer (c) is formed by a casting method. The decorative film according to any one of claims 1 to 6, wherein a release film layer (a ') is provided on the opposite side of the ultraviolet curable hard coat layer (a) from the thermoplastic transparent resin layer (b). The decorative colored film obtained in any one of claims 1 to 7 is placed on a female mold of an injection mold so that the thermoplastic colored layer (c) or the thermoplastic sheet layer (d) is in contact with the injection molding resin. Pre-molded so that it can be inserted into the female mold in advance, or after being molded along the inner wall of the female mold by vacuum and / or heating in the female mold, the male mold is placed in a predetermined position. After closing the mold and pressing the molten resin into the gap between the male mold and the decorative film, the molded product is taken out from the mold, and further from the hard coat layer (a) or the releasable film layer (a ′) side. A method for producing a molded article in which a decorative film layer is formed on a surface by irradiating ultraviolet rays to cure the hard coat layer and then peeling off the release film layer (a ′).   The production method according to claim 8, wherein the mold release film layer (a ') of the decorative film obtained in claim 7 is peeled before being inserted into a mold, before preforming or after being irradiated with ultraviolet rays.

Images