KR20220119028A - Laminated film for decorating three-dimensional molded products, manufacturing method thereof, and three-dimensional decorating method - Google Patents

Abstract

Metal-like laminated film for decorating three-dimensional molded products that can highly improve problems such as cracking and whitening, and suppress Rayleigh scattering and Mie scattering that reduce designability when various articles are decorated provides It has a base film (A), a clear coating film layer (B) made of an energy ray-curable coating film, a metal-clad decoration layer (C) which is a vapor-deposited metal layer made of indium or tin, and an adhesive layer (D), and the metal-clad design The layer has an optical density of 0.6 to 1.4, and the adhesive layer (D) has a total light transmittance of 20% or less.

Description

Laminated film for decorating three-dimensional molded products, manufacturing method thereof, and three-dimensional decorating method

The present invention relates to a laminated film for decorating a three-dimensional molded article, a manufacturing method thereof, and a three-dimensional decorating method.

With respect to a molded article obtained from a plastic, a metal, or other various materials, decoration of a metal strip is performed using a laminated film for decorating a three-dimensional molded article (Patent Documents 1 to 5). In such a method, it is known to decorate a molded article using a decorative laminated film having a metal-like decorative layer made of a vapor-deposited metal layer or a coating film containing a vapor-deposited aluminum pigment.

In the decorative molding by the laminated film for three-dimensional decoration which has such a metal-like decorative layer, it is necessary to extend|stretch a film so that a three-dimensional shape may be followed. However, in the stretching of such a film, the metallic decorative layer did not sufficiently harvest the resin layer, and cracking and whitening of the metallic decorative layer were often generated. The aluminum vapor deposition layer, which is generally used, does not have sufficient stretching properties and is not suitable for decorating articles having complicated shapes. Since the vapor-deposited metal layer made of indium or tin is discontinuous vapor deposition unlike the aluminum vapor-deposited layer, it can be stretched at a relatively high magnification.

Patent Document 1 discloses a laminated film for three-dimensional decoration having a metal-like decorative layer. Here, the effect of being able to prevent the whitening at the time of extending|stretching in the case of using tin or indium is also disclosed. However, for example, in the case of decorating a thing having a complicated shape, such as a wheel, there were cases where a sufficiently good designability was not obtained by whitening. Specifically, whitening is likely to occur in a wheel spoke portion of a wheel or a highly elongated portion inside a rib.

When the metal vapor deposition layer is stretched, there is a problem of coloring by Rayleigh scattering or Mie scattering due to the reflected light from the surface of the target plant, thereby reducing the designability. Therefore, improvement of such a problem is calculated|required in the decoration of the article which requires a high degree of designability.

Patent Document 2 describes laminating a metal vapor deposition layer and an adhesive layer on a resin film, and adding a colorant to the adhesive layer. However, the purpose of adding the colorant is to absorb heat, and it is not used from the viewpoint of designability. In addition, aluminum deposition is mainly performed.

Patent Document 3 describes a metal-like decorative sheet having a metal vapor deposition layer and a colored thermoplastic resin sheet layer. However, it does not color an adhesive layer, and does not have a thermosetting resin layer. For this reason, decorating with sufficient performance in film strength etc. cannot be performed.

Patent Document 4 describes a decorative sheet having a metallic luster layer. However, the metallic luster layer is not due to the metallic vapor deposition layer.

Patent Document 5 describes a decorative sheet having a metal vapor deposition layer. However, the metal deposition layer made of aluminum is specifically described, and the metal deposition layer made of indium or tin is not specifically described.

International Publication No. 2016/080423 Japanese Patent Laid-Open No. 10-735 Japanese Patent Laid-Open No. 2008-55688 Japanese Patent Laid-Open No. 2015-66855 Japanese Patent Laid-Open No. 2015-196288

In view of the above, the present invention highly improves problems such as cracking and whitening, and can suppress Rayleigh scattering and non-scattering that reduce designability when various articles are decorated. It is intended to provide a film.

The present invention has a base film (A), a clear coating layer (B) made of an energy ray-curable coating film, a metallic decorative layer (C) which is a vapor deposition metal layer made of indium or tin, and an adhesive layer (D),

The metallic decorative layer has an optical density of 0.6 to 1.4,

The adhesive layer (D) is a laminated film for decorating a three-dimensional molded article, characterized in that the total light transmittance is 20% or less.

The clear coating film layer (B) made of the energy ray-curable coating film is an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer/oligomer (B2) having an unsaturated double bond, and a polymerization initiator (B3) It is preferably formed by

It is preferable that the said contact bonding layer (D) contains 0.4-20% of carbon.

It is preferable that the said laminated|multilayer film for three-dimensional molded article decoration further has a protective layer (F) between a clear coating-film layer (B) and the metal-like decoration layer (C) which is a vapor deposition metal layer.

It is preferable that the said laminated|multilayer film for three-dimensional molded article decoration further has a design layer (G) formed by printing.

Process (1-1) of this invention forming the clear coating-film layer (B) which consists of an energy-beam curable coating film on a base film layer (A)

Step (1-2) of forming a metal-like decorative layer (C), which is a vapor-deposited metal layer made of indium or tin, on the film subjected to step (1-1);

The manufacturing method of the said laminated|multilayer film for three-dimensional molded article decoration is a process (1-3) of forming an adhesive layer (D) on the film obtained by the process (1-2)

It is also a manufacturing method of the laminated film for decorating the three-dimensional molded article, characterized in that it has.

The manufacturing method of the said laminated|multilayer film for three-dimensional molded article decorating, after performing a process (1-1), before performing a process (1-2), a clear coating-film layer (B) adjacent to a metal-like decorative layer (C) It is preferable to have the process (1-4) of forming the protective layer (F) on it.

The manufacturing method of the said laminated|multilayer film for three-dimensional molded article decorating, after performing a process (1-1), before performing a process (1-2), a process (1-4) of forming the decoration layer (G) by printing ) is preferred.

The present invention is a step (2-1) of forming a clear coating film layer (B) made of an energy ray-curable coating film on a base film layer (A);

Separately, on the base film layer (X), a step (2-2) of forming an adhesive layer (D) and a metal decorative layer (C) which is a vapor deposition metal layer made of indium or tin;

Step (2-3) of bonding the film obtained in the step (2-1) and the film obtained in the step (2-2) above

It is also a manufacturing method of the laminated film for decorating the three-dimensional molded article, characterized in that it has.

After performing the process (2-1), the manufacturing method of the said laminated|multilayer film for three-dimensional molded article decorating, before performing a process (2-3), the clear coating-film layer (B) adjacent to the metal-like design layer (C) It is preferable to have the process (2-4) of forming the protective layer (F) on it.

In the manufacturing method of the laminated|multilayer film for said three-dimensional molded article decoration, after performing a process (2-1) or a process (2-4), before performing a process (2-3), the design layer (G) is formed by printing. It is preferable to have the forming process (2-5).

The present invention is also a three-dimensional molded article decorating method, characterized in that the laminated film for decorating the three-dimensional molded article is adhered to the three-dimensional molded article with an adhesive layer under heating conditions.

The laminated film for decorating a three-dimensional molded article of the present invention can highly improve problems such as cracking and whitening, and can suppress Rayleigh scattering and non-scattering that reduce designability when various articles are decorated.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decoration of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decorating of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decoration of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decoration of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decoration of this invention.
Fig. 6 is a schematic diagram showing an example of a laminated structure of the laminated film for decorating a three-dimensional molded article of the present invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decorating of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decorating of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decorating of this invention.
It is a schematic diagram which shows an example of the laminated structure of the laminated|multilayer film for three-dimensional molded article decorating of this invention.

Hereinafter, the present invention will be described in detail.

(Lamination film for decorating three-dimensional molded products)

The laminated film for three-dimensional molded article decoration of this invention is a film used in the decorative molding of a three-dimensional molded article. That is, the film which has design is made to adhere|attach to various molded objects, and designability is provided to a molded object, or a surface protection function is provided. At that time, it is deformed into a shape along the surface of the three-dimensional shape and adhered.

As a method of making it adhere in this way, although any well-known method can be used, For example, the method of making it deform|transform by methods, such as vacuum forming and air pressure forming, and making it adhere|attach is mentioned. Moreover, the method etc. which deform|transform the laminated|multilayer film for decorative molding in a metal mold|die to the shape of a metal mold|die outer wall surface, and perform injection molding after that are mentioned.

The laminated film for decorating a three-dimensional molded article of the present invention is a base film (A), a clear coating layer (B) made of an energy ray-curable coating film, a metal-like decorative layer (C) and an adhesive layer (D), which are deposited metal layers made of indium or tin ) to have

That is, by forming a coating film layer made of an energy ray-curable coating film while having a layer having a metallic appearance, the combination has a good metallic appearance, and various performances such as hard coat properties, flexibility, chemical resistance, and weather resistance. It is also possible to perform excellent decorating.

In the laminated film for decorating a three-dimensional molded article having the above-mentioned layer structure, the metallic decorative layer (C) has an optical density of 0.6 to 1.4,

The adhesive layer (D) is characterized in that the total light transmittance is 20% or less. That is, the metallic decorative layer has a specific optical density, and the total light transmittance is 20% or less.

By having a metallic decorative layer having an optical density of 0.6 to 1.4, a sufficient metallic decorative layer can be obtained even after stretching, and problems such as whitening are unlikely to occur, which is preferable. As for the lower limit of the said optical density, it is more preferable that it is 0.7, and it is still more preferable that it is 0.8. As for the upper limit of the said optical density, it is more preferable that it is 1.3, and it is more preferable that it is 1.2.

It is also important that the total light transmittance of the adhesive layer (D) is 20% or less. As mentioned above, Rayleigh scattering and non-scattering generate|occur|produce when reflected light hits when a metal vapor deposition layer whitens. Therefore, if the quantity of reflected light from a metal surface can be reduced, the fall of the designability by Rayleigh scattering and non-scattering can be suppressed. Moreover, since the light transmittance falls when the contact bonding layer (D) shall have the said total light transmittance, it is also preferable from the point which the light resistance of a base material improves.

From the above two viewpoints, the present invention is preferably used for imparting designability on a metal substrate in particular. In addition, in a field with a complicated shape, such as a wheel for an automobile and the like, in which a problem due to deformation is likely to occur, the above-described effect becomes more remarkable.

Hereinafter, each layer which comprises the laminated|multilayer film for three-dimensional molded article decoration of this invention is demonstrated in detail.

A base film (A) makes|forms the function as a carrier film at the time of manufacturing the laminated|multilayer film of this invention. That is, it is used as a base material for forming each layer at the time of manufacture of the laminated|multilayer film for three-dimensional molded article decorating of this invention. Moreover, in the aspect as shown to FIG. 3, 4 mentioned above, even after performing a decoration process, some exist on a molded object. In this case, not only the role as a simple base material but also functions, such as a surface protection function, are exhibited.

It does not specifically limit as a film which forms a base film (A), For example, Conventional soft vinyl chloride film, an unstretched polypropylene film, an unstretched polyester film, a polycarbonate film, an acrylic resin film, a fluorine film, etc. A well-known film is mentioned. Among these, the film formed of polyester and/or polyolefin is preferable, and a non-stretched polyester film is more preferable especially from the point of energy-saving low-temperature processability. It is preferable that it is 0.01-0.5 mm, and, as for the thickness of the said base film (A), it is more preferable that it is 0.02-0.3 mm. When it deviates from this range, it is unpreferable from the point of the function as a carrier film, or the economical point at the time of electron beam hardening.

(Clear coating layer (B))

The clear coating film layer (B) used in the present invention is an energy ray-curable coating film, and the specific composition thereof is not particularly limited as long as the physical properties as a laminated film are not impaired, and a known energy ray-curable coating film can be used.

An energy-beam curable coating film can harden resin by energy-beam irradiation after transforming it into the shape of a to-be-planted plant in the state of the laminated|multilayer film for three-dimensional molded article decoration. For this reason, while being able to easily deform into the shape of a plant to be decorated, it exhibits excellent performance in the strength, appearance, chemical resistance, and the like of the coating layer after decoration.

Among these, those formed of an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer/oligomer having an unsaturated double bond (B2) and a polymerization initiator (B3) are preferable. By setting it as such a composition, the drawing at the time of use is made|formed easily, and since it can respond easily also to deep drawing, the yield to a three-dimensional shape becomes favorable. Moreover, it also has the advantage of being able to make blocking difficult to generate|occur|produce.

In the active energy ray-curable coating composition, the total amount of the polyurethane acrylate (B1), the monomer/oligomer having an unsaturated double bond (B2) and the polymerization initiator (B3) based on the total amount of solid content in the composition is 40 to 98% by weight It is preferable that the ratio of Thus, by setting it as a specific compounding ratio, it is preferable at the point which can acquire a predetermined|prescribed effect.

In addition, the active energy ray-curable coating composition contains 50 to 99 parts by weight of (B1) in 100 parts by weight of the total amount ((B1) + (B2)) of the solid content weight of (B1) and the solid content weight of (B2), (B2) is contained within the range of 1 to 50 parts by weight, and (B3) is 0.5 to 100 parts by weight of the total amount ((B1) + (B2)) of the solid content weight of (B1) and the solid content weight of (B2) It is preferable to contain so that it may become within the range of 20 weight part. Thereby, it can have blocking resistance before hardening and deep drawing property (stretchability). In addition, it may have high scratch resistance, surface hardness, chemical resistance, and impact resistance after curing.

Hereinafter, (B1) to (B3) will be described in detail.

(Polyurethane acrylate (B1))

Polyurethane acrylate (B1) is a compound which has a urethane bond in a molecule|numerator and has a (meth)acrylate group in a molecule|numerator. By using this, the stretchability at the time of decorative molding improves, and since it can respond easily also to deep drawing, the yield to a three-dimensional shape becomes favorable.

It does not specifically limit as said polyurethane acrylate (B1), A well-known arbitrary thing can be used. For example,

i) a compound obtained by subjecting a compound having two or more isocyanato groups in a molecule to an equivalent reaction of a compound having one or more hydroxyl groups and one or more double bond groups in the molecule;

ii) a polyol and a condensate of a monobasic acid and/or a polybasic acid and/or an acid anhydride thereof are reacted with a compound having two or more isocyanato groups in a molecule, and then one or more hydroxyl groups and one or more 2 groups in the molecule A compound obtained by further reacting a compound having a heavy bonding group;

iii) a compound obtained by reacting a polyol with a compound having two or more isocyanato groups in a molecule, followed by further reacting a compound having one or more hydroxyl groups and one or more double bond groups in the molecule

and the like.

In the above i) to iii), as the compound having at least one hydroxyl group and at least one double bond group in the molecule, for example, 2-hydroxy(meth)acrylate, 2-hydroxypropyl(meth)acryl rate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, can be heard In the above ii) to iii), as the polyhydric alcohol, for example, polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylolpropane, etc., and in the case of a commercially available product, the Fraxeldiol series (trade name of Daicel Chemicals) ), Fraxeltriol series (trade name of Daicel Chemicals), etc. are mentioned.

It does not specifically limit as said polyol, Well-known acrylic polyol, polyester polyol, polycarbonate polyol, etc. can be used. Moreover, various low molecular weight diols, such as ethylene glycol, butanediol, glycerol, pentaerythritol, and neopentyl glycol, etc. can be used as needed.

As the polyol, polycarbonate concentration: 0.5 to 75 wt% (the ratio of polycarbonate to the total amount of polyurethane acrylate (B1). Also, it is a calculated value based on the ratio of components blended as raw materials). It is preferable to have a diol skeleton. By using what has a polycarbonate diol skeleton, toughness is expressed, and it has the advantage that expansion prevention at the time of decorative molding and maintenance of a design appearance (cracking prevention) become possible.

As for the said polycarbonate diol, it is more preferable that it is 2 to 70 weight%.

The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups, and for example, aromatics such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate. of one's; aliphatic things, such as hexamethylene diisocyanate; alicyclic ones such as isophorone diisocyanate; The monomer, its burette type, nurate type, multimers, such as an adduct type, etc. are mentioned.

As a commercial item of the said polyisocyanate, Duranate 24A-90PX (NCO: 23.6%, brand name, Asahi Kasei Co., Ltd. make), Sumijul N-3200-90M (brand name, Sumitomo Bayer Urethane Co., Ltd. make), Takenate D165N-90X (brand name, Mitsui Chemicals make), Sumijul N-3300, Sumizul N-3500 (all are brand names, the Sumitomo Bayer Urethane make), Duranate THA-100 (trade names, Asahi Chemicals make), etc. are mentioned. Moreover, the blocked isocyanate which blocked these can also be used as needed.

The polyurethane acrylate (B1) may have a urea bond in part.

In order to set it as what has a urea bond, you may use a polyamine compound for a part in the synthesis|combination of a polyurethane acrylate. It does not specifically limit as a polyamine compound which can be used, For example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2, 2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propylenediamine, (2-hydroxyethylpropylene)diamine, (di-2-hydroxyethylethylene)diamine aliphatic polyamines such as (di-2-hydroxyethylpropylene)diamine, (2-hydroxypropylethylene)diamine, (di-2-hydroxypropylethylene)diamine, and piperazine; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4′- and/or alicyclic polyamines such as 4,4'-diamine and norbornanediamine; Phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4 aromatic diamines such as '-bis-(sec-butyl)diphenylmethane; and dimerdiamine in which the carboxy group of dimer acid is converted to an amino group, and a dendrimer having a primary or secondary amino group at the terminal thereof.

It is preferable that a double bond equivalent is 130-600 g/eq, and, as for the said polyurethane acrylate (B1), it is more preferable that it is 150-300 g/eq. If the double bond equivalent is less than 130 g/eq, there is a possibility that the problem of poor crack resistance and impact resistance of the cured film may occur. When the double bond equivalent exceeds 600 g/eq, there is a possibility that the problem of poor abrasion, surface hardness, and chemical resistance may occur. In addition, the said double bond equivalent is a value computed based on the compounding ratio of the raw material used in manufacture of resin.

It is preferable that the weight average molecular weights of the said polyurethane acrylate (B1) are 3000-20000. If the weight average molecular weight is less than 3000, there is a possibility that the problem of poor blocking resistance may arise. When the weight average molecular weight exceeds 200000, the compatibility of the obtained polyurethane acrylate (B1) and the monomer/oligomer (B2) having an unsaturated double bond contained in the clear coating composition, etc. will decrease. In addition, when the weight average molecular weight exceeds 200000, the viscosity of the clear coating composition tends to increase. In addition, when the clear coating composition is diluted with an organic solvent in order to improve such a rise in viscosity, the solid content in the clear coating composition remarkably decreases, which may cause a problem that workability deteriorates. In addition, in this specification, the weight average molecular weight was measured by the method mentioned later.

The polyurethane acrylate (B1) preferably has a urethane concentration of 300 to 2000 g/eq. When the urethane concentration is less than 300 g/eq, the compatibility between the obtained polyurethane acrylate (B1) and the monomer/oligomer (B2) having an unsaturated double bond contained in the clear coating composition decreases. In addition, when the urethane concentration is less than 300 g/eq, the viscosity of the clear coating composition tends to increase. In addition, when the clear coating composition is diluted with an organic solvent in order to improve such a rise in viscosity, the solid content in the clear coating composition remarkably decreases, which may cause a problem that workability deteriorates. When the urethane concentration exceeds 2000 g/eq, there is a possibility that the problem of poor blocking resistance and impact resistance may occur. In addition, urethane concentration shows the numerical value which divided the weight average molecular weight of resin by the number of urethane bonds, and is a value computed based on the compounding ratio of the raw material used in manufacture of resin.

The polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g/eq. When the urea concentration is less than 500 g/eq, compatibility between the obtained polyurethane acrylate (B1) and the monomer/oligomer (B2) having an unsaturated double bond contained in the clear coating composition decreases. In addition, when the urea concentration is less than 500 g/eq, the viscosity of the clear coating composition tends to increase. In addition, when the clear coating composition is diluted with an organic solvent in order to improve such a rise in viscosity, the solid content in the clear coating composition remarkably decreases, which may cause a problem that workability deteriorates. When a urea concentration exceeds 1000 g/eq, there exists a possibility that the problem that blocking resistance is inferior may arise. In addition, a urea concentration shows the numerical value which divided the weight average molecular weight of resin by the number of urea bonds, and is a value computed based on the compounding ratio of the raw material used in manufacture of resin.

The polyurethane acrylate (B1) may be modified with fluorine and/or silicone. That is, the polyurethane acrylate (B1) may be synthesized by the above-mentioned method using a monomer containing fluorine or a silicone unit, and the functional group which the polyurethane acrylate (B1) obtained by the above-mentioned method has is fluorine And/or it may be made to react with the compound which has silicone.

(Monomer/oligomer (B2) having an unsaturated double bond)

As the monomer/oligomer (B2) having an unsaturated double bond, any known one can be used, and for example, the following compounds can be used. Moreover, it is preferable that the weight average molecular weight of the monomer oligomer (B2) which has the said unsaturated double bond is 3000 or less. That is, in order to supplement the performance of the above-described polyurethane acrylate (B1), a monomer/oligomer having a relatively low molecular weight having an unsaturated double bond is used. Moreover, the thing corresponding to the said polyurethane acrylate (B1) does not correspond to the monomer oligomer (B2) which has an unsaturated double bond.

By blending a predetermined amount of the monomer/oligomer (B2) having an unsaturated double bond, a film having a high crosslinking density can be formed, which is preferable in that the physical properties of the clear coating layer can be improved.

Examples of the (meth)acrylate having a functional group number 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, hydroxypivalate neopentyl glycol 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-tricyclodecanedi(meth)acryl rate and the like. Especially, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, etc. can be used preferably.

Examples of the (meth)acrylate having 3 functional groups include trimethylolmethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropaneethylene oxide modified tri(meth)acrylate, and trimethylolpropanepropylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin propoxytri(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, etc. are included. . Especially, trimethylol propane trimethacrylate, pentaerythritol trimethacrylate, etc. can be used preferably.

Examples of the (meth)acrylate having 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 are included. Especially, ditrimethylol propane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. can be used preferably.

Examples of the (meth)acrylate having 4 or more functional groups include pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide-modified tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and dipentaeryth. Ritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) polyfunctional (meth)acrylates such as acrylate, ditrimethylolpropane hexa(meth)acrylate, and hexa(meth)acrylate of a caprolactone-modified product of dipentaerythritol. These monomers may use only 1 type and may use 2 or more types together.

As a (meth)acrylic-type oligomer, epoxy (meth)acrylate, polyester (meth)acrylate, urethane (meth)acrylate, etc. are mentioned, for example. Here, as the polyester acrylate-based prepolymer, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both terminals obtained by condensation of polyhydric carboxylic acid and polyhydric alcohol with (meth)acrylic acid, or It can obtain by esterifying the hydroxyl group of the terminal of the oligomer obtained by adding alkylene oxide to carboxylic acid with (meth)acrylic acid. The epoxy acrylate-based prepolymer can be obtained by, for example, reacting and esterifying (meth)acrylic acid with an oxylan ring of a relatively low molecular weight bisphenol-type epoxy resin or novolak-type epoxy resin. The urethane acrylate can generally be obtained by reacting an acrylate monomer having a hydroxyl group with a product obtained by reacting an isocyanate monomer or a prepolymer with a polyester polyol, polyether polyol, or polycarbonate polyol.

These (meth)acrylic oligomers may use only 1 type, may use 2 or more types together, and may use them together with the said polyfunctional (meth)acrylate type monomer.

As the monomer/oligomer (B2) having an unsaturated double bond, commercially available ones such as UV 1700B manufactured by Nippon Kosei Chemicals can be used.

(Polymerization initiator (B3))

As said polymerization initiator (B3), the energy-beam polymerization initiator in which polymerization is started by electron beams, such as an ultraviolet-ray (UV) or an electron beam, can be used. These energy-beam polymerization initiators are not specifically limited, Well-known arbitrary things can be used.

Specifically, as said energy-beam polymerization initiator, For example, Benzoin type compounds, such as benzoin methyl ether; anthraquinone-based compounds such as 2-ethylanthraquinone; benzophenone compounds such as benzophenone; sulfide compounds such as diphenyl sulfide; thioxanthone-based compounds such as 2,4-dimethylthioxanthone; acetophenone-based compounds such as 2,2-dimethoxy-2-phenylacetophenone; phosphinoxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphinoxide; Polymerization initiators for ultraviolet (UV) hardening, such as Irgacure (trademark)-184 and Irgacure-819 (all are made by BASF Corporation), etc. are mentioned. These compounds can use 1 type, or 2 or more types as a polymerization initiator.

(Amount of (B1) to (B3))

In 100 parts by weight of the total amount ((B1) + (B2)) of the solid content weight of (B1) and the solid content weight of (B2), 50 to 99 parts by weight of (B1) and 1 to 50 parts by weight of (B2) within the range It is preferable to contain (B3) within the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the total amount ((B1) + (B2)) of the solid content weight of (B1) and the solid content weight of (B2). .

When content of the said polyurethane acrylate (B1) is less than 50 weight part, it is not preferable at the point that blocking resistance falls. When content of the said polyurethane acrylate (B1) exceeds 99 weight part, it is not preferable at the point which abrasion resistance and surface hardness become inadequate. As for the said minimum, it is more preferable that it is 55 weight part or more, and it is still more preferable that it is 65 weight part or more. It is more preferable that it is 98 weight part or less, and, as for the said upper limit, it is still more preferable that it is 95 weight part or less.

If the content of the monomer/oligomer (B2) having an unsaturated double bond is less than 1 part by weight, it is not preferable from the viewpoint of insufficient scratch resistance and surface hardness. When content of the monomer-oligomer (B2) which has the said unsaturated double bond exceeds 50 weight part, it is not preferable at the point that blocking resistance falls. As for the said minimum, it is more preferable that it is 2 weight part or more, and it is still more preferable that it is 5 weight part or more. It is more preferable that it is 45 weight part or less, and, as for the said upper limit, it is still more preferable that it is 35 weight part or less.

When the content of the polymerization initiator (B3) is less than 0.5 parts by weight, the clear layer cannot be sufficiently hardened, and there is a possibility that the obtained clear coating film properties of scratch resistance, surface hardness, chemical resistance, and impact resistance cannot be obtained. When the content of the polymerization initiator (B3) exceeds 20 parts by weight, unreacted polymerization initiator (B3) remains in the clear coating film, and the clear coating film deteriorates due to sunlight or the like outdoors, and the weather resistance may deteriorate. There is a possibility.

It is preferable that the said clear coating composition contains 0.5-20 weight part of thiol compound and/or an amine compound with respect to the solid substance whole quantity of coating composition.

It does not specifically limit as said thiol compound and/or an amine compound, A thiol compound normally used, and an amine compound are mentioned.

Examples of the amine compound include aliphatic polyamines such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, and diethylenetriamine; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4′- and/or alicyclic polyamines such as 4,4'-diamine and norbornanediamine; aromatic amines such as phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, and 4,4-bis-(sec-butyl)diphenylmethane; and a dimer acid diamine in which the carboxy group of the dimer acid is converted to an amino group, a dendrimer having an amino group at the terminal, and a polyamine having an amine as a repeating structure may be used, but are not limited thereto.

Examples of the thiol compound include 1,4-bis(3-mercaptobutyryloxy)butane, ethylene glycol dimercaptopropionate, diethylene glycol dimercaptopropionate, and 4-t-butyl-1,2- Benzenedithiol, bis-(2-mercaptoethyl)sulfide, 4,4'-thiodibenzenethiol, benzenedithiol, glycol dimercaptoacetate, glycol dimercaptopropionate, ethylenebis(3-mer captopropionate), polyethylene glycol dimercaptoacetate, polyethylene glycol di-(3-mercaptopropionate), 2,2-bis(mercaptomethyl)-1,3-propanedithiol, 2,5- Dimercaptomethyl-1,4-dithiane, bisphenolfluorenebis(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, etc. difunctional thiol; Trimethylolpropane (trismercaptopropionate) (TMPTMP), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), trimethylolethane tris (3-mercapto) butyrate), trimethylolpropanetris(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 tris(3-mercaptopropionate)triethyl-1,3; trifunctional thiols such as 5-triazine-2,4,6-(1H,3H,5H)-trione; poly(mercaptopropylmethyl)siloxane (PMPMS), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiolpentaerythritoltetrakis(3-mercaptoacetate), and pentaerythritoltetra polyfunctional thiols such as kiss (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), and pentaerythritol tetrakis (3-mercaptobutyrate), but with these not limited

Although the clear coating film layer (B) used in the laminated|multilayer film for three-dimensional molded article decoration of this invention is as above-mentioned, More preferably, polyurethane acrylate (B1)

Double bond equivalent: 130-600 g/eq

Molecular weight Mw: 3000-20000

Urethane Concentration: 300~2000g/eq

It is preferable that it is formed by a phosphorus paint composition. It is preferable to use those satisfying these properties. By forming a clear coating film layer (B) with such a clear coating composition, it is equipped with blocking resistance, high abrasion resistance, surface hardness, and chemical-resistance, and it is preferable at the point which can provide favorable impact resistance. In addition, the polyurethane acrylate (B1) preferably has a urea concentration of 500 to 1000 g/eq.

In addition, the weight average molecular weight in this specification was measured using Tosoh Co., Ltd. product HLC-82220GPC. Measurement conditions are as follows.

Column: TSKgel Super Multipore HZ-M 3ea

Developing solvent: tetrahydrofuran

Column inlet oven 40°C

Flow rate: 0.35ml/min.

Detector: RI

Standard polystyrene: Tosoh Co., Ltd. PS oligomer kit

(Other ingredients)

The clear coating composition may contain the compound normally added as a coating material as another component. In this case, the blending amount of the other components is preferably 60% by weight or less, more preferably 40% by weight or less, and most preferably 20% by weight or less with respect to the total amount of solid content in the coating material. As other components, a ultraviolet absorber (UVA), a light stabilizer (HALS), resin for binders, a crosslinking agent, a pigment, a surface conditioning agent, an antifoamer, a conductive filler, a solvent, etc. are mentioned.

Moreover, you may use a solvent for mixing and viscosity adjustment of each component contained in a clear coating composition. As the solvent, for example, one type of conventionally known organic solvents used in paints, such as ester-based, ether-based, alcohol-based, amide-based, ketone-based, aliphatic hydrocarbon-based, alicyclic hydrocarbon-based and aromatic hydrocarbon-based solvents. Or you may use it in combination of 2 or more type. Moreover, when using the said solvent, when a volatile substance remains in laminated|multilayer film, the decoration to a base material WHEREIN: A volatile substance may volatilize and a pinhole and expansion may generate|occur|produce. Therefore, it is preferable to fully reduce the volatile substance contained in laminated|multilayer film.

Moreover, it is preferable that the said clear coating composition further contains 0.5-60 weight part (solid content in coating material) of the inorganic filler or organic filler whose average primary particle diameter is 100 nm or less. Thereby, blocking resistance, high abrasion resistance, and surface hardness can be improved. As for the lower limit of the said compounding quantity, it is more preferable that it is 1 weight%, and, as for an upper limit, it is more preferable that it is 50 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), zonotolite (calcium silicate), aluminum borate, hydrotal. Site, 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 eutectic mixture thereof, or molding , a non-metallic inorganic material so-called ceramic filler obtained through firing or the like is mentioned. Among them, silica, alumina, zirconia, or a eutectic mixture thereof is preferable in terms of price and effectiveness.

As said organic filler, the bead of each resin of acryl, styrene, silicone, polyurethane, acryl urethane, benzoguanamine, and polyethylene is mentioned.

Moreover, as a commercially available thing, organo silica sol MIBK-ST, MEK-ST-UP, MEK-ST-L, MEK-AC-2140Z (made by Nissan Chemical Industry), SIRMIBK15ET%-H24, SIRMIBK15ET%-H83, ALMIBK30WT% -H06 (CIK Nanotech), etc. can be used.

The clear coating composition may contain 0.5 to 20 weight% (solid content in coating material) of the polyisocyanate compound which has an isocyanate group. By mix|blending a polyisocyanate compound, it is preferable at the point which can provide moldability (stretchability) and abrasion resistance. As for the lower limit of the said compounding quantity, it is more preferable that it is 2 weight%, and, as for an upper limit, it is more preferable that it is 18 weight%.

The clear paint composition may be colored and transparent containing a colored pigment. That is, by the combination of the metal-like design layer and such a colored transparent clear layer, it is possible to perform decoration having a colored metal-like design. The color pigment which can be used in the said clear coating composition is not specifically limited, A well-known arbitrary thing can be used.

(Metal-like decorative layer (C), which is a vapor-deposited metal layer made of indium or tin)

Vapor deposition is a method of forming a thin film by heating and vaporizing a vapor deposition material in a vacuum container and making it adhere to the surface of a base material placed at a distant position. In this invention, the metal used for vapor deposition is tin and indium. Since a vacuum degree of about 10 ^-3 to 10 ^-4 Pa is required for vapor deposition, it is necessary to first put the vessel into a vacuum state. Therefore, the vapor deposition becomes a complete batch process, and a continuous process is impossible.

In addition, the vapor deposition method to a film generally (1) sets a film roll and a target metal in a chamber, (2) evacuates the inside of a chamber (10 ^-3 to 10 ^-4 Pa), and starts traveling of a film. , (3) is deposited on the film surface by target heating and steam generation, and (4) at the completion of deposition, the chamber is opened to the atmosphere. Compared with the direct vapor deposition on parts, since it is a batch process and the film roll part is continuously processed, economic efficiency is high. In addition, there is an advantage in that it is easy to control the thickness and quality of the deposited film. However, as a film, it cannot be applied to a three-dimensional object.

The vapor-deposited metal layer (C) which consists of said indium or tin in this invention can be formed by the normal vapor deposition method using these metals. By using indium or tin, a metal layer with good elongation can be formed. Therefore, cracks or whitening do not occur when molding into a three-dimensional shape, and there is no adverse effect on the appearance. Among these, indium is especially preferable.

In the present invention, by using indium or tin as the vapor deposition metal layer, there is an advantage that cracks and whitening do not easily occur due to the effect of discontinuous vapor deposition.

As for the metal vapor deposition layer of this invention, it is essential that optical density is 0.6-1.4.

When the optical density of the metal deposition layer is less than 0.6, the amount of deposited metal is insufficient, so that sufficient metallic luster is not obtained in the stretched portion. Moreover, when an optical density exceeds 1.4, whitening by microcracks becomes remarkable in an extending|stretching part, and it is unpreferable from the point that favorable metallic luster is not obtained.

In the present invention, the optical density of the vapor deposition metal layer is measured using a color transmission densitometer (manufactured by Dainippon Screens Co., Ltd., DM-500).

When forming such a vapor deposition metal layer, it is preferable that the thickness is 0.02-5 micrometers. By setting it as such thickness, the objective mentioned above can be achieved favorably. Moreover, the thickness and optical density of a metal vapor deposition layer have a close relationship, and it turns into a metal vapor deposition layer with high optical density, so that thickness is large. Although it changes also with the material of a vapor-deposited layer, in general, when an optical density is 0.6-1.4, the thickness of the vapor-deposited metal layer is set to 0.02 micrometer - 0.08 micrometer.

As for the lower limit of the said thickness, it is more preferable that it is 0.03 micrometer. As for the upper limit of the said thickness, it is more preferable that it is 0.1 micrometer, and it is still more preferable that it is 0.05 micrometer.

(Adhesive layer (D))

A contact bonding layer (D) is used in order to make a laminated|multilayer film closely_contact|adherence and adhere|attach a base material surface, when decorating a base material with a laminated|multilayer film.

The adhesive layer (D) of the present invention is characterized in that the total light transmittance is 20% or less. That is, by mix|blending various coloring agents etc., the light transmittance is reduced. In particular, it is preferable to reduce the transmittance|permeability in a visible region (wavelength 380-810 nm). It is preferable that it is 15 % or less, and, as for total light transmittance, it is more preferable that it is 10 % or less.

Thus, because the adhesive layer (D) has a low total light transmittance, reflection on the substrate surface is reduced, Rayleigh scattering and non-scattering in the metal vapor deposition layer are reduced, thereby improving designability. As described above.

In addition, the total light transmittance in this specification measured the total light transmittance using the integrating sphere in the wavelength range of 380.0 nm - 810.0 nm with the spectrophotometer U-4100 (Hitachi High-Technologies). The light source is a value measured by a method using a halogen lamp. A total light transmittance is the transmittance|permeability of only a contact bonding layer (D). Therefore, when measuring the adhesive layer (D) of the laminated film for decorating a three-dimensional molded article, the method of measuring the total light transmittance of the adhesive layer (D) alone by peeling it off, clarifying the composition of the adhesive layer (D), equal composition and thickness A single film having a may be prepared and the total light transmittance of the single film may be measured.

It is preferable that the said contact bonding layer (D) contains a coloring pigment. It does not specifically limit as a color pigment, For example, Bright pigments, such as an interference mica pigment, a white mica pigment, a graphite pigment; inorganic color pigments such as chrome yellow, yellow iron oxide, bengala, carbon black, and titanium dioxide; Extender pigments such as kaolin, clay, silica, zinc oxide, calcium carbonate, and precipitated barium sulfate

etc. can be used.

The color pigment is most preferably carbon black. Carbon black is particularly preferable from the viewpoints of light blocking and hiding properties for the lower coating film. When mix|blending carbon, it is preferable to mix|blend in the ratio of 0.4 to 20 weight% with respect to the total solid content of an adhesive layer (D).

As said carbon black, Carbon black MA100, #2650 (made by Mitsubishi Chemical Co., Ltd.), CORAX N660 (made by Orion Engineered Carbons Co., Ltd.), Color Black FW200P (made by Evonik Deg Japan Co., Ltd.), Monarch 1300 (made by Cabot) ), Raven 1255P, Raven 5000ULTRA3 (manufactured by Columbian), and the like.

The adhesive contained in the adhesive layer (D) is not particularly limited as long as it is a conventionally known adhesive. For example, Byron UR-3200 (manufactured by Toyobo Corporation), UR-1361ET (manufactured by Toagosei), Xp012N35 (manufactured by Mitsui Chemicals) and the like. Various coloring agents, such as carbon, can be mix|blended and used with respect to these commercially available well-known adhesive agents so that a total light transmittance may be set to 20% or less.

The said adhesive agent can be prepared by adding and mixing pigment dispersion resin, a colored pigment, a solvent, and arbitrary components in arbitrary order. Moreover, you may contain an additive as needed. As additives, for example, resin components other than the pigment dispersion resin, thickener, antifoaming agent, film forming aid, antifreezing agent, flow inhibitor, antisettling agent, crosslinking accelerator, curing agent, leveling agent, surface conditioning agent, plasticizer , a preservative, an antifungal agent, an ultraviolet stabilizer, an ultraviolet absorber, and the like.

As a disperser for adjusting the adhesive, SG mill, ball mill, bead mill, spike mill, pearl mill, dyno mill, two or three roll mill, extruder, paint shaker, ultrasonic treatment, homogenizer, kneader , a flushing treatment, and the like. As a medium at the time of dispersion|distribution, a zircon bead, a zirconia bead, a soda-lime glass bead, an alkali free bead, an alumina bead, a silicon bead, etc. are mentioned.

The adhesive layer (D) may be formed by applying and drying the adhesive, or may be formed by laminating an adhesive sheet.

Although the thickness of the said adhesive layer (D) is not specifically limited, For example, it is preferable that it is 3-50 micrometers. As for the said minimum, it is more preferable that it is 5 micrometers. As for the said upper limit, it is more preferable that it is 40 micrometers, It is more preferable that it is 35 micrometers, It is most preferable that it is 30 micrometers.

When it is less than 3 micrometers, adhesion|attachment may not fully be ensured, and when it is larger than 50 micrometers, coating and drying become difficult, and it becomes disadvantageous in the point of cost.

Among the above layers, the adhesive layer (D) needs to be the outermost layer, and the metallic decorative layer (C) is present between the clear coating film layer (B) and the adhesive layer (D) made of an energy ray-curable coating film. Thereby, after decorative molding, the clear coating film layer (B) is formed on the outside of the metal-clad decorative layer (C) having a metal strip, in terms of hard coat properties, chemical resistance, weather resistance, and the like. Excellent effect can be obtained.

The laminated film for decorating a three-dimensional molded article of the present invention may further include a release layer (E), a protective layer (F), and a design layer (G) formed by printing, if necessary, in addition to each of the above layers. A protective layer (F) is preferable at the point which becomes difficult to generate|occur|produce disorder of the external appearance of a metal-like decoration layer (C) by providing this. In addition, when the design layer G formed by printing is provided, it is preferable at the point which can obtain the specific design external appearance in which the designability by printing and the designability by the metal-like decoration layer were combined.

In addition, when the design layer (G) formed by printing is printing using energy-beam curable ink, it is preferable to provide the ultraviolet-ray absorption layer (H). That is, although it is necessary to harden|cure an energy-beam curable ink at the time of film creation, it is because it is preferable to prevent that the clear coating-film layer (B) hardens simultaneously at the time of hardening of this ink. Since the ultraviolet absorption layer (H) is provided for the above-mentioned purpose, it is preferable to provide between the design layer (G) formed by printing, and the clear coating film layer (B).

As a laminated constitution of the laminated|multilayer film for three-dimensional molded article decoration from which the effect as mentioned above is acquired, what is shown, for example to FIGS. 1-10 is mentioned.

The laminated film for decorating a three-dimensional molded article shown in Fig. 1 is an adhesive layer (D), a metal-like decorative layer (C), a clear coating film layer (B) comprising an energy ray-curable coating film, a release layer (E), and a base film layer (A) ) is a film laminated in this order.

The film of such a structure is decorated by adhering to a three-dimensional molded article with the contact bonding layer (D), and peeling the base film layer (A) after decorative molding. Thereby, the decorative layer which consists of three layers of an adhesive layer (D), a metal-like decorative layer (C), and the clear coating-film layer (B) which consists of an energy-beam curable coating film is formed on a three-dimensional molded article.

The laminated film for decorating a three-dimensional molded article shown in Fig. 2 has an adhesive layer (D), a metal decorative layer (C), a protective layer (F), a clear coating film layer (B) comprising an energy ray-curable coating film, and a release layer (E) And it is the film which laminated|stacked the base film layer (A) in this order.

The film of such a structure is decorated by adhering to a three-dimensional molded article with the contact bonding layer (D), and peeling the base film layer (A) after decorative molding. Thereby, a decorative layer consisting of four layers of an adhesive layer (D), a metallic decorative layer (C), a protective layer (F), and a clear coating film layer (B) made of an energy ray-curable coating film is formed on the three-dimensional molded article. will be.

The laminated film for decorating a three-dimensional molded article shown in Fig. 3 is a film in which an adhesive layer (D), a metallic decorative layer (C), a base film layer (A), and a clear coating film layer (B) are laminated in this order. In such a film, the base film layer (A) does not peel, but the decorative layer which also included the said layer is formed on the three-dimensional molded article.

In the laminated film for decorating a three-dimensional molded article shown in Fig. 4, an adhesive layer (D), a metal decorative layer (C), a protective layer (F), a base film layer (A), and a clear coating film layer (B) are laminated in this order. it is one film Also in such a film, the base film layer (A) does not peel, but the decorative layer which also included the said layer is formed on the three-dimensional molded article.

The laminated film for decorating a three-dimensional molded article shown in Figs. 5 to 8 is a laminated film for decorating a three-dimensional molded article having a design layer (G) formed by printing. Each of these is a configuration in which a design layer G formed by printing is added to the aspect shown in FIGS. 1 to 4 described above.

The laminated film for decorating a three-dimensional molded article shown in FIGS. 9 and 10 has a structure in which an ultraviolet absorbing layer (H) is further provided in addition to the design layer (G) formed by printing. By performing energy ray irradiation for curing the decorative layer (G) from the lower side of the figure, and performing energy ray irradiation for curing the clear coating film layer (B) from the upper side of the figure, at the time of film production, the clear coat layer (B) The clear coating film layer (B) can be cured after molding without curing.

(Release layer (E))

A well-known arbitrary thing can be used for the mold release layer (E) in this invention, For example, it can form with a silicone type mold release agent etc.

It is preferable that it is 0.05-8.0 N/25 mm, and, as for the peeling strength of a mold release layer (E) and a clear coating-film layer (B), it is more preferable that it is 0.1-5.0 N/25 mm. When it is less than 0.05N/25mm, workability is bad, such as base film layer (A) peeling at the time of film production and decorative molding, and when it exceeds 8.0N/25mm, when peeling a film after shaping|molding There exists a possibility that peeling may become difficult.

(Protective layer (F))

The laminated|multilayer film for three-dimensional molded article decoration of this invention may further provide the protective layer (F) in the form adjacent to the metal-like decoration layer (C). That is, when the metal-like decorative layer (C) is provided in a position in contact with the clear coating film layer (B), when the uncured clear coating film layer (B) moves by stretching in the uncured state, the metal-like decorative layer (C) may move, thereby causing deterioration of the appearance.

Moreover, formation of the vapor deposition metal layer which consists of indium or tin WHEREIN: It may become difficult to form a vapor deposition metal layer on the clear coating-film layer (B) of an uncured state. Therefore, it is preferable to improve such a problem by providing the protective layer F with good vapor deposition property also from a viewpoint of reducing such a problem.

Moreover, the metal-like decoration layer (C) may have bad adhesiveness with another layer. For this reason, a protective layer (F) made of a material having excellent adhesion to other materials is formed, and a metal-like decorative layer (C) is formed on the protective layer (F), thereby forming a protective layer (C) with other layers. It is also desirable to improve adhesion. Thereby, for example, if it is an aspect of FIG. 2, adhesiveness with a base film layer (A) can be improved in it being an aspect of a clear coating-film layer (B) and FIG.

The protective layer (F) is not particularly limited, and for example, a resin such as an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyamide resin, a polyester resin, a urethane resin, an epoxy resin, and a styrene resin can be used. , a urethane resin is preferable, and a urethane resin containing a urea bond is more preferable. It can be mix|blended individually by 1 type or in combination of 2 or more types.

(Design layer (G) formed by printing)

The laminated film for decorating a three-dimensional molded article of this invention may have a design layer (G) formed by printing. By providing such a layer, it is preferable at the point from which the specific external appearance by the combination of a printed layer and a metal-like decoration layer is acquired. The method of printing is not specifically limited, It can form by well-known methods, such as inkjet printing, screen printing, an offset printing, or flexographic printing. In particular, by using inkjet printing, it is preferable at the point which can form various printing layers at low cost. In addition, in printing, printing using energy-beam curable ink may be performed.

(Ultraviolet absorption layer (H))

The ultraviolet absorption layer (H) is preferably formed of a coating composition containing a binder resin (H-1) and an ultraviolet absorber (H-2).

The binder resin (H-1) is not particularly limited, and resins such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, urethane resin, epoxy resin, and styrene resin can be used, A urethane resin is preferable, and a urethane resin containing a urea bond is more preferable. It can be mix|blended individually by 1 type or in combination of 2 or more types.

It is preferable to exist in the range of 85 to 99 weight% with respect to the ultraviolet-ray absorption layer (H) whole quantity.

It does not specifically limit as said ultraviolet absorber (H-2), For example, a triazine type ultraviolet absorber, a benzophenone type ultraviolet absorber, a benzotriazole type ultraviolet absorber, a cyanoacrylate type ultraviolet absorber, hydroxybenzoate type ultraviolet rays Absorbents and the like can be used.

(Elongation at break)

It is preferable that the laminated|multilayer film for three-dimensional molded article decorating of this invention have a break elongation of 30 to 500% at 40-130 degreeC before hardening. That is, by having such an elongation at break in the above temperature range, it becomes possible to easily respond to deep drawing molding, and the effect of the present invention can be obtained suitably. It becomes possible to set it as the thing within such a numerical range by preparing the component of each layer which forms a film. In the present invention, "having a break elongation of 30 to 500% at 40 to 130 ° C." means that the temperature range in which the elongation at break shows 30 to 500% is within 40 to 130 ° C. It means that stretchability is obtained.

In addition, elongation at break is measured at a tensile rate of 50 mm/min within a temperature range of 40 to 130°C using an autograph AG-IS manufactured by Shimadzu Corporation in the state including the base film layer (A). , is a value obtained by measuring the elongation at the time when any one of the layers is broken. Depending on the properties of the film, at any one arbitrary temperature within the range of 40 to 130°C, the elongation at break may be in the range described above.

(Manufacturing method of laminated film)

Each layer other than the metallic decorative layer (C) and the base film layer (A) constituting the laminated film for decorating the three-dimensional molded article of the present invention prepares a coating composition in which the components constituting each layer are dissolved in a solvent, and this is used as a base film It can form by apply|coating and drying on the layer (A).

Although some examples of more specific methods are shown below, these show examples of a manufacturing method, and the laminated|multilayer film for three-dimensional molded article decorating of this invention is not limited by the specific example of the manufacturing method shown below.

More specifically, for example, on the base film layer (A), the step (1-1) of forming a clear coating film layer (B) made of an energy ray-curable coating film;

Step (1-2) of forming a metal-like decorative layer (C), which is a vapor-deposited metal layer made of indium or tin, on the film subjected to step (1-1);

It can obtain by the manufacturing method characterized by having the process (1-3) of forming the adhesive layer (D) on the film obtained by the process (1-2).

Moreover, after performing the process (1-1), before performing the process (1-2), you may have the process (1-4) of forming the decoration layer G by printing.

Although it does not specifically limit as a coating method for forming said each layer, For example, spray application by spraying, an applicator, a die coater, a bar coater, a roll coater, a comma coater, a roller brush, a brush, a spatula, etc. are used. You may spread it. According to the said coating method, after apply|coating a coating material solution, in order to remove the solvent in the said coating material solution, it can heat-dry and form.

In addition, as mentioned above, regarding the adhesive layer (D), it may adhere|attach by the lamination method instead of the method of application|coating and drying. That is, you may form by the method of preparing the film formed of the contact bonding layer (D), and making it adhere|attach this to a film by lamination. In addition, a laminated film composed of an adhesive layer (D) and a metal decorative layer (C) is created, and this is formed by a method of laminating on a multilayer film having a separately created base film layer (A) and a clear coat layer (B). also be In addition, when manufacturing according to such a method, you may create a film by the same manufacturing method as a laminated|multilayer film which consists of a base film layer (A) and a clear coat layer (B) and a protective layer (F) created separately.

If this is expressed as a more specific process,

Step (2-1) of forming a clear coating film layer (B) made of an energy ray-curable coating film on the base film layer (A);

Separately, on the base film layer (X), a step (2-2) of forming an adhesive layer (D) and a metal decorative layer (C) which is a vapor deposition metal layer (B) made of indium or tin;

Step (2-3) of bonding the film obtained in the step (2-1) and the film obtained in the step (2-2) above

may have

Moreover, when creating the laminated|multilayer film for three-dimensional molded article decoration by such a method, the base film layer (X) may be different from the base film layer (A) mentioned above, and it can also be set as the same thing. In addition, peeling may be performed after the laminated|multilayer film for three-dimensional molded article decorating creation or the process in the middle of creation, and the base film (A) and the base film (X) may exist on both surfaces in a final product, respectively. Moreover, it is generally preferable to peel and use base film (X) in the process of manufacture. Therefore, it is more preferable that the base film (X) does not remain in a final product. By doing in this way, it is preferable from a viewpoint, such as adhesiveness.

In the case where the metal composition decorative layer (C) is a vapor-deposited metal layer (B) made of indium or tin, it is necessary to form a vapor-deposited metal layer. The formation method of such a vapor deposition metal layer is not specifically limited, It can carry out by a normal well-known method.

(How to use)

When decorating a base material using the laminated|multilayer film for three-dimensional molded article decorating of this invention, you may carry out similarly to a conventionally well-known method, and it is not specifically limited. That is, the said laminated|multilayer film is crimped|bonded and decorated so that the base film layer (A) may be peeled from a laminated|multilayer film as needed, a contact bonding layer may be made to face the base material surface, and the laminated|multilayer film may be closely_contact|adhered to the base material surface. Then, electromagnetic wave irradiation or heating is performed, each layer is hardened, and a coating film is obtained. In addition, in the case of the multilayer film of the laminated constitution shown in FIG. 1 and FIG. 2, you may peel the base film layer (A) after crimping|bonding and hardening. Moreover, when making a laminated|multilayer film adhere to the base material surface, heating by vacuum molding, injection molding, shaping|molding, etc. can be performed. In addition, in the case of the aspect of FIG. 3, 4, peeling of a base film layer (A) is not required.

When applying the laminated|multilayer film of this invention in vacuum forming, it is preferable that adhesion|attachment is performed under vacuum conditions which are 70 kPa or less between a base material and a film at the time of shaping|molding. It is preferable at the point that air does not flow in between the contact bonding layer (D) and a molded object by performing shaping|molding in such a vacuum degree, and high adhesiveness decoration can be performed.

In addition, it is preferable that shaping|molding for decoration selects and performs the temperature at which an elongation becomes 30-500% as a laminated|multilayer film within the temperature range of 40-130 degreeC. Thereby, since laminated|multilayer film can respond suitably to high elongation, favorable vacuum forming can be performed.

Moreover, the base material which can be suitably decorated with the laminated|multilayer film of this invention is although it does not specifically limit, For example, For example, bumper, front under spoiler, rear under spoiler, side under skirt, side garnish, door mirrors, etc. automobile interior parts, such as automobile exterior parts, instrument panels, center consoles, and door switch panels, casings of home appliances such as mobile phones and audio products, refrigerators, fan heaters, and lighting fixtures, and washstands.

The laminated|multilayer film of this invention can be used especially suitably in the decoration of a metal wheel among the uses mentioned above. Since the surface of a metal wheel reflects light, it is easy to generate|occur|produce the appearance deterioration by Rayleigh scattering or non-scattering. Moreover, since the shape was complicated, there existed many places used as high elongation, and it was a thing which the appearance deterioration in such a place was easy to generate|occur|produce. Moreover, since it is an article which a favorable external appearance is calculated|required, it is especially preferable to suppress the external appearance deterioration by Rayleigh scattering and non-scattering. When the laminated film for decorating a three-dimensional molded article of the present invention is applied to a metal wheel, such a problem is solved.

(Example)

Hereinafter, the present invention will be described by way of Examples. In Examples, % in the blending ratio means wt% unless otherwise specified. The present invention is not limited to the examples described below.

(Synthesis Example Polyurethane Synthesis)

A reaction vessel equipped with a stirrer, a reflux cooling tube, a thermometer, an air blowing tube, and a material inlet was prepared. While replacing the inside of the reaction vessel with air, polyhexamethylene carbonate diol (trade name "Duranol T6001", manufactured by Asahi Kasei Chemicals Co., Ltd., number average molecular weight according to terminal functional group quantification = 1,000) 200.0 g, 1, 80.0 g of 4-butanediol and 120.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value of 102.9 mgKOH/g) were added.

Next, 238.1 g of methyl ethyl ketone (MEK) was added as a solvent. After the system interior became uniform, 314.2 g of 4,4'-methylenebis-cyclohexyl diisocyanate was added at 50°C, followed by reaction 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 absorption of 2,270 cm ^-1 by free isocyanate groups measured by infrared absorption spectrum analysis disappeared. Cyclohexanone was added until the mass ratio of MEK and cyclohexanone became 1:1, and the resin solution containing a polyurethane was obtained.

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. In addition, the weight average molecular weight of the polyurethane measured by GPC was 44,000.

[Production Example of Laminated Film]

<Adjustment of clear paint solution>

In a container equipped with a stirrer, put polyurethane acrylate (B1) and monomer (B2), add MEK in an amount such that the final coating material becomes NV = 40% while stirring, add a polymerization initiator (B3), 30 It stirred for minutes, and the clear paint solution was obtained. These compositions were set as what was shown in Tables 2-5.

<Production 1 of laminated film; Preparation of a film having the structure shown in FIG. 1>

On the base film (A), the clear paint solution is applied using an applicator so that a clear coat layer (B) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 µm is obtained, and 80°C was dried for 15 minutes to form a clear coat layer (B).

In addition, below, what the clear coating-film layer (B) is formed on the base film layer (A) is described as (A+B) layer film.

Next, on the clear coating film layer (B) of the said (A+B) layer film, it vapor-deposited with the batch type vapor deposition machine using indium so that the metal-like design layer (C) of each optical density might be obtained.

Next, on the metal decorative layer (C), to obtain an adhesive layer (D) having a dry film thickness of 20 µm, Xp012N35 as an adhesive, N660 as carbon black manufactured by Mitsui Chemicals was mixed in the ratio shown in Table 1 The prepared adhesive was apply|coated using the applicator, it was made to dry at 80 degreeC for 15 minutes, and the adhesive bond layer was formed.

<Preparation of laminated film 2; Preparation of a film having the structure shown in FIG. 2>

When providing a protective layer, on the clear coating film layer (B) of the said (A+B) layer film, the protective layer (F) whose film thickness when dried (henceforth dry film thickness) is 20 micrometers is obtained A predetermined binder solution was applied using an applicator, and then dried at 80°C for 15 minutes to form a protective layer (F).

<Production 3 of laminated film; Preparation of a film having the structure shown in FIG. 3>

On the base film (A), the clear paint solution is applied using an applicator so that a clear coat layer (B) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 µm is obtained, and 80°C was dried for 15 minutes to form a clear coat layer (B). In addition, below, what the clear coating-film layer (B) is formed on the base film layer (A) is described as (A+B) layer film.

<Preparation of laminated film 4; Preparation of a film having the structure shown in FIG. 4>

In the case of providing a protective layer, on the opposite side to the clear coat layer (B) of the (A+B) layer film, a protective layer (F) having a dry film thickness (hereinafter, dry film thickness) of 20 µm To obtain this, a predetermined binder solution was applied using an applicator, and then dried at 80°C for 15 minutes to form a protective layer (F).

Next, on the opposite side of the clear coat layer (B) of the (A + B) layer film, indium was used and vapor deposition was performed in a batch-type vapor deposition machine so that a metallic decorative layer (C) having a predetermined optical density was obtained. . Next, on the metal decorative layer (C), an adhesive prepared by mixing Xp012N35, Mitsui Chemicals, and carbon black N660 in the ratio shown in Table 1 so as to obtain an adhesive layer having a dry film thickness of 20 µm, It apply|coated using the applicator, and it dried at 80 degreeC for 15 minutes, and formed the adhesive bond layer.

[Production example of a molded article decorated with a laminated film]

A white PP base material (molded article) was placed on a vertical lifting table equipped in a double-sided vacuum forming apparatus (trade name: NGF-0709, manufactured by Fuse Shinku Co., Ltd.) comprising an upper and lower box. Then, the laminated|multilayer film obtained above was set in the sheet clamp frame in the upper part of the shaping|molding base material (molded article) of the said double-sided vacuum forming apparatus. Subsequently, the pressure is reduced so that the vacuum degree in the upper and lower boxes becomes 1.0 kPa, and the temperature of the laminated film is heated using a near-infrared heater until the temperature of the laminated film reaches 90°C, the molded substrate is raised, the molded substrate and the laminated film are pressed, and then , 200 kPa compressed air was introduced into only the upper box, and held for 35 seconds.

The upper and lower boxes were opened to atmospheric pressure to obtain a decorative molded article decorated with a laminated film.

In addition, from the clear coating layer (B) side of the decorative molded body, using a high-pressure mercury lamp of 120 W/cm, irradiating ultraviolet rays with a light amount of 2,000 mJ/cm 2 to cure the clear coating material of the clear coating layer (B), A UV (ultraviolet ray) curing molded article was obtained.

About the obtained film and a decorative molded object, evaluation was performed based on the following reference|standard. A result is shown to Tables 1-3. In addition, each raw material described in a table|surface shows the following.

UV 1700B (Nihongosei Chemical High School)

Lucirin TPO (BASF)

Nova Clear SG007 (Mitsubishi Juicy)

Soft Shine (Toyobo)

Xp012N35 (manufactured by Mitsui Chemicals): Modified olefin resin

N660 (Orion Engineered Carbons Co., Ltd.): Carbon Black

TE-5430 (made by Mitsui Chemicals) polyurethane resin

Total light transmittance measurement: With the spectrophotometer U-4100 (Hitachi High Technologies), the total light transmittance was measured using the integrating sphere in the wavelength range of 380.0 nm - 810.0 nm. A halogen lamp was used as the light source.

Elongation: It measured at a tensile speed of 50 mm/min under 80 degreeC temperature conditions using the Shimadzu Corporation Autograph AG-IS with a base material. In addition, the elongation was determined when any one of the layers was fractured.

The optical density was measured using a color transmission densitometer (manufactured by Dainippon Screens, Ltd., DM-500).

Formability: It confirmed by TOM molding using Fuse Shinku Co., Ltd. product double-sided vacuum forming machine NGF-0709.

◎: Can be molded by harvesting the substrate to the highly stretched part

○: Can be molded by harvesting to the middle stretched part on the substrate

△: Can be molded by harvesting to the low elongation part on the substrate

×: Cannot be molded

Metal appearance: Visual evaluation of the elongated part after molding

◎: Good metal appearance by harvesting the substrate to the highly stretched part

○: Good metal appearance by harvesting to the middle stretched part on the substrate

△: Good metal appearance by harvesting to the low elongation part on the substrate

×: cracking, whitening

Adhesion: Base wood cello tape (registered trademark) peel test 2 mm 100 grid cut

○: No peeling

△: -50% peel

×: ~100% peeling

Water resistance: After immersion in water at 40°C for 240 hours, the appearance (wrinkle, crack) was confirmed.

Further, a base wood cello tape peeling test (2 mm 100 grid cut) was performed.

○: No peeling

△: -50% peel

×: ~100% peeling

Impact resistance after molding: Using a DuPont impact resistance tester, a weight of 500 g was dropped from a height of 20 cm, and cracking of the coating film was confirmed.

○: No cracks

△: Slight cracks in the coating

×: significant cracks in the coating film

Chemical resistance after molding: A cylindrical poly ring having 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 the cover under each condition, and after a stationary test, wash with water and compare with the initial state of the coating film.

[Table 1]

◎: No change in the coating film

○: slight change in the appearance of the coating film (wrinkle, crack)

△: Appearance of the coating film is clearly changed (wrinkle, crack)

×: Remarkably change in the appearance of the coating film (wrinkle, crack)

Confirmation of molecular weight by GPC

<Analysis device>

Tosoh Corporation

「High-speed GPC HLC-8220GPC」

<Analysis Conditions>

Eluent THF (with antioxidant)

Flow 0.35ml/min

Injection volume 10μl

Temperature control part (溫調部) 40℃

Detector RI

Standard polystyrene... The calculated molecular weight is polystyrene conversion

[Table 2]

[Table 3]

[Table 4]

[Table 5]

From the results of Examples and Comparative Examples described above, it is clear that the laminated film for decorating a three-dimensional molded article of the present invention can obtain an excellent metallic appearance. Moreover, also in the shaping|molding step, it has the outstanding performance in elongation and moldability.

The laminated|multilayer film for three-dimensional molded article decoration of this invention can be used conveniently, when decorating the metal-like which has a three-dimensional shape surface with respect to various molded objects.

(A) base film layer
(B) Clear coating layer
(C) Metallic decorative layer
(D) adhesive layer
(E) release layer
(F) protective layer
(G) Design layer formed by printing
(H) UV absorbing layer

Claims (12)

It has a base film (A), a clear coating layer (B) made of an energy ray-curable coating film, a metal strip design layer (C) which is a vapor deposition metal layer made of indium or tin, and an adhesive layer (D),
The metallic decorative layer has an optical density of 0.6 to 1.4,
The adhesive layer (D) is a laminated film for decorating a three-dimensional molded article, characterized in that the total light transmittance is 20% or less. According to claim 1,
The clear coating film layer (B) made of an energy ray-curable coating film is an active energy ray-curable coating composition containing a polyurethane acrylate (B1), a monomer oligomer (B2) having an unsaturated double bond, and a polymerization initiator (B3). A laminated film for decorating a three-dimensional molded article formed by 3. The method of claim 1 or 2,
The adhesive layer (D) is a laminated film for decorating a three-dimensional molded article containing 0.4 to 20% by weight of carbon. 4. The method according to any one of claims 1 to 3,
A laminated film for decorating a three-dimensional molded article further comprising a protective layer (F) between the clear coat layer (B) and the metal-like decorative layer (C) which is a vapor deposition metal layer. 5. The method according to any one of claims 1 to 4,
A laminated film for decorating a three-dimensional molded article further comprising a design layer (G) formed by printing. Step (1-1) of forming a clear coating film layer (B) made of an energy ray-curable coating film on the base film layer (A);
Step (1-2) of forming a metal-like decorative layer (C), which is a vapor-deposited metal layer (B) made of indium or tin, on the film subjected to step (1-1);
Step (1-3) of forming the adhesive layer (D) on the film obtained by the step (1-2)
It has a manufacturing method of the laminated|multilayer film for three-dimensional molded article decorating of Claim 1 characterized by the above-mentioned. 6. The method of claim 5,
After performing the step (1-1), before performing the step (1-2), the step (1) of forming a protective layer (F) on the clear coating layer (B) adjacent to the metal-like decorative layer (C) -4), a manufacturing method of a laminated film for decorating a three-dimensional molded article. 6. The method of claim 5,
After performing the process (1-1), before performing the process (1-2), the manufacturing method of the laminated|multilayer film for three-dimensional molded article decorating which has the process (1-4) of forming the decoration layer (G) by printing . Step (2-1) of forming a clear coating film layer (B) made of an energy ray-curable coating film on the base film layer (A);
Separately, on the base film layer (X), a step (2-2) of forming an adhesive layer (D) and a metal decorative layer (C) which is a vapor deposition metal layer made of indium or tin;
Step (2-3) of bonding the film obtained in the step (2-1) and the film obtained in the step (2-2) above
It has a manufacturing method of the laminated|multilayer film for three-dimensional molded article decorating of Claim 1 characterized by the above-mentioned. 10. The method of claim 9,
After performing the process (2-1), before performing the process (2-3), the process (2) of forming a protective layer (F) on the clear coating-film layer (B) adjacent to the metal-like decorative layer (C) -4), a manufacturing method of a laminated film for decorating a three-dimensional molded article. 11. The method of claim 9 or 10,
After performing the step (2-1) or (2-4), before performing the step (2-3), a three-dimensional molded article having a step (2-5) of forming a decorative layer (G) by printing A method for producing a laminated film for decoration. A three-dimensional molded article decorating method, characterized in that the laminated film for decorating a three-dimensional molded article according to any one of claims 1 to 4 is adhered with an adhesive layer on the three-dimensional molded article under heating conditions.

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