KR20190114043A - Laminate, and decorative molded product - Google Patents

Abstract

The present invention has a pressure-sensitive adhesive layer, a surface layer laminated on one surface side of the pressure-sensitive adhesive layer, and a resin separator layer laminated on the surface side opposite to the surface on which the surface layer is laminated as the other surface side of the pressure-sensitive adhesive layer, At least any one of a separator layer relates to the laminated body characterized by having a layer whose surface electric resistance is 1 * 10 <^5> -1 * 10 <^{12> (} ohm) / square.

Description

Laminated and Decorated Molded Products {LAMINATE, AND DECORATIVE MOLDED PRODUCT}

The present invention relates to laminates and decorative molded articles. Specifically, the present invention relates to a laminate having a surface layer, a pressure-sensitive adhesive layer, and a separator layer, wherein the laminate can suppress the mixing of foreign matter during molding under vacuum conditions or reduced pressure conditions. The present invention also relates to a decorative molded article which is decorated with such a laminate.

This application claims priority based on Japanese Patent Application No. 2015-013331 for which it applied on January 27, 2015, and uses the content here.

Conventionally, in the case of protecting or decorating (decorating) the surface of automobile interior and exterior parts, home appliance parts, building parts, etc., after processing the molded body by injection molding or vacuum molding, the surface of the molded body is sprayed or the like. Coating, drying, and heat curing were applied. However, in addition to the problem that the discharge of volatile organic solvents worsens the working environment, such coating requires a work process and production equipment for each molded part, and also requires coating of paint, so that the yield of paint is poor. There was a problem that productivity was low.

In recent years, the use of the resin molded object is progressing as a molded object for the purpose of weight-reducing a vehicle interior / exterior component, a home appliance component, a building material component, etc. Spray coating is often unsuitable for decoration (decoration) of the resin molded body, and various methods have been developed to decorate the surface of the resin molded body. Among them, the method of decorating the outermost surface of the molded body with a decorative film to obtain a decorative molded body has the advantage of higher design freedom and superior productivity than a method of coating or printing the surface using a paint or the like. In addition, the decorating method using a decorating film has been used in various applications because the surface of a molded article having three-dimensional unevenness can also be decorated.

As a method of decorating the molded object surface which has three-dimensional unevenness | corrugation with a decorative film, there exists a three-dimensional coating molding (TOM molding) method (patent document 1). TOM molding is a shaping | molding method under a vacuum condition or a reduced pressure condition, and is a method of compressing a decorative film and a molded object and obtaining a decorative molded object. In TOM molding, it is possible to decorate regardless of the material of a molded object. Further, the reverse tapered portion and the end curled portion can be coated and formed without forming a vacuum hole in the molded body.

The decorative film used for TOM shaping | molding includes the film which has only a decorative layer, and the laminated | multilayer film (laminated body) which has a decorative layer (surface layer) and an adhesive layer. When obtaining a decorative molded object using the film which has only a decorative layer, the method of melt | dissolving a film itself and making a molten film and a molded object adhere | attach is used. In addition, when using the laminated | multilayer film which has a decorative layer (surface layer) and an adhesive layer, it is not necessary to melt a decorative layer, but the laminated | multilayer film and a molded object are made to adhere closely using the adhesive force of an adhesive layer.

Japanese Patent No. 3733564

However, when TOM molding is performed using the conventional decorative film, foreign matters, such as dust, may mix between a molded object and laminated | multilayer film, and it became a problem. The mixing of such foreign matters is a problem because unevenness derived from foreign matters is generated on the surface of the decorated molded article, and the yield of the decorated molded article is deteriorated.

Therefore, in order to solve such a subject of the prior art, the present inventors conducted an examination for the purpose of providing a decorative laminated film (laminate) which can suppress the mixing of foreign substances when TOM molding is performed.

As a result of earnestly examining in order to solve the said subject, the present inventors found that in the laminated body which has a surface layer, an adhesive layer, and a separator layer, the surface electrical resistance of any layer may be in a predetermined range, It was found that the incorporation can be suppressed.

Specifically, the present invention has the following configuration.

[1] A pressure-sensitive adhesive layer, a surface layer laminated on one side of the pressure-sensitive adhesive layer, and a resin separator layer laminated on the surface side opposite to the surface on which the surface layer is laminated as the other side of the pressure-sensitive adhesive layer, At least any one of a separator layer has a layer whose surface electric resistance is 1 * 10 <^5> -1 * 10 <^{12> (} ohm) / square, The laminated body characterized by the above-mentioned.

[2] The laminate layer according to [1], wherein the separator layer has a layer having a surface electrical resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □.

[3] The separator layer has a substrate layer, a release agent layer laminated on one surface side of the substrate layer, and an antistatic layer laminated on the surface side opposite to the surface on which the release agent layer is laminated as the other surface side of the substrate layer. The laminated body as described in [1] or [2] whose surface electrical resistance is 1 * 10 <^5> -1 * 10 <^12> ohm / square.

[4] The laminate according to [3], wherein the antistatic layer contains an inorganic antistatic agent.

[5] The laminate according to any one of [1] to [4], wherein the surface electrical resistance of the pressure-sensitive adhesive layer is 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □.

[6] The laminate according to [5], wherein the pressure-sensitive adhesive layer contains an inorganic antistatic agent.

[7] The laminate according to any one of [1] to [6], wherein the surface layer has a surface protective layer containing an ultraviolet absorber and a colored layer.

[8] The laminate according to any one of [1] to [7], which is used for molding under vacuum conditions or reduced pressure conditions.

[9] A decorative molded body comprising a pressure-sensitive adhesive film composed of the surface layer and the pressure-sensitive adhesive layer of the laminate according to any one of [1] to [8], and a molded body impregnated with an adhesive film.

[10] The decorative molded body according to [9], wherein the molded body has a non-planar shape.

[11] A method for producing a decorative molded body using a laminate, wherein the laminate has a pressure-sensitive adhesive layer, a surface layer laminated on one side of the pressure-sensitive adhesive layer, and a surface side opposite to the surface on which the surface layer is laminated as the other side of the pressure-sensitive adhesive layer. It has a resin layer laminated | stacked on the inside, At least any one of an adhesive layer, a surface layer, and a separator layer has a layer whose surface electrical resistance is 1 * 10 <^5> -1 * 10 <^12> ohm / square, The separator layer is made from a laminated body. It includes the process of peeling and obtaining the adhesive film which has a surface layer and an adhesive layer, the process of laminating | stacking an adhesive film to a molded object under vacuum conditions or a reduced pressure condition, and the process of crimping | bonding an adhesive film to a molded object by a pressure difference. The manufacturing method of the decorated molded object characterized by the above-mentioned.

[12] A substrate layer, a resin layer having a surface electrical resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □, laminated on one surface side of the substrate layer, and a release agent layer laminated on the other surface side of the substrate layer. A separator made of resin, which is used for protecting the pressure-sensitive adhesive film used for molding under vacuum conditions or reduced pressure conditions.

[13] A pressure-sensitive adhesive layer and a surface layer laminated on one side of the pressure-sensitive adhesive layer, wherein at least one of the pressure-sensitive adhesive layer and the surface layer has a layer having a surface electrical resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □. Adhesive film made with.

According to this invention, the laminated body which can suppress mixing of a foreign material at the time of TOM shaping | molding can be obtained. Moreover, when the laminated body of this invention is used, the productivity of a decorative molded object can be improved and the decorative molded object excellent in designability can be obtained.

1 is a cross-sectional view showing an example of the configuration of a laminate of the present invention.
2 is a cross-sectional view showing an example of the configuration of a laminate of the present invention.
It is sectional drawing explaining the structure of the decorative molded object of this invention.
It is a figure explaining the molded object used in the Example and the comparative example. Fig. 4A is a top view, Fig. 4B is a right side view, and Fig. 4C is a bottom view.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail. Although description of the element | module described below may be made | formed based on typical embodiment and specific example, this invention is not limited to this embodiment. In addition, in this specification, the numerical range shown using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

(Laminated body)

The laminated body of this invention has an adhesive layer, the surface layer laminated | stacked on one surface side of an adhesive layer, and the resin separator layer laminated | stacked on the surface side opposite to the surface where the surface layer was laminated as the other surface side of an adhesive layer. In addition, at least any one of an adhesive layer, a surface layer, and a separator layer has a layer whose surface electrical resistance is 1 * 10 <^5> -1 * 10 <^12> ohm / square. In addition, in this specification, the layer whose surface electric resistance is 1 * 10 <^5> -1 * 10 <^{12> (} ohm) / (square) shows that the surface electric resistance of either surface of the said layer should just be in the said range.

In this invention, the layer which comprises each layer of an adhesive layer, a surface layer, or a separator layer may have surface electrical resistance within the said range, and each layer itself of an adhesive layer, a surface layer, or a separator layer may have surface electrical resistance within the said range. Especially, it is preferable that at least one surface chosen from both surfaces of the adhesive film comprised from an adhesive layer and a surface layer, and both surfaces of a separator layer has surface electrical resistance within the said range.

In addition, any one of an adhesive layer, a surface layer, or a separator layer should just have surface electrical resistance in the said range, and two or more layers of the said layer may have surface electrical resistance in the said range. For example, an adhesive layer and a separator layer may have surface electrical resistance in the said range.

Since the laminated body of this invention has the said structure, mixing of a foreign material can be suppressed at the time of shaping | molding (at the time of TOM shaping | molding) under a vacuum condition or a reduced pressure condition. Moreover, since the separator layer which comprises the laminated body of this invention is a resin layer, when peeling a separator layer from a laminated body, it can suppress that a foreign material derived from a separator layer adheres to an adhesive layer. For this reason, it becomes possible to suppress mixing of a foreign material more effectively.

In the present invention, the surface electrical resistance of each layer is a value measured by Hirestar UX MCP-HT800 (manufactured by Mitsubishi Chemical Analytical Co., Ltd., measurement method: constant voltage application / leakage current measurement method).

1 is a cross-sectional view showing an example of the configuration of a laminate of the present invention. As shown in FIG. 1, the laminated body 1 of this invention is an adhesive layer 10, the surface layer 20 laminated | stacked on one surface side of the adhesive layer 10, and the other surface side of the adhesive layer 10. As shown in FIG. The separator layer 30 is laminated on the surface side opposite to the surface on which the surface layer 20 is laminated. Since the laminated body 1 has the separator layer 30, it is suppressed that foreign matters, such as dust, adhere to the surface of the adhesive layer 10 at the time of the storage of the laminated body 1, etc. When using the laminated body 1 of this invention, this separator layer 30 is peeled off and the adhesive layer 10 is exposed. And the adhesive layer 10 will adhere to the molded object which is a to-be-adhered body. In this specification, the laminated body from which the separator layer 30 peeled is called the adhesive film 5.

It is sectional drawing which shows the preferable structure of the laminated body of this invention. In the laminated body 1 of this invention, it is preferable that the surface layer 20 is a layer containing the surface protection layer 22 and the colored layer 24. As shown in FIG. In addition, it is preferable that the separator layer 30 is a layer containing the base material layer 32, the releasing agent layer 34, and the antistatic layer 36. As shown in FIG. The laminated body 1 of this invention may have layers other than the above-mentioned layer, the surface layer 20 may further be a structure which has an antistatic layer, and the adhesive layer may be a structure which has a colored layer or an antistatic layer.

Moreover, also in the laminated body 1 as shown in FIG. 2, after the separator layer 30 peels, it becomes the adhesive film 5. The present invention also relates to such an adhesive film.

Since the laminated body of this invention has the above structures, it may be a sheet form and may be wound up in roll shape. When winding up in roll shape, it is preferable to wind up so that a separator layer may be arrange | positioned at a core shaft side.

(Separator layer)

The laminated body of this invention contains a separator layer. The separator layer is made of resin and does not contain a paper substrate. By using such a separator layer, foreign matters, such as dust derived from paper, are prevented from getting caught between the laminate and the molded body, and the mixing of foreign matters can be effectively suppressed.

It is preferable that it is 1 * 10 <^5> -1 * 10 <^12> ohm / square, and, as for the surface electrical resistance of a separator layer, it is more preferable that it is 1 * 10 <^6> -1 * 10 <^12> ohm / square. In a laminated body, there exists a tendency for a foreign material to adhere to an adhesive layer by electrostatic interaction at the time of peeling a separator layer. However, in the present invention, by adhering the surface electrical resistance of the separator layer within the above range, adhesion of foreign matters can be suppressed, and in particular, the incorporation of foreign matters during molding under vacuum conditions or under reduced pressure conditions (TOM molding) can be more effectively suppressed. Can be. Moreover, this invention relates also to the separator laminated | stacked on the adhesive layer side of the adhesive sheet used for TOM shaping | molding.

The separator layer has a single layer configuration, and although the surface electrical resistance of the single layer may be in the above range, it is preferable that the surface electrical resistance has a layer in the above range. Specifically, the separator layer preferably has a base layer, a release agent layer laminated on one side of the base layer, and an antistatic layer laminated on the side opposite to the surface on which the release agent layer is laminated as the other side of the base layer. . Especially, it is preferable that the surface electrical resistance of an antistatic layer is 1 * 10 <^5> -1 * 10 <^12> ohm / square.

In this invention, it is preferable that a separator layer contains an antistatic agent, and it is preferable that an antistatic agent is not contained in the adhesive film comprised from a surface layer and an adhesive layer. In this invention, when using a laminated body, a separator layer peels from a laminated body and becomes an adhesive film comprised from a surface layer and an adhesive layer. And this adhesive film is stuck to the molded object which is a to-be-adhered body. That is, when only a separator layer contains an antistatic agent, an antistatic agent is not contained in a decorative molded object, and the durability of the whole decorative molded object becomes higher.

As shown in FIG. 2, it is preferable that the separator layer 30 is a layer containing the base material layer 32, the releasing agent layer 34, and the antistatic layer 36, and the antistatic layer 36 contains an antistatic agent. It is desirable to. The antistatic agent is preferably at least one kind selected from ionic antistatic agents, organic antistatic agents and inorganic antistatic agents, more preferably at least one kind selected from organic antistatic agents and inorganic antistatic agents, and particularly preferably inorganic antistatic agents. Do. The organic antistatic agent is more preferably a π conjugated conductive polymer antistatic agent. By using at least 1 type chosen from (pi) conjugated system conductive polymer antistatic agent and inorganic antistatic agent as an antistatic agent, the humidity dependence of antistatic performance can be suppressed. That is, antistatic performance can be exhibited in all humidity ranges. In particular, the inorganic antistatic agent can exhibit excellent antistatic performance even in a low humidity environment. In addition, since the ionic antistatic agent is relatively inexpensive, the manufacturing cost of the laminate can be suppressed.

As the ionic antistatic agent, any known ionic antistatic agent can be used in the present invention, but preferably glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Fatty alcohol ethers, alkylsulfonates, alkylbenzenesulfonates, tetraalkylammonium salts, trialkylbenzylammonium salts, monoglycerides stearates, N, N-bis (2-hydroxyethyl) alkylamines, N, N-bis (2- And hydroxyethyl) alkylamides, fatty acid esters of polyoxyethylene alkylamines, alkyl sulfates, alkyl phosphates, alkyl betaines, polystyrene sulfonic acid soda, polyethylene glycol methacrylate copolymers, and polyether ester amides.

As the organic antistatic agent, it is preferable to use a π-conjugated conductive polymer antistatic agent. As the π-conjugated conductive polymer antistatic agent, any known π-conjugated conductive polymer antistatic agent may be used in the present invention, but preferably polythiophene, polypyrrole, polyaniline, and the like, and particularly preferably poly Thiophene.

As the inorganic antistatic agent, any known inorganic antistatic agent may be used in the present invention, and preferably, ATO (antimony-doped tin oxide) filler, ITO (tin-doped indium oxide) filler, silver nano filler, antimony-doped tin oxide coated oxide Titanium etc. are mentioned, Especially preferably, it is a silver nano filler.

When an antistatic layer contains an antistatic agent, it is preferable that it is 2-100 mass% with respect to the total mass of an antistatic layer, and, as for content of an antistatic agent, it is more preferable that it is 50-100 mass%. Moreover, it is preferable that it is 0.001-1 g / m <2>, and, as for the application amount after drying of an antistatic agent layer, it is especially preferable that it is 0.01-0.2 g / m <2>.

It is preferable that the base material layer which comprises a separator layer is a resin layer, and it is preferable that a resin layer is comprised with a thermoplastic resin. Specifically, a polyolefin film, a polyvinyl chloride film, a polyvinyl alcohol film, a polyester film, a polycarbonate film, a polystyrene film, or a polyacrylonitrile film is mentioned as a base material layer. Especially, a polyester film is used preferably, A polyethylene terephthalate (PET) film is used especially preferably. Moreover, you may use the film to which the uneven | corrugated process, such as a lens film, a prism film, a hologram film, was given for the base material layer.

The release agent layer contains a release agent. As the release agent, for example, a general-purpose addition type or condensation type silicone release agent is used. In particular, a highly reactive addition type silicone release agent is preferably used. Specific examples of the silicone release agent include BY24-162, SD-7234 manufactured by Toray Dow Corning Silicone, KS-3600, KS-774, X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd., and the like. And also, SiO ₂ units in the silicone based releasing agent, (CH _{3) 3} SiO _1/2 units, or CH ₂ = CH (CH ₃₎ preferably contains a silicone resin organosilicon compound having a SiO _1/2 unit. As a specific example of silicone resin, Toray Dow Corning Silicone Co., Ltd. BY24-843, SD-7292, SHR-1404, etc., Shin-Etsu Chemical Co., Ltd. KS-3800, X92-183, etc. are mentioned.

Supplementary additives, such as a catalyst and an adhesion promoter, can be added to a releasing agent layer. Preferred examples of the catalyst include platinum and tin catalysts. Moreover, especially if adhesiveness improves adhesiveness, what kind of thing can be used, Any can be used, Preferably a silane coupling agent is mentioned.

It is preferable that it is 0.01-1 g / m <2>, and, as for the application amount after drying of a releasing agent layer, it is especially preferable that it is 0.05-0.2 g / m <2>.

A separator layer can be formed by apply | coating a peeling agent containing liquid and an antistatic agent containing liquid to a base material layer, and drying. When applying each solution, a size press coater, a gate roll coater, a bar coater, a roll coater, an air knife coater, a blade coater, a rod blade coater, a curtain coater, a gravure coater, etc. can be used. Especially, it is preferable to use the 2 head coater which can apply | coat a surface and a back surface once, and the 2 head coater which can coat the surface and back surface which have a gravure head which can control a small application amount is especially preferable. Thereby, a functional layer can be formed simultaneously on both surfaces of a base material layer, and the production efficiency of a separator layer can be improved.

(Adhesive layer)

The laminated body of this invention contains an adhesive layer. In this invention, a molded object can be decorated by affixing an adhesive layer on the surface of a molded object. Moreover, it is preferable that it is 1 * 10 <^5> -1 * 10 <^12> ohm / square, and, as for the surface electric resistance of an adhesive layer, it is more preferable that it is 1 * 10 <^6> -1 * 10 <^12> ohm / square.

The pressure-sensitive adhesive layer contains a polymer as the pressure-sensitive adhesive. Moreover, it is also preferable that an adhesive layer contains an antistatic agent. In particular, when the surface electrical resistance of a separator layer is not in the range of 1 * 10 <^5> -1 * 10 <^{12> (} ohm) / square, it is preferable that an adhesive layer contains an antistatic agent. As an antistatic agent which an adhesive layer contains, the thing similar to the antistatic agent which a separator layer can contain can be mentioned, A preferable antistatic agent is the same.

When an adhesive layer contains an antistatic agent, it is preferable that content of an antistatic agent is 0.1-10 mass% with respect to the total mass of an adhesive layer, It is more preferable that it is 0.5-7 mass%, It is 1-5 mass% More preferred.

It is preferable that the thickness of an adhesive layer is 5-500 micrometers, It is more preferable that it is 10-350 micrometers, It is further more preferable that it is 20-200 micrometers. By setting the thickness of the pressure-sensitive adhesive layer in the above range, even when foreign matter such as dust is mixed between the laminate and the molded body when forming the decorative molded body, it is possible to suppress the appearance of foreign matter on the surface. For this reason, if it is a minute foreign material, even if it mixes, it will not be affected.

It is preferable that it is 10,000-5,000,000, and, as for the average molecular weight of the polymer which comprises an adhesive layer, it is more preferable that it is 300,000-2,000,000. By carrying out the average molecular weight of a polymer in the said range, the followability to a molded object can be improved at the time of shaping | molding (TOM shaping | molding) under a vacuum condition or a reduced pressure condition, and the molded object of a complicated shape can also be decorated. Moreover, 2-30 are preferable and, as for the molecular weight distribution (Mw / Mn) of a polymer, it is especially preferable that it is 4-20. In order to obtain the target molecular weight distribution, two or more types of polymers from which an average molecular weight differs can be mixed and used.

By widening the molecular weight distribution of the polymer, the followability to the molded body can be increased during molding (TOM molding) under vacuum conditions or reduced pressure conditions, and molded articles of complex shapes can also be decorated.

As adhesive force of an adhesive layer, it is preferable that the adhesive force measured based on JISZ0337 is 10-100N / 25mm, It is more preferable that it is 25-75N / 25mm.

It is preferable that the polymer which comprises an adhesive layer contains at least 1 sort (s) of acryl-type polymer. In addition to the acrylic polymer, aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, dicyclopentadiene (DCPD) petroleum resins, coumaroneindene resins, and αmethylstyrene Styrene-based resin, rosin, rosin ester resin, terpene-based resin, aromatic modified terpene resin, terpene phenol resin, and hydrogenated resin containing these resin may be contained.

As a monomer unit which comprises an acryl-type polymer, an alkyl (meth) acrylate, a urethane (meth) acrylate, an epoxy (meth) acrylate, a polyester (meth) acrylate, a polyether (meth) acrylate, etc. are mentioned. Methyl methacrylate, n-butyl methacrylate, and iso-butyl methacrylate are mentioned preferably.

Moreover, in order to improve adhesive force, you may contain the following components as needed. For example, a component having a carboxyl group, preferably an acrylic acid, methacrylic acid, maleic acid, crotonic acid, crotonic acid, β-carboxyethylacrylate and / or a component having a hydroxyl group, preferably 2-hydroxyethyl ( Meta) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6 -Hydroxyhexyl (meth) acrylate, 8-hydrooctyl (meth) acrylate and / or copolymerizable unsaturated components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile, macromers Can be mentioned. The component which has these carboxyl groups, the component which has a hydroxyl group, and the component which can be copolymerized are 0.1-15 mass% of acrylic polymer, Preferably it is preferable that 1-10 mass% is contained.

The pressure-sensitive adhesive layer contains fillers, pigments, thickeners, viscosity modifiers, wetting agents, leveling agents, antifoaming agents, preservatives, dispersants, antioxidants, cryoprotectants, flame retardants, and the like, which are known additives, as necessary, in a range that does not inhibit the effects of the present invention. You can also do it.

(Surface layer)

The laminate of the present invention comprises a surface layer. Although the surface layer may be a single layer structure, it is preferable that it is a layer which has a surface protective layer containing a ultraviolet absorber, and a colored layer. In addition, it is preferable that a colored layer contains a pigment, dye, a metal, a metal oxide, etc. The colored layer may be a resin layer containing a pigment, a dye, a metal, or a metal oxide, or may be a vapor deposition, a sputter layer composed of a pigment, a dye, a metal, a metal oxide, or an ink layer containing a pigment, a dye, a metal, and a metal oxide. May be printed on the surface layer. In this case, you may call the printing part a colored layer (colored part). The printing method in this case is not particularly limited, and examples thereof include convex printing, offset printing, flexographic printing, gravure printing, inkjet printing, and the like. Examples of printing inks used for these printing include oxidation type oil type ink, soybean oil ink, vegetable oil ink and UV curing type UV ink, LED-UV ink, gravure ink, flexo ink, screen ink, etc. Gravure inks, screen inks and inkjet inks are particularly preferred. Additives, such as a pigment dispersant, an antifoamer, an ultraviolet absorber, antioxidant, an antistatic agent, an antiwear agent, and an antiblocking agent, may be added to printing ink as needed.

Moreover, when a colored layer is a resin layer containing a pigment, dye, a metal, and a metal oxide, it is preferable that a resin layer is comprised by the thermoplastic resin. Specifically, ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resin (copolymer of acrylonitrile and styrene), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, Polyphenylene oxide, Phenolic resin, Yuria resin, Melamine resin, Liquid crystalline polymer, Polytetrafluoroethylene, Polyvinylidene fluoride, Polysulfone, Polyether sulfone, Polyacetal, Polyether ether ketone, Polyphenylene sulfide, Polyether Mid, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin and the like are preferable.

As the pigment which the colored layer may contain, inorganic pigments (alumina white, titanium oxide, zinc oxide, black iron oxide, mica-like iron oxide, white lead, white carbon, molybdenum white, carbon black, lysa, lithopone, barite, cadmium Red, cadmium mercury red, bengal, molybdenum red, podium, sulfur lead, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chrome green, ultramarine blue, cobalt, cobalt Blue, cerulean blue, manganese purple, cobalt purple, etc.) and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyeing lakes, etc.), and also toluidine red, toluidine maroon, kanji yellow, Insoluble azo pigments such as benzidine yellow, pyrazolone red, soluble azo pigments such as litoli red, helio bordeaux, pigment scarlet, permanent red 2B, Derivatives such as lizarin, indanthrone and thioindigo maroon, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, quinacridone pigments such as quinacridone red and quinacridone magenta, perylene red, and perylene scarlet Isoindolinone pigments, such as a len pigment, isoindolinone yellow, and isoindolinone orange, imidazolone pigments, such as benzimidazolone yellow, benzimidazolone orange, and benzimidazolone red, and pyrantrone red , Pyrantrone pigments such as pyrantrone orange, thioindigo pigments, condensed azo pigments, diketopyrrolopyrrole pigments, prabangtron yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow And other pigments such as perinone orange, antron orange, dianthraquinonyl red, and dioxazine violet. In this invention, it is not limited to these, Any well-known pigment can be used.

Examples of the dye that the colored layer may contain include an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, or a food dye. In addition, any well-known dye can be used in this invention, It is not limited. Among these dyes, azo and phthalocyanine dyes are particularly preferable, and acid dyes, direct dyes, reactive dyes, food dyes and the like are particularly preferable.

As a metal layer which a colored layer may contain, aluminum, gold, silver, nickel, indium, etc. are mentioned.

A surface protective layer is a layer which comprises the outermost surface of a laminated body, and is a layer which comprises an outermost surface also in a decorative molded object. In particular, when decorating a member for which strength is required, such as automotive interior and exterior parts, it is required that the surface protective layer have damage difficulty, strength, and the like. It is preferable that pencil hardness is B or more, and, as for the surface protection layer in this invention, it is more preferable that it is F or more.

It is preferable that a surface protection layer is a resin layer. Specifically, ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resin (copolymer of acrylonitrile and styrene), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, Polyphenylene oxide, Phenolic resin, Yuria resin, Melamine resin, Liquid crystalline polymer, Polytetrafluoroethylene, Polyvinylidene fluoride, Polysulfone, Polyether sulfone, Polyacetal, Polyether ether ketone, Polyphenylene sulfide, Polyether Mid, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, etc. are mentioned preferably. More preferably, it is an acrylic resin from the point which is excellent in abrasion resistance. In addition, the surface protection layer of this invention may be an ionizing radiation hardening resin. An ionizing radiation hardening resin is resin hardened | cured by irradiating an electron beam or an ultraviolet-ray. In the present invention, the ionizing radiation curable resin is preferably substantially transparent. As the substantially transparent ionizing radiation curable resin, for example, acrylic ultraviolet curable resin is preferably used.

In the present invention, an antistatic agent may be included between the surface protective layer and / or the colored layer. In this case, the antistatic agent can use the same thing as the antistatic agent listed by the item of a separator layer.

(Molding under vacuum condition or reduced pressure (TOM molding))

It is preferable that the laminated body of this invention is used for shaping | molding under vacuum conditions or pressure reduction conditions. By using the laminated body of this invention, it can suppress that a foreign material, such as dust, mixes between an adhesive layer and a molded object in shaping | molding under a vacuum condition or a reduced pressure condition. Thus, the laminated body of this invention can exhibit the effect by being used for shaping | molding under a vacuum condition or a reduced pressure condition.

In this specification, shaping | molding under a vacuum condition or a reduced pressure condition is what is called TOM shaping | molding. In the TOM molding method, a step of laminating an adhesive film (laminated film of the surface layer and the pressure-sensitive adhesive layer) on the molded body under vacuum conditions or reduced pressure conditions, and a step of pressing the pressure-sensitive adhesive film on the molded body by a pressure difference. In addition, in this specification, the shaping | molding under a vacuum condition or a reduced pressure condition does not include the method which adhere | attaches an adhesive film and a molded object using what formed the vacuum hole in the molded object. Specifically, molding under vacuum conditions or reduced pressure conditions can be carried out by using the "vacuum molding apparatus" described in Japanese Patent No. 373564.

The present invention also relates to a method for producing a decorative molded body as described above. Specifically, the manufacturing method of the decorative molded object of this invention peels a separator layer from the laminated body mentioned above, and obtains the adhesive film which has a surface layer and an adhesive layer, and makes an adhesive film and a molded object adhere | attach under vacuum or reduced pressure conditions. The process and the process of crimping | bonding an adhesive film and a molded object under pressurization conditions are included. Moreover, in the manufacturing method of a decorative molded object, it is preferable to include the process of heating the surface of a laminated body to 100-180 degreeC, after the process of contact | adhering an adhesive film and a molded object. In this case, it is preferable to use an infrared heater for heating the surface of the laminate.

(Decorative molded body)

The present invention also relates to a decorative molded article comprising a pressure-sensitive adhesive film composed of the surface layer and the pressure-sensitive adhesive layer of the laminate as described above, and a molded body which is decorated with an adhesive film. The decorative molded body adheres an adhesive film to a part or the whole surface of the molded object. That is, in a decorative molded object, the surface layer is laminated | stacked through the adhesive layer.

3 is a cross-sectional view illustrating the configuration of the decorative molded body 100. FIG. 3 has shown that the molded object 50 which has a recessed part in the surface was decorated with the adhesive film 5. FIG. As shown in FIG. 3, in forming under a vacuum condition or a reduced pressure condition, the reverse tapered portion and the end curled portion can be coated and molded without forming a vacuum hole in the molded body 50. Moreover, it can decorate regardless of the material of a product. Thereby, it can also decorate the molded object surface which has a complicated three-dimensional unevenness | corrugation, and the decorative molded object 100 with high designability can be obtained.

Although the molded object 50 can mention metal materials, such as ED steel plate, Mg alloy, SUS, and an aluminum alloy, and a resin molded object, It is preferable that it is a resin molded object. For example, an acrylonitrile-butadiene-styrene copolymer (ABS resin), a polycarbonate containing resin, and a polyolefin resin can be illustrated preferably. As the polycarbonate-containing resin, a resin in which polycarbonate and polybutylene terephthalate are blended (PCPBT), a resin in which polycarbonate or ABS resin is blended (PCABS) or the like can be preferably used. Moreover, polypropylene (PP) can be used suitably as polyolefin resin.

In this invention, the shape of the molded object 50, ie, the shape of the object to which the adhesive film 5 is laminated | stacked, may be planar, substantially planar, or non-planar may be sufficient as it. For example, as shown in FIG. 3, the shape of the molded object 50 may be a shape which has a recessed part in the surface, or the shape (not shown) which has a convex part in the surface may be sufficient as it. As shown in FIG. 3, the molded object 50 may be a shape which has a reverse taper part and a terminal curl part. According to the present invention, even in the case of a non-planar shaped body which is likely to cause defects in its appearance, the incorporation of foreign matters can be suppressed and defects such as peeling can be prevented.

The decorative molded article obtained by the present invention may be, for example, an automobile part (for example, a body, a bumper, a spoiler, a mirror, a wheel, a interior material, or the like, which is of various materials), a component for a motorcycle, a road material ( For example, it can be used for traffic signs, soundproof walls, and the like, tunnel materials (for example, sidewall plates, etc.), railroad cars, furniture, musical instruments, home appliances, building materials, containers, office supplies, sporting goods, toys and the like.

Example

The features of the present invention will be described in more detail with reference to Examples and Comparative Examples. Materials, usage amounts, ratios, treatment contents, treatment procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the specific example shown below.

(Example 1)

In the clean room (class 1000), the acrylic pressure-sensitive adhesive (A) was applied onto the separate film (A) so that the thickness after drying was 25 µm. It dried over 90 minutes at 90 degreeC, and obtained the separator layer with an adhesive layer.

The adhesive layer surface and hard-coat film (A) of the obtained separator layer with an adhesive layer were bonded together in a clean room (class (1000) using the hard-coat film (A) as a surface protective layer (surface layer), and 23 degreeC). Aging was performed for 7 days in a 50% relative humidity environment. The laminate 1 was obtained in the same manner.

Next, in 23 degreeC and the environment of 50% of a relative humidity, and 15 degreeC and the environment of 30% of relative humidity, the following operation was performed respectively and the decorative molded object was obtained.

<Creation method of decorative molded object>

The separator layer was removed from the laminate 1 to obtain an adhesive film 1. The adhesive film 1 was set to a TOM molding machine. TOM molding machine (Fusion Vacuum Co., Ltd. product, NGF molding machine) so that a rainproof line cover (manufactured by ABS resin, manufactured by Panasonic Corporation, product number: WP9171) faces the outer surface (convex surface) side of the cover and the pressure-sensitive adhesive layer of the adhesive film (1). ). The decorative molded object 1 was obtained by laminating | stacking the adhesive film 1 on the said molded object at 130 degreeC using the TOM molding machine. In the same manner, ten decorative molded bodies 1 were created. Moreover, the shape of the said rainproof line cover is shown to FIG. 4 (a)-(c). As seen from above as shown in FIG.4 (a), the rainproof line cover shown to FIG.4 (a)-(c) has a length of 90 mm in the length (vertical) direction, and 60 mm of the length in the width (horizontal) direction. It was.

<Separate film (A)>

Glycerin monostearate was applied on one side of PET (Toray Co., Lumirror T60) having a thickness of 50 µm in a clean room (class 1000) so that the coating amount after drying was 0.1 g / m 2, and 130 ° C in a dryer. The treatment was carried out for 30 seconds. In this way, an antistatic layer was formed.

Next, on the opposite side, a release agent composed of 100 parts by mass of thermosetting silicone (Toray Dow Corning, LTC300B) and 1 part by mass of catalyst (Toray Dow Corning, SRX212) was 0.1 g / m 2 in weight after drying. It was applied in a clean room (class 1000). The dryer was processed for 130 second at 60 degreeC, and the release agent layer (A) was formed.

The separator film (A) (separator layer (A)) was obtained as mentioned above. As a result of measuring the surface electrical resistance of the separator film (A) on 23 degreeC and 50% of the relative humidity, the peeling agent layer side was 5 * 10 <^16> ohm / square, and the antistatic layer side was 7 * 10 <^11> ohm / square.

<Adhesive (A)>

65 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate, and 5 parts by mass of acrylic acid were added to a reaction vessel (with a temperature controller, agitator and reflux) in a nitrogen atmosphere, 200 parts by mass of ethyl acetate and 0.1 isobisisobutyronitrile A mass part was added, and polymerization reaction was performed at 75 degreeC for 10 hours, and polymer (A) was obtained. The molecular weight (Mw) of the obtained polymer (A) was measured by GPC (gel permeation chromatography) and found to be 800,000. Moreover, it was -25 degreeC when the glass transition temperature (Tg) of the polymer (A) was measured with the differential operation type calorimeter (SEIKO Instruments DSC-6100).

Obtained polymer (A), poly (alpha) styrene (molecular weight Mw = 850,000, Tg = 105 degreeC, Wako Pure Chemical Industries Ltd.), and a crosslinking agent (Mitsubishi Gas Chemical Company make, Tetrad X) so that a dry weight ratio may be 98: 10: 2. It mix | blended and obtained the adhesive (A). The molecular weight distribution of the adhesive (A) was 6.5. In addition, molecular weight and molecular weight distribution were measured by GPC.

It was 2 * 10 <^{15> (} ohm) / square as a result of measuring the surface electric resistance on 23 degreeC and 50% of relative humidity of the adhesive layer which apply | coated the adhesive (A) and formed.

<Hard coat-like film (A)>

A hard coat film (A) was used as the surface protective layer. As hard coat-like film (A), Mitsubishi Rayon Co., Ltd. product and acriprene HBA001P were used. The pencil hardness of this film was 2H and the thickness was 125 micrometers. The surface electrical resistance in 23 degreeC and a 50% relative humidity environment was 2x10 <^{16> (} ohm) / square in both surfaces.

(Example 2)

The decorative molded object 2 was obtained like Example 1 except having used the adhesive (B) instead of the adhesive (A). The results are shown in Table 1.

<Adhesive (B)>

65 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate and 5 parts by mass of 2-hydroxyethyl acrylate were added to a reaction vessel (with a temperature controller, agitator and reflux) in a nitrogen atmosphere, 200 parts by mass of ethyl acetate and aso 0.1 mass part of bisisobutyronitrile were added, and the polymerization reaction was performed at 75 degreeC for 10 hours, and polymer (B1) was obtained. The molecular weight (Mw) and Tg of the obtained polymer (B) were measured in the same manner as in Example 1, and the molecular weight Mw = 800,000 and Tg = -35 ° C.

Next, 90 parts by mass of methyl methacrylate and 10 parts by mass of dimethylaminoethyl methacrylate were added to a reaction vessel in a nitrogen atmosphere, 200 parts by mass of ethyl acetate and 2 parts by mass of asobisisobutyronitrile were added, and the mixture was at 75 ° C. The polymerization reaction was carried out for 10 hours to obtain a polymer (B2). As a result of measuring similarly, only molecular weight Mw = 1 and Tg = 95 degreeC.

The obtained polymer (B1), the polymer (B2), the crosslinking agent (made by Mitsubishi Gas Chemical Co., Ltd., tetrad X), and bistrifluoromethanesulfonimide were mix | blended so that it might be 46: 40: 2: 2 by dry weight ratio, and an adhesive (B) was obtained. The molecular weight distribution of the adhesive (B) was 18. It was 7 * 10 <^{10> (} ohm) / (square) as a result of measuring the surface electric resistance on 23 degreeC of 50 degreeC and 50% of relative humidity of the adhesive layer which apply | coated the adhesive (B) and formed.

(Example 3)

The decorative molded body 3 was obtained like Example 2 except having used the separate film (B) instead of the separate film (A). The results are shown in Table 1.

<Separate film (B)>

Release agent consisting of 100 parts by mass of thermosetting silicone (Toray Dow Corning, LTC300B) and 1 part by mass of catalyst (Toray Dow Corning, SRX212) on one surface of PET (Toray Co., Lumirror T60) having a thickness of 38 µm. Was applied so as to be 0.1 g / m 2 by the weight after drying. The dryer was processed for 130 second at 60 degreeC, and the release agent layer (B) was formed.

In the same manner as above, a separator film (B) (separator layer (B)) was obtained. As a result of measuring surface electric resistance on 23 degreeC and 50% of relative humidity, the peeling agent layer side was 5 * 10 <^16> ohm / square, and the non-peeling agent layer side was 5 * 10 <^16> ohm / square.

(Example 4)

100-micrometer-thick PET-B (organic antistatic agent mixing grade PET film) (Toray Co., Lumirror X53) was used instead of the hard coatable film (A). The surface electrical resistance of PET-B at 23 ° C. and 50% relative humidity was 1 × 10 ¹⁰ Ω / □. In addition, a separate film (B) was used instead of the separate film (A). A decorative molded body 4 was obtained in the same manner as in Example 1 except for the above.

(Example 5)

The decorated molded article 5 was obtained in the same manner as in Example 1 except that the separator film (C) was used instead of the separator film (A) and the adhesive (C) was used instead of the adhesive (A). The results are shown in Table 1.

<Separate film (C)>

Denatron P-502S (manufactured by Nagase Chemtex) containing poly (3,4-ethylenedioxythiophene), which is a π-conjugated organic conductive material, on one surface of PET (Toray Co., Lumirror T60) having a thickness of 38 µm. ) Was applied in a clean room (class 1000) so that the coating amount after drying was 0.07 g / m 2, and treatment was performed at 130 ° C. for 30 seconds in a dryer. In this way, an antistatic layer was formed.

Next, clean the release agent which consists of 100 mass parts of thermosetting silicones (Toray Dow Corning, LTC300B) and 1 mass part of catalysts (Toray Dow Corning, SRX212) on an opposite surface so that it may become 0.1 g / m <2> by the weight after drying. Application was made in a room (class 1000). The dryer was processed for 130 second at 60 degreeC, and the release agent layer (C) was formed.

In the same manner as above, a separator film (C) (separator layer (C)) was obtained. As a result of measuring surface electric resistance on 23 degreeC and 50% of relative humidity, the peeling agent layer side was 5 * 10 <^16> ohm / square, and the antistatic layer side was 3 * 10 <^9> ohm / square.

<Adhesive (C)>

30 parts by mass of butyl acrylate, 30 parts by mass of 2-ethylhexyl acrylate, 35 parts by αmethylstyrene, and 5 parts by mass of 2-hydroxyethyl acrylate were added to a reaction vessel (with a temperature controller, agitator and reflux) in a nitrogen atmosphere. Then, 200 mass parts of ethyl acetate and 0.1 mass part of asobisisobutyronitrile were added, and the polymerization reaction was performed at 75 degreeC for 10 hours, and polymer (C) was obtained. The molecular weight (Mw) and Tg of the obtained polymer (C) were measured in the same manner as in Example 1, and the molecular weight Mw was 1,500,000 and Tg was 5 占 폚.

The obtained polymer (C) and crosslinking agent (Japan Polyurethanes, Colonate L) were mix | blended so that it might become 95: 5 by dry weight ratio, and the adhesive (C) was obtained. The molecular weight distribution of the adhesive (C) was 4.5. It was 7 * 10 <^{10> (} ohm) / (square) as a result of measuring surface electrical resistance on 23 degreeC of 50 degreeC of adhesive layers formed by apply | coating an adhesive (C), and 50% of relative humidity conditions.

(Example 6)

Ink (OS-M [NL], manufactured by Dainichi Seika) was applied to the entire surface of the back surface of the hard coat film A so that the thickness after drying was 5 µm, and the colored layer (ink layer) was applied. The formed surface layer was produced. The decorative molded body 6 was obtained like Example 1 except having used this surface layer. The results are shown in Table 1.

(Example 7)

The decorative molded body 7 was obtained like Example 6 except having used the separate film (C) instead of the separate film (A). The results are shown in Table 1.

(Example 8)

The decorative molded body 8 was obtained like Example 6 except having used the separate film (D) instead of the separate film (A). The results are shown in Table 1.

<Separate film (D)>

Dry a silver nanowire (CST-NW-S40, Coldstones) and a polyester binder (Pes resin A-645GH, Takamatsu oils and fats) on one side of PET (Toray Co., Lumirror T60) of thickness 50micrometer. The antistatic layer (D) which is mix | blended in 20:80 by the following weight was apply | coated in the clean room (class 1000) so that the coating amount after drying might be 0.01 g / m <2>, and it processed by 130 degreeC and 30 second in the dryer. In this way, an antistatic layer was formed.

Next, on the opposite side, the release agent which consists of 100 mass parts of thermosetting silicones (made by Toray Dow Corning, LTC300B) and 1 mass part of catalysts (made by Toray Dow Corning, SRX212) is clean so that it may become 0.1 g / m <2> by the weight after drying. Application was made in a room (class 1000). The dryer was processed for 130 second at 60 degreeC, and the release agent layer (D) was formed.

In the same manner as above, a separator film (D) (separator layer (D)) was obtained. When the surface electric resistance was measured on 23 degreeC and 50% of relative humidity conditions, the peeling agent layer side: 5 * 10 <^{16> (} ohm) / (square), and antistatic layer side: 6 * 10 <^{6> (} ohm) / (square).

(Example 9)

Instead of the hard coatable film (A), the surface layer which performed indium vapor deposition (thickness: 30 nm) on the back surface of reverse molding PET (soft shine TA009, Toyobo Co., Ltd.) was used, and instead of adhesive (A), adhesive (C) A decorative molded body 9 was obtained in the same manner as in Example 1 except that was used. The results are shown in Table 1.

(Comparative Example 1)

The decorative molded body 11 was obtained like Example 1 except having used the separate film (B) instead of the separate film (A). The results are shown in Table 1.

(Comparative Example 2)

The decorative molded body 12 was obtained like Example 1 except having used the adhesive (C) instead of the adhesive (A). The results are shown in Table 1.

(Comparative Example 3)

The decorative molded object 13 was obtained like Example 1 except having used the film (C) instead of the hard coatable film (A). The results are shown in Table 1.

(Comparative Example 4)

A decorative molded body 14 was obtained in the same manner as in Comparative Example 3 except that an adhesive (C) was used instead of the adhesive (A). The results are shown in Table 1.

(Comparative Example 5)

The decorative molded body 15 was obtained like Example 1 except having used separate paper (E) (Ojita Co., Ltd. single-sided polyethylene laminate paper separator (brand name: L6W)) instead of the separate film (A). The results are shown in Table 1.

(Comparative Example 6)

The decorative molded object 16 was obtained like Example 6 except having used separate paper (E) instead of the separate film (A). The results are shown in Table 1.

(Comparative Example 7)

The decorative molded object 17 was obtained like Example 9 except having used the separate film (B) instead of the separate film (A). The results are shown in Table 1.

(evaluation)

(Number of defects)

The surface of the decorative molded object shape | molded in 23 degreeC and the environment of 50% of a relative humidity was observed, and the defect number which swollen in convex shape of the surface was measured. The upper surface (the area corresponding to the upper surface of Fig. 4 (a)) of the decorated molded body obtained in each Example and Comparative Example was observed with a laser microscope (VK-X100, manufactured by Keyence). It was measured. In addition, the number of defects is an average value of the number of defects of the same area | region of ten decorative molded objects produced | generated similarly in each Example and each comparative example.

(Defect number under low humidity environment)

The surface of the decorated molded object molded in 15 degreeC and the environment of 30% of a relative humidity was observed by the same method as the above, the number of defects was measured, and the average value was calculated | required.

(durability)

<Xenon test>

The decorative molded body was treated with a weather resistance tester (xenon weather meter, model: XL75, manufactured by Suga Tester) for 2,000 hours, and visually compared with the untreated decorative molded object and appearance, and evaluated according to the following evaluation criteria. .

(Circle): There is no difference in appearance from an untreated decorative molded object.

(Triangle | delta): A part of the surface of a decorative molded object is whitened compared with the unprocessed decorative molded object.

X: The whole surface of the surface of a decorative molded object is white compared with the unprocessed decorative molded object.

(durability)

<Neck gloves friction test>

10 reciprocating friction of the decorated molded body with a hand wearing a ranch, and visually confirmed the presence of scratches.

(Circle): There is no flaw at all.

(Triangle | delta): Some scratches generate | occur | produce.

X: Many scratches generate | occur | produced.

In the decorative molded body obtained in the Example, it turns out that the number of defects is reduced. In particular, when the laminated body whose surface electrical resistance value of a separator layer is a predetermined range was used, it turns out that it is excellent in durability.

One… Laminated body, 5... Adhesive film, 10.. Pressure-sensitive adhesive layer, 20. Surface layer, 22... Surface protective layer, 24... Colored layer, 30... Separator layer, 32... Substrate layer, 34... Release agent layer, 36... Antistatic layer, 50... Molded object, 100... Decorative molded body

Claims (12)

It has an adhesive layer, the surface layer laminated | stacked on one surface side of the said adhesive layer, and the resin separator layer laminated | stacked on the surface side opposite to the surface where the said surface layer was laminated as the other surface side of the said adhesive layer,
At least one of the said adhesive layer, the said surface layer, and the said separator layer has a layer whose surface electrical resistance is 1 * 10 <^5> -1 * 10 <^12> ohm / square,
The pressure-sensitive adhesive layer includes a polymer having an average molecular weight of 10,000 to 5,000,000 and a molecular weight distribution (Mw / Mn) of 2 to 30,
The adhesive force of the said adhesive layer is 10-100N / 25mm, The laminated body characterized by the above-mentioned. The method of claim 1,
The separator layer has a layer having a surface electric resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □. The method according to claim 1 or 2,
The separator layer has a substrate layer, a release agent layer laminated on one surface side of the substrate layer, and an antistatic layer laminated on the surface side opposite to the surface on which the release agent layer is laminated as the other surface side of the substrate layer. The laminated body whose surface electrical resistance of a protective layer is 1 * 10 <^5> -1 * 10 <^12> ohm / square. The method of claim 3, wherein
The antistatic layer is a laminate comprising an inorganic antistatic agent. The method according to claim 1 or 2,
The laminated body whose surface electrical resistance of the said adhesive layer is 1 * 10 <^5> -1 * 10 <^{12> (} ohm) / square. The method of claim 5,
The pressure-sensitive adhesive layer is a laminate comprising an inorganic antistatic agent. The method according to claim 1 or 2,
The said surface layer is a laminated body which has a surface protective layer containing a ultraviolet absorber, and a colored layer. The method according to claim 1 or 2,
The laminated body used for shaping | molding under a vacuum condition or a reduced pressure condition. The decorative molded object containing the adhesive film which consists of a surface layer and an adhesive layer of the laminated body of Claim 1, and the molded object decorated with the said adhesive film. The method of claim 9,
The decorative molded body of the said molded object is a non-planar shape. As a method of manufacturing a decorative molded body using a laminate,
The said laminated body has an adhesive layer, the surface layer laminated | stacked on one surface side of the said adhesive layer, and the resin separator layer laminated | stacked on the surface side opposite to the surface where the said surface layer was laminated as the other surface side of the said adhesive layer,
At least one of the said adhesive layer, the said surface layer, and the said separator layer has a layer whose surface electrical resistance is 1 * 10 <^5> -1 * 10 <^12> ohm / square,
Peeling a separator layer from the said laminated body, and obtaining the adhesive film which has a surface layer and an adhesive layer,
Laminating the pressure-sensitive adhesive film on a molded body under vacuum or reduced pressure;
A step of pressing the pressure-sensitive adhesive film onto the molded body by a pressure difference,
The pressure-sensitive adhesive layer includes a polymer having an average molecular weight of 10,000 to 5,000,000 and a molecular weight distribution (Mw / Mn) of 2 to 30,
The adhesive force of the said adhesive layer is 10-100N / 25mm, The manufacturing method of the decorative molded object characterized by the above-mentioned. An adhesive layer,
Has a surface layer laminated on one side of the pressure-sensitive adhesive layer,
At least one of the pressure-sensitive adhesive layer and the surface layer has a layer having a surface electrical resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □,
The pressure-sensitive adhesive layer includes a polymer having an average molecular weight of 10,000 to 5,000,000 and a molecular weight distribution (Mw / Mn) of 2 to 30,
The adhesive force of the said adhesive layer is 10-100N / 25mm, The adhesive film characterized by the above-mentioned.

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