TW201706130A - Pressure-sensitive adhesive film, laminate, and decorative molded article - Google Patents

Abstract

This invention provides a pressure-sensitive adhesive film, capable of inhibiting bubbling occurring in the adhesive layer when a TOM molding is carried out. Specifically, this invention relates to a pressure-sensitive adhesive film, characterized by comprising: an adhesive layer, and a decorative layer laminated on one side of the adhesive layer, wherein the volatile substance contained in the adhesive layer is less than 50 ppm.

Description

Adhesive film, laminated body and decorative molded body

The present invention relates to an adhesive film, a laminate, and a decorative molded article.

The present application claims priority from Japanese Patent Application No. 2015-120042, filed on Jun. 15, 2015, the content of which is hereby incorporated by reference.

When protecting the surface of automotive interior and exterior parts, home appliance parts, building materials parts, etc., or decorating (decorating), it is necessary to apply a spray to the molded body by injection molding or vacuum forming. The coating is applied to the surface of the molded body, followed by drying and heat hardening. However, in addition to the problem that the discharge of the volatile organic solvent causes the work environment to deteriorate, such a coating process is necessary for each molded part, and the production equipment becomes necessary, and the overlapping coating of the paint becomes necessary. The problem of poor yield and low productivity of the coating.

In recent years, the use of a resin molded body has been developed as a molded body for the purpose of reducing the weight of interior and exterior parts of automobiles, parts for home appliances, and parts for building materials. In many cases, the decoration (decoration) of the resin molded body is not applicable to spray coating, and various methods have been developed for decorating the surface of the resin molded body. Among them, the decorative film is used to decorate the outermost surface of the formed body. The method of decorating a molded body has an advantage of high design freedom and excellent productivity compared to a method of coating or printing on a surface using a paint or the like. Further, the decorative method of the decorative film can also be used to decorate the surface of the molded body having the three-dimensional unevenness, and thus it can be used for various purposes.

A method of decorating a surface of a molded body having a three-dimensional unevenness by a decorative film is a three-dimensional coating forming (TOM forming) method (Patent Document 1). The forming method of the TOM forming system under vacuum conditions or under reduced pressure is a method of obtaining a decorative molded body by pressure-bonding a decorative film and a molded body. The TOM forming system can be decorated without depending on the material of the molded body. Further, in the molded body, the vacuum pressing hole is not provided, and the reverse push-out portion and the end winding portion can be formed.

The decorative film used for TOM molding is an adhesive film in which an adhesive layer or an adhesive layer is laminated on a decorative layer. When a decorative molded body is obtained by using a film having a decorative layer and an adhesive layer, an adhesive for obtaining adhesiveness by heating at the time of TOM molding is used, and a decorative layer is attached to the adherend. Further, when an adhesive film having a decorative layer and an adhesive layer is used, the adhesive film is adhered to the molded body by the adhesive force of the adhesive layer.

The adhesive which constitutes the adhesive layer is generally a solvent-based adhesive, but the use of the ultraviolet-curable adhesive is also reviewed. For example, Patent Document 2 discloses a decorative sheet having a decorative layer and an optional radiation-curable adhesive layer. Here, the free-radiation-curable adhesive layer has a property of being able to perform preliminary adhesion for a certain period of time, and the polymerization of the monomer component constituting the adhesive is carried out over time.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent No. 3733564

Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-142107

As described above, when an adhesive film having a decorative layer and an adhesive layer is used as a decorative film, a solvent-based adhesive is often used as the adhesive layer. However, when a solvent-based adhesive is used, there is a problem that the adhesive layer is easily foamed.

In addition, in the case of using the ultraviolet curable adhesive in the adhesive layer, the inventors of the present invention have found that when the decorative film of Patent Document 2 is used for TOM molding, it is easy to apply after preliminary adhesion. The foam deteriorates the yield of the decorative molded body and the like.

In order to solve the problem of the prior art, the inventors of the present invention have reviewed the purpose of suppressing the foaming of the adhesive layer from the adhesive layer.

In order to solve the above problems, the inventors have found that in the adhesive film having the decorative layer and the adhesive layer, by setting the volatile component contained in the adhesive layer to a certain level or less, when performing TOM forming The foaming can be suppressed.

Specifically, the present invention has the following constitution.

[1] An adhesive film comprising: an adhesive layer; and a decorative layer laminated on one side of the adhesive layer, and the volatile substance contained in the adhesive layer is less than 50 ppm.

[2] The adhesive film according to [1], wherein the adhesive constituting the adhesive layer is an ultraviolet curable adhesive.

[3] The adhesive film according to [1] or [2], wherein the volatile substance is a monomer constituting a component constituting the adhesive layer of the adhesive layer, and an adhesive component constituting the adhesive layer. At least one of the oligomers is selected.

[4] The adhesive film according to any one of [1] to [3] wherein the adhesive constituting the adhesive layer contains a (meth) acrylate monomer unit.

[5] The adhesive film according to any one of [1] to [4] wherein the thickness of the adhesive layer is 20 μm or more.

[6] The adhesive film according to any one of [1] to [5] wherein the thickness of the decorative layer is 75 μm or more.

[7] The adhesive film according to any one of [1] to [6], which is used for molding under vacuum or under reduced pressure.

[8] A laminate comprising: an adhesive layer, a decorative layer laminated on one side of the adhesive layer, and a separator layer laminated on the other side of the adhesive layer and on the back side of the layer on which the decorative layer is deposited; Among them, the volatile substance contained in the adhesive layer is less than 50 ppm.

[9] The laminate according to the above aspect, wherein at least one of the adhesive layer, the decorative layer and the separator layer has a layer having a surface resistance of from 1 × 10 ⁵ to 1 × 10 ¹² Ω/□.

[10] The laminate according to [8], wherein the separator layer has a layer having a surface resistance of from 1 × 10 ⁵ to 1 × 10 ¹² Ω/□.

[11] A decorative molded article comprising: the adhesive described in any one of [1] to [7] A film, and a molded body decorated with an adhesive film.

[12] A method for producing a decorative molded body, comprising: laminating an adhesive film on a molded body under vacuum or reduced pressure; and crimping the adhesive film to the formed body by using a gas pressure difference The adhesive film is provided with an adhesive layer and a decorative layer laminated on one side of the adhesive layer, and the volatile substance contained in the adhesive layer is less than 50 ppm.

According to the present invention, it is possible to obtain an adhesive film capable of suppressing foaming from the adhesive layer when performing TOM molding. Therefore, when the adhesive film of the present invention is used, the productivity of the decorative molded article can be improved, and a decorative molded article excellent in design can be obtained.

20‧‧‧Adhesive film

22‧‧‧Decorative layer

24‧‧‧Adhesive layer

26‧‧‧Separator layer

30‧‧‧Layered body

32‧‧‧Surface protection layer

34‧‧‧Color layer

42‧‧‧Substrate layer

44‧‧‧ Stripper layer

46‧‧‧Antistatic layer

50‧‧‧Formed body

100‧‧‧Decorative molded body

Fig. 1 is a cross-sectional view showing an example of the structure of an adhesive film of the present invention.

2(a) and 2(b) are cross-sectional views showing the structure of a laminate of the present invention.

Fig. 3 is a cross-sectional view showing the structure of a decorative molded body of the present invention.

Fig. 4 is a view showing a molded body used in Examples and Comparative Examples. 4(a) is a plan view, FIG. 4(b) is a right side view, and FIG. 4(c) is a bottom view.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below is based on representative embodiments and specific examples, but the present invention is not limited to the embodiments. In addition, in this specification, the numerical range represented by "~" means the range which has the lower-limit and upper-limit-

(adhesive film)

The adhesive film of the present invention has an adhesive layer and a decorative layer laminated on one surface side of the adhesive layer. The volatile matter contained in the adhesive layer is less than 50 ppm. The volatile matter contained in the adhesive layer is preferably less than 30 ppm, more preferably 15 ppm or less, and particularly preferably 5 ppm or less. Here, the volatile substance means a substance which is volatilized under vacuum at 150 °C. Further, the adhesive film of the present invention refers to a film before TOM molding adhered to a target (molded body), and the present invention is characterized in that the volatile matter content in the adhesive film before bonding is as described above. Within the scope.

The volatile substance is, for example, at least one selected from the group consisting of a solvent, a monomer which is an adhesive component constituting the pressure-sensitive adhesive layer, and an oligomer which is an adhesive component constituting the pressure-sensitive adhesive layer. Further, the oligomer which is a constituent component of the adhesive is formed by polymerizing 2 to 5 monomers which are constituent components of the adhesive.

Since the adhesive film of the present invention has the above-described configuration, foaming of the adhesive layer can be suppressed when it is molded under vacuum or under reduced pressure (when TOM is molded). Moreover, since the adhesive film of the present invention can exhibit excellent adhesion to a molded article belonging to a target to be adhered, it is preferable to use a pressure-sensitive adhesive film for molding under vacuum or under reduced pressure.

Fig. 1 is a cross-sectional view showing an example of the structure of an adhesive film of the present invention. As shown in FIG. 1, the adhesive film 20 of the present invention has a decorative layer 22 and an adhesive layer 24. The adhesive layer 24 is laminated on one side of the decorative layer 22. In the adhesive film 20, the adhesive layer 24 is adhered to the surface of the molded body belonging to the object to be adhered, and the decorative film can be formed. body.

In the adhesive film of the present invention, the thickness of the adhesive layer is preferably 20 μm or more, more preferably 35 μm or more, particularly preferably 70 μm or more, and most preferably 150 μm or more. In the present invention, by setting the thickness of the pressure-sensitive adhesive layer within the above range, even if the adhesive layer is bitten with foreign matter, the foreign matter shape can be suppressed from floating on the surface of the decorative molded body. Therefore, if it is a tiny foreign object or air bubble, even if it is bitten, it will not be affected.

Further, the thickness of the decorative layer is preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 180 μm or more. In the present invention, by setting the thickness of the decorative layer within the above range, even if the adhesive layer is immersed in foreign matter, the shape of the foreign matter can be suppressed from floating on the surface of the decorative molded body.

(adhesive layer)

The adhesive constituting the adhesive layer is preferably an ultraviolet curable adhesive (UV curable adhesive), and more preferably an acrylic ultraviolet curable adhesive. The ultraviolet curable adhesive is, for example, a solventless adhesive containing an acrylic monomer and/or an acrylic oligomer and a photopolymerization initiator.

The adhesive constituting the adhesive layer preferably contains a (meth) acrylate monomer unit as a unit constituting the acrylic polymer. Here, the term "unit" means a repeating unit (monomer unit) constituting a polymer. Moreover, "(meth)acrylic" means both "acrylic" and "methacrylic".

Examples of the (meth) acrylate single system include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). N-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl (meth)acrylate P-hexyl ester, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, ( Isodecyl methacrylate, n-undecyl (meth) acrylate, lauryl (meth) acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, ( Isostearyl methacrylate, (meth) acrylate Ester, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, and the like. These may be used alone or in combination of two or more.

Among them, it is preferred to use at least 1 selected from the group consisting of methyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Kind.

Further, the following components may be contained as needed. For example: ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(a) Acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol diacrylate, polybutylene glycol di(meth)acrylate, neopentyl glycol di(a) Acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like. Further, for example, a component having a carboxyl group is preferably acrylic acid, methacrylic acid, maleic acid, crotonic acid, or β-carboxyethyl acrylate; and/or a component having a hydroxyl group, preferably 2-hydroxyl Ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate; and/or copolymerizable unsaturated component, preferably acrylamide, methacrylamide, vinyl acetate , (meth)acrylonitrile, macromer. The component having a carboxyl group, the component having a hydroxyl group, and the component copolymerizable are preferably 0.1 to 30% by mass, more preferably 1 to 10% by mass, based on the acrylic polymer.

The adhesive constituting the adhesive layer preferably contains monomers and/or oligomers exemplified as the unit constituting the acrylic polymer. The monomer and/or oligomer is preferably 30 to 98% by mass, more preferably 70 to 95% by mass based on the total mass of the adhesive layer. By setting the compounding amount of the monomer and/or the oligomer within the above range, the viscosity of the adhesive can be easily adjusted to a desired range, and the adhesive layer can be formed by coating.

Further, the adhesive constituting the pressure-sensitive adhesive layer may contain, in addition to the acrylic polymer, an aliphatic (C5) petroleum resin, an aromatic (C9) petroleum resin, a copolymerized (C5/C9) petroleum resin, and Cyclopentadiene (DCPD) petroleum resin, benzofuran-indene resin, styrene resin containing α-methyl styrene resin, rosin, rosin ester resin, terpene resin, aromatic modified terpene The resin, the terpene phenol resin, and the hydrogenated resin or the like are preferably contained in the adhesive in an amount of from 0 to 40% by mass, more preferably from 10 to 25% by mass.

The adhesive constituting the adhesive layer preferably contains 0.1 to 10% by mass of the polymerization initiator, and more preferably 0.5 to 5% by mass. The polymerization initiator is preferably a photopolymerization initiator. The polymerization initiator may, for example, be an acetophenone-based initiator, a benzoin ether-based initiator, a diphenylketone-based initiator, a hydroxyalkylphenone-based initiator, or a 9-oxosulfuric acid. An initiator, an amine initiator, a sulfhydryl phosphine oxide initiator, and the like.

Specific examples of the acetophenone-based initiator include diethoxyacetophenone and benzyldimethylketal.

Specific examples of the benzoin ether-based initiator include benzoin and benzoin methyl ether.

Specific examples of the diphenyl ketone-based initiator include diphenyl ketone and methyl phthalic acid benzoate.

Specific examples of the hydroxyalkylphenone-based initiator include 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

9-oxygen sulfur Specific examples of the initiator include 2-isopropyl 9-oxosulfur 2,4-dimethyl 9-oxosulfur Wait.

Specific examples of the amine-based initiator include triethanolamine and ethyl 4-dimethylbenzoate.

Specific examples of the fluorenylphosphine oxide-based initiator include 2,4,6-trimethylbenzimidium-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzhydrazide). - phenylphosphine oxide or the like.

In the adhesive layer, a crosslinking agent, a chain transfer agent, a sensitizer, a photostabilizer, a filler, a pigment, and a tackifier which are known additives may be contained as needed within the range which does not impair the effects of the present invention. , viscosity modifier, wetting agent, leveling agent, defoamer, preservative, dispersant, antioxidant, antifreeze, flame retardant, etc.

The average molecular weight of the acrylic polymer constituting the adhesive layer is preferably from 10,000 to 5,000,000, more preferably from 300,000 to 3,000,000, and particularly preferably from 700,000 to 2.5 million. When the average molecular weight of the acrylic polymer is within the above range, when it is molded under vacuum or under reduced pressure (TOM molding), the traceability to the molded body can be improved, and the molded body having a complicated shape can be decorated. . Further, the molecular weight distribution (Mw/Mn) of the acrylic polymer is preferably 1~30, better 1~20, especially good 1~6. In order to obtain the target molecular weight distribution, two or more polymers having different average molecular weights may be used in combination.

By expanding the molecular weight distribution of the acrylic polymer, when it is molded under vacuum or under reduced pressure (TOM molding), the traceability to the molded body can be improved, and a molded body having a complicated shape can be decorated.

The surface resistance of the adhesive layer is preferably 1 × 10 ⁵ to 1 × 10 ¹² Ω / □, more preferably 1 × 10 ⁶ to 1 × 10 ¹² Ω / □. In particular, when the surface resistance of the separator layer to be described later is not in the range of 1 × 10 ⁵ to 1 × 10 ¹² Ω/□, the surface resistance of the pressure-sensitive adhesive layer is preferably within the above range. Further, the surface resistance of the adhesive layer may be such that the surface resistance of either surface is within the above range.

In order to set the surface resistance of the adhesive layer to 1 × 10 ⁵ to 1 × 10 ¹² Ω/□, the adhesive layer preferably contains an antistatic agent. In particular, when the surface resistance of the separator layer to be described later is not in the range of 1 × 10 ⁵ to 1 × 10 ¹² Ω / □, the pressure-sensitive adhesive layer preferably contains an antistatic agent. The antistatic agent contained in the adhesive layer is the same as the antistatic agent which can be contained in the separator layer described later, and the preferred antistatic agent is also the same.

Further, the surface resistance of the adhesive layer can be measured by Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Analytech Co., Ltd., measurement method: plus constant voltage/leak current measurement method).

When the adhesive layer contains an antistatic agent, the content of the antistatic agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 7 mass%, and particularly preferably 1 to 5, based on the total mass of the adhesive layer. quality%.

The adhesive force of the adhesive layer is preferably 10 to 200 N/25 mm, more preferably 25 to 100 N/25 mm, as measured according to JIS Z 0237.

(decorative layer)

The laminate system of the present invention contains a decorative layer. The decorative layer may be a single layer, but is preferably a layer having a surface protective layer containing an ultraviolet absorber and a colored layer. Further, the colored layer preferably contains a pigment, a dye, a metal, a metal oxide or the like. The colored layer may be a resin layer containing a pigment, a dye, a metal, or a metal oxide, or may be an evaporation coating or a sputtering layer composed of a pigment, a dye, a metal, or a metal oxide, or may be applied to the decorative layer by printing. An ink layer containing pigments, dyes, metals, and metal oxides. In this case, the printed portion may also be referred to as a colored layer (colored portion). The printing method in this case is not particularly limited, and examples thereof include relief printing, lithography, flexographic printing, gravure printing, and inkjet printing. The printing ink used for such printing may, for example, be an oxidative polymerization type oily ink, a soybean oil ink, a vegetable oil, an ultraviolet curing type UV ink, an LED-UV ink, a gravure ink, a flexographic ink, or a screen printing ink. Etc., especially good gravure ink, screen ink, inkjet ink. Printing inks may also be added as needed: pigment dispersants, defoamers, ultraviolet absorbers, antioxidants, antistatic agents, abrasion resistant agents, anti-adhesives and the like.

Further, when the colored layer contains a resin layer of a pigment, a dye, a metal or a metal oxide, the resin layer is preferably made of a thermoplastic resin. Specifically, preferred are: ABS resin (a copolymer of acrylonitrile, butadiene, and styrene), AS resin (acrylonitrile and benzene). Ethylene copolymer), AAS resin (acrylonitrile, copolymer of acrylic acid and styrene), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polycondensation Phenyl ether, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polyfluorene, polyether oxime, polyacetal, polyether ether ketone, polyphenylene sulfide, polyether醯imine, polyamidimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, vinylidene chloride, vinyl chloride, and the like.

The colored layer may also have pigments such as inorganic pigments (alumina white, titanium oxide, zinc oxide, black iron oxide, micaceous iron oxide, white lead, white carbon, molybdenum white, carbon black, lead oxide, zinc).钡 white, barite, cadmium red, cadmium mercury red, iron red, molybdenum red, lead dan, lead yellow, cadmium yellow, yttrium yellow, yttrium yellow, titanium yellow, titanium black, chrome oxide green, cobalt oxide, cobalt green , cobalt ‧ chrome green, ultramarine blue, iron blue, cobalt blue, sky blue, manganese violet, cobalt violet, etc.) and organic pigments (shellac, insoluble azo pigment, soluble azo pigment, condensed azo pigment, phthalocyanine blue, color Or insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, pyrazolone red; lithol red, Bordeaux red (Helio Bordeaux), pigment scarlet, permanent red 2B and other soluble azo pigments; derivatives such as alizarin, indanthrene, and sulphur blue jujube; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; quinacridone red, Quinophthalone pigments such as quinacridone magenta; anthraquinone pigments such as ruthenium and anthraquinone; isoindolinone yellow, isoindolinone orange Isoindolinone pigment; imidazolidone pigment such as benzimidazolone yellow, benzimidazolone orange, benzimidazolone red; dermatone pigment such as ketone ketone red, ketone ketone orange; thioindigo blue Pigment, condensed azo pigment, pyrrolopyrroledione pigment, flavanthrone yellow; acrylamide yellow, quinoline yellow, nickel azo yellow, copper azomethine yellow ; perinone orange, ketone orange, dianthraquinonyl red, two Other pigments such as purple. The present invention is not limited to these, and any known pigment can be used.

The dye which the colored layer may have may be, for example, an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, or a food coloring matter. Further, any dye known in the art may be used without limitation. Among these dyes, particularly preferred are azo-based and phthalocyanine-based dyes, and acid dyes, direct dyes, reactive dyes, and food dyes.

The metal layer which the colored layer may have may be, for example, aluminum, gold, silver, nickel, indium or the like.

The surface protective layer is a layer constituting the outermost surface of the laminated body, and the decorative molded body is also the layer constituting the outermost surface. In particular, when decorating members requiring strength such as interior and exterior parts of automobiles, the surface protective layer is required to be less susceptible to scratches and strength. The pencil hardness of the surface protective layer of the present invention is preferably B or more, more preferably F or more.

The surface protective layer is preferably a resin layer. Specifically, for example, ABS resin (a copolymer of acrylonitrile, butadiene, and styrene), AS resin (a copolymer of acrylonitrile and styrene), and AAS resin (acrylonitrile, acrylic acid, and benzene) are preferable. Ethylene copolymer), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene ether, phenol resin, urea resin, melamine resin, liquid crystal polymer , polytetrafluoroethylene, polyvinylidene fluoride, polyfluorene, polyether oxime, polyacetal, polyether ether ketone, polyphenylene sulfide, polyether sulfimine, polyamidimide, polycarbonate, Poly Alkene, polypropylene, polystyrene, urethane resin, vinylidene chloride resin, vinyl chloride resin, and the like. From the viewpoint of excellent scratch resistance, an acrylic resin is more preferable. Further, the surface protective layer of the present invention may be an epitaxial radiation-curable resin. The free radiation curing resin refers to a resin which is cured by irradiation with an electron beam or ultraviolet rays. In the present invention, the free radiation curing resin is preferably substantially transparent. As the substantially transparent free radiation curing resin, for example, an acrylic ultraviolet curing resin is preferably used.

The surface resistance of the decorative layer is preferably 1 × 10 ⁵ to 1 × 10 ¹² Ω / □, more preferably 1 × 10 ⁶ to 1 × 10 ¹² Ω / □. In particular, when the surface resistance of the separator layer and the pressure-sensitive adhesive layer described later is not in the range of 1 × 10 ⁵ to 1 × 10 ¹² Ω/□, the surface resistance of the decorative layer is preferably within the above range. Further, the surface resistance of the decorative layer may be such that the surface resistance of either surface is within the above range.

When the surface resistance of the decorative layer is set to the above range, an antistatic agent may be contained between the surface protective layer and the colored layer. In this case, the antistatic agent can be used in the same manner as the antistatic agent listed in the separator layer item to be described later.

In addition, the surface resistance of the decorative layer can be measured using Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Analytech Co., Ltd., measurement method: plus constant voltage/leakage current measurement method).

(layered body)

The present invention relates to a laminate comprising an adhesive layer, a decorative layer and a separator layer, the decorative layer being laminated on one side of the adhesive layer, the separator layer being laminated on the adhesive layer The other side, and the side opposite to the surface on which the decorative layer is laminated. Here, the volatile matter contained in the adhesive layer is less than 50 ppm.

Fig. 2 (a) is a cross-sectional view showing an example of the structure of the laminated body of the present invention. As shown in Fig. 2 (a), the laminated body 30 of the present invention includes an adhesive layer 24, a decorative layer 22 laminated on one surface side of the adhesive layer 24, and a laminate layer on the other surface side of the adhesive layer 24 and The separator layer 26 on the side opposite to the surface on which the decorative layer 22 is laminated. Since the laminated body 30 has the separator layer 26, when the laminated body 30 or the like is stored, foreign matter such as dust adheres to the surface of the adhesive layer 24. When the laminated body 30 of the present invention is used, the separator layer 26 is peeled off to expose the adhesive layer 24. Then, the adhesive layer 24 is adhered to the molded body belonging to the adherend. In the present specification, the laminated body of the peeled separator layer 26 is referred to as an adhesive film 20.

Fig. 2 (b) is a cross-sectional view showing a preferred configuration of the laminated body of the present invention. In the laminated body 30 of the present invention, the decorative layer 22 preferably contains a layer of the surface protective layer 32 and the colored layer 34. Further, the separator layer 26 preferably includes a layer of the base material layer 42, the release agent layer 44, and the antistatic layer 46. The layered body 30 of the present invention may have a layer other than the above layer, or the decorative layer 22 may further have an antistatic layer, and the adhesive layer may have a colored layer and/or an antistatic layer.

Further, the laminated body 30 shown in Fig. 2(b) is also adhered to the separator layer 26 to form the adhesive film 20.

Since the laminated body of the present invention has the above configuration, it can be in the form of a sheet or can be wound up in a roll shape. When the winding is in the form of a roll, it is preferably arranged on the side of the mandrel according to the separator layer. Way to take it.

(separator layer)

The laminate system of the present invention contains a separator layer. The separator layer is preferably made of a resin and does not contain a layer of a paper substrate. By using such a separator layer, foreign matter such as dust derived from paper is not caught between the laminate and the molded body, and the foreign matter bite can be effectively suppressed.

The surface resistance of the separator layer is preferably 1 × 10 ⁵ to 1 × 10 ¹² Ω / □, more preferably 1 × 10 ⁶ to 1 × 10 ¹² Ω / □. In the laminated body, foreign matter tends to adhere to the adhesive layer due to electrostatic interaction when the separator layer is peeled off. However, in the present invention, by setting the surface resistance of the separator layer within the above range, adhesion of foreign matter can be suppressed, particularly when forming under vacuum or under reduced pressure (when TOM is formed), and foreign matter can be more effectively suppressed. Bite into. Further, the surface resistance of the separator layer may be such that the surface resistance of either surface is within the above range.

The separator layer is composed of a single layer, and the surface resistance of the single layer may be within the above range, but is preferably a layer having a surface resistance within the above range. Specifically, the separator layer is preferably provided with a base material layer, a release agent layer laminated on one surface side of the base material layer, and a laminate layer on the other surface side of the base material layer and opposite to the surface on which the release agent layer is laminated. Antistatic layer on the side. Among them, the surface resistance of the antistatic layer is preferably 1 × 10 ⁵ to 1 × 10 ¹² Ω / □.

In the present invention, the separator layer preferably contains an antistatic agent, and the adhesive film composed of the decorative layer and the adhesive layer preferably contains no antistatic agent. In the present invention, when a laminate is used, the separator layer is peeled off from the laminate to become a thin adhesive layer composed of a decorative layer and an adhesive layer. membrane. However, the adhesive film is adhered to the molded body belonging to the adherend. That is, when only the separator layer contains the antistatic agent, the decorative molded body does not contain the antistatic agent, and the durability of the entire decorative molded body can be further improved.

Further, the surface resistance of the separator layer can be measured by Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Analytech Co., Ltd., measurement method: applied constant voltage/leakage current measurement method).

As shown in FIG. 2(b), the separator layer 26 preferably includes a substrate layer 42, a release agent layer 44, and a layer of the antistatic layer 46, and the antistatic layer 46 preferably contains an antistatic agent. The antistatic agent is preferably at least one selected from the group consisting of an ionic antistatic agent, an organic antistatic agent, and an inorganic antistatic agent, and more preferably at least one selected from the group consisting of an organic antistatic agent and an inorganic antistatic agent. One type, especially excellent inorganic antistatic agent. Further, the organic antistatic agent is more preferably a π-conjugated conductive polymer antistatic agent. By using at least one selected from the group consisting of a π-conjugated conductive polymer antistatic agent and an inorganic antistatic agent as an antistatic agent, the humidity dependency of the antistatic property can be suppressed. That is, antistatic performance can be exhibited in a so-called humidity zone. In particular, the inorganic antistatic agent exhibits excellent antistatic properties even in a low humidity environment. Further, since the ionic antistatic agent is relatively inexpensive, the production cost of the laminate can be suppressed.

The ionic antistatic agent may be any known ionic antistatic agent in the present invention, and preferably, for example, glyceric acid fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene Sorbitol fatty acid ester, polyoxyethylene fatty alcohol ether, alkyl sulfonate, alkyl benzene sulfonate, tetraalkyl ammonium salt, trialkyl benzyl ammonium salt, stearic acid monoglyceride, N, N-bis(2-hydroxyethyl)alkylamine, N,N-bis(2-hydroxyethyl)alkylguanamine, fatty acid ester of polyoxyethylene alkylamine, alkyl sulfate, alkyl phosphate Salt, alkyl beet , sodium polystyrene sulfonate, polyethylene glycol methacrylate copolymer, polyether ester decylamine and the like.

The organic antistatic agent is preferably a π-conjugated conductive polymer antistatic agent. Π-conjugated conductive polymer-based antistatic agent Any known π-conjugated conductive polymer-based antistatic agent can be used in the present invention, and preferably, for example, polythiophene, polypyrrole, or polyaniline Etc., especially good polythiophene.

Inorganic antistatic agent Any known inorganic antistatic agent may be used in the present invention, and examples thereof include an ITO filler, a silver nano filler, and a titanium oxide coated with tin oxide doped with cerium oxide. Very good silver nano filler.

When the antistatic layer contains an antistatic agent, the content of the antistatic agent is preferably from 2 to 100% by mass, more preferably from 50 to 100% by mass, based on the total mass of the antistatic layer. Further, the amount of the antistatic layer after drying is preferably 0.001 to 1 g/m ² , more preferably 0.01 to 0.2 g/m ² .

The base material layer constituting the separator layer is preferably a resin layer, and the resin layer is preferably made of a thermoplastic resin. Specifically, the base material layer may, for example, be a polyolefin film, a polyvinyl chloride film, a polyvinyl alcohol film, a polyester film, a polycarbonate film, a polystyrene film or a polyacrylonitrile film. Among them, a polyester film is preferably used, and a polyethylene terephthalate (PET) film is more preferably used. Further, as the base material layer, a film obtained by performing uneven processing such as a lens film, a brightness enhancement film, or a hologram film may be used.

The release agent layer contains a release agent. As the release agent, for example, a general-purpose addition or condensation type polyoxynitride type release agent can be used. It is particularly preferred to use a highly reactive addition polyoxynitride-based release agent. Specific examples of the polyoxane-based release agent include BY24-162, SD-7234, etc., manufactured by Toray Dow Corning, and the KS-3600, KS-774, and X62- manufactured by Shin-Etsu Chemical Co., Ltd. 2600 and so on. Further, in the polyoxo-based release agent, a polymer having an SiO ₂ unit, a (CH ₃ ) ₃ SiO _1/2 unit or a CH ₂ =CH(CH ₃ )SiO _1/2 unit, which is an organic ruthenium compound, is preferred. Oxygenated resin. Specific examples of the polyoxyxylene resin include BY24-843, SD-7292, SHR-1404, etc., manufactured by Toray Dow Corning, and KS-3800 and X92-183 manufactured by Shin-Etsu Chemical Co., Ltd. Wait.

An auxiliary additive such as a catalyst or an adhesion promoter may be added to the release agent layer. The catalyst is preferably a platinum-based or tin-based catalyst. Further, the adhesion enhancer can be used without any particular limitation until the adhesion can be improved. For example, a decane coupling agent is preferable.

The coating amount after the release agent layer is dried is preferably 0.01 to 1 g/m ² , more preferably 0.05 to 0.2 g/m ² .

The separator layer is formed by applying a release agent solution, a solution containing an antistatic agent, and drying the substrate layer. When coating each solution, a sizing coater, a gate roll coater, a bar coater, a roll coater, an air knife coater, a knife coater, and a bar coating can be used. Machine, curtain coating, gravure coating machine, etc. Among them, it is preferred to use a double-head coater for coating the back side of the watch in a single pass, and more preferably a double-head coater capable of controlling a gravure print head with a small amount of coating and capable of performing back and surface coating. . Thereby, the functional layer can be simultaneously formed on both sides of the substrate layer, and the production efficiency of the separator layer can be improved.

(Manufacturing method of laminated body)

In the step of producing the laminate of the present invention, as described above, it is preferred to irradiate light (ultraviolet rays or electron beams) after the build-up decorative layer, the adhesive layer, and the separator layer. Further, the above-described configuration can be formed by irradiating light (ultraviolet rays or electron beams) after laminating the separator layer, the adhesive layer, and the separator layer, and then bonding them to the decorative layer. When the illuminating light is constituted by the composition containing the decorative layer, it is preferred that the ray (ultraviolet light or electron beam) is irradiated from the side of the separator layer.

The step of irradiating light (ultraviolet rays) is preferably performed by using ultraviolet rays having an illuminance of at least 50 to 400 nm and having an illuminance of 50 mW/cm ² or more, more preferably irradiating ultraviolet rays of 70 to 3000 mW/cm ² , and particularly irradiating 100 to 1000 mW. /cm ² of ultraviolet light. The integrated light amount is preferably 100 to 10000 mJ/cm ² , more preferably 300 to 3000 mJ/cm ² . The illuminator that performs such irradiation is preferably at least one selected from the group consisting of a high-pressure mercury ultraviolet ray irradiator, a metal halogen ultraviolet ray irradiator, and an electrodeless ultraviolet ray irradiator. By setting the ultraviolet irradiation conditions in which the illuminance in the range of 200 to 400 nm is 50 mW/cm ² or more to the above range, the amount of the monomer component remaining in the adhesive layer can be reduced. Further, by setting the irradiation conditions within the above range, it is possible to suppress yellowing of the decorative layer due to ultraviolet rays.

The present invention, in addition to a wavelength range of 200 ~ 400nm illumination of 50mW / cm ² or more of ultraviolet irradiation step performed outside the preferred system using a wavelength of 200 ~ 400nm range for the purposes of the illuminance of the ^ultraviolet rays irradiated 20mW / cm. More preferably, the illuminance in the range of 200 to 400 nm is 1 to 10 mW/cm ² , and the ultraviolet ray of 2 to 5 mW/cm ² is used. The illuminator that performs such irradiation preferably uses at least one selected from the group consisting of chemical lamps and/or black light. By using the illuminators, it is preferred to perform irradiation for 0.01 to 30 minutes, more preferably for 0.1 to 20 minutes, and the integrated light amount can be set to 10 to 1000 mJ/cm ² , more preferably 40 to 600 mJ/cm ² , The special system is 100~400mJ/cm ² . By setting the ultraviolet irradiation conditions in which the illuminance in the range of 200 to 400 nm is 20 mW/cm ² or less to the above range, the traceability of the adhesive layer can be improved during TOM molding.

When the front step of the present invention used in a wavelength range of 200 ~ 400nm illuminance is 20mW / cm ² or less of ultraviolet irradiation performed, preferably in a range of illumination system 200 ~ 400nm wavelength is ² or more of ultraviolet 50mW / cm irradiation purposes will Implementation.

In the present invention, by irradiating ultraviolet rays under the above conditions, the ratio of the volatile matter contained in the adhesive layer can be set to a predetermined value or less in a state in which the degree of polymerization of the monomer is increased.

(Forming under vacuum or under reduced pressure (TOM forming))

The laminate of the present invention is preferably used for molding under vacuum or under reduced pressure. By using the laminate of the present invention, it is possible to prevent foreign matter such as dust from being trapped between the adhesive layer and the molded body when molded under vacuum or under reduced pressure. Accordingly, the layered body of the present invention can be used for forming under vacuum or under reduced pressure.

In the present specification, the molding under vacuum conditions or under reduced pressure conditions is so-called TOM molding. The TOM forming method includes a step of laminating an adhesive film on a molded body under vacuum or reduced pressure, and a step of crimping the adhesive film to the molded body by a difference in air pressure. In addition, in this specification, under vacuum conditions or under reduced pressure conditions The lower molding does not include a method in which a vacuum film is provided in the molded body to adhere the adhesive film to the molded body. Specifically, the molding system under vacuum conditions or under reduced pressure can be carried out by using the "vacuum molding apparatus" described in Japanese Patent No. 3733564.

The present invention also relates to a method of producing a decorative molded body as described above. Specifically, the method for producing a decorative molded article of the present invention includes the steps of laminating an adhesive film to a molded body under vacuum or reduced pressure; and pressing the adhesive film under a compressed air condition by using a gas pressure difference The step of joining the shaped body. Moreover, the method for producing a decorative molded article of the present invention preferably includes a step of heating the surface of the laminated body to 100 to 180 ° C after the step of pressure-bonding the adhesive film to the molded body. In this case, it is preferable to use an infrared heater when heating the surface of the laminated body.

Further, the adhesive film used in the method for producing a decorative molded article of the present invention is the adhesive film, and the volatile matter contained in the adhesive layer is less than 50 ppm.

(decorative molded body)

The present invention also relates to a decorative molded article comprising an adhesive film composed of a decorative layer and an adhesive layer of the above laminated body, and a molded body decorated with an adhesive film. The decorative forming system adheres the adhesive film to a part or a whole of the surface of the formed body. That is, the decorative molding system laminates the decorative layer via an adhesive.

Fig. 3 is a cross-sectional view showing the configuration of the decorative molded body 100. Fig. 3 shows a state in which the molded body 50 having a concave portion on its surface is decorated with the adhesive film 20. As shown in FIG. 3, even when formed under vacuum or under reduced pressure, it is not provided in the molded body 50. The vacuum hole is formed, and the reverse push-out portion and the end winding portion can be formed. Moreover, it can be decorated regardless of the material of the product. Thereby, the surface of the molded body having the complicated three-dimensional unevenness can be decorated, and the decorative molded body 100 having high design can be obtained.

The molded body 50 is, for example, a metal material such as an ED steel plate, a Mg alloy, a stainless steel (SUS), or an aluminum alloy, or a resin molded body, and is preferably a resin molded body. Preferably, for example, ABS resin (a copolymer of acrylonitrile, butadiene, and styrene), AS resin (a copolymer of acrylonitrile and styrene), and AAS resin (a copolymer of acrylonitrile, acrylic acid, and styrene) can be used. ), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene ether, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene Ethylene, polyvinylidene fluoride, polyfluorene, polyether oxime, polyacetal, polyether ether ketone, polyphenylene sulfide, polyether phthalimide, polyamidimide, polycarbonate, polyethylene, poly Propylene, polystyrene, urethane resin, vinylidene chloride resin, vinyl chloride resin, and the like. These resins can also be blended. For example, a polycarbonate-containing resin or the like is preferably exemplified. Polycarbonate-containing resin, more preferably: a resin blended with polycarbonate and polybutylene terephthalate (PC‧PBT), a resin blended with polycarbonate and ABS resin (PC‧ABS) Polycarbonate and PET resin (PC‧PET), etc. Further, as the polyolefin resin, polypropylene (PP) can be used.

Specifically, for example, ABS resin (a copolymer of acrylonitrile, butadiene, and styrene), AS resin (a copolymer of acrylonitrile and styrene), and AAS resin (acrylonitrile, acrylic acid, and benzene) are preferable. Ethylene copolymer), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene ether, phenol resin, urea resin, melamine resin, liquid crystal polymer , polytetrafluoroethylene, polyvinylidene fluoride, polyfluorene, polyether oxime, polyacetal, polyetheretherketone, polyphenylene sulfide, polyether Amine, polyamidimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, and the like.

The decorative molding system obtained by the present invention can be used, for example, for automotive parts (for example, a vehicle body, a bumper, a spoiler, a mirror, a wheel, an interior material, and the like), and a two-wheeled vehicle. Use parts, road materials (such as traffic signs, soundproof walls, etc.), tunnel materials (such as side wall panels, etc.), railway vehicles, furniture, musical instruments, home appliances, construction materials, containers, business supplies, sporting goods, toys, etc.

(Example)

The features of the present invention will be more specifically described below by way of examples and comparative examples. The materials, the amounts used, the ratios, the contents of the treatment, the order of treatment, and the like in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the invention is not limited by the specific examples shown below.

(Example 1) <decorative layer 1>

A black ink (DIC system, TRC1268) layer (colored layer) was provided on the single surface of the acrylic film (ACRYPLEN HBA001P, pencil hardness 2H, thickness: 125 μm) on the single side of the acrylic film by a thickness of 5 μm. , get the decorative layer 1.

<separator layer 1>

On a single surface of a 38 μm thick PET (manufactured by Toray Industries, Inc., LUMIRROR® T60), a coating material containing π-conjugated organic conductive material: poly(3, was applied so that the coating amount after drying was 0.07 g/m ² . DENATRON P-502S (manufactured by Nagase ChemteX) of 4-ethylenedioxythiophene was subjected to a treatment at 130 ° C for 30 seconds using a dryer. An antistatic layer is formed in accordance therewith.

Then, on the opposite side, 100 parts by mass of a thermosetting polyfluorene (manufactured by Toray Dow Corning Co., Ltd., LTC300B) and a catalyst (Toray ‧ were applied so that the weight after drying became 0.1 g/m ² ) A release agent composed of 1 part by mass of manufactured by Dow Corning Co., Ltd., SRX212) to form a release agent layer. Then, it was treated by a dryer at 130 ° C for 60 seconds to obtain a separator layer 1.

<Adhesive 1>

In a reaction vessel for nitrogen atmosphere gas, 95 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were charged, and an initiator (2,2'-azobis(4-methoxy-2) was used. , 4-dimethylpentanenitrile)) 0.01 part by mass of the polymerization reaction was carried out to obtain an adhesive 1 having a polymer concentration of 9% and a weight average molecular weight Mw of 1.5 million.

<Layer 1>

0.1 parts by mass of hexanediol diacrylate and 1 part by mass of benzyl dimethyl ketal were added to 100 parts by mass of the adhesive 1 , and the dissolved oxygen was completely removed by nitrogen purge, and the separator layer 1 was removed. The (wet laminate) adhesive 1 was applied between the release agent layer side and the ink layer side of the 130 μm decorative layer 1 so that the thickness of the adhesive layer was 50 μm. Then, a chemical lamp was used from the separator layer 1 side, and the illuminance was 4 mW/cm ^{2 of} ultraviolet light having a wavelength of 365 nm, and the integrated light amount was 300 mJ/cm ² . Then, the illuminance of the ultraviolet light having a wavelength of 365 nm was 100 mW/cm by a high-pressure mercury lamp. ^{2. When the} integrated light amount is 2000 mJ/cm ² , irradiation is performed to obtain the laminated body 1. The volatile matter contained in the adhesive layer of the laminated body 1 was measured by a gas chromatography layer analyzer and found to be 5 ppm.

<Method of Making Decorative Shaped Body>

The separator layer 1 is removed from the laminated body 1 to form an adhesive film 1. The adhesive film 1 was attached to a TOM molding machine. The rain cover (Model: WP9171, manufactured by Panasonic Co., Ltd.) is attached to the TOM molding machine in such a manner that the outer (convex) side of the cover faces the adhesive layer of the adhesive film 1 (Busch Vacuum Co., Ltd.) Company system, NGF molding machine). The decorative molded body 1 was obtained by laminating the adhesive film 1 on the molded body at 130 ° C using a TOM molding machine. Ten decorative molded bodies 1 were produced in the same manner.

Further, the shape of the rain cover described above is shown in Figs. 4(a) to 4(c). As shown in Fig. 4(a), the rain cover shown in Figs. 4(a) to 4(c) has a length in the longitudinal (longitudinal) direction of 90 mm and a length in the width (horizontal) direction of 60 mm as viewed from above.

(Example 2)

The thickness of the adhesive layer 1 was changed to 75 μm, and the separator layer 1 was changed to the separator layer 2, and the ultraviolet irradiation system was set to have a high-intensity mercury lamp with an ultraviolet illuminance of 300 mW/cm ² at a wavelength of 365 nm, and an integrated light amount of 3000 mJ/ The decorative molded body 2 was obtained in the same manner as in Example 1 except that the condition of cm ² was obtained. The result of measuring the volatile matter contained in the adhesive layer was 23 ppm.

<separator layer 2>

The glycerin monostearate was applied to a single surface of PET (manufactured by Toray Industries, Inc., LUMIRROR® T60) having a thickness of 50 μm so that the coating amount after drying was 0.15 g/m ² , and 130 ° C was applied by a dryer. 30 seconds processing. An antistatic layer is formed in accordance therewith.

Then, on the opposite side, 100 parts by mass of a thermosetting polyfluorene (manufactured by Toray Dow Corning Co., Ltd., LTC300B) and a catalyst (Toray ‧ were applied so that the weight after drying became 0.1 g/m ² ) A release agent composed of 1 part by mass of manufactured by Dow Corning Co., Ltd., SRX212) to form a release agent layer. Then, it was treated by a dryer at 130 ° C for 60 seconds to obtain a separator layer 2 .

(Example 3)

In addition to replacing the adhesive 1 with the adhesive 3 and the adhesive layer 3 to have a thickness of 25 μm, a chemical lamp was used from the separator layer 2 side, and the illuminance of the ultraviolet light at a wavelength of 365 nm was 4 mW/cm ² , and the integrated light amount was 100 mJ/cm ^{2 .} In the same manner as in the ^second embodiment, the high-pressure mercury lamp was irradiated so that the ultraviolet illuminance at a wavelength of 365 nm became 100 mW/cm ² and the integrated light amount was 2000 mJ/cm ² to obtain the laminated body 3 in the same manner as in the second embodiment. A decorative molded body 3 is obtained. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 3 was 3 ppm.

<Adhesive 3>

In a reaction vessel for a nitrogen atmosphere gas, 90 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of acrylic acid, and acrylic acid are charged. 5 parts by mass of the ester, and a polymerization reaction was carried out using 0.01% by mass of an initiator (2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile)) to obtain a polymer concentration of 8%. Adhesive 3 having a weight average molecular weight of Mw of 2 million.

(Example 4)

In addition to replacing the adhesive layer 1 with the adhesive 4 to form the adhesive layer 4, and using the separator layer 3 instead of the decorative layer 1, the metal halide lamp is used instead of the high-pressure mercury lamp to have an illuminance of 100 mW/cm ² depending on the wavelength of 365 nm ultraviolet light, and the integrated light amount is obtained. When the film was irradiated at 2000 mJ/cm ² to form the separator 1 / the adhesive layer 4 / the separator 3, the separator 1 was peeled off, and the decorative layer was attached to the exposed adhesive layer 4 by a roll bonding machine. 1, the decorative formed body 4 was obtained in the same manner as in Example 1 except that the laminated body 4 was obtained. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 4 was 14 ppm.

<Adhesive 4>

In a reaction vessel for a nitrogen atmosphere gas, 95 parts by mass of butyl acrylate and 5 parts by mass of 2-hydroxymethyl acrylate were charged, and an initiator (2,2'-azobis(4-methoxy-) was used. 2,4-Dimethylvaleronitrile)) 0.01 part by mass of a polymerization reaction was carried out to obtain a solution 4 having a polymer concentration of 11% and a weight average molecular weight of Mw of 1,000,000. 15 parts by mass of a rosin-based adhesive (manufactured by Arakawa Chemical Co., Ltd., KE311) was added to the solution 4, and the adhesive 4 was obtained by stirring.

<separator layer 3>

Silver nanowires (CST-NW-S40, manufactured by Cold Stones) and polyester-based adhesives (made from Takamatsu Oil Co., Ltd., PESRESIN A-645GH) were blended according to the weight after drying to 20:80, and then coated. It is spread on a single side of PET (manufactured by Toray Industries, Inc., LUMRIROR® T60) having a thickness of 50 μm. The coating amount was such that the coating amount after drying was 0.01 g/m ² , and the coating was carried out in a clean room (grade 1000). Then, the antistatic layer D was formed by performing a treatment at 130 ° C for 30 seconds using a dryer.

Then, on the opposite side, 100 parts by mass of a thermosetting polyfluorene (manufactured by Toray Dow Corning Co., Ltd., LTC300B) and a catalyst (Toray ‧ were applied so that the weight after drying became 0.1 g/m ² ) A release agent composed of 1 part by mass of manufactured by Dow Corning Co., Ltd., SRX212) to form a release agent layer. Then, it was treated by a dryer at 130 ° C for 60 seconds to obtain a separator layer 3 .

(Example 5)

The decorative body 5 was obtained in the same manner as in Example 4 except that the adhesive 1 was replaced with the adhesive 5 and the thickness of the adhesive layer 5 was changed to 25 μm.

The result of measuring the volatile matter contained in the adhesive layer of the laminated body 5 was 4 ppm.

<Adhesive 5>

In a reaction vessel for a nitrogen atmosphere gas, 90 parts by mass of 2-ethylhexyl acrylate and 10 parts by mass of acrylic acid were charged, and an initiator (2,2'-azobis(4-methoxy-2) was used. 4-dimethylpentanenitrile)) 0.01 part by mass of a polymerization reaction was carried out to obtain a solution 5 having a polymer concentration of 11% and a weight average molecular weight of Mw of 1.5 million. To the solution 5, 10 parts by mass of a terpene-based adhesive (TH130), and an aliphatic hydrocarbon-based adhesive (ArkON M100, manufactured by Arakawa Chemical Co., Ltd.) were added, and the adhesive 5 was obtained by stirring.

(Example 6)

The decorative body 6 was obtained in the same manner as in Example 2 except that the thickness of the adhesive layer was set to 200 μm, and the separator layer 2 was replaced with the separator layer 4. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 6 was 30 ppm.

<separator layer 4>

On a single surface of PET (manufactured by Toray Industries, Inc., LUMIRROR® T60) having a thickness of 38 μm, the weight of the dried polyester was 0.1 g/m ² , and the coating was made of thermosetting polyfluorene (manufactured by Toray Dow Corning Co., Ltd.). LTC300B) 100 parts by mass of a release agent comprising 1 part by mass of a catalyst (manufactured by Toray Dow Corning Co., Ltd., SRX212) to form a release agent layer. Then, it was treated by a dryer at 130 ° C for 60 seconds to obtain a separator layer 4.

(Comparative Example 1)

Although the decorative film 11 from which the separator layer 4 has been peeled off from the laminated body 11 is used to obtain the decorative molded body 11, when the TOM molding machine is used for processing at 130 ° C, the adhesive layer is foamed, and good decorative molding cannot be obtained. body. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 11 was 80 ppm.

<Laminated body 11>

The adhesive 11 was applied to the release agent layer of the separator layer 4 so as to have a thickness of 25 μm after drying, and dried at 90 ° C for 10 minutes, and then the decorative layer 1 was bonded by a roll bonding machine. Laminated body 11.

<Adhesive 11>

65 parts by mass of butyl acrylate, 30 parts by mass of methacrylate, and 5 parts by mass of acrylic acid were placed in a reaction container (with a temperature controller, a stirrer, and a reflux device) for nitrogen atmosphere gas, and 200 parts by mass of ethyl acetate was added. Polymerization was carried out by reacting with 0.1 parts by mass of azobisisobutyronitrile to obtain a polymer A. The weight average molecular weight Mw of the obtained polymer A was 800,000. The obtained polymer A, poly-α-methylstyrene (molecular weight Mw = 850,000, Tg = 105 ° C, manufactured by Wako Pure Chemical Industries, Ltd., and a crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X), and the dry weight ratio was 98:10:2, and the adhesive 11 was obtained. .

(Comparative Example 2)

Although the decorative film 12 is obtained by peeling the adhesive film 12 from the laminated body 12, when the TOM molding machine is used for processing at 130 ° C, the adhesive layer is foamed, and good decorative molding cannot be obtained. body. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 12 was 140 ppm.

<Laminated body 12>

The laminate 12 was obtained in the same manner as in Comparative Example 1, except that the adhesive 12 was applied to the release agent layer of the separator layer 2 in a thickness of 75 μm after drying.

<Adhesive 12>

65 parts by mass of butyl acrylate, 30 parts by mass of methacrylate, and 5 parts by mass of 2-hydroxyethyl acrylate were placed in a reaction container (with a temperature controller, a stirrer, and a reflux device) for nitrogen atmosphere gas, and added. 200 parts by mass of ethyl acetate and 0.1 parts by mass of azobisisobutyronitrile were subjected to a polymerization reaction to obtain a polymer B. The weight average molecular weight Mw of the obtained polymer B was 800,000.

The obtained polymer B, a crosslinking agent (manufactured by Mitsubishi Gas Chemical Co., Ltd., TETRAD-X), and bistrifluoromethanesulfonimide were blended in such a manner that the dry weight ratio was 96:2:2, and the adhesive 12 was obtained. .

(Comparative Example 3)

Although the decorative film 13 is obtained by peeling the adhesive film 13 from the laminated body 13 from the laminated body 13, when the TOM molding machine is used for processing at 130 ° C, the adhesive layer is foamed, and good decorative molding cannot be obtained. body.

<Laminated body 13>

The laminate 13 was obtained in the same manner as in Example 1 except that the illuminance of the ultraviolet light having a wavelength of 365 nm was set to 100 mW/cm ² and the integrated light amount was set to 50 mJ/cm ² by a high pressure mercury lamp. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 13 was 610 ppm.

(Comparative Example 4)

The adhesive film 14 from which the separator layer 1 has been peeled off from the laminate 14 is used to obtain the decorative molded body 14, but when the TOM molding machine is used for processing at 130 ° C, the adhesive layer is foamed, and good decorative molding cannot be obtained. body.

<Laminated body 14>

A separator 1 / an adhesive was prepared in the same manner as in Example 4 except that the illuminance of the ultraviolet light having a wavelength of 365 nm was 100 mW/cm ² and the integrated light amount was 50 mJ/cm ² . The structure of the layer 4/separator 3 is followed by peeling off the separator 1, and the decorative layer 1 is bonded to the exposed adhesive layer 4 by a roll bonding machine to obtain a laminated body 14. The result of measuring the volatile matter contained in the adhesive layer of the laminated body 14 was 310 ppm.

(Evaluation) (Measurement of surface resistance value)

Surface resistance The laminate was placed in a humidity of 23 ° C and 50% H for one day, and then measured by Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.).

(TOM formability)

When the adhesive films of Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to molding, those who did not exhibit foaming were evaluated as having good moldability (○). At the time of film formation, those who found foaming were evaluated as poor formability (x). The results are shown in Table 1.

(number of defects)

The surface of the decorative molded body using the laminate (adhesive film) which had been aged at 23 ° C and a relative humidity of 50% was observed, and the number of defects in which the surface expansion was convex was measured. The upper surface (corresponding to the upper surface of FIG. 4(a)) of the decorative molded body obtained in each of the examples and the comparative examples was observed with a laser microscope (VK-X100, manufactured by KEYENCE), and a height of 3 μm or more was regarded as a defect. And calculate the quantity. Further, the number of defects is an average value of the number of defects in the same region of the ten decorative molded bodies produced in the same manner in each of the examples and the comparative examples.

(Number of defects in low humidity environment)

The surface of the decorative molded body using the laminate (adhesive film) which had been aged at 15 ° C and a relative humidity of 30% was observed in the same manner as above, and the number of defects was calculated to obtain an average value.

(adhesion)

A 25×50 mm test piece was attached to the ABS plate, and a pressure bonding (2 kg roller, 1 reciprocating) and heat treatment (130 ° C, 1 minute) were applied. After standing for 24 hours, a tensile tester was used. When the peeling speed of the peeling speed of 300 mm/min, the peeling angle of 180 degrees, the measurement temperature of 23 degreeC, and the humidity of 50% were peeled off the test piece, the force required for peeling was measured.

(Durability (Hundred Test))

The decorative shaped body was allowed to stand in an environment of 80 ° C for 500 hours, and after being placed, at room temperature, 11 cut marks of vertical and horizontal were cut at intervals of 2 mm on the surface of the film to prepare 100 checkerboards. When the transparent tape is adhered to the surface thereof and then peeled off in one breath, the number of squares remaining without being peeled off is indicated.

When the TOM molding was carried out using the adhesive film obtained in the examples, the TOM formability was good. On the other hand, the TOM forming was carried out using the adhesive film obtained in the comparative example. At the time, foaming occurs from the adhesive layer.

Further, the number of defects of the laminate obtained in the examples was small, and the adhesion to the molded body was good. Further, it was found that the decorative molded article obtained in the examples was excellent in durability.

20‧‧‧Adhesive film

22‧‧‧Decorative layer

24‧‧‧Adhesive layer

Claims (12)

An adhesive film comprising: an adhesive layer; and a decorative layer laminated on one side of the adhesive layer, wherein the volatile layer contained in the adhesive layer is less than 50 ppm. The adhesive film of claim 1, wherein the adhesive constituting the adhesive layer is an ultraviolet curable adhesive. The adhesive film according to claim 1 or 2, wherein the volatile substance is an oligomer derived from a solvent, a component constituting an adhesive constituting the adhesive layer, and an adhesive component constituting the adhesive layer. At least one of them is selected. The adhesive film according to any one of claims 1 to 3, wherein the adhesive constituting the adhesive layer contains a (meth) acrylate monomer unit. The adhesive film according to any one of claims 1 to 4, wherein the thickness of the adhesive layer is 20 μm or more. The adhesive film according to any one of claims 1 to 5, wherein the decorative layer has a thickness of 75 μm or more. The adhesive film according to any one of claims 1 to 6, which is used for forming under vacuum or under reduced pressure. A laminated body comprising: an adhesive layer; a decorative layer laminated on one surface side of the adhesive layer; and a separator layer laminated on the other surface side of the adhesive layer and opposite to a surface on which the decorative layer is laminated; The volatile matter contained in the adhesive layer is less than 50 ppm. The laminate according to claim 8, wherein at least one of the adhesive layer, the decorative layer and the separator layer has a layer having a surface resistance of from 1 × 10 ⁵ to 1 × 10 ¹² Ω/□. The laminate according to claim 8 or 9, wherein the separator layer has a layer having a surface resistance of from 1 × 10 ⁵ to 1 × 10 ¹² Ω/□. A decorative molded article comprising: the adhesive film of any one of claims 1 to 7, and a molded body decorated with the above adhesive film. A method for producing a decorative molded body, comprising: laminating an adhesive film on a molded body under vacuum or reduced pressure; and crimping the adhesive film onto the formed body by a difference in air pressure The adhesive film has an adhesive layer and a decorative layer laminated on one surface side of the adhesive layer, and the volatile substance contained in the adhesive layer is less than 50 ppm.