TW201637862A - Laminate film for decorating molded article and decorative molding - Google Patents

Abstract

Provided is a film for decorating having a design layer formed by ink-jet printing. This film is capable of maintaining the stretching properties of a clear coating layer, and allows the ink-jet printing to be satisfactorily preformed without generating repelling and bleeding. The film according to the invention of the present application is a laminate film for decorating a three-dimensional molded article, provided with an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a clear coating layer (D), and a substrate film layer (E). The design film (B) is formed by ink-jet printing using an energy ray-curable ink. The ultraviolet absorbing layer (C) is formed of a coating composition containing a binder resin (C-1), an ultraviolet absorber (C-2), and a surface conditioner (C-3), and has a strength of 3-1000 N/cm2 at 40-130 DEG C, a surface tension of 20-60 mN/m, and an ultraviolet transmittance of 20% or lower at 290-430 nm. The ultraviolet absorbing layer (C) is formed between the design layer (B) and the clear coating layer (D). The clear coating layer (D) is an energy ray-curable coating film. The laminate film for decorating a three-dimensional molded article has, before curing, a breaking elongation of 30-400% at 40-130 DEG C as a laminate film.

Description

Laminated film for decorative articles and decorative molded body

The present invention relates to a laminated film for decorative articles and a decorative molded article.

In the molded articles obtained from various materials such as plastics and metals, the surface is generally decorated to impart design or protective surface to the surface.

As one of the methods of such decoration, a film decoration method using a laminated film is known. This is a method in which a layer for decorating a molded article is formed into a film and attached to a molded article to be decorated. In this case, it is disclosed that the base film layer, the clear coating layer, and the design layer are used, and various curable coating materials are used for the clear coating layer. A method of forming a transparent coating film layer by an energy ray-curable coating composition, forming it, and then hardening it is known.

In the method of such decoration, in recent years, research has been made to form a design layer by an ink jet printer (Patent Documents 1 to 3). Inkjet printers can form a variety of design layers that are not as versatile as conventional coatings. As the ink used in such an ink jet printer, an energy ray-curable ink is known. In the manufacturing step of the decorative laminated film having the ink jet printing step using such an energy ray-curable ink, the step of hardening the design layer by the energy ray is necessary.

However, in the hardening step of the ink having energy ray curability, there is a problem that the hardening reaction also occurs simultaneously in the transparent coating layer. If it is transparent in the manufacturing steps of the laminated film When the coating layer is hardened, there is a problem that sufficient elongation cannot be ensured at the time of decoration, and good decoration cannot be performed.

Patent Document 1 discloses that the above problem is solved by setting the ultraviolet wavelength for curing the UV ink to be different from the ultraviolet wavelength for curing the protective layer. In such an invention, it is important to select the light source in the energy line hardening step, usually as a light source for the energy line hardening step, using a high pressure mercury lamp, a metal halide lamp, a chemical lamp, an LED-UV lamp, etc., but generally photopolymerization initiation The agent has absorption in a wide range of wavelength regions, and it is difficult to make the UV wavelength for curing the UV ink different from the ultraviolet wavelength for curing the protective layer, and only a light source having a specific extremely narrow wavelength range can be used, so that it is in the manufacturing step. Became the reason for the increase in costs.

Patent Document 2 discloses that an ultraviolet absorbing layer is provided between the UV ink layer and the protective layer. However, Patent Document 2 does not describe the specific configuration of the ultraviolet absorbing layer. However, in order to obtain such a laminate, a UV ink layer is formed by inkjet printing on the ultraviolet absorbing layer, so that shrinkage or bleeding of the ink must be prevented. Further, since elongation at the time of molding is required, it is preferable to have an ability to cope with elongation.

Patent Document 3 also discloses that a film for decoration is produced by inkjet printing. However, in the cited document 3, regarding the formation of a solvent absorbing layer for absorbing an organic solvent in inkjet printing, there is no mention of a problem in the case where an inkjet ink is formed into a UV ink layer, and there is no such problem. Tips on ways to improve the problem.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-206262

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-116167

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2013-56459

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide a film which is formed by a inkjet printing to form a decorative film having a design layer which maintains the extensibility of a clear coating film layer and is inkjet printed. Inkjet printing is performed well without shrinkage or bleeding.

The present invention relates to a laminated film for three-dimensional molded article decoration, comprising an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a transparent coating film layer (D), and a base film layer (E). The design layer (B) is formed by inkjet printing using an energy ray-curable ink, and the ultraviolet absorbing layer (C) is composed of a binder resin (C-1) and an ultraviolet absorber (C-2). The coating composition is formed and satisfies the surface tension of 20 to 60 mN/m, and the ultraviolet transmittance is 20% or less at 290 nm to 430 nm, and the ultraviolet absorbing layer (C) is formed on the design layer (B) and the transparent coating layer ( Between D), the clear coating layer (D) is an energy ray-curable coating film, and as a laminated film, it has an elongation at break of 30 to 400% at 40 to 130 ° C before curing.

The ultraviolet absorbing layer (C) preferably has a strength of from 3 to 1000 N/cm ² at 40 ° C to 130 ° C.

The ultraviolet absorbing layer (C) preferably further contains a surface conditioning agent (C-3).

The above-mentioned three-dimensional molded product decorative laminated film may be sequentially laminated with an adhesive layer (A), design layer (B), ultraviolet absorbing layer (C), clear coating layer (D), and substrate film layer (E).

The laminated film for three-dimensional molded article decoration may be provided with a release layer (F) between the transparent coating layer (D) and the base film layer (E).

The laminated film for three-dimensional molded article decoration may be a layer in which the adhesive layer (A), the design layer (B), the ultraviolet absorbing layer (C), the base film layer (E), and the clear coating layer (D) are sequentially laminated. .

Preferably, the transparent coating layer (D) is composed of a coating containing a polyurethane acrylate (D1), a monomer/oligomer (D2) having an unsaturated double bond, and a polymerization initiator (D3). Formation, about the above polyurethane acrylate (D1), double bond equivalent: 130-600 g / eq molecular weight Mw: 3000 ~ 200000 amine ester concentration: 300 ~ 2000 g / eq.

The present invention is also a decorative molded article obtained by decorating a molded substrate by the laminated film for three-dimensional molded article decoration.

In the laminated film for three-dimensional molded article decoration of the present invention, the transparent coating film layer is not cured by the curing step of inkjet printing using an energy ray-curable ink, and thus has sufficient elongation. Further, in inkjet printing, printing can be performed satisfactorily without shrinkage or bleeding.

(A) ‧‧‧Next layer

(B) ‧‧‧Design layer

(C) ‧ ‧ UV absorbing layer

(D) ‧ ‧ transparent coating

(E) ‧ ‧ base film layer

(F) ‧ ‧ release layer

Fig. 1 is a schematic view showing an example of a laminated structure of a laminated film for three-dimensional molded article decoration of the present invention.

Fig. 2 is a schematic view showing an example of a laminated structure of a laminated film for three-dimensional molded article decoration of the present invention.

Fig. 3 is a schematic view showing an example of a laminated structure of a laminated film for three-dimensional molded article decoration of the present invention.

Hereinafter, the present invention will be described in detail.

(Laminated film for decorative three-dimensional molded products)

The laminated film for three-dimensional molded article decoration of the present invention is a film used for decorative molding of a three-dimensional molded article. That is, the design film is attached to various molded bodies to impart design properties or surface protection functions to the molded body.

At this time, it is deformed so as to be in close contact with the shape of the surface of the three-dimensional shape.

As a method of performing the adhesion in this manner, any known method can be used, and for example, a method of performing adhesion by deformation such as vacuum molding or press molding can be used. Moreover, the method of deforming the laminated film for decorative molding into the shape of the outer wall surface of a mold in the mold, and then performing injection molding, etc. are mentioned.

The laminated film for three-dimensional molded article decoration of the present invention has a decorative film of a design layer (B) formed by inkjet printing using an energy ray-curable ink, and an ultraviolet absorbing layer (C) is formed at a specific position. When the ultraviolet light is blocked and the design layer (B) is cured by the irradiation of the energy ray, the transparent coating layer (D) is not irradiated with ultraviolet rays. Therefore, the transparent coating layer (D) does not harden when the laminated film is produced. Thereby, the elongation can be maintained at the time of forming.

In order to achieve the above object, the ultraviolet absorbing layer (C) must be formed between the design layer (B) and the clear coating layer (D).

The layer structure of the laminated film for three-dimensional molded article decoration which can obtain the above-mentioned effects, for example, as shown in FIGS. 1 to 3 can be mentioned.

The layer shown in Fig. 1 is sequentially laminated with an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a clear coating film layer (D), and a base film layer (E). In such a configuration, the base film layer (E) is peeled off before or after the molding to form the adhesive layer (A), the design layer (B), the ultraviolet absorbing layer (C), and the transparent coating layer (D). The surface is covered.

As shown in Fig. 2, a release layer (F) is provided between the transparent coating layer (D) formed of the layer of Fig. 1 and the base film layer (E). When the base film layer (E) is a substrate having excellent releasability such as a PET film, it is not necessary to provide a release layer, but in the case of using a substrate having poor peelability, it is preferable to provide a release layer (F). . Therefore, it is preferable in terms of being easy to peel off the film at the time of decorative molding.

As shown in Fig. 3, an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a base film layer (E), and a clear coating film layer (D) are laminated in this order. In the case of this aspect, the base film is not peeled off after the formation, and the adhesive layer (A), the design layer (B), the ultraviolet absorbing layer (C), the base film layer (E), and the clear coating film are formed. Layer (D) constitutes a coating layer.

In the decorative film of FIGS. 1 to 3, when the energy ray-curable ink in the design layer (B) is cured, the energy ray is irradiated from the direction of the arrow (Y) in the drawing. Then, the energy ray is shielded by the ultraviolet absorbing layer (C) shown in the drawing, whereby the transparent coating film layer (D) does not harden. Further, when the transparent coating film layer is cured, the energy ray is irradiated from the side of the arrow (X).

Therefore, the light source in the case where the energy ray-curable ink is cured is not particularly limited, and any known light source such as a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a chemical lamp, or an LED-UV lamp can be used.

Hereinafter, each layer constituting the laminated film for three-dimensional molded article decoration will be described in order.

(Next layer (A))

Next, the layer is used to closely bond the laminated film to the surface of the substrate when the substrate is decorated by the laminated film.

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

The above-mentioned adhesive may be formed by applying the above-mentioned adhesive and drying it, or may be formed by laminating an adhesive sheet.

The adhesive layer (A) is not particularly limited in thickness, and is, for example, preferably 3 to 30 μm, and more preferably 5 to 25 μm. If it is less than 3 μm, it may not be sufficiently ensured. If it is more than 30 μm, coating and drying are difficult, and it is disadvantageous in terms of cost.

(design layer (B))

The design layer (B) of the present invention is a layer in which a design appearance imparted by a laminate film for three-dimensional molded article decoration is formed. The design layer (B) in the present invention is a layer formed by inkjet printing using an energy ray-curable ink. The component of the ink, the device or method used in inkjet printing, and the like are not particularly limited, and any known one can be used.

(UV absorption layer (C))

The ultraviolet absorbing layer (C) satisfies the surface tension of 20 to 60 mN/m, and the ultraviolet transmittance is 20% or less at 290 nm to 430 nm.

Further, if the surface tension is low, the ink bleeds out, and if the ink is high, the ink shrinks, and a good printed image cannot be obtained.

Moreover, if the ultraviolet transmittance is high, a sufficient ultraviolet shielding effect cannot be obtained.

That is, the ultraviolet absorbing layer (C) is formed to have sufficient surface tension for inkjet printing, and has sufficient ultraviolet shielding ability for preventing curing of the transparent coating layer, and has no defects during molding. The strength of the situation.

The ultraviolet absorbing layer (C) preferably has a strength of from 3 to 1000 N/cm ² at 40 ° C to 130 ° C. When the strength is low, there is a tendency to bulge during molding, and if it is high, the formability is insufficient. The intensity of the ultraviolet absorbing layer (C) is obtained by using Autograph AG-IS manufactured by Shimadzu Corporation under the temperature of 60 ° C at a tensile speed of 50 mm/min and measuring the elongation at 200%. Film strength.

The surface tension of the ultraviolet absorbing layer (C) was calculated by measuring the contact angle of water and diiodomethane using an automatic contact angle gauge DSA20 (manufactured by Kurz Co., Ltd.).

The ultraviolet ray transmittance of the above ultraviolet absorbing layer (C) was measured using a UV-Vis spectrophotometer U-4100 (Hitachi High-Tech) at a wavelength of 290.0 nm to 430.0 nm.

Further, the ultraviolet absorbing layer (C) preferably absorbs ultraviolet rays, but easily transmits visible light. The reason for this is that it is difficult to see the design layer from the outside without transmitting visible light.

The above ultraviolet absorbing layer (C) is composed of a binder resin (C-1) and a violet The composition of the coating composition of the external absorbent (C-2). Moreover, by adjusting the blending or combination of the components, a layer that satisfies the above parameters can be formed.

The binder resin (C-1) is not particularly limited, and an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyamide resin, a polyester resin, an amine ester resin, an epoxy resin, or a styrene resin can be used. The resin is preferably an amine ester resin, and more preferably a urea-containing amine ester resin. These may be used alone or in combination of two or more.

It is preferably in the range of 85 to 99% by weight based on the total amount of the ultraviolet absorbing layer (C).

The ultraviolet absorber (C-2) is not particularly limited, and for example, three can be used. The ultraviolet absorber, the benzophenone-based ultraviolet absorber, the benzotriazole-based ultraviolet absorber, the cyanoacrylate-based ultraviolet absorber, the hydroxybenzoate-based ultraviolet absorber, and the like.

As the above three A UV absorber, for example, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl symmetry III 2-(2-hydroxy-4-hydroxymethylphenyl)-4,6-diphenyl symmetrical three 2-(2-hydroxy-4-hexyloxyphenyl)-4,6-diphenyl symmetrical three , 2-(2-hydroxy-4-hydroxymethylphenyl)-4,6-bis(2,4-dimethylphenyl) symmetric three 2-[2-hydroxy-4-(2-hydroxyethyl)phenyl]-4,6-diphenyl symmetrical three Wait.

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, and 2,2'. , 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy- 4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n-benzyloxybenzophenone, 2-hydroxy-4-positive Octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'- Dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxy Benzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2'-di Hydroxy-4,4'-bis(hydroxymethyl)benzophenone, 2,2'-dihydroxy-4,4'-bis(2-hydroxyethyl)benzophenone, 2,2'-di Hydroxy-3,3'-dimethoxy-5,5'-bis(hydroxymethyl)benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5' - bis(2-hydroxyethyl)benzophenone or the like.

Examples of the benzotriazole-based ultraviolet absorber include 2-(2-hydroxy-5-trimethylphenyl)-2H-benzotriazole and 2-(2-hydroxy-3,5-. Di-tert-butylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, 2-[2'-hydroxy- 5'-(hydroxymethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(2-hydroxyethyl)phenyl]-2H-benzotriazole, 2- [2'-Hydroxy-5'-(3-hydroxypropyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-methyl-5'-(hydroxymethyl)benzene Base]-2H-benzotriazole and the like.

Examples of the cyanoacrylate-based ultraviolet absorber include 2-cyano-3,3'-diphenyl 2-ethylhexyl acrylate and 2-cyano-3,3'-diphenyl acrylate. Ethyl ester, methyl 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and the like.

Examples of the hydroxybenzoate-based ultraviolet absorber include phenyl salicylate, resorcinol monobenzoate, 4-tert-butylphenyl salicylate, and 2,5-third. N-hexadecyl butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl 3,5-di-t-butyl-4'-hydroxybenzoate, 3',5-di 2,4-di-p-tripentylphenyl ester of tert-butyl-4'-hydroxybenzoic acid, hexadecyl 3',5-di-tert-butyl-4'-hydroxybenzoate, and the like.

The ultraviolet absorber (C-2) is preferably three in terms of high ultraviolet absorption from a short-wavelength region over a wide range of wavelengths (about 280 to 360 nm) in a long wavelength region. A benzophenone-based or benzotriazole-based ultraviolet absorber.

The ultraviolet absorbing agent may be used alone or in combination of two or more kinds thereof.

Specifically, Tinuvin 400, 900, 447, and 1130 (manufactured by BASF) can be used. The amount of the ultraviolet absorber (C-2) to be blended varies depending on the ultraviolet absorber to be used, and is not particularly limited as long as it satisfies the above ultraviolet transmittance, and is preferably 1 with respect to the total amount of the ultraviolet absorbing layer (C). It is in the range of ~15% by weight, and more preferably in the range of 3 to 10% by weight. If it is less than 1% by weight, the ultraviolet blocking effect may become insufficient. When it exceeds 15% by weight, the strength of the ultraviolet absorbing layer may be lowered to deteriorate the formability, which is disadvantageous in terms of cost.

The above ultraviolet absorbing layer (C) may contain a surface conditioning agent (C-3). In other words, depending on the type of the resin used in the ultraviolet absorbing layer (C), it is difficult to set the surface tension within the range as described above. In this case, by blending the surface conditioning agent (C-3), the surface tension within the above range can be set.

The surface conditioning agent (C-3) is not particularly limited, and for example, polyether modified polydimethylsiloxane, polyether modified polymethylalkyloxirane, or aralkyl modified polycondensation can be used. Methyl alkyl siloxane or the like. Specific examples thereof include BYK-300, BYK-342, and BYK-349 (manufactured by BYK-Chemie Japan Co., Ltd.).

The blending amount of the surface conditioning agent (C-3) is not particularly limited, but is preferably in the range of 0.01 to 5% by weight based on the total amount of the ultraviolet absorbing layer (C).

The ultraviolet absorbing layer (C) is not particularly limited in thickness, and is, for example, preferably 3 to 30 μm, more preferably 5 to 25 μm. When it is too thin, it is easy to obtain purple The outer line shielding performance or strength, even if it is too thick, does not particularly improve the performance, which is not only disadvantageous in terms of cost, but also difficult to apply and dry.

(transparent coating layer (D))

The transparent coating film layer (D) 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 of the laminated film are not impaired, and a known energy ray-curable coating film can be used.

Among them, an active energy ray-curable coating composition containing a polyurethane acrylate (D1), a monomer/oligomer (D2) having an unsaturated double bond, and a polymerization initiator (D3) is preferably used. By adopting such a composition, it is easy to extend during use, and it is possible to easily cope with deep drawing, so that the three-dimensional shape is improved. Moreover, there is also the advantage that it can be made to be less likely to cause obstruction.

Further, the active energy ray-curable coating composition is preferably in a total amount ((D1) + (D2)) 100 parts by weight of the solid content component weight of (D1) and the solid content component weight of (D2). (D1) is contained in a range of from 50 to 99 parts by weight, and (D2) is contained in a range of from 1 to 50 parts by weight, and the weight of the solid component relative to (D1) and (D2) 100 parts by weight of the total weight of the solid content component ((D1) + (D2)) is contained in the range of 0.5 to 20 parts by weight (D3). Thereby, it is possible to have blocking resistance and deep drawability (extensibility) before hardening. Further, it can have high scratch resistance after hardening, surface hardness, chemical resistance, and impact resistance.

Hereinafter, (D1) to (D3) will be described in detail.

(Polyurethane acrylate (D1))

Polyurethane acrylate (D1) is a compound having an amine ester bond in its molecule and having a (meth) acrylate group in its molecule. By using polyurethane acrylate (D1), it can be improved when it is used for decorative molding. The extensibility can easily cope with deep drawing, so the follow-up of the three-dimensional shape becomes good.

The polyurethane acrylate (D1) is not particularly limited, and any of the known ones can be used. For example, i) a compound obtained by equivalently reacting a compound having one or more hydroxyl groups and one or more double bond groups in the molecule with a compound having two or more isocyanate groups in the molecule; The compound having two or more isocyanate groups is reacted with a condensate of a polyhydric alcohol and a monobasic acid and/or a polybasic acid and/or an acid anhydride thereof, and further has one or more hydroxyl groups and one or more double bond groups in the molecule. a compound obtained by reacting a compound; iii) reacting a compound having two or more isocyanate groups in the molecule with a polyhydric alcohol, and further performing a compound having one or more hydroxyl groups and one or more double bond groups in the molecule. A compound obtained by the reaction or the like.

In the above-mentioned 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, 4-hydroxybutyl (meth)acrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, or the like, or Placcel F (M) A series (trade name of Daicel Chemical Co., Ltd.). Further, in the above ii) to iii), examples of the polyhydric alcohol include polyethylene glycol, polycarbonate diol, polytetramethylene glycol, trimethylolpropane, and the like, or commercially available products. Listed: Placcel diol series (trade name of Daicel Chemical Co., Ltd.), Placcel triol series (trade name of Daicel Chemical Co., Ltd.), and the like.

The polyhydric alcohol is not particularly limited, and a known acryl-based polyhydric alcohol, a polyester polyol, a polycarbonate polyol, or the like can be used. Further, various low molecular weight diols such as ethylene glycol, butylene glycol, glycerin, neopentyl alcohol, and neopentyl glycol may be used as needed.

As the above polyol, it is preferred that the polycarbonate concentration be 0.5 to 75 wt% (phase The ratio of the ratio of the total amount of the polyurethane acrylate (D1) has a polycarbonate diol skeleton. By using a polycarbonate diol skeleton, it exhibits excellent toughness and prevents bulging during decorative molding, thereby maintaining the design appearance (preventing cracking). The above 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, and examples thereof include methylphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate, and mercapto diisocyanate. An aromatic polyisocyanate such as decyl diisocyanate; an aliphatic polyisocyanate such as hexamethylene diisocyanate; an alicyclic polyisocyanate such as isophorone diisocyanate; a monomer thereof and a biuret type and trimerization A polymer such as an isocyanurate type or an addition type.

As a commercial item of the above polyisocyanate, Duranate 24A-90PX (NCO: 23.6%, trade name, manufactured by Asahi Kasei Co., Ltd.), Sumidur N-3200-90M (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Takenate D165N- 90X (trade name, manufactured by Mitsui Chemicals Co., Ltd.), Sumidur N-3300, Sumidur N-3500 (all trade names, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate THA-100 (trade name, manufactured by Asahi Kasei Corporation), and the like. Further, a blocked isocyanate obtained by blocking these may be used as needed.

The above polyurethane acrylate (D1) may partially have a urea bond.

In order to form a urea bond, a polyamine compound may be partially used in the synthesis of the polyurethane acrylate. The polyamine compound which can be used is not particularly limited, and examples thereof include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triple extension. Ethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine, 2-hydroxyethylethylenediamine, N-(2-hydroxyethyl)propane Diamine, (2-hydroxyethyl-propyl)diamine, (di-2-hydroxyethylexene)diamine, (di-2-hydroxyethyl-propyl)diamine, (2-hydroxypropyl) Diamine, (di-2-hydroxypropylethyl)diamine, piperazine Aliphatic polyamines; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophoronediamine (IPDA), sub Alicyclic amines such as methylbicyclohexane 2,4'- and/or 4,4'-diamine, norbornanediamine; phenylenediamine, decyldiamine, 2,4-methylbenzene Diamine, 2,6-methylphenylene diamine, diethyltoluenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-double- An aromatic diamine such as (t-butyl)diphenylmethane; and a dimer diamine obtained by converting a carboxyl group of a dimer acid into an amine group, and a dendrimer having a primary or secondary amine group at the end Wait.

The double bond equivalent of the above polyurethane acrylate (D1) is preferably from 130 to 600 g/eq, and more preferably from 150 to 300 g/eq. When the double bond equivalent is less than 130 g/eq, there is a problem that crack resistance and impact resistance of the cured film are poor. When the double bond equivalent exceeds 600 g/eq, there is a problem that scratch resistance, surface hardness, and chemical resistance are poor.

The above polyurethane acrylate (D1) preferably has a weight average molecular weight of from 3,000 to 200,000. If the weight average molecular weight is less than 3,000, there is a problem that the blocking resistance is poor. When the weight average molecular weight exceeds 200,000, the compatibility of the obtained polyurethane acrylate (D1) with the monomer/oligomer (D2) having an unsaturated double bond contained in the clear coating composition is lowered. Further, when the weight average molecular weight exceeds 200,000, the viscosity of the clear coating composition tends to increase. Further, when the transparent coating composition is diluted with an organic solvent in order to improve the viscosity, the amount of the solid content in the clear coating composition is remarkably lowered, and the workability is deteriorated. Further, in the present specification, the weight average molecular weight is measured by the following method.

The above polyurethane acrylate (D1) preferably has an amine ester concentration of 300 to 2000 g. /eq. When the concentration of the amine ester is less than 300 g/eq, the compatibility of the obtained polyurethane acrylate (D1) with the monomer/oligomer (D2) having an unsaturated double bond contained in the clear coating composition is lowered. Further, when the concentration of the amine ester is less than 300 g/eq, the viscosity of the clear coating composition tends to be high. Further, when the transparent coating composition is diluted with an organic solvent in order to improve the viscosity, the amount of the solid content in the clear coating composition is remarkably lowered, and the workability is deteriorated. When the concentration of the amine ester exceeds 2000 g/eq, there is a problem that the blocking resistance and the impact resistance are poor.

The above polyurethane ester acrylate (D1) preferably has a urea concentration of 500 to 1000 g/eq. When the urea concentration is less than 500 g/eq, the compatibility of the obtained polyurethane acrylate (D1) with the monomer/oligomer (D2) having an unsaturated double bond contained in the clear coating composition is lowered. Further, if the urea concentration is less than 500 g/eq, the viscosity of the clear coating composition tends to be high. Further, when the transparent coating composition is diluted with an organic solvent in order to improve the viscosity, the amount of the solid content in the clear coating composition is remarkably lowered, and the workability is deteriorated. If the urea concentration exceeds 1000 g/eq, there is a problem that the blocking resistance is poor.

The polyurethane acrylate (D1) can be modified with fluorine and/or polyfluorene. That is, the polyurethane acrylate (D1) can be synthesized by the above method using a monomer containing a fluorine or polyoxyl unit, and the functional group of the polyurethane acrylate (D1) obtained by the above method can also have The fluorine and/or polyoxo compound is reacted.

(monomer/oligomer (D2) with unsaturated double bond)

As the monomer/oligomer (D2) having an unsaturated double bond, any of the known ones can be used, and for example, the following compounds can be used.

Examples of the (meth) acrylate having a functional group number of 2 include: 1,4-butanediol di(a) Acrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol Di(meth)acrylate, propylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tri-propylene glycol di(a) Acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxytrimethylacetic acid neopentyl glycol di(meth)acrylate, 1,6-hexane Alcohol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, glycerol di(meth)acrylate, dihydroxy Methyl-tricyclodecane di(meth)acrylate or the like. Among them, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate or the like can be preferably used.

Examples of the functional group 3 (meth) acrylate include: trimethylol methane tri(meth) acrylate, trimethylolpropane tri(meth) acrylate, trimethylolpropane oxirane Tris(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerol propoxy tri(meth)acrylate And tris(2-(meth)acryloxyethyl)isocyanurate or the like. Among them, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and the like can be preferably used.

Examples of the functional group 4 (meth) acrylate include: dipentaerythritol tetra (meth) acrylate, neopentyl alcohol tetra (meth) acrylate, neopentyl alcohol ethylene oxide modified four (Meth) acrylate, neopentyl alcohol propylene oxide modified tetra(meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, and the like. Among them, di-trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, or the like can be preferably used.

Examples of the (meth) acrylate having a functional group number of 4 or more include pentaerythritol tetra(meth) acrylate, neopentyl alcohol ethylene oxide modified tetra (meth) acrylate, and di-trihydroxyl. Methylpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(methyl) Acrylate, di-trimethylolpropane penta (meth) acrylate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, di- A polyfunctional (meth) acrylate such as trimethylolpropane hexa(meth) acrylate or a hexa(meth) acrylate of a caprolactone modified product of dipentaerythritol. These monomers may be used alone or in combination of two or more.

Examples of the (meth)acrylic oligomer include epoxy (meth) acrylate, polyester (meth) acrylate, and (meth) acrylate. Here, as the polyester acrylate-based prepolymer, for example, a hydroxyl group of a polyester oligomer having a hydroxyl group at both terminals obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol can be esterified by using (meth)acrylic acid. It is obtained by esterifying a hydroxyl group at the terminal of the oligomer obtained by adding an alkylene oxide to a polyvalent carboxylic acid by using (meth)acrylic acid. The epoxy acrylate-based 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 a novolak type epoxy resin, and esterifying it. As the urethane acrylate, a hydroxy group monomer having a hydroxyl group is generally obtained by reacting a product obtained by reacting an isocyanate monomer or a prepolymer with a polyester polyol, a polyether polyol, or a polycarbonate polyol. . These (meth)acrylic oligomers may be used alone or in combination of two or more kinds thereof, or may be used in combination with the above polyfunctional (meth)acrylate monomer.

As the monomer/oligomer (D2) having an unsaturated double bond, a commercially available product such as UV 1700B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. may be used.

(Polymerization initiator (D3))

As the polymerization initiator (D3), an energy ray polymerization initiator which starts polymerization by electromagnetic rays such as ultraviolet rays (UV) or electron beams can be used. The energy ray polymerization initiator is not particularly limited, and any of those known can be used.

Specific examples of the energy ray polymerization initiator include benzoin compounds such as benzoin methyl ether; oxime compounds such as 2-ethyl hydrazine; and benzophenone compounds such as benzophenone; a thioether compound such as phenyl sulfide; 2,4-dimethyl 9-oxosulfur 9-oxosulfur a compound; an acetophenone compound such as 2,2-dimethoxy-2-phenylacetophenone; a phosphine oxide compound such as 2,4,6-trimethylbenzoin diphenylphosphine oxide; Irgacure (registered trademark) - 184, Irgacure-819 (all manufactured by the company), and other polymerization initiators for ultraviolet (UV) curing. These compounds may be used alone or in combination of two or more as a polymerization initiator.

((D1)~(D3) blending amount)

It is preferably contained in a range of 50 to 99 parts by weight, based on 100 parts by weight of the total amount of the solid content of (D1) and the weight of the solid content of (D2) ((D1) + (D2)). (D1), which contains (D2) in a range of from 1 to 50 parts by weight, and a total amount of the solid component weight of (D1) and the solid component weight of (D2) ((D1)+( D2)) 100 parts by weight, and (D3) is contained so as to be in the range of 0.5 to 20 parts by weight.

When the content of the above-mentioned polyurethane acrylate (D1) is less than 50 parts by weight, the blocking resistance is lowered, which is not preferable in this respect. When the content of the above-mentioned polyurethane acrylate (D1) exceeds 99 parts by weight, the scratch resistance and the surface hardness are insufficient, which is not preferable in this respect. The lower limit is more preferably 55 parts by weight or more, still more preferably 65 parts by weight or more. The upper limit is more preferably 98 parts by weight or less, still more preferably 95 parts by weight or less.

When the content of the monomer/oligomer (D2) having an unsaturated double bond is less than 1 part by weight, the scratch resistance and the surface hardness are insufficient, which is not preferable in this respect. When the content of the monomer/oligomer (D2) having an unsaturated double bond exceeds 50 parts by weight, the blocking resistance is lowered, which is not preferable in this respect. The lower limit is more preferably 2 parts by weight or more, still more preferably 5 parts by weight or more. The upper limit is more preferably 45 parts by weight or less, still more preferably 35 parts by weight or less.

When the content of the polymerization initiator (D3) is less than 0.5 part by weight, the transparent layer may not be sufficiently cured, and the scratch resistance, surface hardness, chemical resistance, and impact resistance of the obtained transparent layer may not be obtained. Film properties. When the content of the polymerization initiator (D3) is more than 20 parts by weight, the unreacted polymerization initiator (D3) may remain in the clear coating film, and the transparent coating film may be deteriorated by outdoor sunlight or the like to improve weather resistance. Getting worse.

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.

The monomer having a thiol group and/or an amine group is not particularly limited, and examples thereof include a commonly used thiol compound and an amine compound.

As the above amine compound, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylidenetetraamine, diethylidene can also be used. Aliphatic polyamines such as triamine; 1,2- and 1,3-cyclobutanediamine, 1,2-, 1,3- and 1,4-cyclohexanediamine, isophorone diamine (IPDA) , alicyclic polyamines such as methylene bicyclohexane 2,4'- and/or 4,4'-diamine, norbornanediamine; phenylenediamine, decyldiamine, 2,4-A An aromatic amine such as phenyldiamine, 2,6-methylphenylene diamine, diethyltoluenediamine, 4,4-bis-(t-butyl)diphenylmethane; and a dimer The dimer acid diamine in which the carboxyl group of the acid is converted into an amine group, the dendrimer having an amine group at the terminal, and the polyamine having an amine as a repeating structure are not limited thereto.

As the above thiol compound, 1,4-bis(3-mercaptobutyloxy)butane, ethylene glycol dimercaptopropionate, diethylene glycol dimercaptopropionate, 4-tert-butyl- 1,2-benzenedithiol, bis-(2-mercaptoethyl) sulfide, 4,4'-thiodiphenylthiol, benzenedithiol, diol dimercaptoacetate, diol didecyl Propionate, exoethyl bis(3-mercaptopropionate), polyethylene glycol dimercaptoacetate, polyethylene glycol bis-(3-mercaptopropionate), 2,2-bis(indenyl) Base)-1,3-propanedithiol, 2,5-dimercaptomethyl-1,4-dithiane, bisphenol bis(ethoxy-3-mercaptopropionate), 4 , 8-bis(decylmethyl)-3,6,9-trithia (torichia)-1,11-undecanedithiol, 2-mercaptomethyl-2-methyl-1,3-propane Difunctional thiol such as dithiol, 1,8-dihydrothio-3,6-dioxooctane, thioglyceryl bis-indenyl-acetate; trimethylolpropane (tridecylpropionate) (TMPTMP) ), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(3-mercaptobutyrate), trishydroxyl Methylpropane tris(3-mercaptoacetate), tris(3-mercaptopropyl)isocyanurate, 1,3,5 -Tris(3-mercaptobutyloxyethyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione, 1,2,3-trimercaptopropane and tris(3-mercaptopropionate)triethyl-1,3,5-tri 3-functional thiol such as 2,4,6-(1H,3H,5H)-trione; poly(mercaptopropylmethyl) decane (PMPMS), 4-mercaptomethyl-3,6-disulfide Dithia-1,8-octanedithiol neopentyl alcohol tetrakis(3-mercaptoacetate), and pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol A polyfunctional thiol such as 3-mercaptopropionate or neopentyltetrakis(3-mercaptobutyrate) is not limited thereto.

The clear coating layer (D) used in the laminated film for three-dimensional molded article decoration of the present invention is as described above, and further the polyurethane acrylate (D1) is preferably composed of

Double bond equivalent: 130~600g/eq

MMW: MW~200000

Amine ester concentration: 300~2000g/eq

The coating composition is formed. It is preferred to use those who satisfy these properties. By forming the clear coating layer (D) from such a clear coating composition, it is possible to provide blocking resistance, high scratch resistance, surface hardness, chemical resistance, and impart good impact resistance, in terms of such aspects. Preferably. Further, the polyurethane acrylate (D1) preferably has a urea concentration of 500 to 1000 g/eq.

Further, the weight average molecular weight in the present specification is measured using HLC-82220GPC manufactured by Tosoh Corporation. The measurement conditions are as follows.

Column: TSK gel Super Multipore HZ-M 3

Developing solvent: tetrahydrofuran

Column injection oven 40 ° C

Flow rate: 0.35ml/min.

Detector: RI

Standard polystyrene: PS oligomer set of Tosoh Corporation

(other ingredients)

The clear coating composition usually contains a compound added as a coating material as another component. Examples of other components include a UV absorber (UVA), a light stabilizer (HALS), a binder resin or a crosslinking agent, a pigment, a surface conditioner, an antifoaming agent, a conductive filler, and a solvent.

Further, a solvent may be used in order to mix the components contained in the clear coating composition or to adjust the viscosity. As the solvent, for example, an organic solvent such as an ester, an ether, an alcohol, a guanamine, a ketone, an aliphatic hydrocarbon, an alicyclic hydrocarbon, or an aromatic hydrocarbon is used as a coating material. Two or more types may be used in combination or in combination. Further, in the case of using the above solvent, when a volatile substance remains in the laminated film, the volatile substance may be volatilized when the substrate is decorated, and pinholes or bulging may occur. Therefore, it is preferable to sufficiently reduce the volatile substances contained in the laminated film.

Further, the clear coating composition preferably further contains 0.5 to 60 parts by weight of an inorganic or organic filler having an average primary particle diameter of 100 nm or less. Thereby, the resistance to obstruction and resistance can be improved Scratch, surface hardness. The lower limit of the above blending amount is more preferably 1% by weight, and the upper limit is more preferably 50% by weight.

Examples of the inorganic filler include cerium oxide, fine powder glass, alumina, calcium carbonate, kaolin, clay, sepiolite (magnesium silicate), talc (magnesium citrate), mica (aluminum silicate), and Hard calcite (calcium citrate), aluminum borate, hydrotalcite, ash stone (calcium citrate), potassium titanate, titanium oxide, barium sulfate, magnesium sulfate, magnesium hydroxide, barium oxide, barium oxide, barium carbide , boron carbide, zirconia, aluminum nitride, tantalum nitride or the like; or a non-metallic inorganic material obtained by molding, firing, or the like, a so-called ceramic filler. Among them, in terms of price and effect, it is preferably cerium oxide, aluminum oxide, zirconium oxide or the like.

Examples of the organic filler include beads of acrylic resin, styrene, polyfluorene oxide, polyurethane, urethane amide, benzoguanamine, and polyethylene. Further, as a commercially available person, ORGANOSILICASOL MIBK-ST, MEK-ST-UP, MEK-ST-L, MEK-AC-2140Z (manufactured by Nissan Chemical Industries), SIRMIBK15ET%-H24, SIRMIBK15ET%-H83, ALMIBK30WT% can be used. -H06 (CIK NanoTek) and so on.

The clear coating composition may contain 0.5 to 20% by weight of the polyisocyanate compound having an isocyanate group (solid content ratio in the coating). It is preferable in this respect to impart moldability (elongation property) and scratch resistance by blending a polyisocyanate compound. The lower limit of the above blending amount is more preferably 2% by weight, and the upper limit is more preferably 18% by weight.

The above clear coating composition may be blended with an ultraviolet absorber. In other words, in the casing of an automobile exterior panel, an automobile interior component, a mobile phone, a lighting fixture, or the like, there is a change in the appearance of the design due to the irradiation of ultraviolet rays during use. In order to prevent such deterioration, an ultraviolet absorber may be blended in the clear coating composition.

The ultraviolet absorber which can be blended in the transparent coating composition is the same as the above-mentioned ultraviolet absorbing layer, and the total amount of the solid content in the transparent coating composition can be set as the blending amount. 1 to 10% by weight.

When the ultraviolet absorbing agent is blended in the clear coating layer, the effect of both the ultraviolet ray absorbing agent contained in the transparent layer and the ultraviolet absorbing agent contained in the ultraviolet absorbing layer can be obtained when the weather resistance is required. It is preferable in terms of sufficiently protecting the ink-jet layer on the substrate side.

(base film layer (E))

The base film layer (E) also functions as a carrier film when the laminated film of the present invention is produced. That is, when manufacturing the laminated film for three-dimensional molded article decoration of the present invention, it is used as a substrate for forming each layer. Further, in the aspect as shown in Fig. 3 described above, there is also a case where it is also present on the molded body after the decoration treatment. In this case, not only the function as a substrate but also a function of a surface protection function is exhibited.

The film forming the base film layer (E) is not particularly limited, and examples thereof include a soft vinyl chloride film, an unstretched polypropylene film, an unstretched polyester film, a polycarbonate film, an acrylic resin film, a fluorine film, and the like. A well-known film. Among these, a film formed of a polyester and/or a polyolefin is preferable, and in particular, in terms of energy saving and low-temperature processability, an unstretched polyester film is more preferable. The thickness of the base film layer (E) is preferably from 0.01 to 0.5 mm, more preferably from 0.02 to 0.3 mm. If it deviates from this range, it is inferior in terms of the action of a carrier film or the economical efficiency at the time of hardening of an electromagnetic ray.

(release layer (F))

Any known one can be used for the release layer (F) in the present invention, and for example, it can be formed by a polyfluorene-based release agent or the like.

The peeling strength of the release layer (F) and the clear coating layer (D) is preferably from 0.05 to 8.0 N/25 mm, more preferably from 0.1 to 5.0 N/25 mm. When it is less than 0.05 N/25 mm, when the film is produced and the base film layer (E) is peeled off during the decorative molding, the workability is poor, and when it exceeds 8.0 N/25 mm, the film is peeled off after the molding. There are difficulties in stripping.

(elongation at break)

The laminated film for three-dimensional molded article decoration of the present invention preferably has an elongation at break of 30 to 400% at 40 to 130 ° C before curing. That is, by having such a degree of elongation at break in the above temperature range, deep drawing can be easily handled, and the effects of the present invention can be suitably obtained. Setting within such a range of values is achieved by preparing the components of the layers forming the film. In the present invention, "having an elongation at break of 30 to 400% at 40 to 130 ° C" means that the elongation at break exhibits a temperature range of 30 to 400% in the range of 40 to 130 ° C, and is formed at this temperature. Ample extensibility is available.

In addition, the elongation at break was measured using a Autograph AG-IS manufactured by Shimadzu Corporation under the condition of containing the base film (E) at a tensile speed of 50 mm/min in a temperature range of 40 to 130 ° C. The value obtained by the elongation at break of any layer. Depending on the nature of the film, the elongation at break may be within the above range at any temperature within the range of 40 to 130 °C.

(Manufacturing method of laminated film)

Each of the layers other than the design layer (B) and the base film layer (E) constituting the laminated film for three-dimensional molded article decoration of the present invention can be coated by preparing a coating composition in which a component constituting each layer is dissolved in a solvent. It is formed by drying on the base film layer (E). As described above, the above design layer (B) is formed by inkjet printing.

Furthermore, in the layer constitution of the present invention as shown in FIGS. 1 to 3, at the time of manufacture, The step of ink-jet printing the design layer (B) on the ultraviolet absorbing layer (C). In the present invention, the surface tension of the ultraviolet absorbing layer (C) is adjusted to a fixed range, so that good printing can be performed in such a step.

The coating method for forming each of the above layers is not particularly limited, and for example, a spray coating by a spray, an applicator, a die coater, a bar coater, a roll coater, or the like is used. A comma coater, a roller brush, a brush, a spatula, or the like may be applied. After the coating solution is applied by the above coating method, it can be formed by heating and drying in order to remove the solvent in the coating solution.

Further, as described above, the adhesive layer (A) can be subsequently laminated by a lamination method instead of coating or drying. That is, it can be formed by preparing a film formed of the adhesive layer (A) by laminating it with a film.

(Instructions)

In the case where the substrate is decorated by using the laminated film for three-dimensional molded article decoration of the present invention, it may be carried out in the same manner as a conventionally known method, and is not particularly limited. That is, the base film layer (E) is peeled off from the laminated film as needed, and the adhesive layer is faced to the surface of the substrate, and the laminated film is pressure-bonded to adhere the laminated film to the surface of the substrate to be decorated. Thereafter, electromagnetic wave irradiation or heating is performed to harden each layer to obtain a coating film. Further, in the case of the multilayer film composed of the layers shown in Fig. 1 and Fig. 2, the base film layer (E) can be peeled off after pressure bonding and hardening. Further, when the laminated film is in close contact with the surface of the substrate, heating by vacuum forming, injection molding, molding, or the like can be performed.

Further, the substrate to be suitably decorated by the laminated film of the present invention is not particularly limited, and examples thereof include a bumper, a front lower spoiler, a lower underflow spoiler, a side lower skirt, and a side ornament (side). Garnish), door mirror and other automotive exterior parts; instrument panel, center console, door switch Automotive interior parts such as panels; housings for home appliances such as mobile phones or audio products, refrigerators, heaters, lighting fixtures, etc.;

[Examples]

Hereinafter, the present invention will be described by way of examples. In the examples, among the blending ratios, % means weight % unless otherwise specified. The present invention is not limited to the embodiments described below.

(Synthesis of synthesis of polyurethane)

Prepare a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a material inlet. On the other hand, the inside of the reaction vessel was replaced with air, and polyhexamethylene carbonate diol (trade name "Duranol T6001", manufactured by Asahi Kasei Chemicals Co., Ltd., quantitatively obtained by quantification of terminal functional groups = 1,000) was added. 200.0 g, 1,4-butanediol 80.0 g, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 102.9 mgKOH/g) 120.0 g.

Then, 238.1 g of methyl ethyl ketone (MEK) as a solvent was added. After being homogeneous in the system, 314.2 g of 4,4'-methylenebis-cyclohexyl diisocyanate was added at 50 ° C, and the reaction was carried out at 80 ° C using dibutyltin laurate as a catalyst.

The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was carried out until the absorption of 2,270 cm ^-1 by the free isocyanate group was confirmed by infrared absorption spectrum analysis. The cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1:1, and a 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. Further, the weight average molecular weight of the polyurethane measured by GPC was 44,000.

[Manufacturing example of laminated film]

<Preparation of clear coating solution>

Adding polyurethane acrylate (D-1) and monomer (D-2) to a vessel equipped with a stirrer, adding the final coating to the final coating to obtain MEK in an amount of NV=40%, and further adding a polymerization initiator (C3) ), stirring for 30 minutes to obtain a clear coating solution.

<Preparation of UV Absorbing Coating Solution>

After adding the binder resin (C-1) and the ultraviolet absorber (C-2) to the container equipped with the stirrer, the final coating was added to the final coating to obtain MIBK in an amount of NV=35%, and the mixture was stirred for 30 minutes to obtain ultraviolet absorption. Coating solution.

<Production of laminated film 1; production of film of laminated structure shown in Fig. 2>

The resin composition and the like which form each layer are shown in the table, respectively. Based on this composition, a film of a laminate structure was produced by the method shown below.

On the base film (E) on which the release layer (F) was formed, a clear coating film layer (D) having a film thickness at the time of drying (hereinafter, a dry film thickness) of 20 μm was obtained, and coated with an applicator. The above clear coating solution was dried at 80 ° C for 15 minutes to form a clear coating layer (D).

In the following, the transparent coating film layer (D) is formed on the base film layer (E) and is described as an (E+D) layer film.

Then, on the transparent coating layer (D) of the above (E+D) layer film, to obtain a UV absorbing layer (C) having a dry film thickness of 20 μm, the above ultraviolet absorbing coating solution is applied using an applicator, Thereafter, it was dried at 80 ° C for 15 minutes to form an ultraviolet absorbing layer (C).

Further, a UV ink layer (B) was formed on the ultraviolet absorbing layer (C) using an ink jet printer UJF-3042 (manufactured by Yumu Engineering Co., Ltd.). Furthermore, in the formation of the UV ink layer (B), in the layer After the formation, the ink was hardened by ultraviolet irradiation from the (Y) side of Fig. 2 .

Then, on the UV ink layer (B), an applicator coating adhesive (Vylon UR-3200, manufactured by Toyobo Co., Ltd.; or UR-1361ET, Aron Ever) was obtained in such a manner as to obtain an adhesive layer having a dry film thickness of 10 μm. It was dried at 80 ° C for 15 minutes to form an adhesive layer.

<Production 2 of laminated film; production of film of laminated structure shown in FIG. 2 (Example 7)>

In the formation of the adhesive layer (A), a film composed of an adhesive layer was prepared by using a lamination method of MRK-650Y of Macro Chemical Co., Ltd., and (B) obtained by the above method. The laminated film composed of the ~(E) layer is then passed, whereby a laminated film is obtained. Lamination is carried out under the following conditions.

Heat-resistant rubber roller with a diameter of 80mm

Temperature: 85 ° C, speed: 42 cm / min

<Production of laminated film 3; production of film of laminated structure shown in Fig. 3>

On the base film (E), the clear coating layer (D) having a film thickness at the time of drying (hereinafter, the dry film thickness) of 20 μm was obtained, and the clear coating solution was applied using an applicator at 80 ° C. It was dried for 15 minutes to form a clear coating layer (D).

In the following, the transparent coating film layer (D) is formed on the base film layer (E) and is described as an (E+D) layer film.

Then, on the side opposite to the transparent coating layer (D) of the above (E+D) layer film, a UV absorbing layer (C) having a dry film thickness of 20 μm was obtained, and the above ultraviolet ray absorption was applied using an applicator. The coating solution is then dried at 80 ° C for 15 minutes to form an ultraviolet absorbing layer. (C).

Further, a UV ink layer (B) was formed on the ultraviolet absorbing layer (C) using an ink jet printer UJF-3042 (manufactured by Yumu Engineering Co., Ltd.). Further, in the formation of the UV ink layer (B), after the layer is formed, the ink is cured by ultraviolet irradiation from the (Y) side of Fig. 3 .

Then, on the UV ink layer (B), an applicator coating adhesive (Vylon UR-3200, manufactured by Toyobo Co., Ltd. or UR-1361ET, Aron Ever Grip) was obtained in such a manner as to obtain an adhesive layer having a dry film thickness of 10 μm. The company was made to dry at 80 ° C for 15 minutes to form an adhesive layer.

[Production Example of Shaped Body Decorated by Laminated Film]

ABS base material (molded article) was placed on the upper and lower lifting tables equipped with a double-sided vacuum forming apparatus (trade name: NGF-0709, manufactured by Busch Vacuum Co., Ltd.). Thereafter, the laminated film obtained as described above is placed on the sheet jig frame of the upper surface of the molded base material (molded article) of the double-sided vacuum forming apparatus. Then, the vacuum in the lower case was reduced to 1.0 kPa, and the temperature was raised to 90 ° C using a near-infrared heater to raise the molded substrate, and the molded substrate and the laminated film were pressure-bonded. Thereafter, only 200 kPa of compressed air was introduced into the upper tank 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. Furthermore, from the side of the transparent coating layer (D) of the decorative molded body, a high-pressure mercury lamp of 120 W/cm was used, and ultraviolet rays of a light amount of 2000 mJ/cm ^{2 were} irradiated to cure the transparent coating material of the transparent coating layer (D) to obtain UV. (Ultraviolet light) hardened molded body.

In addition, the following components were used in each table shown below.

UV 1700B (Japan Synthetic Chemical Industry): Amino acrylate oligomer

Lucirin TPO: 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide

Novaclear SG007 (Mitsubishi Resin): A-PET sheet

Softshine: Biaxially stretched polyester film

MAU-2000 (Daily Refined): Olefin resin

Xp012N35 (Mitsui Chemical): Olefin resin

1321 (East Asian synthesis): vinyl chloride-vinyl acetate copolymer resin

TE-5430 (Mitsui Chemical): Amine ester resin

RT-87140 (Morton): Acrylic resin

D-178N (Mitsui Chemical): Polyhexamethylene diisocyanate modified by ureacarboxylate

Tinuvin 900: 2,2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol

Tinuvin 477 (Badus): hydroxyphenyl three (HPT) is a UV absorber

The laminated film obtained was evaluated based on the following criteria.

(Elongation)

The measurement was carried out at a tensile speed of 50 mm/min under the temperature of 80 ° C using Autograph AG-IS manufactured by Shimadzu Corporation under the condition of containing a substrate.

The elongation was judged when a fracture occurred in any of the layers.

(Surface Tension)

The contact angle automatic measuring instrument DSA20 (manufactured by Kurz Co., Ltd.) was used to measure the contact angle of water and diiodomethane.

(ultraviolet transmission)

The measurement was carried out in the range of wavelengths of 290.0 nm to 430.0 nm using an ultraviolet-visible spectrophotometer U-4100 (Hitachi High-Tech). Furthermore, as a light source, a xenon lamp is used in the ultraviolet region, Use halogen lamps in the light and near-infrared areas.

(film strength)

The ultraviolet absorbing layer was separately subjected to Autograph AG-IS manufactured by Shimadzu Corporation, and the film strength at an elongation of 200% was measured at a tensile speed of 50 mm/min at a temperature of 60 ° C.

(formability)

The two-sided vacuum forming machine NGF-0709 manufactured by Busch Vacuum Co., Ltd. was used for confirmation by TOM forming.

◎: Formable after the substrate follows the high extension

○: Formable after the substrate follows the middle extension

△: Formable after the substrate follows to the low extension

×: Cannot be formed

(printing adaptability)

The printing suitability of the printing step was judged by the following criteria.

○: The ink dots are well formed

○△: The ink shrinks slightly (the spot diameter is small) or slightly oozes (the spot diameter is large)

△: ink shrinkage (small diameter) or bleed (large dot diameter)

△×: defective printed image due to shrinkage or bleed

×: Cannot form a printed image

Resistance after molding SW: the use of steel wool resistance tester to 100g / cm ² load so that the steel wool # 0000 10 times reciprocally

◎: no damage

○: 2~3 damages

△: countable damage

×: There are countless injuries

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

○: no crack

△: The coating film is slightly cracked

×: The coating film has obvious cracks

Chemical resistance after molding: A poly ring of a cylinder having an inner diameter of 38 mm and a height of 15 mm was fixed to a coating film, and the following solution was added dropwise. Cover and stand under each condition. After the test, the water was washed and compared with the initial state of the coating film.

◎: no change in coating film

○: The appearance of the coating film slightly changed (wrinkles, cracks)

△: Apparent changes in the appearance of the coating film (wrinkles, cracks)

×: The appearance of the coating film changes significantly (wrinkles, cracks)

The results are shown in Tables 1, 2, 4, and 5 below.

Further, in the above-mentioned Table 2, the formulations A to D were used as the formulae shown in Table 3 below.

According to the results of the above examples, the laminated film for three-dimensional molded article decoration of the present invention has good moldability and printability, so that the three-dimensional molded article can be well decorated.

[Industrial availability]

The laminated film for three-dimensional molded article decoration of the present invention can be suitably used when three-dimensional decoration having a three-dimensional shape surface is used for various molded articles.

(A) ‧‧‧Next layer

(B) ‧‧‧Design layer

(C) ‧ ‧ UV absorbing layer

(D) ‧ ‧ transparent coating

(E) ‧ ‧ base film layer

(X)‧‧‧ arrow

(Y)‧‧‧ arrows

Claims (8)

A laminated film for three-dimensional molded article decoration, comprising an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a transparent coating film layer (D), and a base film layer (E), wherein: The design layer (B) is formed by inkjet printing using an energy ray-curable ink, and the ultraviolet absorbing layer (C) is a coating containing a binder resin (C-1) and an ultraviolet absorber (C-2). The composition is formed and satisfies the surface tension of 20 to 60 mN/m, and the ultraviolet transmittance is 20% or less at 290 nm to 430 nm, and the ultraviolet absorbing layer (C) is formed in the design layer (B) and the transparent coating layer (D). The transparent coating layer (D) is an energy ray-curable coating film, and as a laminated film, it has an elongation at break of 40 to 400% at 40 to 130 ° C before curing. The laminated film for three-dimensional molded article decoration according to the first aspect of the invention, wherein the ultraviolet absorbing layer (C) has a strength of from 3 to 1000 N/cm ² at 40 ° C to 130 ° C. The laminated film for three-dimensional molded article decoration according to claim 1 or 2, wherein the ultraviolet absorbing layer (C) further contains a surface conditioning agent (C-3). The laminated film for three-dimensional molded article decoration according to the first, second or third aspect of the patent application is sequentially laminated with an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), and a transparent coating layer (D). And the substrate film layer (E). A laminated film for three-dimensional molded article decoration according to the first, second, third or fourth aspect of the patent application, wherein a release layer (F) is provided between the transparent coating layer (D) and the base film layer (E) . For example, the laminated film for the decoration of three-dimensional molded articles of the first, second or third patent application scope The layer has an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a base film layer (E), and a clear coating film layer (D). For example, the laminated film for three-dimensional molded product decoration of the first, second, third, fourth, fifth or sixth aspect of the patent application, wherein the transparent coating layer (D) contains polyurethane acrylate (D1), has no A coating composition of a saturated double bond monomer/oligomer (D2) and a polymerization initiator (D3), with respect to the above polyurethane acrylate (D1), double bond equivalent: 130 to 600 g/eq molecular weight Mw: 3000 to 200000 Amine ester concentration: 300~2000g/eq. A decorative molded article obtained by decorating a molded substrate with a laminated film for three-dimensional molded article decoration according to any one of claims 1 to 7.