WO2016117555A1

WO2016117555A1 - Laminate film for decorating molded article and decorative molding

Info

Publication number: WO2016117555A1
Application number: PCT/JP2016/051436
Authority: WO
Inventors: 長谷高和; 北村昌弘; 栄田正三郎
Original assignee: 日本ペイント・オートモーティブコーティングス株式会社
Priority date: 2015-01-20
Filing date: 2016-01-19
Publication date: 2016-07-28
Also published as: TW201637862A

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°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°C as a laminate film.

Description

Laminated film for decorative molded product and decorative molded body

The present invention relates to a laminated film for decorative molded products and a decorative molded body.

In a molded product obtained from various materials such as plastic, metal and the like, it is generally performed to decorate the surface in order to impart design properties to the surface or protect the surface.

As one of such decoration methods, a film decoration method using a laminated film 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 particular, there is known a method of decorating by forming a clear coating layer with an energy ray curable coating composition and curing it after molding.

In such a decoration method, in recent years, it has been studied to form a design layer by an ink jet printer (Patent Documents 1 to 3). The ink jet printer can form various design layers having high design properties that cannot be obtained by ordinary coating. As an ink used in such an ink jet printer, an energy ray curing type ink is known. In the process of producing a decorative laminated film having an ink jet printing process using such an energy ray curable ink, a step of curing the design layer with energy rays is required.

However, in the curing process of the ink having energy ray curability, there is a problem that a curing reaction occurs simultaneously in the clear coating layer. If the clear coating layer is cured in the production process of the laminated film, there is a problem that sufficient stretchability cannot be ensured at the time of decoration, and good decoration cannot be performed.

Patent Document 1 describes that the problem described above is improved by making the ultraviolet wavelength for curing the UV ink different from the ultraviolet wavelength for curing the protective layer. In such an invention, it is important to select a light source in the energy beam curing process, and a high pressure mercury lamp, a metal halide lamp, a chemical lamp, an LED-UV lamp, etc. are usually used as the light source in the energy beam curing process. In general, a photopolymerization initiator has absorption in a wide wavelength range, and it is difficult to make the ultraviolet wavelength for curing the UV ink different from the ultraviolet wavelength for curing the protective layer. Since only a light source in a narrow wavelength range can be used, there is a risk of increasing costs in the manufacturing process.

Patent Document 2 describes that an ultraviolet absorbing layer is provided between the UV ink layer and the protective layer. However, Patent Document 2 does not describe a specific configuration of the ultraviolet absorbing layer. However, in order to obtain such a laminate, a UV ink layer is formed on the ultraviolet absorbing layer by ink jet printing, so that it is necessary to prevent ink repelling and bleeding. Furthermore, since stretching at the time of molding is necessary, it is preferable to have a performance that can cope with stretching.

Also in patent document 3, manufacturing the film for decorating using inkjet printing is described. However, the cited document 3 is an invention relating to the formation of a solvent absorbing layer for absorbing an organic solvent during ink jet printing, and mentions the problems when the ink for ink jet printing is a UV ink layer. There is no suggestion on how to improve this.

JP 2012-206262 A JP 2012-116167 A JP 2013-56459 A

The present invention solves the above-mentioned problems, maintains the stretchability of the clear coating layer in a decorative film in which a design layer is formed by ink jet printing, and causes repelling and bleeding in ink jet printing. The object is to provide a film that can be satisfactorily performed.

The present invention is a laminated film for decorating a three-dimensional molded product having an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a clear coating layer (D) and a base film layer (E). The design layer (B) is formed by inkjet printing with an energy ray curable ink,
The ultraviolet absorbing layer (C) is formed of a coating composition containing a binder resin (C-1) and an ultraviolet absorber (C-2), and
Surface tension 20-60 mN / m, and
UV transmittance of 290 nm to 430 nm satisfying 20% or less,
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,
The laminated film is a laminated film for decorating a three-dimensional molded product characterized by having a breaking elongation of 30 to 400% at 40 to 130 ° C. before curing.
The ultraviolet absorbing layer (C) preferably has a strength of 40 to 130 ° C. and 3 to 1000 N / cm ² .
The ultraviolet absorbing layer (C) preferably further contains a surface conditioner (C-3).

The laminated film for decorating the three-dimensional molded product has an adhesive layer (A), a design layer (B), an ultraviolet absorption layer (C), a clear coating layer (D), and a base film layer (E) in this order. It may be laminated.
The laminated film for decorating the three-dimensional molded product may be one in which a release layer (F) is provided between the clear coating layer (D) and the base film layer (E).

The laminated film for decorating the three-dimensional molded product has an adhesive layer (A), a design layer (B), an ultraviolet absorption layer (C), a base film layer (E), and a clear coating layer (D) in this order. It may be laminated.

The clear coating layer (D) is formed of a coating composition containing polyurethane acrylate (D1), a monomer / oligomer (D2) having an unsaturated double bond, and a polymerization initiator (D3). Because
The polyurethane acrylate (D1) is
Double bond equivalent: 130-600 g / eq
Molecular weight Mw: 3000-200000
Urethane concentration: 300-2000 g / eq
It is preferable that

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 the three-dimensional molded product of the present invention has sufficient stretchability because the clear coating layer is not cured even by the curing process of ink jet printing using the energy ray curable ink. Further, the ink-jet printing can be favorably printed without causing repelling or bleeding.

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.

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 three-dimensional molded product decoration of the present invention is a decorative film having a design layer (B) formed by ink jet printing with an energy ray curable ink, and an ultraviolet absorbing layer (C) at a specific position. ) Is cut off, and when the design layer (B) is cured by irradiation with energy rays, the clear coating layer (D) is not irradiated with ultraviolet rays. In the case where the clear coating layer (D) is not cured, the elongation can be maintained during molding.

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

Examples of the layer structure of the laminated film for decorating a three-dimensional molded product that can achieve the above-described effects include those shown in FIGS.
1 is a laminate of an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a clear coating layer (D) and a base film layer (E) in this order. is there. In such a configuration, the base film layer (E) is peeled off before or after molding, and from the adhesive layer (A), the design layer (B), the ultraviolet absorbing layer (C), and the clear coating layer (D). A surface coating is formed.

In the structure shown in FIG. 2, a release layer (F) is provided between the clear coating layer (D) having the layer structure shown in FIG. 1 and the base film layer (E). In the case where the substrate film layer (E) is a substrate having excellent releasability such as a PET film, it is not necessary to provide a release layer, but when a substrate inferior in releasability is used, the release layer It is preferable to provide (F). This is preferable in that the film can be easily peeled at the time of decorative molding.

The one shown in FIG. 3 is obtained by laminating an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a base film layer (E), and a clear coating layer (D) in this order. is there. In the case of this embodiment, the base film is not peeled even after molding, and the adhesive layer (A), the design layer (B), the ultraviolet absorbing layer (C), the base film layer (E) and A coating layer composed of the clear coating layer (D) is formed.

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 figure, and thereby the clear coating layer (D) is not cured. And when hardening a clear coating film layer, an energy ray is irradiated from the arrow (X) side.

Therefore, the light source for curing the energy ray curable ink 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 may be used. Can be used.

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

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

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

The thickness of the adhesive layer (A) is not particularly limited, but is preferably 3 to 30 μm, and more preferably 5 to 25 μm. If it is less than 3 μm, there is a possibility that sufficient adhesion cannot be secured. If it is more than 30 μm, coating and drying are difficult, and this is disadvantageous in terms of cost.

(Design layer (B))
The design layer (B) in this invention is a layer which formed the design external appearance provided with the laminated | multilayer film for three-dimensional molded article decoration. The design layer (B) in the present invention is a layer formed by ink jet printing with an energy ray curable ink. The components of the ink, the apparatus and method used for inkjet printing are not particularly limited, and any known one can be used.

(Ultraviolet absorbing layer (C))
The ultraviolet absorbing layer (C) has a surface tension of 20 to 60 mM / m and an ultraviolet transmittance of 290 nm to 430 nm and satisfies 20% or less.
Further, if the surface tension is low, the ink bleeds, and if it is high, the ink repellates.
Further, when the ultraviolet transmittance is high, a sufficient ultraviolet blocking effect cannot be obtained.
That is, it has sufficient surface tension to perform ink jet printing, has sufficient ultraviolet shielding ability to prevent curing of the clear coating layer, and has strength that does not cause a problem in molding. It is a thing.

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

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

The ultraviolet absorbing layer (C) preferably absorbs ultraviolet rays but easily transmits visible light. This is because if the visible light does not transmit, the design layer is difficult to see from the outside.

The ultraviolet absorbing layer (C) preferably has a strength of 40 to 130 ° C. and 3 to 1000 N / cm ² . If the strength is low, swelling may occur during molding, and if it is high, moldability may be insufficient. The strength of the ultraviolet absorbing layer (C) is the film strength when the ultraviolet absorbing layer alone is an autograph AG-IS manufactured by Shimadzu Corporation, at a temperature of 60 ° C., at a tensile rate of 50 mm / min, and an elongation of 200%. Is measured.

The ultraviolet absorbing layer (C) is formed of a coating composition containing a binder resin (C-1) and an ultraviolet absorber (C-2). And the layer which satisfy | fills the parameter mentioned above can be formed by adjusting the mixing | blending and combination of these components.

The binder resin (C-1) is not particularly limited, and resins such as acrylic resin, vinyl chloride-vinyl acetate copolymer, polyamide resin, polyester resin, urethane resin, epoxy resin, and styrene resin can be used. Urethane resin is preferable, and urea bond-containing urethane resin is more preferable. One type can be used alone, or two or more types can be used in combination.
It is preferably in the range of 85 to 99% by weight with respect to the total amount of the ultraviolet absorbing layer (C).

The ultraviolet absorber (C-2) is not particularly limited. For example, a triazine ultraviolet absorber, a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a cyanoacrylate ultraviolet absorber, or a hydroxybenzoate ultraviolet absorber. An agent or the like can be used.

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

Examples of the benzophenone-based ultraviolet absorber include 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone 2,4-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4- Methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-n- Benzyloxybenzophenone, 2-hydroxy-4-n-octadecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy -4,4 ' Diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-propoxy Benzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2'-dihydroxy-4,4'-di (hydroxymethyl) benzophenone, 2,2 '-Dihydroxy-4,4'-di (2-hydroxyethyl) benzophenone, 2,2'-dihydroxy-3,3'-dimethoxy-5,5'-di (hydroxymethyl) benzophenone, 2,2'-dihydroxy -3,3'-dimethoxy-5,5'-di (2-hydroxyethyl) benzopheno Etc. The.

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

Examples of the cyanoacrylate-based ultraviolet absorber include 2-ethylhexyl-2-cyano-3,3′-diphenyl acrylate, ethyl-2-cyano-3,3′-diphenyl acrylate, and methyl-2-cyano-3- And methyl-3- (p-methoxyphenyl) acrylate.

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

The ultraviolet absorber (C-2) is a triazine-based, benzophenone-based, or benzotriazole-based UV absorber because it has a high UV-absorbing property over a wide wavelength range (from about 280 to 360 nm) from a short wavelength region to a long wavelength region. Agents are preferred.
The ultraviolet absorber can be blended with the above compounds singly or in combination of two or more.
Specifically, Tinuvin 400, 900, 447, 1130 (manufactured by BASF) can be used. The blending amount of the ultraviolet absorber (C-2) varies depending on the ultraviolet absorber used, and is not particularly limited as long as it satisfies the above-described ultraviolet transmittance, but is 1 to 15 with respect to the total amount of the ultraviolet absorbing layer (C). It is preferably in the range of wt%, more preferably in the range of 3 to 10 wt%. If it is less than 1% by weight, the ultraviolet blocking effect may be insufficient. If it exceeds 15% by weight, the strength of the ultraviolet absorbing layer may be lowered, the moldability may be insufficient, and it is disadvantageous in terms of cost.

The ultraviolet absorbing layer (C) may contain a surface conditioner (C-3). That is, depending on the type of resin used in the ultraviolet absorbing layer (C), it may be difficult to make the surface tension within the range described above. In this case, the surface tension within the above-mentioned range can be obtained by blending the surface conditioner (C-3).

The surface conditioner (C-3) is not particularly limited, and for example, polyether-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, and the like can be used. Specific examples include BYK-300, BYK-342, BYK-349 (manufactured by Big Chemie Japan).
The blending amount of the surface conditioner (C-3) is not particularly limited, and is preferably in the range of 0.01 to 5% by weight with respect to the total amount of the ultraviolet absorbing layer (C).

The thickness of the ultraviolet absorbing layer (C) is not particularly limited, but is preferably 3 to 30 μm, for example, and more preferably 5 to 25 μm. If it is too thin, it is difficult to obtain sufficient UV shielding performance and strength, and if it is too thick, the performance is not particularly improved, it will be disadvantageous in terms of cost, and coating and drying will be difficult. Become.

(Clear coating layer (D))
The clear coating layer (D) used in the present invention is an energy ray curable coating, and its specific composition is not particularly limited as long as it does not impair the physical properties of the laminated film. It can be set as an energy ray curable coating film.
Especially, it is preferable that it is formed by the active energy ray-curable coating composition containing the polyurethane acrylate (D1), the monomer / oligomer (D2) having an unsaturated double bond, and the polymerization initiator (D3). . By adopting such a composition, stretching during use is facilitated, and it is possible to 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.

Furthermore, the active energy ray-curable coating composition comprises (D1) in a total amount of (D1) solid content weight and (D2) solid content weight ((D1) + (D2)) in 100 parts by weight. 50 to 99 parts by weight, and (D2) is contained so as to fall within the range of 1 to 50 parts by weight, and the total amount of (D1) solid content weight and (D2) solid content weight ((D1) + (D2 )) It is preferable that (D3) is contained within a range of 0.5 to 20 parts by weight per 100 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, (D1) to (D3) will be described in detail.

(Polyurethane acrylate (D1))
The polyurethane acrylate (D1) 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 (D1), A well-known arbitrary thing can be used. For example, i) a compound obtained by equivalently reacting a compound having two or more isocyanate groups in a molecule with a compound having one or more hydroxyl groups and one or more double bond groups in the molecule, ii ) After reacting a compound having two or more isocyanate groups in the molecule with a condensate of a polyol with a monobasic acid and / or polybasic acid and / or acid anhydride thereof, one more in the molecule A compound obtained by reacting the above hydroxyl group with a compound having one or more double bond groups, iii) after reacting a polyol with a compound having two or more isocyanate groups in the molecule, And compounds obtained by reacting a compound having one or more hydroxyl groups and one or more double bond groups.

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 4-hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and other commercially available products 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 (D1)). 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, and examples thereof include aromatics 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.), Sumidur N-3200-90M (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Takenate D165N- 90X (trade name, manufactured by Mitsui Chemicals), 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) be able to. Moreover, the blocked isocyanate which blocked these can also be used as needed.

The polyurethane acrylate (D1) 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 and piperazine; 1,2- and 1,3-cyclobutane Alicyclic 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 An aromatic diamine such as-(sec-butyl) diphenylmethane; dimer diamine obtained by converting a carboxyl group of a dimer acid into an amino group; a dendrimer having a primary or secondary amino group at a terminal;

The polyurethane acrylate (D1) 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 (D1) 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 (D1) and the monomer / oligomer (D2) 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 (D1) 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 (D1) and the monomer / oligomer (D2) 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 (D1) 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 (D1) and the monomer / oligomer (D2) 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 (D1) may be modified with fluorine and / or silicone. That is, the polyurethane acrylate (D1) may be synthesized by the above-described method using a monomer containing fluorine or a silicone unit, or the polyurethane acrylate (D1) obtained by the above-described method has. The functional group may be reacted with a compound having fluorine and / or silicone.

(Monomer / oligomer having unsaturated double bond (D2))
As the monomer / oligomer (D2) 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 (D2) 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 (D3))
As said polymerization initiator (D3), the energy-beam polymerization initiator which superposition | polymerization is started by electromagnetic rays, such as an ultraviolet-ray (UV) and an electron beam, can be used. These energy beam polymerization initiators are not particularly limited, and any known one can be used.

Specifically, examples of the energy ray polymerization initiator include benzoin compounds such as benzoin methyl ether; anthraquinone compounds such as 2-ethylanthraquinone; benzophenone compounds such as benzophenone; sulfide compounds such as diphenyl sulfide; Thioxanthone compounds such as 2,4-dimethylthioxanthone; acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone; phosphinoxide compounds such as 2,4,6-trimethylbenzoindiphenylphosphinoxide; 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.

(Amount of (D1) to (D3))
In 100 parts by weight of the solid content weight of (D1) and the solid content weight of (D2) ((D1) + (D2)), 50 to 99 parts by weight of (D1) and 1 to 50 of (D2) It is contained so as to be in the range of parts by weight, and (D3) is 0 with respect to 100 parts by weight of the total weight of the solid content of (D1) and the solid content of (D2) ((D1) + (D2)). It is preferable that it is contained so as to be in the range of 5 to 20 parts by weight.

When the content of the polyurethane acrylate (D1) is less than 50 parts by weight, the blocking resistance is not preferable. When the content of the polyurethane acrylate (D1) 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 (D2) 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 (D2) 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 (D3) 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 (D3) exceeds 20 parts by weight, unreacted polymerization initiator (D3) 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 compound include aliphatic diamines 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 tris (3-mercaptopropionate) triethyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, and the like trifunctional thiols: 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-merca) Including but not limited to polyfunctional thiols such as ptobutyrate).

The clear coating layer (D) used in the three-dimensional molded product decorative laminated film of the present invention is as described above, and more preferably, the polyurethane acrylate (D1) has a double bond equivalent of 130. ~ 600g / eq
Molecular weight Mw: 3000-200000
Urethane concentration: 300 to 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. By forming the clear coating layer (D) 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. Further, the polyurethane acrylate (D1) preferably has a urea concentration of 500 to 1000 g / eq.

The weight average molecular weight in this specification was measured using HLC-82220GPC manufactured by Tosoh Corporation. The measurement conditions are as follows.
Column: TSKgel Super Multipore HZ-M 3 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 the clear coating composition, a compound that is usually added as a coating material may contain 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.

Further, 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. In addition, 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 0.5 to 20% by weight (solid content ratio in the coating) of a polyisocyanate compound having an isocyanate group. By blending a polyisocyanate compound, it is preferable in 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.

The clear coating composition may contain a UV absorber. That is, in the case of a housing for home appliances such as an automobile outer plate, an automobile interior part, a mobile phone, and a lighting fixture, the design appearance may change due to irradiation with ultraviolet rays during use. In order to prevent such deterioration, an ultraviolet absorber may be added to the clear coating composition.

Examples of the ultraviolet absorber that can be blended in the clear coating composition include the same ones that can be used in the ultraviolet absorbing layer described above, and the blending amount is the total solid content in the clear coating composition. The content may be 1 to 10% by weight.

When a UV absorber is blended in the clear coating layer, if the weather resistance is required, the effect of both the UV absorber contained in the clear and the UV absorber contained in the UV absorbing layer is effective. It is preferable at the point which can fully protect a layer.

(Base film layer (E))
The base film layer (E) 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 in FIG. 3 described above, there are some which are present on the molded body even after the 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 (E) is not particularly limited, and 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 (E) is preferably from 0.01 to 0.5 mm, and more preferably from 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.

(Release layer (F))
As the release layer (F) 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.
The peel strength between the release layer (F) and the clear coating layer (D) is preferably 0.05 to 8.0 N / 25 mm, and more preferably 0.1 to 5.0 N / 25 mm. When it is less than 0.05 N / 25 mm, workability is poor, such as peeling of the base film layer (E) during film production and decorative molding, and when it exceeds 8.0 N / 25 mm, a film after molding is obtained. In the case of peeling, there is a possibility that peeling becomes difficult.

(Elongation at break)
The three-dimensional molded decorative laminated film 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 by using an autograph AG-IS manufactured by Shimadzu Corporation with the base film (E) in a temperature range of 40 to 130 ° C. and a tensile speed of 50 mm / min. It is a value obtained by measuring the elongation at the time when such a layer broke. Depending on the properties of the film, the elongation at break may be in the above-described range at any arbitrary temperature within the range of 40 to 130 ° C.

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

In the layer structure of the present invention as shown in FIGS. 1 to 3, there is a step of inkjet printing the design layer (B) on the ultraviolet absorbing layer (C) during production. In the present invention, since the surface tension of the ultraviolet absorbing layer (C) is adjusted within a certain range, good printing can be performed in such a process.

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 coating solution is applied by the above application method, the coating solution 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) may be bonded by a laminating method instead of the coating / drying method. That is, the film formed by the adhesive layer (A) 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 (E) is peeled off from the laminated film as necessary, and the laminated film is pressure-bonded so that the laminated film is in close contact with the base material surface so that the adhesive layer faces 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 (E) 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 Polyurethane synthesis)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a material inlet 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 of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 102.9 mg KOH / g) were charged.
Next, 238.1 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became homogeneous, 314.2 g of 4,4′-methylenebis-cyclohexyl diisocyanate was charged at 50 ° C. and reacted at 80 ° C. using dibutyltin laurate as a catalyst.
The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until 2,270 cm-1 absorption due to free isocyanate groups as 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.

[Production example of laminated film]
<Preparation of clear paint solution>
Put a polyurethane acrylate (D-1) and a monomer (D-2) in a container equipped with a stirrer, add MEK in such an amount that the final coating becomes NV = 40% while stirring, and further a polymerization initiator (C3) And stirred for 30 minutes to obtain a clear coating solution.

<Preparation of UV absorbing coating solution>
In a container equipped with a stirrer, the binder resin (C-1) and the ultraviolet absorber (C-2) are placed, and while stirring, the amount of MIBK in which the final paint is NV = 35% is placed, and stirred for 30 minutes. An ultraviolet absorbing coating solution was obtained.

<Production 1 of laminated film; Production of film having a laminated structure shown in FIG. 2>
The resin composition forming each layer is shown in the table. Based on such a composition, a film having a laminated structure was prepared by the following method.
On the base film (E) on which the release layer (D) is formed, the clear coating material is used so that a clear coating film layer (D) having a dry film thickness (hereinafter referred to as dry film thickness) of 20 μm is obtained. The solution was applied using an applicator and dried at 80 ° C. for 15 minutes to form a clear coating layer (D).
In addition, below, what formed the clear coating film layer (D) on the base film layer (E) is described as an (E + D) layer film.

Next, the UV absorbing coating solution is applied using an applicator so that an ultraviolet absorbing layer (C) having a dry film thickness of 20 μm is obtained on the clear coating layer (D) of the (E + D) layer film. Thereafter, the film 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 inkjet printer UJF-3042 (manufactured by Mimaki Engineering). In the formation of the UV ink layer (B), the ink was cured by ultraviolet irradiation from the (Y) side in FIG. 2 after the layer formation.

Subsequently, an adhesive (Byron UR-3200, manufactured by Toyobo Co., Ltd. or UR-1361ET, manufactured by Aron Evergrip Co., Ltd.) is obtained on the UV ink layer (B) so as to obtain an adhesive layer having a dry film thickness of 10 μm. It apply | coated using the applicator and it was made to dry at 80 degreeC for 15 minute (s), and the adhesive bond layer was formed.

<Production 2 of laminated film 2; Production 2 of film having a laminated structure shown in FIG. 2 (Example 7)>
In the formation of the adhesive layer (A), a film composed of the adhesive layer was prepared, and this was obtained by laminating using MCK MRK-650Y, and the layers (B) to (E) obtained by the above-described method. A laminated film was obtained by adhering to a laminated film consisting of Lamination was performed under the following conditions.
Heat-resistant silicone rubber roll with a diameter of 80 mm Temperature: 85 ° C., Speed: 42 cm / min

<Production 3 of laminated film; Production of film having laminated structure shown in FIG. 3>
On the base film (E), the clear coating solution is applied using an applicator so that a clear coating layer (D) having a dry film thickness (hereinafter, dry film thickness) of 20 μm is obtained. And dried at 80 ° C. for 15 minutes to form a clear coating layer (D).
In addition, below, what formed the clear coating film layer (D) on the base film layer (E) is described as an (E + D) layer film.

Next, the applicator is used to apply the UV-absorbing coating solution so that an ultraviolet-absorbing layer (C) having a dry film thickness of 20 μm is obtained on the side opposite to the clear coating layer (D) of the (E + D) layer film. And 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 inkjet printer UJF-3042 (manufactured by Mimaki Engineering). In the formation of the UV ink layer (B), the ink was cured by ultraviolet irradiation from the (Y) side in FIG. 3 after the layer formation.

Subsequently, an adhesive (Byron UR-3200, manufactured by Toyobo Co., Ltd. or UR-1361ET, manufactured by Aron Evergrip Co., Ltd.) is applied on the UV ink layer (B) so as to obtain an adhesive layer having a dry film thickness of 10 μm. Then, it 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.

In the following tables, the following components were used.
UV 1700B (Nippon Synthetic Chemical Industry); Urethane acrylate oligomer Lucillin TPO (BASF); 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide Novaclear SG007 (Mitsubishi Resin) A-PET sheet Soft Shine (Toyobo) II Axial stretched polyester film MAU-2000 (Daiichi Seika): Olefin resin Xp012N35 (Mitsui Chemicals): Olefin resin 1321 (Toagosei): Vinyl chloride / vinyl acetate copolymer resin TE-5430 (Mitsui Chemicals): Urethane resin RT-87140 Morton): acrylic resin D-178N (Mitsui Chemicals): allophanate-modified polyhexamethylene diisocyanate tinuvin 900 (BASF): 2,2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl) -1 -Phenylethyl) phenol tinuvin 477 (BASF): hydroxyphenyltriazine (HPT) UV absorber

The obtained laminated film was evaluated based on the following criteria.
(Elongation)
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 including the base material.
Elongation was determined when any layer broke.

(surface tension)
Using an automatic contact angle meter DSA20 (manufactured by Kurz), the contact angles of water and methylene iodide were measured and calculated.

(Ultraviolet transmission)
Using a UV-visible spectrophotometer U-4100 (Hitachi High-Technologies), measurement was performed in the wavelength range of 290.0 nm to 430.0 nm. As the light source, a deuterium lamp was used in the ultraviolet region, and a halogen lamp was used in the visible / near infrared region.

(Membrane strength)
The film strength at an elongation of 200% was measured using an autograph AG-IS manufactured by Shimadzu Corporation under a temperature condition of 60 ° C. and a tensile speed of 50 mm / min.

(Formability)
This was confirmed by TOM molding using a double-sided vacuum molding machine NGF-0709 manufactured by Fuse Vacuum Co., Ltd.
◎: The base material can be traced to the highly stretched part and can be molded ○: The base material can be traced to the middle stretched part and can be molded Δ: The base material can be traced to the low stretched part and molded

(Printability)
The printability in the printing process was judged according to the following criteria.
○: Ink dot formation is good ○ △: Ink slightly repels (small dot diameter) or slightly blurs (large dot diameter)
Δ: Ink is repelled (small dot diameter) or smeared (large dot diameter)
Δ: Print image failure due to repellency or blurring ×: Print image cannot be formed

After molding resistance SW resistance: using a steel wool resistance tester, 100g / cm ² 10 reciprocates steel wool # 0000 under a load ◎: No scratches ○: 2 ~ 3 pieces of scratches △: the degree counted scratches ×: Countless scratches

Impact resistance after molding: Using a DuPont impact resistance tester, drop a weight from 20cm to 500g in weight and check the crack of the coating film. ○: No cracking △: Slight crack in coating film ×: Coating film Remarkable cracks

Chemical resistance after molding: A cylindrical polyring having an inner diameter of 38 mm and a height of 15 mm is fixed to the coating film, and the following solution is dropped. Cap and leave under each condition. After the test, it is 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 B: Slight change in coating film appearance (wrinkles, cracks)
Δ: Appearance of coating is clearly changed (wrinkles, cracks)
×: Remarkably changes in appearance of coating film (wrinkles, cracks)

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

The formulations A to D in Table 2 used were those having the formulations shown in Table 3 below.

From the result of the above Example, since the laminated film for 3D molded product decoration of the present invention has good moldability and printability, it can perform good decoration on the 3D molded product. it is obvious.

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) Adhesive layer (B) Design layer (C) Ultraviolet absorbing layer (D) Clear coating layer (E) Base film layer (F) Release layer

Claims

A laminated film for decorating a three-dimensional molded product having an adhesive layer (A), a design layer (B), an ultraviolet absorbing layer (C), a clear coating layer (D) and a base film layer (E),
The design layer (B) is formed by ink jet printing with an energy ray curable ink,
The ultraviolet absorbing layer (C) is formed of a coating composition containing a binder resin (C-1) and an ultraviolet absorber (C-2), and
Surface tension 20-60 mN / m, and
UV transmittance of 290 nm to 430 nm satisfying 20% or less,
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,
A laminated film for decorating a three-dimensional molded product characterized by having a breaking elongation of 30 to 400% at 40 to 130 ° C. before being cured as a laminated film.
2. The laminated film for decorating a three-dimensional molded product according to claim 1, wherein the ultraviolet absorbing layer (C) has a strength of 3 to 1000 N / cm 2 at 40 to 130 ° C.
The laminated film for decorating a three-dimensional molded product according to claim 1 or 2, wherein the ultraviolet absorbing layer (C) further contains a surface conditioner (C-3).
The adhesive layer (A), the design layer (B), the ultraviolet absorbing layer (C), the clear coating layer (D) and the base film layer (E) are laminated in this order. The laminated film for decorating the three-dimensional molded product described.
The three-dimensional molded product decoration according to claim 1, 2, 3, or 4, wherein a release layer (F) is provided between the clear coating layer (D) and the base film layer (E). Laminated film.
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 laminated in this order. The laminated film for decorating the three-dimensional molded product described.
The clear coating layer (D) is a coating composition containing polyurethane acrylate (D1), a monomer / oligomer (D2) having an unsaturated double bond, and a polymerization initiator (D3),
The polyurethane acrylate (D1) is
Double bond equivalent: 130-600 g / eq
Molecular weight Mw: 3000-200000
Urethane concentration: 300-2000 g / eq
The laminated film for decorating a three-dimensional molded article according to claim 1, 2, 3, 4, 5 or 6.
A decorative molded article obtained by decorating a molded substrate with the three-dimensional molded article decorative laminated film according to any one of claims 1 to 7.