JP6353659B2 - Laminated film for decorative molded product, coating composition, and decorative molded body - Google Patents

Description

The present invention relates to a laminated film for decorative molded product, a coating composition, and a decorative molded body.

In a molded product obtained from various materials such as plastic, metal, and the like, decoration on the surface is generally performed for the purpose of imparting designability to the surface or protecting the surface.

As one of such decoration methods, a film decoration method using a laminated film as described in Patent Documents 1 to 3 is known. In this method, a layer for decorating a molded product is created as a film, and this is applied to the molded product for decoration. In that case, it consists of a base film layer, a clear coating layer, and a design layer, and it is disclosed that various curable paints are used in the clear coating layer.

In the decoration using the laminated film for decoration, the film is deformed according to the three-dimensional shape of the molded product to cover the entire molded product. Therefore, depending on the shape of the molded product, it is preferable that deep drawing is possible. Furthermore, the film after deep drawing also requires hardness, flexibility and impact resistance. However, a laminated film for decorating molded articles having excellent performance in all of these is not known.

Furthermore, it is necessary to wind up the film in the process of manufacturing, storing and transporting the film. In that case, the films wound up by blocking may adhere to each other. Anti-blocking performance that does not cause such problems is also necessary.

JP 2004-299220 A JP 2005-255781 A JP 2002-240202 A

An object of the present invention is to solve the above-mentioned problems and to provide a laminated film for decorating molded products that can obtain excellent performance when used for decorating various molded products. .

The present invention is a laminated film for decorating a three-dimensional molded product having a base film layer (A), a clear coating layer (B) and a design layer (C),
The clear coating layer (B) is formed by 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). And
The active energy ray-curable coating composition comprises (B1) in a total amount of (B1) and (B2) in a total amount of (B1) + (B2)) of 100 parts by weight of (B1). 99 parts by weight, containing (B2) in the range of 1 to 50 parts by weight, (B1) solid content weight, (B2) solid content weight total amount ((B1) + (B2)) Containing (B3) in a range of 0.5 to 20 parts by weight with respect to 100 parts by weight ;
The polyurethane acrylate (B1) is
Double bond equivalent: 130-600 g / eq
Molecular weight Mw: 4000-200000
Urethane concentration: 300-2000 g / eq,
It is a laminated film for decorating a three-dimensional molded product characterized by the following.

The laminated film for decorating the three-dimensional molded product may be obtained by laminating a base film layer (A), a clear coating film layer (B), and a design layer (C) in this order.
The laminated film for decorating the three-dimensional molded product may further include a release layer (D) provided between the base film layer (A) and the clear coating layer (B).
The laminated film for decorating the three-dimensional molded product may further be provided with an adhesive layer (E) on the outside of the design layer (C).

The laminated film for decorating the three-dimensional molded product may be a laminate of a clear coating layer (B), a base film layer (A), and a design layer (C) in this order.
The laminated film for decorating the three-dimensional molded product may further be provided with an adhesive layer (E) on the outside of the design layer (C).

The adhesive layer (E) is preferably a layer formed by coating or laminating.
The design layer (C) contains at least the polyurethane resin (C1) and the glittering material (C2), and the total amount of the solid content weight of (C1) and the solid content weight of (C2) ((C1) + ( C2)) It is preferably a layer formed of a colored paint containing (C2) in a range of 0.5 to 60 parts by weight in 100 parts by weight.
The brightening agent (C2) is preferably at least one selected from the group consisting of aluminum, glass, inorganic pigments and organic pigments.

The polyurethane resin (C1) is
Molecular weight Mw: 10,000 to 200,000
Tg: -30 ° C to 30 ° C
It is preferable that

The design layer (C) may be a layer formed by printing.
The printing is preferably performed by any one method of inkjet printing, screen printing, offset printing, or flexographic printing.

The laminated film for decorating the three-dimensional molded product preferably has a breaking elongation of 30 to 400% at 40 to 130 ° C. before curing.

Upper Symbol polyurethane acrylate (B1) is urea concentration is preferably 500 to 1000 g / eq.

The polyurethane acrylate (B1) preferably has a polycarbonate diol skeleton at a ratio of polycarbonate concentration: 0.5 to 75 wt%.

The clear coating layer (B) forming coating composition preferably further contains 0.5 to 60 parts by weight of an inorganic / organic filler having an average primary particle size of 100 nm or less.
The clear coating layer (B) forming coating composition preferably further contains 0.5 to 20 parts by weight of a polyisocyanate compound having an isocyanate group.

The polyurethane acrylate (B1) preferably contains 0.5 to 20 parts by weight of a monomer having a thiol group and / or an amine group.
The polyurethane acrylate (B1) is preferably modified with fluorine or silicone.
The present invention is also a three-dimensional molded decorative laminate film having a clear coating layer (B) formed using the clear coating layer (B) forming coating composition described above.

The present invention is also a decorative molded body obtained by decorating a molded base material with the above-described three-dimensional molded product decorative laminated film.

The laminated film for decorating a three-dimensional molded product of the present invention has excellent performance in hardness, flexibility and impact resistance after decoration. Furthermore, since deep drawing is possible, it is possible to easily decorate an article having a three-dimensional shape. Furthermore, it is excellent also in blocking resistance.

It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. It is a schematic diagram which shows an example of the laminated structure of the laminated film for three-dimensional molded product decoration of this invention. In the measuring method of Tg in this invention, it is a figure which shows concretely the reading method at the time of reading Tg from a chart.

Hereinafter, the present invention will be described in detail.
(Three-dimensional molded product laminated film)
The laminated film for decorating a three-dimensional molded product of the present invention is a film used in decorative molding of a three-dimensional molded product. That is, a film having design properties is adhered to various molded products to impart design properties to the molded products or to provide a surface protection function.
In that case, it deform | transforms into the shape along the surface of a three-dimensional shape, and it adheres.
As a method for the close contact, a known arbitrary method can be used, and examples thereof include a method for making the contact by deforming by a method such as vacuum forming or pressure forming. Moreover, the method etc. which deform | transform the laminated film for decorative shaping | molding into the shape of a metal mold | die outer wall surface in a metal mold | die, and perform injection molding after that can be mentioned.

The laminated film for decorating a three-dimensional molded product of the present invention has a base film layer (A), a clear coating layer (B), and a design layer (C). That is, a base film layer (A) serving as a base during film production, a design layer (C) for imparting a target design, and a clear coating layer (B) for protecting the surface It is what has. Furthermore, you may have a release layer (D) and an adhesive layer (E) as needed. These layers can be made into various laminated forms as required.

Hereinafter, specific embodiments of the laminated structure will be described with reference to the drawings.
The first laminated structure shown in FIG. 1 has a release layer (D), a clear coating layer (B), a design layer (C), and an adhesive layer (E) in this order on a base film (A). It is the laminated film laminated | stacked by. In the first laminated structure, the base film (A) is peeled off together with the release layer (D) at the time of use, and a clear coating layer (B), a design layer (C), and an adhesive layer (E) are three layers. As a laminated film consisting of the above, it is used by adhering it to a molded product and curing it.

The second laminated structure shown in FIG. 2 is a laminated film in which a release layer (D), a clear coating layer (B), and a design layer (C) are laminated in this order on a base film (A). is there. Here, the design layer (C) is also provided with a function as an adhesive layer at the same time. Therefore, a two-layer film composed of the clear coating layer (B) and the design layer (C) is bonded onto the molded product. The decoration is performed by making it.

In the third laminated structure shown in FIG. 3, the clear coating layer (B) is formed on one side of the base film (A), and the design layer (C) and the adhesive layer (E) are laminated in this order on the opposite side. It is a thing. This is different from the laminated film shown in FIG. 1 and FIG. 2 in that the base film is stuck on the base material in the state of these four layers without being peeled off at the time of use. is there.

The fourth laminated structure shown in FIG. 4 is obtained by forming a clear coating layer (B) on one side of the base film (A) and laminating a design layer (C) on the opposite side. Here, the design layer (C) is also provided with a function as an adhesive layer.

In the fifth laminated structure shown in FIG. 5, an adhesive layer (E) is formed on one side of the base film (A), and a design layer (C) and a clear coating layer (B) are laminated in this order on the opposite side. It is a thing. Similar to the laminated structure shown in FIG. 3, this is different from the laminated film shown in FIGS. 1 and 2, and the base film remains in the state of these four layers without peeling off during use. It is used by sticking on the material.

Each layer constituting these three-dimensional molded product decorative laminated films will be sequentially described below.

(Base film layer (A))
The base film layer (A) serves as a carrier film when the laminated film of the present invention is produced. That is, it is used as a base material for forming each layer during the production of the laminated film for decorating a three-dimensional molded product of the present invention. Moreover, in the aspect as shown to FIG.3, 4 mentioned above, there exists what exists on a molded object even after performing a decoration process. In this case, not only a role as a base material but also functions such as a surface protection function are exhibited.

The film for forming the base film layer (A) is not particularly limited. For example, a conventionally known film such as a soft vinyl chloride film, an unstretched polypropylene film, an unstretched polyester film, a polycarbonate film, an acrylic resin film, and a fluorine film. A film is mentioned. Among these, a film formed of polyester and / or polyolefin is preferable, and an unstretched polyester film is more preferable from the viewpoint of energy-saving and low-temperature processability. The thickness of the base film layer (A) is preferably 0.01 to 0.5 mm, and more preferably 0.02 to 0.3 mm. Outside this range, it is not preferable in terms of the function as a carrier film and the economical efficiency at the time of electromagnetic radiation curing.

(Clear coating layer (B))
The clear coating layer (B) used in the present invention comprises a polyurethane acrylate (B1), a monomer / oligomer (B2) having an unsaturated double bond, and a polymerization initiator (B3). It is formed by things. This facilitates stretching during use and can easily cope with deep drawing, so that the follow-up to the three-dimensional shape is good. In addition, there is an advantage that blocking can hardly occur.

Further, the active energy ray-curable coating composition comprises (B1) in a total amount of (B1) solid content weight and (B2) solid content weight ((B1) + (B2)) in 100 parts by weight. 50 to 99 parts by weight, (B2) is contained so as to be in the range of 1 to 50 parts by weight, and the total amount of (B1) solid content and (B2) solid content ((B1) + (B2 )) 100 parts by weight of (B3) is contained in a range of 0.5 to 20 parts by weight. By this, it can have blocking resistance before hardening and deep drawability (stretchability). Furthermore, it can 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))
The polyurethane acrylate (B1) is a compound having a urethane bond in the molecule and a (meth) acrylate group in the molecule. By using this, the stretchability at the time of performing decorative molding is improved, and it is possible to easily cope with deep drawing, so that the follow-up to the three-dimensional shape is good.

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 isocyanate groups in the 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) After reacting a condensate of a polyol with a monobasic acid and / or a polybasic acid and / or an acid anhydride thereof with a compound having two or more isocyanate groups in the molecule, 1 in the molecule A compound obtained by reacting a compound having one or more hydroxyl groups and 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 further reacting a compound having one or more hydroxyl groups and one or more double bond groups in the molecule Compound,
Etc.

In the above i) to iii), examples of the compound having one or more hydroxyl groups and one or more double bond groups in the molecule include 2-hydroxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Examples of commercially available products such as 4-hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and the like include Plaxel F (M) A series (trade name of Daicel Chemical Industries). In the above ii) to iii), examples of the polyhydric alcohol include polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylol propane and the like, and commercially available products such as Plaxeldiol series (trade name of Daicel Chemical Industries). ), Plaxel Triol series (trade name of Daicel Chemical).

It does not specifically limit as said polyol, A well-known acrylic polyol, polyester polyol, polycarbonate polyol, etc. can be used. Further, various low molecular weight diols such as ethylene glycol, butanediol, glycerin, pentaerythritol, and neopentyl glycol can be used as necessary.

The polyol preferably has a polycarbonate diol skeleton at a ratio of polycarbonate concentration: 0.5 to 75 wt% (ratio to the total amount of polyurethane acrylate (B1)). By using a material having a polycarbonate diol skeleton, toughness is exhibited, and there is an advantage that it is possible to prevent swelling during decorative molding and to maintain the design appearance (prevention of cracks).
The polycarbonate diol is more preferably 2 to 70% by weight.

The polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, aromatic compounds such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and metaxylylene diisocyanate. Aliphatic groups such as hexamethylene diisocyanate; alicyclic groups such as isophorone diisocyanate; monomers thereof and multimers such as burette type, nurate type and adduct type.

Commercially available products of the above polyisocyanates include Duranate 24A-90PX (NCO: 23.6%, trade name, manufactured by Asahi Kasei Co., Ltd.), Sumijour N-3200-90M (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Takenate D165N- 90X (trade name, manufactured by Mitsui Takeda Chemical Co., Ltd.), Sumijoule N-3300, Sumijoule N-3500 (both trade names, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate THA-100 (trade name, manufactured by Asahi Kasei) Can be mentioned. Moreover, the blocked isocyanate which blocked these can also be used as needed.

The polyurethane acrylate (B1) may partially have a urea bond.
In order to have a urea bond, a polyamine compound may be partially used in the synthesis of polyurethane acrylate. The polyamine compound that can be used is not particularly limited. For example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 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-cyclobutane Cycloaliphatic such as amine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4′- and / or 4,4′-diamine, norbornanediamine Polyamine: phenylenediamine, xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis Examples thereof include aromatic diamines such as-(sec-butyl) diphenylmethane; dimer diamine obtained by converting a carboxyl group of a dimer acid into an amino group, and a dendrimer having a primary or secondary amino group at a terminal.

The polyurethane acrylate (B1) 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 may be a problem that the cured film is inferior in crack resistance and impact resistance. When the double bond equivalent exceeds 600 g / eq, there is a possibility that problems such as inferior scratch resistance, surface hardness, and chemical resistance may occur.

The polyurethane acrylate (B1) preferably has a weight average molecular weight of 3000 to 200000. If the weight average molecular weight is less than 3000, there is a possibility of causing a problem that the blocking resistance is poor. When the weight average molecular weight exceeds 200,000, the compatibility between the obtained polyurethane acrylate (B1) and the monomer / oligomer (B2) having an unsaturated double bond contained in the clear coating composition is lowered. In addition, when the weight average molecular weight exceeds 200,000, the viscosity of the clear coating composition tends to increase. Further, when the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the amount of solid content in the clear coating composition is remarkably reduced, and the processability may be deteriorated. There is. In the present specification, the weight average molecular weight was measured by the method described 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 is lowered. In addition, when the urethane concentration is less than 300 g / eq, the viscosity of the clear coating composition tends to increase. Further, when the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the amount of solid content in the clear coating composition is remarkably reduced, and the processability may be deteriorated. There is. When the urethane concentration exceeds 2000 g / eq, there is a possibility that problems such as inferior blocking resistance and impact resistance may occur.

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, the compatibility between the obtained polyurethane acrylate (B1) and the monomer / oligomer (B2) having an unsaturated double bond 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. Further, when the clear coating composition is diluted with an organic solvent in order to improve such an increase in viscosity, the amount of solid content in the clear coating composition is remarkably reduced, and the processability may be deteriorated. There is. When the urea concentration exceeds 1000 g / eq, there is a possibility of causing a problem that the blocking resistance is poor.

The polyurethane acrylate (B1) may be modified with fluorine and / or silicone. That is, the polyurethane acrylate (B1) may be synthesized by the method described above using a monomer containing fluorine or a silicone unit, or the polyurethane acrylate (B1) obtained by the method described above has. The functional group may be reacted with a compound having fluorine and / or 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. For example, the following compounds can be used.

Examples of (meth) acrylates having 2 functional groups are 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, hydroxypivalic acid neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9 Nonane diol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, glycerin di (meth) acrylate, dimethylol over tricyclodecane (meth) acrylate. Of these, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and the like can be preferably used.

Examples of the (meth) acrylate having 3 functional groups are 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. Of these, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like can be preferably used.

Examples of (meth) acrylates having 4 functional groups are dipentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethylene oxide modified tetra (meth) acrylate, pentaerythritol propylene oxide modified tetra (meth) acrylate. , Ditrimethylolpropane tetra (meth) acrylate and the like. Of these, 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 a caprolactone modified product of erythritol. These monomers may use only 1 type and may use 2 or more types together.

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 group of a polyester oligomer having a hydroxyl group at both ends obtained by condensation of a polyvalent 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. The 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 and esterifying it. The urethane acrylate can be generally obtained by reacting a polyester polyol, polyether polyol, or polycarbonate polyol with an isocyanate monomer or a product obtained by reacting a prepolymer with an acrylate monomer having a hydroxyl group.
These (meth) acrylic oligomers may be used alone or in combination of two or more, or may be used in combination with the polyfunctional (meth) acrylate monomer.

As the monomer / oligomer (B2) having an unsaturated double bond, commercially available products such as UV 1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. can also be used.

(Polymerization initiator (B3))
The clear coating composition contains a polymerization initiator (B3) in addition to the polyurethane acrylate (B1) and the monomer / oligomer (B2) having an unsaturated double bond. Examples of the polymerization initiator (B3) include, but are not limited to, an electromagnetic radiation polymerization initiator that initiates polymerization by electromagnetic radiation such as ultraviolet rays (UV) and electron beams, and a radical polymerization initiator for thermosetting. .

Specifically, examples of the electromagnetic radiation 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; Examples thereof include a polymerization initiator for ultraviolet (UV) curing such as Irgacure (registered trademark) -184, Irgacure-819 (all manufactured by BASF). These compounds can use 1 type (s) or 2 or more types as a polymerization initiator.

Examples of the thermosetting radical polymerization initiator include t-amylperoxy-2-ethylhexanoate, bis (4-t-butylcyclohexyl) peroxydicarbonate, and Trigonox (registered trademark) 121-50. Organic peroxides such as (manufactured by Kayaku Akzo) can be mentioned. The organic peroxide as the radical polymerization initiator for thermosetting may be used alone or in combination of two or more.

(Amount of (B1) to (B3))
In 100 parts by weight of the solid content weight of (B1) and the solid content weight of (B2) ((B1) + (B2)), 50 to 99 parts by weight of (B1) and 1 to 50 of (B2) It is contained so as to be within the range of parts by weight, and (B3) is 0 with respect to 100 parts by weight of the total weight of the solid content of (B1) and the solid content of (B2) ((B1) + (B2)). It contains so that it may become in the range of 0.5-20 weight part.

When the content of the polyurethane acrylate (B1) is less than 50 parts by weight, it is not preferable in that the blocking resistance is lowered. When the content of the polyurethane acrylate (B1) exceeds 99 parts by weight, it is not preferable in that the scratch resistance and surface hardness are insufficient. The lower limit is more preferably 55 parts by weight or more, and still more preferably 65 parts by weight or more. The upper limit is more preferably 98 parts by weight or less, and still more preferably 95 parts by weight or less.

When the content of the monomer / oligomer (B2) having an unsaturated double bond is less than 1 part by weight, it is not preferable in terms of insufficient scratch resistance and surface hardness. When the content of the monomer / oligomer (B2) having an unsaturated double bond exceeds 50 parts by weight, it is not preferable in that the blocking resistance is lowered. The lower limit is more preferably 2 parts by weight or more, and still more preferably 5 parts by weight or more. The upper limit is more preferably 45 parts by weight or less, and still more preferably 35 parts by weight or less.

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

The clear coating composition preferably contains 0.5 to 20 parts by weight of a monomer having a thiol group and / or an amine group.
It does not specifically limit as a monomer which has the said thiol group and / or amine group, The thiol compound and amine compound which are normally used 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, 1, Alicyclic polyamines such as 2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), methylenebiscyclohexane 2,4′- and / or 4,4′-diamine, norbornanediamine: phenylenediamine Aromatic amines such as xylylenediamine, 2,4-tolylenediamine, 2,6-tolylenediamine, diethyltoluenediamine, 4,4-bis- (sec-butyl) diphenylmethane: and the carboxy group of dimer acid Dimer acid diamine was converted into amino group, a dendrimer having a terminal amino group, can also be used a polyamine having the structural repeat amine without limitation.

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, ethylenebis (3-mercaptopropionate), polyethylene glycol dimercaptoacetate , Polyethylene glycol di- (3-mercaptopyropionate), 2,2-bis (mercaptomethyl) -1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bisphenofluorene (Ethoxy-3-mercaptopropionate), 4,8-bis (mercaptomethyl) -3,6,9-trithia-1,11-undecanedithiol, 2-mercaptomethyl-2-methyl-1,3- Bifunctional thiols such as propanedithiol, 1,8-dimercapto-3,6-dioxaoctane, thioglycerol bismercapto-acetate: trimethylolpropane (trismercaptopropionate) (TMPTMP), trimethylolpropane tris (3- Mercaptobutyrate), 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, etc .: poly (mercaptopropylmethyl) siloxane ( PMPMS), 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol pentaerythritol tetrakis (3-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3- Mercaptopropionate), pentaerythritol tetrakis (3-mercap) Containing polyfunctional thiol butyrate), etc., but not limited thereto.

The clear coating layer (B) used in the three-dimensional molded article decorative laminated film of the present invention is as described above, and more preferably, the polyurethane acrylate (B1) has a double bond equivalent of 130. ~ 600g / eq
Molecular weight Mw: 3000-200000
Urethane concentration: 300-2000 g / eq,
It is preferable that it is formed with the coating composition which is. It is preferable to use a material satisfying these properties. A clear coating composition that satisfies all such conditions is also one aspect of the present invention. By forming the clear coating layer (B) with such a clear coating composition, it has blocking resistance, high scratch resistance, surface hardness, chemical resistance, and can impart good impact resistance. It is preferable in terms. Furthermore, 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. The measurement conditions are as follows.
Column: TSKgel Super Multipore HZ-M 3 developing solvents: tetrahydrofuran column inlet oven 40 ° C
Flow rate: 0.35 ml / min.
Detector: RI
Standard polystyrene: Tosoh Corporation PS oligomer kit

(Other ingredients)
In addition to the above-mentioned polyurethane acrylate (B1), the monomer / oligomer (B2) having an unsaturated double bond, and the polymerization initiator (B3), the clear coating composition usually contains a compound that is added as a coating material. It may be contained as other components. Examples of other components include an ultraviolet absorber (UVA), a light stabilizer (HALS), a binder resin and a crosslinking agent, a pigment, a surface conditioner, an antifoaming agent, a conductive filler, and a solvent.

Furthermore, you may use a solvent for mixing of each component contained in a clear coating composition, and viscosity adjustment. Examples of the solvent include conventionally known organic materials used for paints such as ester, ether, alcohol, amide, ketone, aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon. Solvents may be used alone or in combination of two or more. In addition, when using the said solvent, when a volatile substance remains in a laminated | multilayer film, a volatile substance may volatilize at the time of decorating to a base material, and a pinhole and a swelling may arise. For this reason, 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 of an inorganic / organic filler having an average primary particle size of 100 nm or less. Thereby, blocking resistance, high scratch resistance, and surface hardness can be improved. The lower limit of the amount is more preferably 1% by weight, and the upper limit is more preferably 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), zonotlite (calcium silicate), aluminum borate, hydro Talsite, 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 thereof Examples thereof include non-metallic inorganic materials so-called ceramic fillers obtained through a melt mixture, molding, firing, or the like. Among them, silica, alumina, zirconia, or a eutectic mixture thereof is preferable from the viewpoint of cost and effect.

Examples of the organic filler include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins.
Further, as commercially available products, 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 a polyisocyanate compound having an isocyanate group in an amount of 0.5 to 20% by weight (solid content ratio in the coating). By blending a polyisocyanate compound, it is preferable in terms of imparting moldability (stretchability) and scratch resistance. The lower limit of the amount is more preferably 2% by weight, and the upper limit is more preferably 18% by weight.

(Design layer (C))
The design layer (C) in the present invention is a layer formed with a design appearance provided by a laminated film for decorating a three-dimensional molded product. As such a layer, a layer formed by applying and then drying a colored coating composition, a layer formed by printing, and the like can be used. Each of these will be described below.

(Design layer (C) formed by the colored coating composition)
Although the coloring coating composition which can be used in formation of the said design layer (C) is not specifically limited, It is preferable to contain a urethane resin (C1) and a luster material (C2). In addition to the above components, the colored coating composition includes an ultraviolet absorber (UVA), a light stabilizer (HALS), a binder resin and a crosslinking agent, a pigment, a surface conditioner, an antifoaming agent, a conductive agent. Other components such as a conductive filler and a solvent may be contained. The colored coating composition may be cured by electromagnetic radiation, or may be thermoplastic or thermosetting.

In addition, as shown in FIG. 2, FIG. 4, in the case of the aspect which does not provide an adhesive layer, it is preferable to provide an adhesive function to a design layer. That is, it is preferable that the design layer (C) is formed by a colored coating composition using a resin having high adhesiveness.

(Urethane resin (C1))
The urethane resin (C1) 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 preferable. When the weight average molecular weight Mw is less than 10,000, the flexibility of the design layer (C) is lowered, and when the weight average molecular weight Mw exceeds 200,000, production of a colored coating composition and application to a film are performed. It becomes difficult.

The polyurethane resin (C1) is preferably Tg: −30 ° C. to 30 ° C. If the Tg is less than -30 ° C, there may be a problem that the coating tackiness (blocking) after coating and drying is lowered. As a result, there may be a problem of low-temperature physical property deterioration.

In the present specification, Tg means a value measured by the following process using 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 rate of temperature rise of 10 ° C./min (step 1), a step of lowering the temperature from 150 ° C. to −50 ° C. at a rate of temperature drop 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 of increasing the temperature from −50 ° C. to 150 ° C. at a temperature rate of 10 ° C./min (step 3). That is, the temperature indicated by the arrow in the chart shown in FIG.

(Luminescent material (C2))
The luster material (C2) 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, metallic pigments using metallic glitter materials such as coating aluminum, aluminum flakes, metals or alloys such as copper, zinc, nickel, tin, and aluminum oxide; mica systems such as interference mica and white mica A pigment etc. can be mentioned.
The colored coating composition contains (C2) in an amount of 0.5 to 60 wts in 100 parts by weight of the total solid weight (C1) and (C2) ((C1) + (C2)). It is preferable to use a product contained so as to be in the range of parts.

(Other ingredients)
Examples of other components contained in the colored coating composition include binder resins and crosslinking agents such as modified acrylic resins, polyester resins, epoxy resins, olefin resins, modified olefin resins, melamine resins, polyisocyanate compounds, block isocyanates. Examples thereof include a nate compound. Examples of the solvent contained in the colored coating composition include ester, ether, alcohol, amide, ketone, aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon. What is necessary is just to use the organic solvent normally used for a coating material in combination of 1 type, or 2 or more types. In addition, when using the said solvent, when a volatile substance remains in a laminated | multilayer film, a volatile substance may volatilize at the time of decorating to a base material, and a pinhole and a swelling may arise. For this reason, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

(Design layer (C) formed by printing)
The design layer (C) of the present invention may be formed by printing. 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.

(Release layer D)
As the release layer (D) in the present invention, any known one can be used, and for example, it can be formed with a silicone release agent or the like.

(Adhesive layer (E))
The adhesive layer is used for adhering the laminated film to the substrate surface when the substrate is decorated with the laminated film.

Although it will not specifically limit if it is a conventionally well-known adhesive agent as an adhesive agent contained in a contact bonding layer, For example, Byron UR-3200 (made by Toyobo Co., Ltd.), UR-1361ET (made by Toa Gosei) etc. can be mentioned.
The adhesive may be formed by applying and drying the adhesive, or may be formed by laminating an adhesive sheet.

(Elongation at break)
The laminated film for decorating a three-dimensional molded product of the present invention preferably has a breaking elongation of 30 to 400% at 40 to 130 ° C. before curing. That is, by having such elongation at break in the above temperature range, it is possible to easily cope with deep drawing, and the effects of the present invention can be suitably obtained. It is possible to make it within such a numerical range by preparing the components of each layer forming the film. In the present invention, “having a breaking elongation of 30 to 400% at 40 to 130 ° C.” means that a temperature range in which the breaking elongation is 30 to 400% is within 40 to 130 ° C., and molding is performed at that temperature. Sufficient stretchability is obtained. It means that.

The elongation at break was measured using an autograph AG-IS manufactured by Shimadzu Corporation with the base film (A) at 80 ° C. and a tensile speed of 50 mm / min. This is a value obtained by measuring the elongation at the time of breaking.

(Laminated film manufacturing method)
Each layer other than the base film layer (A) constituting the laminated film for decorating the three-dimensional molded product of the present invention is prepared by preparing a coating composition in which components constituting each layer are dissolved in a solvent. (A) It can form by apply | coating and drying on. The design layer (C) can also be formed by printing as described above.

The coating method for forming each layer is not particularly limited. For example, spray coating by spray, applicator, die coater, bar coater, roll coater, comma coater, roller brush, brush, spatula, etc. are used. And apply. After the colored coating solution is applied by the above application method, it can be formed by heating and drying in order to remove the solvent in the colored coating solution.

Further, as described above, the adhesive layer (E) may be bonded by a laminating method instead of the coating / drying method. That is, a film formed by the adhesive layer (E) may be prepared and formed by a method of adhering the film to the film by lamination.

(how to use)
When decorating a base material using the laminated film for decorating a three-dimensional molded product of the present invention, it may be performed in the same manner as a conventionally known method, and is not particularly limited. That is, the base film layer (A) is peeled off from the laminated film as necessary, and the laminated film is pressure-bonded so that the adhesive film faces the base material surface so that the laminated film adheres to the base material surface. Let them decorate. Thereafter, electromagnetic wave irradiation or heating is performed to cure each layer to obtain a coating film. Moreover, in the case of the multilayer film of the layer structure shown in FIG.1 and FIG.2, you may peel a base film layer (A) after pressure bonding and hardening. In the case where the laminated film is brought into close contact with the substrate surface, vacuum molding, heating by injection molding, molding or the like can be performed.

The base material that can be suitably decorated with the laminated film of the present invention is not particularly limited, but for example, automotive exteriors such as bumpers, front under spoilers, rear under spoilers, side under skirts, side garnishes, and door mirrors. Examples include automobile interior parts such as parts, instrument panels, center consoles, door switch panels, cellular phones, audio products, refrigerators, fan heaters, housings for household appliances such as lighting fixtures, and vanities.

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

<Synthesis Example 1 Preparation of Polyurethane Acrylate (B1)>
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) was charged. Next, 171.8 g of ethyl acetate was charged as a solvent. After the system became uniform, 11,5.3 g of 4,4′-methylenebis-cyclohexyl diisocyanate was charged at 50 ° C. and reacted at 75 ° C. using dibutyltin laurate as a catalyst to obtain a prepolymer. Next, 12.5 g of isophoronediamine diluted to 171.8 g of isopropyl alcohol after cooling to 30 ° C. was gradually added dropwise, and the absorption at 2,270 cm −1 due to free isocyanate groups measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until it disappeared. Dilution was performed until the mass ratio of ethyl acetate to isopropyl alcohol was 1: 1 and the solid content was 40%, to obtain a resin solution containing polyurethane. The resulting resin solution had a viscosity of 60 mPa · s / 20 ° C., a solid content of 40%, and a double bond equivalent of 133 g / eq. Moreover, the weight average molecular weight of the polyurethane measured by GPC was 3,000.

<Synthesis Example 2 Preparation of polyurethane acrylate (B1)>
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared.
While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) was charged. Next, 197.4 g of ethyl acetate was charged as a solvent. After the system became uniform, 192.2 g of 4,4′-methylenebis-cyclohexyl diisocyanate was charged at 50 ° C. and reacted at 75 ° C. using dibutyltin laurate as a catalyst to obtain a prepolymer. Next, 62.3 g of isophorone diamine diluted with 197.4 g of isopropyl alcohol after cooling to 30 ° C. was gradually added dropwise, and absorption at 2,270 cm ⁻¹ due to free isocyanate groups measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until it disappeared. Dilution was performed until the mass ratio of ethyl acetate to isopropyl alcohol was 1: 1 and the solid content was 40%, to obtain a resin solution containing polyurethane. The resulting resin solution had a viscosity of 150 mPa · s / 20 ° C., a solid content of 40%, and a double bond equivalent of 164 g / eq. Moreover, the weight average molecular weight of the polyurethane measured by GPC was 4,000.

<Synthesis Example 3 Preparation of Polyurethane Acrylate (B1)>
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 200.0 g of polyhexamethylene carbonate diol (trade name “Duranol T6001”, manufactured by Asahi Kasei Chemicals Corporation, number average molecular weight by terminal functional group determination = 1,000), 1, 80.0 g of 4-butanediol and 120.0 g of a mixture (hydroxyl value 102.9 mgKOH / g) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were charged. Next, 238.1 g of methyl ethyl ketone (MEK) was charged as a solvent. After the inside of the system became uniform, 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 2,270 cm −1 absorption due to free isocyanate groups measured by infrared absorption spectrum analysis disappeared. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin solution containing polyurethane. The resulting 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.

<Preparation of clear paint solution>
Put the polyurethane acrylate (B1) and monomer / oligomer (B2) obtained as described above in a container equipped with a stirrer, and put MEK in an amount such that the final paint becomes NV = 40% while stirring, and further polymerize The initiator (B3) was added and stirred for 30 minutes to obtain a clear coating solution.

<Preparation of colored paint solution>
In a container equipped with a stirrer, put urethane resin (C1) and brightening agent (C2), put MIBK in an amount that the final paint is NV = 35% while stirring, and stir for 30 minutes to obtain a colored paint solution It was.

<Production 1 of laminated film>
On the base film (A), the clear coating solution is applied using an applicator so that a clear coating layer (B) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm is obtained. And dried at 80 ° C. for 15 minutes to form a clear coating layer (B). In addition, below, what formed the clear coating film layer (B) on a base film layer (A) is described as an (A + B) layer film.
Next, the colored coating solution is applied using an applicator so that a design layer (C) having a dry film thickness of 20 μm is obtained on the clear coating layer (B) of the (A + B) layer film. And dried at 80 ° C. for 15 minutes to form a design layer (C).
In the case of providing an adhesive layer, an adhesive (Byron UR-3200, manufactured by Toyobo Co., Ltd. or UR-1361ET, Toa Gosei Co., Ltd.) is obtained so that an adhesive layer having a dry film thickness of 10 μm is obtained on the design layer (C). Was applied with an applicator and dried at 80 ° C. for 15 minutes to form an adhesive layer.

<Preparation of laminated film 2>
On the base film (A), the clear coating solution is applied using an applicator so that a clear coating layer (B) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm is obtained. And dried at 80 ° C. for 15 minutes to form a clear coating layer (B). In addition, below, what formed the clear coating film layer (B) on a base film layer (A) is described as an (A + B) layer film.
Next, the colored coating solution is applied using an applicator so that a design layer (C) having a dry film thickness of 20 μm is obtained on the side opposite to the clear coating layer (B) of the (A + B) layer film. Then, it was dried at 80 ° C. for 15 minutes to form a design layer (C).
In the case of providing an adhesive layer, an adhesive (Byron UR-3200, manufactured by Toyobo Co., Ltd. or UR-1361ET, Toa Gosei Co., Ltd.) is obtained so that an adhesive layer having a dry film thickness of 10 μm is obtained on the design layer (C). Was applied using an applicator and dried at 80 ° C. for 15 minutes to form an adhesive layer.

<Production 3 of laminated film>
On the base film (A), the colored coating solution is applied using an applicator so that a design layer (C) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm is obtained. The design layer (C) was formed by drying at 15 ° C. for 15 minutes. In addition, below, what the design layer (C) is formed on a base film layer (A) is described as an (A + C) layer film.
Next, the clear coating solution is applied using an applicator so that a clear coating layer (B) having a dry film thickness of 20 μm is obtained on the design layer (C) of the (A + C) layer film. And dried at 80 ° C. for 15 minutes to form a clear coating layer (B).
In order to provide the adhesive layer, the adhesive (Byron UR) was then obtained on the base film (A) opposite to the colored coating layer (C) so that an adhesive layer having a dry film thickness of 10 μm was obtained. -200, manufactured by Toyobo Co., Ltd.) was applied using an applicator and dried at 80 ° C. for 15 minutes to form an adhesive layer.

[Production Example of Molded Body Decorated with Laminated Film]
An ABS base material (molded product) was placed on a vertical lift table equipped in a double-sided vacuum forming apparatus (trade name NGF-0709, manufactured by Fuse Vacuum Co., Ltd.) consisting of upper and lower boxes. Thereafter, the laminated film obtained above was set on the sheet clamp frame at the upper part of the molding substrate (molded product) of the double-sided vacuum molding apparatus. Subsequently, the pressure in the upper and lower boxes is reduced to 1.0 kPa, and the laminated film is heated using a near infrared heater until the temperature of the laminated film reaches 90 ° C. Then, 200 kPa of compressed air was introduced only into the upper box and held for 35 seconds. The upper and lower boxes were opened to atmospheric pressure to obtain a decorative molded body decorated with a laminated film. Further, the clear coating layer (B) was irradiated with UV light of 2000 mJ / cm ² using a 120 W / cm high-pressure mercury lamp from the clear coating layer (B) side of the decorative molded body. Was cured to obtain a UV (ultraviolet) cured product.

Inkjet printing is performed using MIMAKI ENGINEERING UJF-3042, and laminating is using MRK-650Y manufactured by MCK Co., Ltd., temperature: 85 ° C., speed: 42 cm / min. A rubber roll was used.

The raw materials used in the table are as follows.
UN-951 (Negami Industry)
UV 1700B (Nippon Synthetic Chemical Industry)
ALMIBK30WT% -H06 (CIK Nanotech) (Alumina)
PEMP (SC Organic Chemical Co., Ltd.) (thiol)
Lucilin TPO (BASF)
Nova Clear SG007 (Mitsubishi Resin)
Soft Shine (Toyobo)
Alpaste 65-388 aluminum (Toyo Aluminum)
NCO (Crossnate XCR manufactured by Dainichi Seika)

The obtained laminated film and molded product were evaluated based on the following criteria. The results are shown in the table.
(Blocking property)
The presence or absence of tack was confirmed by finger touch.
A: No tack
○: Slightly tacky but able to be wound
Δ: Slightly tacky, unwindable level ×: Tack is noticeable

(Elongation at break)
It was measured at a tensile rate of 50 mm / min under the temperature condition of 80 ° C. using an autograph AG-IS manufactured by Shimadzu Corporation with the base material included. Elongation was determined when any layer broke.

(Formability)
This was confirmed by TOM molding using a double-sided vacuum molding machine NGF-0709 manufactured by Fuse Vacuum Co., Ltd.
A: Can be formed by following the base material to the highly stretched part.
○: Moldable by following the base material to the middle stretched part
Δ: Moldable by following the base material to the low stretched part
×: Not moldable

(SW resistance)
Using a steel wool resistance tester, # 0000 steel wool was reciprocated 10 times at a load of 100 g / cm ^{2 and the} surface of the coating film was visually observed.
◎: No scratch ○: 2-3 scratches
Δ: Scratches that can be counted
×: Countless scratches

(Impact resistance)
Using a DuPont impact resistance tester, a weight having a height of 20 cm to a weight of 500 g was dropped and the crack of the coating film was visually confirmed.
○: No crack
Δ: Slight crack on the coating
×: Remarkable cracks in the coating film

(chemical resistance)
A cylindrical polyring having an inner diameter of 38 mm and a height of 15 mm was fixed to the laminated film, and the following solution was dropped. The lid was left standing under each condition, and after the test, it was washed with water and compared with the initial state of the coating film.
Acid resistant 0.1N H2SO4 solution 5ml 20 ℃ × 24h
Alkali resistance 0.1N NaOH solution 5ml 55 ° C x 4h
Water resistant Distilled water 5ml 55 ℃ × 4h
A: No change in coating film
○: Slight change in appearance of coating film (wrinkles, cracks)
Δ: Appearance of coating is clearly changed (wrinkles, cracks)
×: Remarkably changes in appearance of coating film (wrinkles, cracks)

From the table, it was shown that the laminated film of the present invention has excellent performance in any evaluation item.

The laminated film for decorating a three-dimensional molded product of the present invention can be suitably used when performing three-dimensional decoration having a three-dimensional shape surface on various molded bodies.

(A) Base film layer (B) Clear coating layer (C) Design layer (D) Release layer (E) Adhesive layer

Claims (22)

A laminated film for decorating a three-dimensional molded product having a base film layer (A), a clear coating layer (B) and a design layer (C),
The clear coating layer (B) is formed by 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). And
The active energy ray-curable coating composition comprises (B1) in a total amount of (B1) and (B2) in a total amount of (B1) + (B2)) of 100 parts by weight of (B1). 99 parts by weight, containing (B2) in the range of 1 to 50 parts by weight, the total amount of solid content weight of (B1) and solid content weight of (B2) ((B1) + (B2)) Containing (B3) in a range of 0.5 to 20 parts by weight with respect to 100 parts by weight ;
The polyurethane acrylate (B1) is
Double bond equivalent: 130-600 g / eq
Molecular weight Mw: 4000-200000
Urethane concentration: 300-2000 g / eq,
A laminated film for decorating a three-dimensional molded product. The laminated film for decorating a three-dimensional molded product according to claim 1, wherein the base film layer (A), the clear coating layer (B), and the design layer (C) are laminated in this order. The laminated film for decorating a three-dimensional molded product according to claim 2, further comprising a release layer (D) provided between the base film layer (A) and the clear coating layer (B). The laminated film for decorating a three-dimensional molded product according to claim 2 or 3, further comprising an adhesive layer (E) provided outside the design layer (C). The laminated film for decorating a three-dimensional molded product according to claim 1, wherein the clear coating layer (B), the base film layer (A) and the design layer (C) are laminated in this order. Furthermore, the laminated | multilayer film for three-dimensional molded article decoration of Claim 5 which provides the contact bonding layer (E) in the outer side of the design layer (C). The laminated film for decorating a three-dimensional molded article according to claim 1, wherein the clear coating layer (B), the design layer (C), and the base film layer (A) are laminated in this order. Furthermore, the laminated | multilayer film for three-dimensional molded product decoration of Claim 7 which provides the contact bonding layer (E) in the outer side of the base film layer (A). The laminated film for decorating a three-dimensional molded product according to claim 4, 6 or 8, wherein the adhesive layer (E) is a layer formed by coating or laminating. The design layer (C) contains at least the polyurethane resin (C1) and the glittering material (C2), and the total amount of the solid content weight of (C1) and the solid content weight of (C2) ((C1) + ( The layer according to any one of claims 1 to 9, which is a layer formed of a colored paint containing (C2) in a range of 0.5 to 60 parts by weight in 100 parts by weight of C2). Multi-layer film for decorative three-dimensional molded products. The three-dimensional molded article decorative laminated film according to claim 10, wherein the brightening agent (C2) is at least one selected from the group consisting of aluminum, glass, inorganic pigments and organic pigments. The polyurethane resin (C1) is
Molecular weight Mw: 10,000 to 200,000
Tg: -30 ° C to 30 ° C
The laminated film for decorating a three-dimensional molded product according to claim 10 or 11. The design layer (C) is a layer formed by printing. The three-dimensional molded product decorative laminated film according to any one of claims 1 to 9. The three-dimensional molded article decorative laminated film according to claim 13, wherein the printing is performed by any one of inkjet printing, screen printing, offset printing or flexographic printing. The laminated film for decorating a three-dimensional molded product according to any one of claims 1 to 14, which has a breaking elongation of 30 to 400% at 40 to 130 ° C before curing. The polyurethane acrylate (B1) has a urea concentration of 500 to 1000 g / eq, The laminated film for decorating a three-dimensional molded product according to any one of claims 1 to 15. Polyurethane acrylate (B1)
Polycarbonate concentration: 0.5-75 wt%
Has a polycarbonate diol skeleton at a ratio of
The laminated film for decorating a three-dimensional molded product according to any one of claims 1 to 16. The active energy ray curable coating composition is:
Furthermore, it contains 0.5 to 60 parts by weight of an inorganic / organic filler having an average primary particle size of 100 nm or less.
The laminated film for decorating a three-dimensional molded product according to any one of claims 1 to 17. The active energy ray curable coating composition is:
Furthermore, the laminated | multilayer film for three-dimensional molded article decoration of any one of Claims 1-18 containing 0.5-20 weight part of polyisocyanate compounds which have an isocyanate group . The active energy ray curable coating composition is:
Furthermore, the laminated | multilayer film for three-dimensional molded article decoration of any one of Claims 1-19 containing 0.5-20 weight part of monomers which have a thiol group and / or an amine group . 21. The laminated film for decorating a three-dimensional molded product according to any one of claims 1 to 20, wherein the polyurethane acrylate (B1) is modified with fluorine or silicone . A decorative molded body, which is obtained by decorating a molded substrate with the laminated film for three-dimensional molded product decoration according to any one of claims 1 to 21 .