JP2022123593A - Laminated film for decorating three-dimensional molded articles, method for producing the same and method for decorating three-dimensional molded articles - Google Patents

Abstract

To provide a laminated film for decorating three-dimensional molded articles that solves problems in terms of cost, the environment, and shape followability during molding and can give molded articles good design.SOLUTION: A laminated film for decorating three-dimensional molded articles has a clear coating layer (A) composed of an energy ray-curable coating and a design layer (B). The laminated film further may have an adhesive layer (C); or the design layer (B) may be a design layer (B-C) that also serves as an adhesive layer. The coating strength is 1.95-39.5 N at 40°C, 2.45-20.0 N at 60°C, or 0.49-4.9 N at 80°C.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a laminated film for decorating a three-dimensional molded article, a method for producing the same, and a method for decorating a three-dimensional molded article.

In the three-dimensional molded products obtained from plastics, metals and various other materials, it is possible to decorate the surface using a decorative laminated film for the purpose of imparting design to the surface and protecting the surface. (Patent Documents 1 to 3).

In the conventional technique, a layer for decorating a molded product is created as a film, and the film is adhered onto the molded product for decoration. Specifically, each layer that makes up the laminate film for decoration, such as a clear layer, a design layer such as printing, and an adhesive layer, is applied and laminated on a film that serves as a base material, and then transferred or coated on the object to be decorated. It was something to do.

In the prior art, it was necessary to use a heat-resistant base film in order to prevent tearing of the laminate film for decoration. For this reason, the conformability to the three-dimensional shape of the laminated film for decoration depends on the stretching property of the base film. In addition, in the case of transfer, the peeled base film becomes industrial waste, which poses problems in terms of cost and environment.

JP-A-10-735 JP-A-2008-55688 JP 2011-200804 A

In view of the above, the present invention provides a laminated film for decorating a three-dimensional molded product that solves the problems of cost, environmental protection, and shape-following in molding, and that can impart good design to the molded product. offer.

The present invention has a clear coating layer (A) and a design layer (B) comprising an energy ray-curable coating,
Further, a laminated film for decorating a three-dimensional molded product, which comprises an adhesive layer (C), or the design layer (B) is a design layer (BC) that also functions as an adhesive layer, ,
A three-dimensional molded product having a coating strength of 1.95 to 39.5 N at 40 ° C., 2.45 to 20.0 N at 60 ° C., or 0.49 to 4.9 N at 80 ° C. It relates to a laminated film for decoration.

In the laminated film for decorating a three-dimensional molded product, the film thickness before curing is preferably 10 to 200 μm at 23°C.
The film thickness is measured by, for example, a dial gauge or linear gauge sensor.

The clear coating film layer (A) comprising the energy ray-curable coating film comprises polyurethane acrylate (A1),
It is preferably formed from an active energy ray-curable coating composition containing a monomer/oligomer (A2) having an unsaturated double bond and a polymerization initiator (A3).
The polyurethane acrylate (A1) preferably has a molecular weight Mw of 3,000 to 200,000.

The design layer (B) and the design layer (BC) having an adhesive function are a layer formed by drying after applying a colored coating composition, a layer formed by printing, and a metallic design layer. It is preferably at least one layer selected from the group consisting of.

The design layer (B) and the design layer (BC) having an adhesive function contain a polyurethane resin (B1) and a glitter material (B2), and the solid weight of (B1) and the solid content of (B2) It is formed by a colored coating composition containing (B2) in the range of 0.5 to 60 parts by weight in 100 parts by weight of the total amount ((B1) + (B2)) of the component weight is preferred.
The polyurethane resin (B1) preferably has a molecular weight Mw of 10,000 to 200,000.

The present invention also provides a method for decorating a three-dimensional molded article, characterized by adhering the laminated film for decorating a three-dimensional molded article on a three-dimensional molded article under heating conditions.
The heating described above is preferably carried out in a range in which the temperature of the laminated film is 40 to 80°C.

The laminated film for decorating a three-dimensional molded product of the present invention is excellent in terms of cost and environment because the base film can be reused. follow-up becomes good.

FIG. 2 is a schematic diagram showing an example of the laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention before the base film layer is peeled off. FIG. 2 is a schematic diagram showing an example of the laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention before the base film layer is peeled off. FIG. 2 is a schematic diagram showing an example of the laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention before the base film layer is peeled off. FIG. 2 is a schematic diagram showing an example of the laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention before the base film layer is peeled off. FIG. 2 is a schematic diagram showing an example of the laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention before the base film layer is peeled off. FIG. 2 is a schematic diagram showing an example of the laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention before the base film layer is peeled off. FIG. 4 is a diagram specifically showing a reading method for reading Tg from a chart in the Tg measuring method of the present invention.

The present invention will be described in detail below.
(Laminated film for decorating three-dimensional molded products)
The laminated film for decorating a three-dimensional molded article of the present invention is a film used in the decorative molding of a three-dimensional molded article. That is, by adhering a film having a design property to various molded products, the molded product is imparted with a design property or a surface protection function.
At that time, it is brought into close contact by deforming it along the surface of the three-dimensional shape. Moreover, the laminated film for decorating a three-dimensional molded product of the present invention is suitably used for vacuum forming. In the present invention, the term "vacuum forming" means forming such that the laminate film for decoration is adhered to a molded product as a substrate under vacuum.

Laminated films for decorating three-dimensional molded products require a layer that serves as a base material when forming each layer in the manufacturing process, and from the viewpoint of preventing blocking between films during storage after manufacturing, etc. It has a base film layer.

However, since such a base film layer is not required in the final product after decoration, it has generally been peeled off after decoration. However, in the vacuum forming process, conventionally, the decoration is performed in the presence of the base film layer.

If such vacuum forming is carried out in a state in which the substrate film layer is present, the substrate film layer will also be deformed into the shape of the substrate, and this substrate film will be discarded.

The present invention is characterized in that the base film of the laminated film for decorating a three-dimensional molded product is peeled off before vacuum forming, and the laminated film without the base film layer is used for decoration. have. In this way, even a film without a base film layer can be decorated, so that the base film can be peeled off before the three-dimensional decoration. As a result, the peeled base film can be recovered and reused. Therefore, it is preferable from the viewpoint of environment and resource saving.

However, the laminated film for decorating a three-dimensional molded product in the absence of the base film has a weak strength. Therefore, even in the absence of the base film, it is necessary to have a certain strength in order to perform good decoration without causing problems such as tearing. From this point of view, the laminated film for decorating a three-dimensional molded article of the present invention is required to have a predetermined strength.

The laminated film for decorating a three-dimensional molded product of the present invention has a clear coating layer (A) made of an energy ray-curable coating and a design layer (B),
Further, the adhesive layer (C) is provided, or the design layer (B) is a design layer (BC) that also functions as an adhesive layer,
The laminated film is characterized by a coating film strength of 1.95 to 39.5N at 40°C, 2.45 to 20.0N at 60°C, or 0.49 to 4.9N at 80°C. By setting the coating film strength within the above range, fluttering of the coating film during vacuum forming can be suppressed even if the base film is peeled off before molding, and it has been found that molding is possible with only the coating film. be.

The above coating film strength was measured by using Autograph AG-IS manufactured by Shimadzu Corporation with the base film layer peeled off, and using a sample of 10 mm width × 50 mm length within the temperature range of 40 to 80 ° C., tensile at 50 mm / min. It is a value obtained by measuring the strength at the time of breaking at speed. The measurement is performed 3 times and the average value is adopted. At any temperature within the range of 40 to 80° C., depending on the properties of the film, the breaking strength should be in the ranges mentioned above.
The lower limit of the coating film strength is preferably 2.90 N at 40 ° C., 3.40 N at 60 ° C., and 0.58 N at 80 ° C., respectively, 4.90 N, 3.90 N, and 0.78 N. is more preferred. In addition, the upper limit of the coating film strength is preferably 34.5 N at 40 ° C., 18.0 N at 60 ° C., and 4.5 N at 80 ° C., which are 29.5 N, 15.0 N, and 4.0 N, respectively. is more preferred. Note that the coating film strength here is a measured value for the film after the base film layer has been peeled off.

The laminated film for decorating a three-dimensional molded product preferably has a film thickness of 10 to 200 μm at 23° C. before curing. In addition, the said film thickness is a film thickness in the state which peeled the base film from the produced laminated|multilayer film.
The laminated film for decorating a three-dimensional molded product of the present invention is required to have a certain strength even when the base film is peeled off. Therefore, in order to ensure sufficient strength, it is preferable to have the thickness as described above.
The lower limit of the film thickness is more preferably 20 μm, still more preferably 30 μm. The upper limit is more preferably 150 μm, still more preferably 120 μm, and most preferably 100 μm.

The laminated film for decorating a three-dimensional molded product of the present invention has at least a clear coating layer (A) made of an energy ray-curable coating and a design layer (B),
Furthermore, the adhesive layer (C) is provided, or the design layer (B) is a design layer (BC) that also functions as an adhesive layer.
That is, it has a three-layer structure consisting of a clear coating layer (A), a design layer (B) and an adhesive layer (C), or a design layer ( It has a two-layer structure consisting of BC).
Furthermore, if necessary, it may have a release layer (D), a protective layer (F), an ultraviolet absorbing layer (G), and the like. These layers can be made into various lamination|stacking forms as needed.

Furthermore, the laminated film for decorating a three-dimensional molded product of the present invention can be suitably applied to vacuum forming. When a laminated film for decorating a three-dimensional molded product is adhered to a molded product by injection molding, the uneven pattern may be distorted or cracked due to the high temperature treatment. On the other hand, vacuum forming does not require high-temperature treatment, so there is no such problem, but sufficient stretchability is required. When the laminated film for decorating a three-dimensional molded product of the present invention has an elongation at break of 30 to 500% at 40 to 80° C. before curing, it exhibits stretchability suitable for vacuum molding. can be

Hereinafter, specific aspects of the laminated structure will be described with reference to the drawings.
The first laminated structure shown in FIG. 1 comprises a base film layer (H), a release layer (D), a clear coating layer (A), and a design layer (BC) having an adhesive function. It is a laminated film laminated in order. In the first laminated structure, the film having such a configuration is adhered to the three-dimensional molded product by the design layer (BC), and the base film layer (H) is attached to the release layer ( After peeling together with D), decoration is performed. As a result, a decorative layer consisting of two layers, the clear coating layer (A) and the design layer (BC) having an adhesive function, is formed on the three-dimensional molded product.
The first laminated structure also applies to the case where the release layer (D) is not included.

The second laminated structure shown in FIG. 2 has a release layer (D), a clear coating layer (A), a design layer (B), and an adhesive layer (C) on a base film layer (H). It is a laminated film laminated in order. In the second laminated structure, the film having such a configuration is adhered to the three-dimensional molded product by the adhesive layer (C), and the base film layer (H) is attached to the release layer (D) before decorative molding. After peeling it off together, it is decorated. As a result, a decorative layer consisting of three layers, the clear coating layer (A), the design layer (B) and the adhesive layer (C), is formed on the three-dimensional molded product.
The second laminated structure also applies to the case where the release layer (D) is not included.

The third laminate structure shown in FIG. 3 is a laminate in which a clear coating layer (A), a metallic design layer (B), and an adhesive layer (C) are laminated in this order on a base film layer (H). It's a film. In the third laminated structure, the film having such a configuration is adhered to the three-dimensional molded product by the adhesive layer (C), and after the base film layer (H) is peeled off before the decorative molding, the decorative I do. As a result, a decorative layer consisting of three layers, the clear coating layer (A), the metallic design layer (B), and the adhesive layer (C), is formed on the three-dimensional molded article.
Note that the case of including the release layer (D) also applies to the third laminated structure.

The fourth laminated structure shown in FIG. 4 comprises a base film layer (H), a clear coating layer (A), a protective layer (F), a metallic design layer (B), and an adhesive layer (C). It is a laminated film laminated in this order. In the fourth laminated structure, the film having such a configuration is adhered to the three-dimensional molded product by the adhesive layer (C), and after the base film layer (H) is peeled off before the decorative molding, the decorative film is applied. I do. As a result, a decorative layer consisting of four layers, the clear coating layer (A), the protective layer (F), the metallic design layer (B), and the adhesive layer (C), is formed on the three-dimensional molded product. be.
Note that the case of including the release layer (D) also applies to the fourth laminated structure.

The fifth laminated structure shown in FIG. 5 comprises a base film layer (H), a clear coating layer (A), an ultraviolet absorbing layer (G), a printed design layer (B), and an adhesive layer (C). is laminated in this order. In the fifth laminated structure, the film having such a configuration is adhered to the three-dimensional molded product by the adhesive layer (C), and after the base film layer (H) is peeled off before the decorative molding, the decorative I do. As a result, a decorative layer consisting of four layers: a clear coating layer (A), an ultraviolet absorbing layer (G), a printed design layer (B), and an adhesive layer (C) is formed on the three-dimensional molded product. is.
Note that the case of including the release layer (D) is also applicable to the fifth laminated structure.

The sixth laminated structure shown in FIG. 6 comprises a base film layer (H), a clear coating layer (A), an ultraviolet absorbing layer (G), a printed design layer (B), and a protective layer (F). , a metallic design layer (B), and an adhesive layer (C) are laminated in this order. In the sixth laminated structure, the film having such a configuration is adhered to the three-dimensional molded product by the adhesive layer (C), and after the base film layer (H) is peeled off before the decorative molding, the decorative I do. As a result, it consists of six layers: a clear coating layer (A), an ultraviolet absorbing layer (G), a printed design layer (B), a protective layer (F), a metallic design layer (B), and an adhesive layer (C). A decorative layer is formed on the three-dimensional molded product.
Note that the case of including the release layer (D) also applies to the sixth laminated structure.
Each layer constituting these laminated films for decorating a three-dimensional molded product will be sequentially described below.

(Clear coating layer (A))
The clear coating layer (A) used in the present invention is an energy ray-curable coating, and its specific composition is not particularly limited as long as it does not impair the physical properties of the laminated film. It can be an energy ray-curable coating film.
In the energy ray-curable coating film, the resin can be cured by irradiating the energy ray in the state of the laminate film for decorating the three-dimensional molded article, after being deformed into the shape of the object to be decorated. Therefore, it can be easily deformed into the shape of the object to be decorated, and exhibits excellent performance in terms of strength, appearance, chemical resistance, etc. of the coating layer after decoration.

Among them, it is preferably formed from an active energy ray-curable coating composition containing a polyurethane acrylate (A1), a monomer/oligomer having an unsaturated double bond (A2), and a polymerization initiator (A3). . Such a composition facilitates stretching during use and can be easily applied to deep drawing, so that it can follow a three-dimensional shape well. It also has the advantage of being able to make it difficult for blocking to occur.

In the active energy ray-curable coating composition, the total amount of polyurethane acrylate (A1), unsaturated double bond-containing monomer/oligomer (A2), and polymerization initiator (A3) is added to the total solid content of the composition. Preferably the amount is in the proportion of 40 to 98% by weight. Such a specific blending ratio is preferable in that a predetermined effect can be obtained.

Furthermore, the active energy ray-curable coating composition contains (A1) in the total amount of the solid content weight of (A1) and the solid content weight of (A2) ((A1) + (A2)) 100 parts by weight 50 to 99 parts by weight, containing (A2) in the range of 1 to 50 parts by weight, the total amount of the solid weight of (A1) and the solid weight of (A2) ((A1) + (A2 )) preferably contains 0.5 to 20 parts by weight of (A3) per 100 parts by weight. By this, it is possible to have anti-blocking property and deep drawability (stretchability) before curing. Furthermore, it can have high scratch resistance, surface hardness, chemical resistance, and impact resistance after curing.
(A1) to (A3) will be described in detail below.

(Polyurethane acrylate (A1))
Polyurethane acrylate (A1) is a compound having a urethane bond in the molecule and a (meth)acrylate group in the molecule. By using this, stretchability is improved when decorative molding is performed, and deep drawing can be easily applied, so that follow-up to a three-dimensional shape is improved.

The polyurethane acrylate (A1) is not particularly limited, and any known one can be used. for example,
i) a compound obtained by equivalently reacting a compound having two or more isocyanate groups in the molecule with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule;
ii) a condensate of a polyol and a monobasic acid and/or a polybasic acid and/or an acid anhydride thereof is reacted with a compound having two or more isocyanate groups in the molecule; a compound obtained by reacting the above hydroxyl group with a compound having one or more double bond groups,
iii) Obtained by reacting a polyol with a compound having two or more isocyanate groups in the molecule, and then reacting a compound having one or more hydroxyl groups and one or more double bond groups in the molecule. Compound,
etc.

In i) to iii) above, compounds having one or more hydroxyl groups and one or more double bond groups in the molecule include, for example, 2-hydroxy(meth)acrylate, 2-hydroxypropyl(meth)acrylate, Examples thereof include 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and the like, and commercially available products such as Plaxel C(M)A series (trade name of Daicel Chemical Industries, Ltd.). In ii) to iii) above, polyhydric alcohols include, for example, polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylolpropane, etc., and commercial products such as Plaxel diol series (trade name of Daicel Chemical Co., Ltd. ), Plaxel Triol series (trade name of Daicel Chemical Industries, Ltd.), and the like.

The polyol is not particularly limited, and known acrylic polyols, polyester polyols, polycarbonate polyols, and the like can be used. Various low-molecular-weight diols such as ethylene glycol, butanediol, glycerin, pentaerythritol, and neopentyl glycol can also be used as necessary.

As the above polyol, a polycarbonate diol skeleton is added at a ratio of polycarbonate concentration: 0.5 to 75 wt% (ratio of polycarbonate to the total amount of polyurethane acrylate (A1). Note that it is a calculated value based on the ratio of components blended as raw materials). It is preferable to have By using a material having a polycarbonate diol skeleton, it has the advantage of exhibiting toughness, preventing swelling during decorative molding, and maintaining the design appearance (prevention of cracking).
More preferably, the content of the polycarbonate diol is 2 to 70% by weight.

The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups. ; aliphatic compounds such as hexamethylene diisocyanate; cycloaliphatic compounds such as isophorone diisocyanate; monomers thereof and multimers thereof such as biuret type, isocyanurate type and adduct type.

Commercially available products of the polyisocyanate include Duranate 24A-90PX (NCO: 23.6%, trade name, manufactured by Asahi Kasei Corporation), Sumidule N-3200-90M (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), and Takenate D165N-. 90X (trade name, manufactured by Mitsui Chemicals), Sumidule N-3300, Sumidule N-3500 (trade name, manufactured by Sumitomo Bayer Urethane), Duranate THA-100 (trade name, manufactured by Asahi Kasei), etc. be able to. In addition, blocked isocyanates in which these are blocked can also be used as necessary.

The polyurethane acrylate (A1) may partially have a urea bond.
In order to have a urea bond, a polyamine compound may be used in part in the synthesis of polyurethane acrylate. Polyamine compounds that can be used are not particularly limited, and examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, and 2,2,4-trimethylhexamethylene. diamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine, (di-2-hydroxyethylpropylene)diamine, Aliphatic polyamines such as (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, piperazine; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1 ,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4′- and/or 4,4′-diamine, norbornanediamine; aromatic diamines such as tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3′-dichloro-4,4′-diaminodiphenylmethane, 4,4′-bis-(sec-butyl)diphenylmethane; and dimer diamines obtained by converting the carboxyl groups of dimer acids into amino groups, dendrimers having primary or secondary amino groups at the terminals, and the like.

The polyurethane acrylate (A1) preferably has a double bond equivalent of 130 to 600 g/eq, more preferably 150 to 300 g/eq. If the double bond equivalent is less than 130 g/eq, there is a possibility that the crack resistance and impact resistance of the cured film may be deteriorated. If the double bond equivalent exceeds 600 g/eq, there is a possibility that problems such as poor scratch resistance, surface hardness, and chemical resistance may occur. The double bond equivalent is a value calculated based on the mixing ratio of the raw materials used in the production of the resin.

The polyurethane acrylate (A1) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight-average molecular weight is less than 3,000, the problem of poor blocking resistance may occur. If the weight average molecular weight exceeds 200,000, the compatibility between the obtained polyurethane acrylate (A1) and the unsaturated double bond-containing monomer/oligomer (A2) contained in the clear coating composition is reduced. In addition, when the weight average molecular weight exceeds 200,000, the viscosity of the clear coating composition tends to increase. In addition, if the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the solid content in the clear coating composition will be significantly reduced, which may lead to the problem of poor workability. There is In addition, in this specification, the weight average molecular weight was measured by the below-mentioned method.

The polyurethane acrylate (A1) preferably has a urethane concentration of 300 to 2000 g/eq. If the urethane concentration is less than 300 g/eq, the compatibility between the obtained polyurethane acrylate (A1) and the unsaturated double bond-containing monomer/oligomer (A2) contained in the clear coating composition is lowered. In addition, when the urethane concentration is less than 300 g/eq, the viscosity of the clear coating composition tends to increase. In addition, if the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the solid content in the clear coating composition will be significantly reduced, which may lead to the problem of poor workability. There is If the urethane concentration exceeds 2000 g/eq, there is a possibility that problems such as poor blocking resistance and impact resistance may occur. The urethane concentration represents a numerical value obtained by dividing the weight average molecular weight of the resin by the number of urethane bonds, and is a value calculated based on the mixing ratio of raw materials used in the production of the resin.

The polyurethane acrylate (A1) preferably has a urea concentration of 500 to 1000 g/eq. If the urea concentration is less than 500 g/eq, the compatibility between the obtained polyurethane acrylate (A1) and the unsaturated double bond-containing monomer/oligomer (A2) contained in the clear coating composition is lowered. In addition, when the urea concentration is less than 500 g/eq, the viscosity of the clear coating composition tends to increase. In addition, if the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the solid content in the clear coating composition will be significantly reduced, which may lead to the problem of poor workability. There is If the urea concentration exceeds 1000 g/eq, the problem of poor blocking resistance may occur. The urea concentration represents a numerical value obtained by dividing the weight average molecular weight of the resin by the number of urea bonds, and is a value calculated based on the mixing ratio of raw materials used in the production of the resin.

Polyurethane acrylate (A1) may be modified with fluorine and/or silicone. That is, the polyurethane acrylate (A1) may be synthesized by the above-described method using a monomer containing a fluorine or silicone unit, or the polyurethane acrylate (A1) obtained by the above-described method has It may be a functional group reacted with a compound having fluorine and/or silicone.

(Monomer/oligomer having an unsaturated double bond (A2))
As the monomer/oligomer (A2) having an unsaturated double bond, any known one can be used, and for example, the following compounds can be used. The monomer/oligomer (A2) having an unsaturated double bond preferably has a weight-average molecular weight of 3,000 or less. That is, in order to complement the performance of the polyurethane acrylate (A1) described above, a relatively low molecular weight monomer/oligomer having an unsaturated double bond is used. The polyurethane acrylate (A1) does not correspond to the monomer/oligomer (A2) having an unsaturated double bond.

By blending a predetermined amount of the monomer/oligomer (A2) having an unsaturated double bond, it is possible to form a coating with a high crosslink density, thereby improving the physical properties of the clear coating layer. It is preferred.

Examples of (meth)acrylates with a functionality of 2 include 1,4-butanediol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol. Di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol Di(meth)acrylate, neopentyl glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , 1,10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate and the like. Among them, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and the like can be preferably used.

Examples of (meth)acrylates having a functionality of 3 include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri( meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxytri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate and the like. Among them, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like can be preferably used.

Examples of (meth)acrylates with 4 functional groups include dipentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, and pentaerythritol propylene oxide-modified tetra(meth)acrylate. , ditrimethylolpropane tetra(meth)acrylate and the like. Among them, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like can be preferably used.

Examples of (meth)acrylates having 4 or more functional groups include pentaerythritol tetra(meth)acrylate, pentaerythritol ethylene oxide-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, Dipentaerythritol penta(meth)acrylate, ditrimethylolpropane penta(meth)acrylate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane hexa(meth)acrylate, dipenta Examples include polyfunctional (meth)acrylates such as hexa(meth)acrylate of caprolactone-modified erythritol. Only one of these monomers may be used, or two or more thereof may be used in combination.

Examples of (meth)acrylic oligomers include epoxy (meth)acrylate, polyester (meth)acrylate, and urethane (meth)acrylate. Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyhydric carboxylic acid and a polyhydric alcohol, with (meth)acrylic acid, or It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid with (meth)acrylic acid. An epoxy acrylate prepolymer can be obtained, for example, by reacting (meth)acrylic acid with an oxirane ring of a relatively low-molecular-weight bisphenol-type epoxy resin or novolak-type epoxy resin to esterify it. Urethane acrylates can generally be obtained by reacting a product obtained by reacting a polyester polyol, a polyether polyol, or a polycarbonate polyol with an isocyanate monomer or a prepolymer, with an acrylate monomer having a hydroxyl group.
These (meth)acrylic oligomers may be used alone, or two or more of them may be used in combination, or may be used in combination with the polyfunctional (meth)acrylate monomer.

Commercially available products such as UV 1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can also be used as the unsaturated double bond-containing monomer/oligomer (A2).

(Polymerization initiator (A3))
As the polymerization initiator (A3), an energy ray polymerization initiator that initiates polymerization by electromagnetic rays such as ultraviolet rays (UV) and electron beams can be used. These energy ray polymerization initiators are not particularly limited, and any known ones can be used.

Specifically, examples of the energy ray polymerization initiator include benzoin compounds such as benzoin methyl ether; anthraquinone compounds such as 2-ethylanthraquinone; benzophenone compounds such as benzophenone; sulfide compounds such as diphenyl sulfide; thioxanthone compounds such as 2,4-dimethylthioxanthone; acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone; phosphinoxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphinoxide; Polymerization initiators for ultraviolet (UV) curing such as Irgacure (registered trademark)-184 and Irgacure-819 (both manufactured by BASF) can be mentioned. One or more of these compounds can be used as a polymerization initiator.

(Combination amount of (A1) to (A3))
In 100 parts by weight of the solid weight of (A1) and the total weight of solid weight of (A2) ((A1) + (A2)), 50 to 99 parts by weight of (A1) and 1 to 50 parts by weight of (A2) It is contained so as to be within the range of parts by weight, and the total amount of the solid content weight of (A1) and the solid content weight of (A2) ((A1) + (A2)) is 100 parts by weight (A3) is 0 It is preferably contained in the range of 5 to 20 parts by weight.

If the content of the polyurethane acrylate (A1) is less than 50 parts by weight, the anti-blocking property is lowered, which is not preferable. If the content of the polyurethane acrylate (A1) exceeds 99 parts by weight, the scratch resistance and surface hardness will be insufficient, which is not preferable. The above lower limit is more preferably 55 parts by weight or more, and even more preferably 65 parts by weight or more. The upper limit is more preferably 98 parts by weight or less, and even more preferably 95 parts by weight or less.

If the content of the unsaturated double bond-containing monomer/oligomer (A2) is less than 1 part by weight, the scratch resistance and surface hardness are unsatisfactory. If the content of the unsaturated double bond-containing monomer/oligomer (A2) exceeds 50 parts by weight, the anti-blocking property is lowered, which is not preferable. The above lower limit is more preferably 2 parts by weight or more, and even more preferably 5 parts by weight or more. The upper limit is more preferably 45 parts by weight or less, and even more preferably 35 parts by weight or less.

If the content of the polymerization initiator (A3) is less than 0.5 parts by weight, the clear layer cannot be sufficiently cured, and the scratch resistance, surface hardness, chemical resistance, and impact resistance of the resulting clear are There is a possibility that the physical properties of the coating film cannot be obtained. When the content of the polymerization initiator (A3) exceeds 20 parts by weight, the unreacted polymerization initiator (A3) remains in the clear coating film, and the clear coating film deteriorates due to outdoor sunlight and the like. , weather resistance may deteriorate.

The above clear coating composition preferably contains 0.5 to 20 parts by weight of a thiol compound and/or an amine compound.
The thiol compound and/or amine compound is not particularly limited, and commonly used thiol compounds and amine compounds can be mentioned.

Examples of the amine compounds include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, and diethylenetriamine; 1,2- and 1,3-cyclobutanediamine; Alicyclic polyamines such as 2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4'- and/or 4,4'-diamine, norbornanediamine: phenylenediamine , xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 4,4-bis-(sec-butyl)diphenylmethane; A dimer acid diamine converted to an amino group, a dendrimer having an amino group at its terminal, and a polyamine having an amine as a repeating structure can also be used, but are not limited to these.

Examples of the thiol compound include 1,4-bis(3-mercaptobutyryloxy)butane, ethylene glycol dimercaptopropionate, diethylene glycol dimercaptopropionate, 4-t-butyl-1,2-benzenedithiol, bis -(2-mercaptoethyl) sulfide, 4,4'-thiodibenzenethiol, benzenedithiol, glycol dimercaptoacetate, glycol dimercaptopropionate, ethylene bis(3-mercaptopropionate), polyethylene glycol dimercaptoacetate , polyethylene glycol di-(3-mercaptopyropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bisphenofluorene bis ( ethoxy-3-mercaptopropionate), 4,8-bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, 2-mercaptomethyl-2-methyl-1,3-propanedithiol , 1,8-dimercapto-3,6-dioxaoctane, thioglycerol bismercapto-acetate and other bifunctional thiols: trimethylolpropane (trismercaptopropionate) (TMPTMP), trimethylolpropane tris (3-mercaptobutyl rate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptoacetate), tris (3-mercaptopropyl) isocyanurate, 1 , 3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,2,3-trimercaptopropane, and Trifunctional thiols such as tris(3-mercaptopropionate)triethyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione:poly(mercaptopropylmethyl)siloxane (PMPMS) ), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol pentaerythritol tetrakis (3-mercaptoacetate), and pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercapto propionate), pentaerythritol tetrakis (3 - mercaptobutyrate), including but not limited to polyfunctional thiols.

The clear coating layer (A) used in the laminated film for decorating the three-dimensional molded article of the present invention is as described above, but more preferably polyurethane acrylate (A1) has a double bond equivalent of 130 ~600g/eq
Molecular weight Mw: 3000-200000
Urethane concentration: 300 to 2000 g/eq,
It is preferably formed by a coating composition that is It is preferable to use one that satisfies these properties. By forming the clear coating film layer (A) with such a clear coating composition, blocking resistance, high scratch resistance, surface hardness and chemical resistance can be provided, and good impact resistance can be imparted. It is preferable in that respect. Furthermore, the polyurethane acrylate (A1) preferably has a urea concentration of 500 to 1000 g/eq.

The weight average molecular weight in this specification was measured using HLC-82220GPC manufactured by Tosoh Corporation. The measurement conditions are as follows.
Column: TSKgel Super Multipore HZ-M 3-developed Solvent: Tetrahydrofuran column inlet oven 40°C
Flow rate: 0.35 ml/min.
Detector: RI
Standard polystyrene: Tosoh Corporation PS Oligomer Kit

(other ingredients)
The clear coating composition may contain, as other components, a compound that is usually added as a coating material. In this case, the blending amount of other components is preferably 60% by weight or less, more preferably 40% by weight or less, most preferably 20% by weight or less, based on the total solid content in the paint. preferable. Other components include ultraviolet absorbers (UVA), light stabilizers (HALS), binder resins, cross-linking agents, pigments, surface conditioners, antifoaming agents, conductive fillers, solvents, and the like.

Furthermore, a solvent may be used for mixing each component contained in the clear coating composition and adjusting the viscosity. Examples of the solvent include ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, aromatic hydrocarbon-based, and other conventionally known organic solvents used in paints. Solvents may be used singly or in combination of two or more. When the above solvent is used, if the volatile substance remains in the laminated film, the volatile substance may volatilize during the decoration of the substrate, resulting in pinholes or swelling. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

Furthermore, the clear coating composition preferably further contains 0.5 to 60 parts by weight (solid content ratio in the coating) of an inorganic filler or an organic filler having an average primary particle size of 100 nm or less. This can improve blocking resistance, high scratch resistance, and surface hardness. More preferably, the lower limit of the blending amount is 1% by weight, and the upper limit is 50% by weight.

Examples of the inorganic filler include silica, fine powder glass, alumina, calcium carbonate, kaolin, clay, sepiolite (magnesium silicate), talc (magnesium silicate), mica (aluminum silicate), xonotlite (calcium silicate), aluminum borate, hydro Talcite, wollastonite (calcium silicate), potassium titanate, titanium oxide, barium sulfate, magnesium sulfate, magnesium hydroxide, yttria, ceria, silicon carbide, boron carbide, zirconia, aluminum nitride, silicon nitride, or a combination of these Non-metallic inorganic materials, so-called ceramic fillers, which are obtained through molten mixtures, molding, firing, or the like, can be mentioned. Among them, silica, alumina, zirconia, or eutectic mixtures thereof are preferred from the aspect of cost and effectiveness.

Examples of the organic filler include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins.
In addition, commercially available organosilica sol MIBK-ST, MEK-ST-UP, MEK-ST-L, MEK-AC-2140Z (manufactured by Nissan Chemical Industries), SIRMIBK15ET%-H24, SIRMIBK15ET%-H83, ALMIBK30WT%- H06 (CIK Nanotech) or the like can be used.

The clear coating composition may contain 0.5 to 20% by weight (solid content ratio in the coating) of a polyisocyanate compound having an isocyanate group. By blending a polyisocyanate compound, it is preferable in that moldability (stretchability) and scratch resistance can be imparted. More preferably, the lower limit of the blending amount is 2% by weight, and the upper limit is 18% by weight.

The above clear coating composition may be a colored transparent composition containing a coloring pigment. That is, the combination of the vapor-deposited metal layer and such a colored and transparent clear layer enables decoration with the vapor-deposited metal. Coloring pigments that can be used in the above clear coating composition are not particularly limited, and any known coloring pigments can be used.

(Design layer (B))
The design layer (B) in the present invention is a layer having a design appearance provided by a laminated film for decorating a three-dimensional molded product. As such a layer, at least one layer selected from the group consisting of a layer formed by drying after applying a colored coating composition, a layer formed by printing, and a metallic design layer can be used. can be done. The design layer may be a single layer, or may include two or more layers. For example, a layer formed by drying after applying a colored coating composition and a combination of a metallic design layer, or a layer or metallic tone formed by drying after applying a colored coating composition A design layer and a layer formed by printing may be combined.
Each of these will be described below.

(Design layer (B) formed by colored coating composition)
The colored coating composition that can be used to form the design layer (B) is not particularly limited, but preferably contains a urethane resin (B1) and a glitter material (B2). In addition to the above components, the colored coating composition contains an ultraviolet absorber (UVA), a light stabilizer (HALS), a binder resin and a cross-linking agent, a pigment, a surface control agent, an antifoaming agent, a conductive Other ingredients such as polymeric fillers, solvents, etc. may also be included. The colored coating composition may be cured by irradiation with electromagnetic radiation, or may be thermoplastic or thermosetting.

In addition, as shown in FIG. 1, in the case of the embodiment in which no adhesive layer is provided, it is preferable to impart an adhesive function to the design layer. That is, it is preferable that the design layer (BC) also functioning as an adhesive layer is formed from a colored coating composition using a highly adhesive resin as the resin.

(Urethane resin (B1))
The urethane resin (B1) contained in the colored coating composition is not particularly limited, but the weight average molecular weight Mw is preferably 10,000 or more and 200,000 or less, and is 30,000 or more and 150,000 or less. is more preferred. When the weight-average molecular weight Mw is less than 10,000, the design layer (B) has reduced flexibility, and when the weight-average molecular weight Mw exceeds 200,000, production of a colored coating composition and application to a film are difficult. becomes difficult.

The urethane resin (B1) preferably has a Tg of -30°C to 30°C. If the Tg is less than -30 ° C., there may be a problem that the coating film tackiness (blocking) after coating and drying decreases. There may be a problem of deterioration of low temperature physical properties as.

In addition, Tg in this specification means the value measured by the following processes with a differential scanning calorimeter (DSC) (thermal analyzer SSC5200 (manufactured by Seiko Electronics)). That is, a step of raising the temperature from 20 ° C. to 150 ° C. at a temperature increase rate of 10 ° C./min (step 1), a step of lowering the temperature from 150 ° C. to −50 ° C. at a temperature decrease rate of 10 ° C./min (step 2), It is a value obtained from the chart at the time of temperature increase in step 3 in the step (step 3) in which the temperature is raised from −50° C. to 150° C. at a temperature rate of 10° C./min. That is, the temperature indicated by the arrow in the chart shown in FIG. 7 was taken as Tg.

(Bright material (B2))
The glittering material (B2) is not particularly limited, and is preferably at least one selected from the group consisting of aluminum, glass, inorganic pigments and organic pigments. More specifically, coating aluminum, aluminum flakes, metals such as copper, zinc, nickel, tin, aluminum oxide, etc., or metallic pigments using metallic luster materials such as alloys; mica-based pigments such as interference mica and white mica A pigment etc. can be mentioned.
The colored coating composition contains 0.5 to 60 parts by weight of (B2) in 100 parts by weight of the total solid weight of (B1) and the solid weight of (B2) ((B1) + (B2)). It is preferable to use a product containing so as to be in the range of parts.

(other ingredients)
Binder resins and cross-linking agents that are other components contained in the colored coating composition include, for example, modified acrylic resins, polyester resins, epoxy resins, olefin resins, modified olefin resins, melamine resins, polyisocyanate compounds, block isocyanates, nate compounds and the like. In addition, the solvent contained in the colored coating composition includes ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based, and aromatic hydrocarbon-based solvents. One or a combination of two or more organic solvents that are commonly used in paints may be used. When the above solvent is used, if the volatile substance remains in the laminated film, the volatile substance may volatilize during the decoration of the substrate, resulting in pinholes or swelling. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

(Design layer (B) formed by printing)
The laminated film for decorating a three-dimensional molded product of the present invention may have a design layer (B) formed by printing. Providing such a layer is preferable in that a unique appearance can be obtained. The printing method is not particularly limited, and can be formed by a known method such as inkjet printing, screen printing, offset printing, or flexographic printing. In particular, the use of inkjet printing is preferable in that various printed layers can be formed at low cost. Also, when printing, the printing may be performed using an energy ray curable ink.

(Metallic design layer (B))
In order to obtain an excellent metallic appearance as if it were made of metal, the present invention uses a coating layer (B-1) containing vapor-deposited aluminum or a vapor-deposited metal layer (B -2) A metallic design layer (B) may be formed. By forming such a metallic design layer (B), it is possible not only to obtain a good metallic appearance, but also to prevent the occurrence of cracks and whitening due to stretching when decorating a three-dimensional molded product. It is possible to perform decoration with a good metallic tone.

The coating film layer (B-1) containing vapor-deposited aluminum and the vapor-deposited metal layer (B-2) made of indium or tin are described in detail below.

(Coating layer (B-1) containing evaporated aluminum)
The coating film layer for forming the metallic design layer is firstly formed by a paint containing a vapor deposited aluminum pigment.

The coating film layer (B-1) containing such a vapor deposited aluminum pigment is, for example, one formed from a metallic base paint containing 30 to 85% by weight of the vapor deposited aluminum pigment relative to the solid content of the paint. can be done.

The vapor-deposited aluminum pigment is obtained by chopping a vapor-deposited aluminum film into flakes. Such non-leafing evaporated aluminum pigments can be obtained, for example, by using a plastic film such as oriented polypropylene, crystalline polypropylene, or polyethylene terephthalate as a base film, applying a release agent thereon, and performing aluminum evaporation on the release agent. can be manufactured by

Unlike ordinary aluminum pigments such as aluminum flakes, the vapor-deposited aluminum pigments have less graininess, and thus can provide a design layer having a mirror-like appearance like a metal surface.

More preferably, the vapor-deposited aluminum pigment is a non-leafing vapor-deposited aluminum pigment. The non-leafing evaporated aluminum pigment preferably has a particle diameter of 3 to 20 μm and a thickness of 0.01 to 0.1 μm. By having the above particle size, it is possible to obtain a new metallic design with less graininess. More preferably, the particle size is 5 to 15 μm. The particle size in the present specification is a value measured with a laser diffraction particle size distribution analyzer LA-910 (manufactured by HORIBA, Ltd.). Commercially available non-leafing evaporated aluminum that can be used in the present invention includes Metascene 11-0010, 41-0010, 71-0010, 91-0010, MS-750, MS-650 (manufactured by Ciba Specialty Co., Ltd.) and silver. Line P1000, P4100, Metalure L, Metalure A21010BG (manufactured by Ecarto) and the like can be mentioned.

The leafing treatment is a treatment performed on the surface of aluminum with a hydrophobic and/or oleophobic agent. The non-leafing vapor-deposited aluminum pigment used in the present invention is preferably a non-leafing vapor-deposited aluminum pigment that has not been subjected to such leafing treatment. When leafing-evaporated aluminum is used, the adhesion to the adjacent coating layer is reduced, resulting in poor adhesion. Therefore, in the present invention, it is preferred to use non-leafing evaporated aluminum.

The vapor-deposited aluminum pigment is 30 to 85% by mass with respect to the total solid content of the coating film layer (B-1) containing the vapor-deposited aluminum. If it is less than 30% by mass, a glittering coating film that satisfies a dense metallic luster cannot be obtained, and if it exceeds 85% by mass, the physical properties of the coating film deteriorate. The content of the non-leafing evaporated aluminum pigment is more preferably 40 to 80% by mass.

The coating film layer (B-1) containing vapor-deposited aluminum further contains a binder resin in addition to the non-leafing vapor-deposited aluminum pigment. The binder resin is not particularly limited, and vinyl chloride resins, acrylic resins, urethane resins, polyester resins and the like can be used, and two or more of these resins may be used in combination. Among these, vinyl chloride resin is particularly preferred.

Commercially available vinyl chloride resins can be used. The vinyl chloride resin may be a vinyl chloride homopolymer or a copolymer of vinyl chloride and other vinyl monomers that can be copolymerized. More specific examples of the above copolymer include copolymers of vinyl chloride and vinyl acetate, maleic anhydride or esters thereof, vinyl ether, acrylic acid, acrylic hydroxyl group-containing monomers, and the like.

The degree of polymerization of these vinyl chloride resins is usually 200-2000, preferably 300-1000. Commercially available vinyl chloride resins include Solbin C, CN, A, TA2, TAO, TAOL, M5 manufactured by Nissin Chemical Industry; Vinnol H11/59, E15/48A, LL4320, E15/45M manufactured by Wacker; Dow UCAR VYHD, VAGD, VMCH, VMCC and the like can be mentioned. Among these, two or more kinds can be mixed and used.

The coating film layer (B-1) containing vapor-deposited aluminum may be one to which an aluminum aggregation inhibitor is added. In this case, cohesive failure between the aluminum and the resin can be suppressed by the action of the aluminum anti-aggregation agent, which is preferable. Specifically, DIANAL RE360 (manufactured by Mitsubishi Rayon Co., Ltd.) or the like can be used as the aluminum aggregation inhibitor.

The coating layer (B-1) containing vapor-deposited aluminum can contain other luster pigments and/or color pigments in addition to the specific non-leafing vapor-deposited aluminum pigment.

Other bright pigments include, for example, metal oxide-coated alumina flake pigments, metal oxide-coated silica flake pigments, graphite pigments, metal oxide-coated mica pigments, metal titanium flake pigments, stainless steel flake pigments, and plate-like iron oxide pigments. , metal-plated glass flake pigments, metal oxide-coated glass flake pigments, hologram pigments and flake pigments made of cholesteric liquid crystal polymers, more preferably metal oxide-coated alumina At least one pigment selected from the group consisting of flake pigments, metal oxide-coated silica flake pigments, graphite pigments, metal oxide-coated mica pigments and metal oxide-coated glass flake pigments can be used.

Examples of the colored pigments include azo lake pigments, phthalocyanine pigments, indigo pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, isoindolinone pigments, and metal complex pigments. , and inorganic pigments include, for example, yellow iron oxide, red iron oxide, titanium dioxide, and carbon black.

The metallic base paint for forming the coating film layer (B-1) containing vapor-deposited aluminum includes, in addition to the above components, polyethylene wax, anti-settling agent, curing catalyst, ultraviolet absorber, antioxidant, and leveling agent. , surface conditioners such as silicones and organic polymers, anti-sagging agents, thickeners, antifoaming agents, cross-linkable polymer particles (microgel) and the like can be appropriately added and contained. The metallic base paint can be in the form of a solvent-based paint, a water-based paint, or the like.

The coating film layer (B-1) containing vapor-deposited aluminum preferably has a thickness of 0.05 to 5 μm. If it is outside the above range, problems such as whitening and cracking are likely to occur, which is not preferable.

(Evaporated metal layer (B-2) made of indium or tin)
First, the evaporated metal layer will be described.
Vapor deposition is a method of forming a thin film by heating and evaporating a vapor deposition material in a vacuum vessel and depositing it on the surface of a substrate placed at a distance. In the present invention, metals used for vapor deposition are tin and indium. Since vapor deposition requires a degree of vacuum of about 10 ⁻³ to 10 ⁻⁴ Pa, it is necessary to once evacuate the container. Vapor deposition therefore becomes a complete batch process and continuous processing is not possible.

In addition, the vapor deposition method for films generally includes (1) setting a film roll and a target metal in a chamber, (2) evacuating the chamber (10 ⁻³ to 10 ⁻⁴ Pa), and running the film. (3) heating the target and generating vapor to vapor-deposit on the film surface; and (4) completing the vapor deposition and opening the chamber to the atmosphere. Compared to direct vapor deposition on parts, it is a batch process, but since one roll of film is continuously processed, the economic efficiency is high. Another advantage is that the thickness and quality of the deposited film can be easily controlled. However, the film as it is cannot be applied to a three-dimensional object.

The vapor-deposited metal layer (B-2) made of indium or tin in the present invention can be formed by a normal vapor deposition method using these metals. By using indium or tin, it is possible to form a metal layer with good elongation, so that cracks and whitening do not occur when molding into a three-dimensional shape, and the appearance is not adversely affected.

In the present invention, by using indium or tin as the vapor-deposited metal layer, there is an advantage that cracking and whitening are less likely to occur due to the action of discontinuous vapor deposition.

When forming such a deposited metal layer, the thickness is preferably 0.05 to 5 μm. By setting it as such thickness, the objective mentioned above can be achieved satisfactorily.

(Release layer D)
When the release layer (D) is provided in the present invention, any known layer can be used, and for example, it can be formed from a silicone release agent or the like.
The peel strength between the release layer (D) and the clear coating layer (A) is preferably 0.05 to 8.0 N/25 mm, more preferably 0.1 to 5.0 N/25 mm. If it is less than 0.05 N/25 mm, the base film layer (H) peels off during film production or during decorative molding, resulting in poor workability. When peeling, there is a possibility that peeling may become difficult.

(Adhesion layer (C))
The adhesive layer is used to adhere and adhere the laminated film to the surface of the molded product when decorating the molded product with the laminated film.

The adhesive contained in the adhesive layer is not particularly limited as long as it is a conventionally known adhesive, and examples thereof include Vylon UR-3200 (manufactured by Toyobo Co., Ltd.) and UR-1361ET (manufactured by Toagosei Co., Ltd.).
The adhesive may be formed by applying and drying the adhesive, or may be formed by laminating adhesive sheets.

(Protective layer (F))
In the laminate film for decorating a three-dimensional molded product of the present invention, in particular when a metallic design layer is provided as the design layer (B), the protective layer (F) is formed adjacent to the design layer (B). is preferred. That is, when the metallic design layer (B) is provided at a position in contact with the clear coating layer (A), when the uncured clear coating layer (A) moves due to stretching in the uncured state, the metal The design layer (B) moves, which may deteriorate the appearance.

Furthermore, when the design layer (B) is a vapor deposited metal layer (B-2) made of indium or tin, it is possible to form the vapor deposited metal layer on the uncured clear coating layer (A) in the production thereof. It can be difficult. Therefore, from the viewpoint of alleviating such problems, it is desirable to improve such problems by providing a protective layer (F) having good vapor deposition properties.

The protective layer (F) is not particularly limited, and for example, resins such as acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, urethane resins, epoxy resins, and styrene resins can be used. , urethane resins are preferred, and urea bond-containing urethane resins are more preferred. They can be blended singly or in combination of two or more.

(Ultraviolet absorbing layer (G))
When the UV absorbing layer (G) is provided, it should satisfy 3 to 1000 N/cm ² at a strength of 40° C. to 130° C., a surface tension of 20 to 60 mN/m, and a UV transmittance of 290 nm to 430 nm and 20% or less. is preferred.
If the strength is low, swelling will occur during molding, and if the strength is high, the moldability will be insufficient. In addition, if the surface tension is low, the ink bleeds, and if the surface tension is high, the ink repels. Also, if the UV transmittance is high, a sufficient UV shielding effect cannot be obtained. That is, it has sufficient surface tension for inkjet printing, has sufficient UV shielding ability to prevent hardening of the clear coating layer, and has sufficient strength not to cause problems in molding. It is what I did.

The strength of the UV-absorbing layer (G) is measured by using the UV-absorbing layer alone with Autograph AG-IS manufactured by Shimadzu Corporation at a temperature of 60° C., at a tensile speed of 50 mm/min, and at an elongation of 200%. is measured.

The surface tension of the ultraviolet absorbing layer (G) was calculated by measuring the contact angles of water and methylene iodide using an automatic contact angle meter DSA20 (manufactured by Kurz).

The UV transmittance of the UV absorbing layer (G) was measured in a wavelength range of 290.0 nm to 430.0 nm using a UV-visible spectrophotometer U-4100 (Hitachi High Technologies).

Moreover, it is preferable that the ultraviolet absorbing layer (G) absorbs ultraviolet rays but easily transmits visible light. This is because the design layer becomes difficult to see from the outside unless visible light is transmitted.

The ultraviolet absorbing layer (G) is formed from a coating composition containing a binder resin (G1) and an ultraviolet absorbent (G2). By adjusting the blending and combination of these components, it is possible to form a layer that satisfies the above parameters.

The binder resin (G1) is not particularly limited, and resins such as acrylic resins, vinyl chloride-vinyl acetate copolymers, polyamide resins, polyester resins, urethane resins, epoxy resins, and styrene resins can be used. A urethane resin is preferred, and a urea bond-containing urethane resin is more preferred. They can be blended singly or in combination of two or more.
It is preferably in the range of 85 to 99% by weight with respect to the total amount of the ultraviolet absorbing layer (G).

The ultraviolet absorber (G2) is not particularly limited, and examples thereof include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and hydroxybenzoate-based ultraviolet absorbers. can be used.

Examples of the triazine-based ultraviolet absorber include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-hydroxymethylphenyl)-4, 6-diphenyl-s-triazine, 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-hydroxymethylphenyl)-4,6- bis(2,4-dimethylphenyl)-s-triazine, 2-[2-hydroxy-4-(2-hydroxyethyl)phenyl]-4,6-diphenyl-s-triazine and the like.

Examples of the benzophenone-based ultraviolet absorbers include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2′,4,4′-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n- benzyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy -4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4 -Methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2'-dihydroxy-4,4'-di(hydroxymethyl ) benzophenone, 2,2′-dihydroxy-4,4′-di(2-hydroxyethyl)benzophenone, 2,2′-dihydroxy-3,3′-dimethoxy-5,5′-di(hydroxymethyl)benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-di(2-hydroxyethyl)benzophenone and the like.

Examples of the benzotriazole-based ultraviolet absorbers include 2-(2-hydroxy-5-t-methylphenyl)-2H-benzotriazole and 2-(2-hydroxy-3,5-di-t-butylphenyl). -2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, 2-[2'-hydroxy-5'-(hydroxymethyl)phenyl]-2H-benzotriazole , 2-[2′-hydroxy-5′-(2-hydroxyethyl)phenyl]-2H-benzotriazole, 2-[2′-hydroxy-5′-(3-hydroxypropyl)phenyl]-2H-benzotriazole , 2-[2′-hydroxy-3′-methyl-5′-(hydroxymethyl)phenyl]-2H-benzotriazole and the like.

Examples of the cyanoacrylate ultraviolet absorbers include 2-ethylhexyl-2-cyano-3,3'-diphenyl acrylate, ethyl-2-cyano-3,3'-diphenyl acrylate, methyl-2-cyano-3- methyl-3-(p-methoxyphenyl)acrylate, and the like.

Examples of the hydroxybenzoate-based ultraviolet absorbers include phenyl salcylate, resorcinol monobenzoate, 4-t-butylphenyl salcylate, 2,5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3′,5-di-t-butyl-4′-hydroxybenzoate, 2,4-di-t-amylphenyl-3′,5-di-t-butyl-4 '-hydroxybenzoate, hexadecyl-3',5-di-t-butyl-4'-hydroxybenzoate and the like.

As the ultraviolet absorber (G2), triazine-based, benzophenone-based, and benzotriazole-based ultraviolet absorbers are used because they have high ultraviolet absorbability in a wide range of wavelengths (about 280 to 360 nm) from short wavelength regions to long wavelength regions. preferable.
The ultraviolet absorber can be blended with the above compounds singly or in combination of two or more.
Specifically, Tinuvin 400, 900, 447 and 1130 (manufactured by BASF) can be used. The blending amount of the ultraviolet absorber (G2) varies depending on the ultraviolet absorber to be used, and is not particularly limited as long as it satisfies the above-mentioned ultraviolet transmittance. is preferably within the range of , more preferably within the range of 3 to 10% by weight. If it is less than 1% by weight, the UV shielding effect may be insufficient. If the amount exceeds 15% by weight, the strength of the UV-absorbing layer may be lowered, resulting in insufficient moldability, and is disadvantageous in terms of cost.

The ultraviolet absorbing layer (G) may contain a surface conditioner (G3). That is, depending on the type of resin used in the ultraviolet absorbing layer (G), it may be difficult to keep the surface tension within the above range. In this case, the surface tension can be adjusted within the range described above by blending the surface conditioner (G3).

The surface conditioner (G3) is not particularly limited, and for example, polyether-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, etc. can be used. Specific examples include BYK-300, BYK-342, BYK-349 (manufactured by BYK-Chemie Japan). The amount of the surface conditioner (G3) to be blended is not particularly limited, and is preferably within the range of 0.01 to 5% by weight with respect to the total amount of the ultraviolet absorbing layer (G).

Although the thickness of the ultraviolet absorbing layer (G) is not particularly limited, it is preferably 3 to 30 μm, more preferably 5 to 25 μm. If it is too thin, it tends to be difficult to obtain sufficient UV shielding performance and strength. Become.

(Breaking elongation)
The laminated film for decorating a three-dimensional molded product of the present invention preferably has an elongation at break of 30 to 500% at 40 to 80°C before curing. That is, by having such a breaking elongation within the above temperature range, it becomes possible to easily adapt to vacuum forming, and the effects of the present invention can be suitably obtained. Such a numerical range can be achieved by adjusting the components of each layer forming the film. In the present invention, "having an elongation at break of 30 to 500% at 40 to 80 ° C." means that the temperature range in which the elongation at break is 30 to 500% is within 40 to 80 ° C., and molding is performed at that temperature. , means that sufficient stretchability can be obtained.

The breaking elongation is measured using Autograph AG-IS manufactured by Shimadzu Corporation with the base film layer peeled off, within a temperature range of 40 to 80 ° C., at a tensile speed of 50 mm / min. It is a value obtained by measuring the elongation at the time when the layer of is broken. Depending on the properties of the film, the elongation at break should be within the ranges mentioned above at any arbitrary temperature within the range of 40-80°C.

(Method for manufacturing laminated film)
The laminated film for decorating a three-dimensional molded article of the present invention is prepared by preparing a coating composition in which the components constituting each layer are dissolved in a solvent, and coating and drying this on a base film layer as a carrier film. can be formed. The design layer (B) can also be formed by printing as described above. The laminate film for decorating a three-dimensional molded article of the present invention is in a state in which the base film layer used during production is peeled off before the decorative molding.

The film forming the base film layer is not particularly limited, and conventionally known films such as soft vinyl chloride film, biaxially stretched polypropylene film, biaxially stretched polyester film, polycarbonate film, acrylic resin film, fluorine film, etc. mentioned. Among these, a film formed of polyester and/or polyolefin is preferred, and a biaxially oriented polyester film is particularly preferred from the viewpoint of energy saving and low temperature processability. The thickness of the base film layer is preferably 0.01 to 0.5 mm, more preferably 0.02 to 0.3 mm. If the thickness is out of this range, it is not preferable in terms of the function as a carrier film.

The coating method for forming each layer is not particularly limited, but for example, spray coating, applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. are used. should be applied with After the coating solution is applied by the above-described coating method, heating and drying can be performed to remove the solvent in the coating solution.

Further, as described above, the adhesive layer (C) may be adhered by a lamination method instead of the coating and drying method. That is, it may be formed by a method of preparing a film formed by the adhesive layer (C) and laminating it to the film.

When the design layer (B) is an evaporated metal layer (B-2) made of indium or tin, it is necessary to form an evaporated metal layer. A method for forming such a vapor-deposited metal layer is not particularly limited, and can be carried out by an ordinary known method.

(how to use)
When the laminated film for decorating a three-dimensional molded product of the present invention is used to decorate a base material, it may be carried out in the same manner as a conventionally known vacuum forming technique, and is not particularly limited. That is, the base film layer is peeled off from the laminated film, and the adhesive layer (C) or the design layer (B-C) that also functions as an adhesive layer faces the base surface, and is laminated on the base surface. The laminated film is crimped and decorated so as to adhere the film. Thereafter, electromagnetic wave irradiation or heating is performed to cure each layer to obtain a coating film.

A method for decorating a three-dimensional molded article, which comprises adhering the above laminated film for decorating a three-dimensional molded article on a three-dimensional molded article under heating conditions, is also one aspect of the present invention. Since the laminated film of the present invention does not contain a base film during decorative molding, it can be molded at a lower temperature than conventional decorative methods. Furthermore, since molding can be performed at a low temperature, fluttering of the coating film can be suppressed even in a state in which no substrate film is included, and decorative molding can be preferably performed.
Specifically, it is preferable to mold the laminated film at a temperature of 40 to 80°C.

The base film peeled off before decorative molding can be reused. That is, according to the present invention, the substrate film can be repeatedly used (reused) and the amount of industrial waste can be reduced, which is advantageous in terms of cost and environment.

Furthermore, in the method for decorating a three-dimensional molded article of the present invention, since the clear coating film layer is in an uncured state, surface processing can be performed. For example, by further molding and embossing a film whose surface shape has been processed with design unevenness by matting or embossing, any texture such as matte, rough, silky, leather, or wood grain can be obtained. was able to be given.

Substrates that can be suitably decorated with the laminated film of the present invention are not particularly limited, but for example, automobile exteriors such as bumpers, front underspoilers, rear underspoilers, side underskirts, side garnishes, and door mirrors. Automobile interior parts such as parts, instrument panels, center consoles, door switch panels, housings of home electric appliances such as mobile phones, audio products, refrigerators, fan heaters, and lighting fixtures, washstands, and the like can be mentioned.

EXAMPLES The present invention will now be described by way of examples. In the examples, % means weight % unless otherwise specified. The invention is not limited to the examples described below.

(Synthesis example preparation of polyurethane acrylate (A1))
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a material inlet was prepared. 200.0 g of polyhexamethylene carbonate diol (trade name "Duranol T6001", manufactured by Asahi Kasei Chemicals Corp., number average molecular weight determined by terminal functional group determination = 1,000) while replacing the inside of the reaction vessel with air. 80.0 g of 4-butanediol and 120.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 102.9 mg KOH/g) were charged. Then, 238.1 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became homogeneous, 314.2 g of 4,4'-methylenebis-cyclohexyl diisocyanate was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm −1 due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1:1 to obtain a resin solution containing polyurethane. The obtained resin solution had a viscosity of 200 dPa·s/20° C., a solid content of 45%, and a double bond equivalent of 600 g/eq. Moreover, the weight average molecular weight of the polyurethane measured by GPC was 44,000.

[Production example of laminated film]
<Preparation of base film>
When a release layer was provided, a release layer was formed by applying a silicon-based release agent to one surface of the substrate film on which the coating layer was to be formed.

<Preparation of clear paint solution>
Polyurethane acrylate (A1) and monomer (A2) are placed in a container equipped with a stirrer, MEK is added in an amount that makes the final coating NV = 40% while stirring, and polymerization initiator (A3) is added. After stirring for 1 minute, a clear coating solution was obtained.

<Adjustment of colored paint solution>
Put the urethane resin (B1) and the glitter material (B2) into a container equipped with a stirrer, add MIBK in an amount that makes the final paint NV = 35% while stirring, and stir for 30 minutes to obtain a colored paint solution. rice field.

<Preparation of coating solution containing evaporated aluminum>
A binder resin and vapor-deposited aluminum were placed in a container equipped with a stirrer, MIBK was added in an amount such that NV=2% in the final paint while stirring, and stirred for 30 minutes to obtain a coating solution containing vapor-deposited aluminum.

<Preparation of UV-absorbing paint solution>
Put the binder resin (G1) and the UV absorber (G2) into a container equipped with a stirrer, add MEK in an amount that makes the final coating NV = 40% while stirring, stir for 30 minutes, and prepare the UV absorbing coating solution. got

<Production of laminated film 1>
The above clear coating solution is applied onto the substrate film layer (H) using an applicator so that a clear coating layer (A) having a predetermined thickness (hereinafter referred to as dry thickness) is obtained when dried. , and dried at 80°C for 15 minutes to form a clear coating layer (A). In the following description, a film obtained by forming a clear coating layer (A) on a base film layer (H) is referred to as a (H+A) layer film.
Next, on the clear coating layer (A) of the (H+A) layer film, the colored coating solution is applied using an applicator so as to obtain a design layer (B) with a predetermined dry thickness, and then , and dried at 80°C for 15 minutes to form a design layer (B).
When the adhesive layer (C) is provided, an adhesive (Vylon UR-3200, manufactured by Toyobo Co., Ltd.) is subsequently applied on the design layer (B) so as to obtain an adhesive layer (C) having a predetermined dry thickness. , and dried at 80° C. for 15 minutes to form an adhesive layer (C).

<Production of laminated film 2>
The clear coating solution is applied onto the base film layer (H) by an applicator so as to obtain a clear coating layer (A) having a predetermined thickness when dried (hereinafter referred to as a dry film thickness). and dried at 80°C for 15 minutes to form a clear coating layer (A).
In the following description, a film obtained by forming a clear coating layer (A) on a base film layer (H) is referred to as a (H+A) layer film.
Next, on the clear coating layer (A) of the (H+A) layer film, the above vapor-deposited aluminum-containing coating solution is applied using a bar coater so as to obtain a metal design layer (B) having a predetermined dry thickness. It was applied and then dried at 80° C. for 15 minutes to form a metallic design layer (B).
Subsequently, an adhesive (Vylon UR-3200, manufactured by Toyobo Co., Ltd.) was applied onto the metallic design layer (B) using an applicator so as to obtain an adhesive layer (C) having a predetermined dry film thickness. , and dried at 80°C for 15 minutes to form an adhesive layer.

<Lamination of protective layer>
When a protective layer is provided, a predetermined binder solution is applied using an applicator so as to obtain a protective layer (F) having a dry film thickness of 20 μm, and then dried at 80° for 15 minutes to form a protective layer. (F) was formed.

<Lamination of UV absorbing layer>
When providing an ultraviolet absorbing layer, the above ultraviolet absorbing coating solution is applied using an applicator so as to obtain an ultraviolet absorbing layer (G) having a dry film thickness of 20 μm, and then dried at 80° C. for 15 minutes. to form an ultraviolet absorbing layer (G).

The film thickness of the multilayer coating film obtained in each example before curing was measured at 23° C. with a linear gauge sensor. The results are shown in the table.

[Production example of molding decorated with laminated film]
A base material (molded product) was placed on a vertical lifting table provided in a double-sided vacuum forming apparatus (trade name: NGF-0709, manufactured by Fuse Vacuum Co., Ltd.) consisting of an upper and lower box. After that, the laminated film obtained above was set on the sheet clamp frame above the molding base material (molded product) of the double-sided vacuum forming apparatus after peeling off the base film. Subsequently, the vacuum in the upper and lower boxes is reduced to 1.0 kPa, the laminated film is heated to a predetermined temperature using a near-infrared heater, and the molding substrate is raised to raise the molding substrate. The laminated film was press-bonded, and then compressed air of 200 kPa was introduced only into the upper box and held for 35 seconds. The upper and lower boxes were opened to the atmospheric pressure to obtain a decorated molding decorated with the laminated film. Furthermore, from the side of the clear coating film layer (A) of the decorative molding, using a high-pressure mercury lamp of 120 W/cm, ultraviolet rays with a light amount of 2000 mJ/cm ² are irradiated, and the clear coating of the clear coating film layer (A) is applied. was cured to obtain a UV (ultraviolet) cured molding.

In addition, the following components were used in each table|surface shown below. Further, inkjet printing and lamination were performed using the following apparatus and conditions.
UV 1700B (Nippon Synthetic Chemical Industry): urethane acrylate oligomer silin TPO (BASF): 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide mirror (registered trademark) S-10 (Toray): biaxially oriented polyester Film Purex #38A54 (Toyobo Film Solution): Biaxially oriented polyester film Film Bina (registered trademark) NT-2 (Fujimori Kogyo): Biaxially oriented polyester film Alpaste 65-388 Aluminum (Toyo Aluminum): Aluminum paste Byron UR -3200 (Toyobo): polyester urethane resin Xp012N35 (Mitsui Chemicals): modified olefin resin TE-5430 (Mitsui Chemicals): urethane resin Tinuvin 900 (BASF): 2,2-(2H-benzotriazol-2-yl)-4 , 6-Bis(1-methyl-1-phenylethyl)phenol Solbin M5 (Nissin Chemical Industry): Vinyl chloride resin Metascene 71-0010 (Chiba Specialty): Vapor deposition aluminum inkjet printing → Mimaki Engineering UJF-3042
Laminate → MCK Co., Ltd. MRK-650Y, 80 mm diameter heat-resistant silicone rubber roll, temperature: 85°C, speed: 42 cm/min

(elongation)
With the base film layer peeled off, measurement was made using Shimadzu Autograph AG-IS at a temperature of 80° C. and a tensile speed of 50 mm/min. Elongation was determined when any layer broke.
○: 200% or more △: 30% or more ×: less than 30%

(Moldability)
Confirmed by TOM molding using a double-sided vacuum forming machine NGF-0709 manufactured by Fuse Vacuum Co., Ltd. Possible to mold even to the low stretched part of the material ×: Not moldable

(SW resistance after molding)
Using a steel wool resistance tester, #0000 steel wool was reciprocated 10 times with a load of 100 g / cm ² ◎: No scratches ○: 2 to 3 scratches △: Countable scratches ×: Countless scratches

(Impact resistance after molding)
Using a DuPont impact resistance tester, drop a weight of 500 g from a height of 20 cm and check for cracks in the coating film.

(Chemical resistance after molding)
A cylindrical poly ring with an inner diameter of 38 mm and a height of 15 mm was fixed to the coating film, and the following solution was added dropwise. Cover and let stand under each condition. After the test, wash with water and compare the state of the coating film with the initial state.
Acid resistance 0.1N H2SO4 solution 5ml 20°C x 24h
Alkali resistance 0.1N NaOH solution 5ml 55°C x 4h
Water resistance Distilled water 5ml 55°C x 4h
◎: No change in coating film ○: Slight change in coating film appearance (wrinkles, cracks)
△: Clear change in paint film appearance (wrinkles, cracks)
×: Significant change in paint film appearance (wrinkles, cracks)

Tables 1 to 8 show that the laminated film for decorating a three-dimensional molded product of the present invention can perform good decoration even when the base film is peeled off. In addition, it has become clear that sufficient strength, impact resistance and chemical resistance can be imparted.

The laminated film for decorating a three-dimensional molded article of the present invention can be suitably used when decorating various molded articles with a three-dimensional surface.

(A) Clear coating layer (B) Design layer (BC) Design layer with adhesive function (C) Adhesive layer (D) Release layer (F) Protective layer (G) Ultraviolet absorption layer (H) Base material film layer

Claims (10)

Having a clear coating layer (A) made of an energy ray-curable coating and a design layer (B),
Furthermore, a laminated film for decorating a three-dimensional molded product, which further comprises an adhesive layer (C), or the design layer (B) is a design layer (BC) that also functions as an adhesive layer, ,
A three-dimensional molded product having a coating strength of 1.95 to 39.5 N at 40 ° C., 2.45 to 20.0 N at 60 ° C., or 0.49 to 4.9 N at 80 ° C. Laminated film for decoration. The laminate film for decorating a three-dimensional molded product according to claim 1, wherein the film thickness before curing is 10 to 200 µm at 23°C. The clear coating layer (A) composed of an energy ray-curable coating comprises polyurethane acrylate (A1),
2. The three-dimensional molding for decorating according to claim 1, which is formed from an active energy ray-curable coating composition containing a monomer/oligomer (A2) having an unsaturated double bond and a polymerization initiator (A3). laminated film. 4. The laminated film for decorating a three-dimensional molded product according to claim 3, wherein the polyurethane acrylate (A1) has a molecular weight Mw of 3,000 to 200,000. The design layer (B) and the design layer (BC) having an adhesive function are a layer formed by drying after applying a colored coating composition, a layer formed by printing, and a metallic design layer. The laminated film for decorating a three-dimensional molded article according to claim 1, 2, 3 or 4, which is at least one layer selected from the group consisting of: The design layer (B) and the design layer (BC) having an adhesive function contain a polyurethane resin (B1) and a glitter material (B2), and the solid content weight of (B1) and the solid content of (B2) It is formed by a colored coating composition containing (B2) in the range of 0.5 to 60 parts by weight in the total weight ((B1) + (B2)) of 100 parts by weight. Item 6. The laminated film for decorating a three-dimensional molded product according to item 5. 7. The laminated film for decorating a three-dimensional molded product according to claim 6, wherein the polyurethane resin (B1) has a molecular weight Mw of 10,000 to 200,000. 3. A three-dimensional molded product, wherein the laminated film for decorating a three-dimensional molded product according to claim 1, 2, 3, 4, 5, 6 or 7 is adhered on a three-dimensional molded product under heating conditions. decoration method. 9. The three-dimensional molded article decoration according to claim 8, further comprising a step of preparing a laminated film for decorating a three-dimensional molded article having a base film layer, and peeling off the base film layer before decorating the three-dimensional molded article. decoration method. 10. The method for decorating a three-dimensional molded product according to claim 8 or 9, wherein the heating is carried out in a range in which the temperature of the laminated film is 40 to 80°C.

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