KR20180002830A - An adhesive film, a laminate, and a decorative molded article - Google Patents

Abstract

The present invention provides an adhesive film in which foaming from a pressure-sensitive adhesive layer is suppressed when TOM molding is performed. More specifically, the present invention relates to an adhesive film having a decorative layer laminated on one surface side of a pressure-sensitive adhesive layer and a pressure-sensitive adhesive layer, wherein the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm.

Description

An adhesive film, a laminate, and a decorative molded article

The present invention relates to a pressure-sensitive adhesive film, a laminate, and a decorated molded article.

The present application claims priority based on Japanese Patent Application No. 2015-120042 filed on June 15, 2015, the contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION [0002] Conventionally, in the case of protecting or decorating (decorating) the surfaces of automobile interior and exterior parts, home electric appliances parts, and building materials parts, after the green body is processed by injection molding or vacuum molding, , And drying and heating and curing were carried out. However, such a coating is problematic in that the discharge of the volatile organic solvent deteriorates the working environment, the working process and the production equipment are required for each of the molded parts, and further the coating of the paint is required, There was a problem that productivity was low.

In recent years, the use of a resin molded article as a molded article has been progressing for the purpose of reducing the weight of parts in automobile interior and exterior parts, parts for household appliances, and parts for building materials. Spray coating is often not suitable for decorating (decorating) the resin molded article, and various methods for decorating the surface of the resin molded article have been developed. Among them, the method of obtaining the decorative molded object by embossing with the decorative film on the outermost surface of the molded article has an advantage that the degree of freedom of design is high and the productivity is also superior to the method of applying or printing on the surface using a paint or the like. Further, the edible method using the edible film is also used for various purposes because the surface of a molded body having three-dimensional irregularities can be displayed.

As a method of embedding a surface of a molded article having three-dimensional unevenness with a decorative film, there is a method of three-dimensionally coating (TOM molding) (Patent Document 1). TOM molding is a molding method under a vacuum condition or a reduced pressure condition, and is a method of obtaining a decorative molded object by pressing an edible film and a molded body. In TOM molding, it is possible to embellish the molded article irrespective of the material of the molded article. Further, the reverse tapered portion and the end curled portion can be formed by coating without forming a vacuum hole in the formed body.

Examples of the edible film used for TOM molding include an adhesive film in which an adhesive layer or a pressure-sensitive adhesive layer is laminated on a decorative layer. When a decorative molded object is obtained by using a film having a decorative layer and an adhesive layer, the decorative layer is attached to an adherend by using an adhesive which is obtained by heating at the time of TOM molding. When an adhesive film having a decorative layer and a pressure-sensitive adhesive layer is used, the pressure-sensitive adhesive film and the formed article are brought into close contact with each other using the adhesive force of the pressure-sensitive adhesive layer.

A solvent-based pressure-sensitive adhesive is generally used for the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, but it is also considered to use an ultraviolet-curable adhesive. For example, Patent Document 2 discloses a decorative sheet having an decorative layer and an ionizing radiation curable adhesive layer. Here, the ionizing radiation curing type adhesive layer has a property that it can bond for a certain period of time, and the polymerization reaction of the monomer component constituting the adhesive progresses with time.

Japanese Patent No. 3733564 Japanese Patent Application Laid-Open No. 2004-142107

As described above, when a pressure-sensitive adhesive film having a decorative layer and a pressure-sensitive adhesive layer is used as an edible film, a solvent-based pressure-sensitive adhesive is often used in the pressure-sensitive adhesive layer. However, in the case of using a solvent-based pressure-sensitive adhesive, the pressure-sensitive adhesive layer is liable to be foamed.

In Patent Document 2, use of an ultraviolet curing adhesive agent in a pressure-sensitive adhesive layer has been studied. However, when the decorative film of Patent Document 2 is used for TOM molding, it tends to be foamed after adhesion and deteriorates the yield of the decorative molded article Have been clarified by the inventors of the present invention.

Accordingly, the present inventors have conducted studies for the purpose of providing an adhesive film in which foaming from a pressure-sensitive adhesive layer is suppressed when TOM molding is performed in order to solve the problems of the prior art.

As a result of diligent studies to solve the above problems, the inventors of the present invention have found that, in the pressure-sensitive adhesive film having the decorative layer and the pressure-sensitive adhesive layer, the volatile component contained in the pressure- I can find out.

Specifically, the present invention has the following configuration.

[1] A pressure-sensitive adhesive film comprising a pressure-sensitive adhesive layer and a decorative layer laminated on one side of the pressure-sensitive adhesive layer, wherein the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm.

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

[3] The pressure-sensitive adhesive film according to [1] or [2], wherein the volatile substance is at least one selected from the monomers constituting the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer and oligomers constituting the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer.

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

[5] The pressure-sensitive adhesive film according to any one of [1] to [4], wherein the pressure-sensitive adhesive layer has a thickness of 20 μm or more.

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

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

[8] A laminate having a pressure-sensitive adhesive layer, a decorative layer laminated on one surface side of the pressure-sensitive adhesive layer, and a separator layer laminated on the surface side opposite to the surface on which the decorative layer is laminated as another surface side of the pressure- And the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm.

[9] The laminate according to [8], wherein at least one of the pressure-sensitive adhesive layer, the decorative layer and the separator layer has a layer having a surface electric resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □.

[10] The laminate according to [8] or [9], wherein the separator layer has a layer having a surface electric resistance of 1 × 10 ^{5 to} 1 × 10 ¹² Ω / square.

[11] A decorative molded article comprising the adhesive film according to any one of [1] to [7] and a molded article edged with an adhesive film.

[12] A process for producing a pressure-sensitive adhesive sheet, comprising the steps of: laminating an adhesive film on a molded article under a vacuum condition or under reduced pressure; and pressing the adhesive film onto a molded article by a pressure difference, And a volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a pressure-sensitive adhesive film in which foaming from the pressure-sensitive adhesive layer is suppressed when performing TOM molding. Therefore, when the pressure-sensitive adhesive film of the present invention is used, the productivity of the decorative molded article can be increased and an decorative molded article excellent in designability can be obtained.

1 is a cross-sectional view showing an example of the constitution of a pressure-sensitive adhesive film of the present invention.
2 is a cross-sectional view for explaining the constitution of the laminate of the present invention.
3 is a cross-sectional view for explaining the constitution of the decorative molded object of the present invention.
Fig. 4 is a view for explaining a molded body used in Examples and Comparative Examples. Fig. 4 (a) is a top 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. Descriptions of the constituent elements described below are based on representative embodiments and concrete examples, but the present invention is not limited to these embodiments. In the present specification, the numerical range indicated by "~" means a range including numerical values before and after "~" as a lower limit value and an upper limit value.

(Adhesive film)

The pressure-sensitive adhesive film of the present invention has a pressure-sensitive adhesive layer and a decorative layer laminated on one surface side of the pressure-sensitive adhesive layer. The volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm. The volatile substance contained in the pressure-sensitive 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 refers to a substance which volatilizes under a vacuum condition of 150 ° C. The adhesive film of the present invention refers to a film before TOM molding to be adhered to an object to be adhered (molded article). The present invention is characterized in that the content of volatile substances in the adhesive film before adhering is within the above range.

Examples of the volatile substance include at least one selected from the group consisting of a solvent, a monomer constituting a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, and an oligomer constituting a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. Here, the oligomer as a constituent component of the pressure-sensitive adhesive is obtained by polymerizing 2 to 5 monomers constituting the pressure-sensitive adhesive.

Since the pressure-sensitive adhesive film of the present invention has the above-described configuration, foaming in the pressure-sensitive adhesive layer can be suppressed during molding under vacuum condition or under reduced pressure condition (TOM molding). Further, the pressure-sensitive adhesive film of the present invention is preferably used as a pressure-sensitive adhesive film for molding under a vacuum condition or under a reduced pressure condition because it can exert an excellent adhesive force to a molded article to be adhered.

1 is a cross-sectional view showing an example of the constitution of a pressure-sensitive 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 a pressure-sensitive adhesive layer 24. The pressure-sensitive adhesive layer (24) is laminated on one surface side of the decorative layer (22). In such an adhesive film 20, the pressure-sensitive adhesive layer 24 is adhered to the surface of the object to be adhered, so that the object can be edited.

In the pressure-sensitive adhesive film of the present invention, the thickness of the pressure-sensitive adhesive layer is preferably 20 占 퐉 or more, more preferably 35 占 퐉 or more, further preferably 70 占 퐉 or more, and particularly preferably 150 占 퐉 or more. In the present invention, by setting the thickness of the pressure-sensitive adhesive layer within the above-mentioned range, it is possible to prevent the foreign matter form from spreading on the surface of the edible molded object, even when foreign substances are mixed in the pressure-sensitive adhesive layer. Therefore, even if minute foreign substances or bubbles are mixed, they are not affected.

Further, the thickness of the decorative layer is preferably 50 占 퐉 or more, more preferably 100 占 퐉 or more, and even more preferably 180 占 퐉 or more. In the present invention, by setting the thickness of the decorative layer in the above-described range, it is possible to prevent the foreign matter shape from spreading on the surface of the decorative molded object, even when foreign matter is mixed in the adhesive layer.

(Pressure-sensitive adhesive layer)

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is preferably an ultraviolet curable pressure-sensitive adhesive (UV curable pressure-sensitive adhesive), and more preferably an acrylic ultraviolet curable pressure-sensitive adhesive. Examples of the ultraviolet curable pressure sensitive adhesive include a solventless pressure sensitive adhesive containing an acrylic monomer and / or an acrylic oligomer and a photopolymerization initiator.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer preferably comprises a (meth) acrylic acid ester monomer unit as a unit constituting the acrylic polymer. Here, the "unit" is a repeating unit (monomer unit) constituting the polymer. Further, the term "(meth) acrylic acid" means that it includes both of "acrylic acid" and "methacrylic acid".

Examples of the (meth) acrylic ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl Propyl (meth) acrylate, n-butyl (meth) acrylate, n-pentyl (meth) acrylate, (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl stearyl (meth) acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (Meth) acrylate, and the like. These may be used singly or in combination of two or more.

Among them, at least one selected from methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is preferably used.

If necessary, the following components may be contained. Examples of the di (meth) acrylate include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, 1,6-hexanediol diacrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. It is also possible to use a component having a carboxyl group, preferably a component having acrylic acid, methacrylic acid, maleic acid, crotonic acid,? -Carboxyethyl acrylate, and / or hydroxyl group, preferably 2-hydroxyethyl (meth) (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, 8-hydrooctyl (meth) acrylate, and / or copolymerizable unsaturated components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile, . The component having a carboxyl group, the component having a hydroxyl group, and the component capable of copolymerization are preferably contained in an amount of 0.1 to 30 mass%, preferably 1 to 10 mass%, of the acrylic polymer.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer preferably contains a monomer and / or an oligomer as a unit constituting the acrylic polymer. The monomer and / or oligomer is preferably contained in an amount of from 30 to 98 mass%, more preferably from 70 to 95 mass%, based on the total mass of the pressure-sensitive adhesive layer. When the blending amount of the monomer and / or oligomer is within the above range, the viscosity of the pressure-sensitive adhesive easily adjusts to a desired range, and the pressure-sensitive adhesive layer can be formed by coating.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer may contain, in addition to the acrylic polymer, aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, copolymerized (C5 / C9) petroleum resin, dicyclopentadiene (DCPD) Rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, and their water-soluble resins, and the like, preferably in a pressure-sensitive adhesive 0 to 40% by mass, more preferably 10 to 25% by mass.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer preferably contains the polymerization initiator in an amount of 0.1 to 10 mass%, more preferably 0.5 to 5 mass%. The polymerization initiator is preferably a photopolymerization initiator. Examples of the polymerization initiator include an acetophenone initiator, a benzoin ether initiator, a benzophenone initiator, a hydroxyalkylphenone initiator, a thioxanthone initiator, an amine initiator, an acylphosphine oxide initiator, etc. .

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

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

Specific examples of the benzophenone-based initiator include benzophenone and methyl o-benzoylbenzoate.

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

Specific examples of the thioxanthone initiator include 2-isopropylthioxanthone and 2,4-dimethylthioxanthone.

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

Specific examples of the acylphosphine oxide-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

The pressure-sensitive adhesive layer may contain additives such as known additives such as crosslinking agents, chain transfer agents, sensitizers, light stabilizers, fillers, pigments, viscosity adjusters, wetting agents, leveling agents, antifoaming agents, preservatives, dispersants, May be added in an amount not to impair the effect of the present invention.

The average molecular weight of the acryl-based polymer constituting the pressure-sensitive adhesive layer is preferably 10,000 to 5,000,000, more preferably 300,000 to 3,000,000, and particularly preferably 700,000 to 2,500,000. By setting the average molecular weight of the acrylic polymer within the above range, it is possible to improve the followability to the molded body at the time of molding (TOM molding) under a vacuum condition or a reduced pressure condition, and a molded body having a complicated shape can also be displayed. The molecular weight distribution (Mw / Mn) of the acrylic polymer is preferably 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 6. Two or more kinds of polymers having different average molecular weights may be mixed and used in order to obtain a desired molecular weight distribution.

By broadening the molecular weight distribution of the acrylic polymer, it is possible to improve the followability to the molded body at the time of molding under vacuum condition or under reduced pressure (TOM molding), and the molded body having a complicated shape can also be displayed.

The surface electrical resistance of the pressure-sensitive adhesive layer is preferably 1 x 10 ^{5 to} 1 x 10 ¹² Ω / square, more preferably 1 × 10 ^{6 to} 1 × 10 ¹² Ω / square. Particularly, when the surface electrical resistance of the separator layer described below is not within the range of 1 10 ^{5 to} 1 10 ¹² ? / ?, the surface electrical resistance of the pressure-sensitive adhesive layer is preferably within the above range. Here, the surface electrical resistance of the pressure-sensitive adhesive layer may be such that the surface electrical resistance of one surface is within the above range.

In order to set the surface electrical resistance of the pressure-sensitive adhesive layer to 1 x 10 ^{5 to} 1 x 10 ¹² ? / G, the pressure-sensitive adhesive layer preferably contains an antistatic agent. In particular, when the surface electrical resistance of the separator layer described below is not within the range of 1 x 10 ^{5 to} 1 x 10 ¹² ? / ?, the pressure-sensitive adhesive layer preferably contains an antistatic agent. As the antistatic agent contained in the pressure-sensitive adhesive layer, the same antistatic agent as that contained in the separator layer described later can be exemplified, and the preferable antistatic agent is also the same.

On the other hand, the surface electrical resistance of the pressure-sensitive adhesive layer can be measured by Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Engineering Co., Ltd., measurement method: constant voltage application / leakage current measurement method).

When the pressure-sensitive adhesive layer contains an antistatic agent, the content of the antistatic agent is preferably 0.1 to 10 mass%, more preferably 0.5 to 7 mass%, and more preferably 1 to 5 mass%, based on the total mass of the pressure- Is more preferable.

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

(Decorative layer)

The laminate of the present invention includes a decorative layer. The decorative layer may have a single layer structure, but is preferably a layer having a surface protective layer containing a ultraviolet absorbent and a colored layer. Here, 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, and a metal oxide, or may be a vapor deposition layer formed of a pigment, a dye, a metal, or a metal oxide, a sputter layer, or an ink layer containing a pigment, a dye, May be printed on the decorative layer. In this case, the printing portion may be referred to as a colored layer (colored portion). The printing method in this case is not particularly limited, and examples thereof include, for example, relief printing, offset printing, flexographic printing, gravure printing, and inkjet printing. Examples of the printing inks used in these printing include oil-based inks of oxidation polymerization type, soybean oil ink, vegetable oil ink, ultraviolet curable UV ink, LED-UV ink, gravure ink, flexo ink and screen ink. Gravure ink, screen ink, and inkjet ink are preferable. Additives such as a pigment dispersant, a defoaming agent, an ultraviolet absorber, an antioxidant, an antistatic agent, an abrasion inhibitor, and an antiblocking agent may be added to the printing ink, if necessary.

When the colored layer is a resin layer containing a pigment, a dye, a metal, or a metal oxide, the resin layer is preferably composed of a thermoplastic resin. Specific examples include ABS resins (copolymers of acrylonitrile, butadiene and styrene), AS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acryl and styrene), acrylic resins, But are not limited to, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, Preferred are polyacetal, polyether ether ketone, polyphenylene sulfide, polyether imide, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, vinylidene chloride and vinyl chloride.

Examples of the pigment that the colored layer may have include inorganic pigments (alumina white, titanium oxide, zinc oxide, black iron oxide, mica white iron oxide, white carbon, molybdenum white, carbon black, litharge, lithopone, , Cadmium mercury red, red brick, molybdenum red, podium, chrome yellow, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chrome green, (Condensation azo pigment, phthalocyanine blue, staining lake, etc.), and organic pigments such as toluidine red, toluidine maroon, hansa yellow, benzidine yellow , Pyrazolone red, soluble azo pigments such as lithol red, heliobordo, pigment scarlet and permanent red 2B, alizarin, Indanthrone and thioindigo maroon; phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; quinacridone pigments such as quinacridone red and quinacridone magenta; perylene pigments such as perylene red and perylene scarlet; Isoindolinone pigments such as isoindolinone yellow and isoindolinone orange, imidazolone pigments such as benzimidazolone yellow, benzimidazolone orange and benzimidazolone red, pyranthrone red, pyranthrone red, Orange, etc., thioindigo pigments, condensed azo pigments, diketopyrrolopyrrole pigments, propanthrone yellow, acyl amide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone yellow pigment, And other pigments such as orange, anthrone orange, dianthraquinonyl red, and dioxazine violet. The present invention is not limited to these, and any known pigment may be used.

Examples of the dyes that the colored layer may have include acid dyes, basic dyes, direct dyes, reactive dyes, disperse dyes, or food colors. In the present invention, any of known dyes may be used, but is not limited thereto. Among these dyes, azo-based and phthalocyanine-based dyes are preferable, and acid dyes, direct dyes, reactive dyes, food coloring agents and the like are particularly preferable.

Examples of the metal layer that the colored layer may have include aluminum, gold, silver, nickel, and indium.

The surface protective layer is a layer constituting the outermost surface of the laminate, and is also the layer constituting the outermost surface in the decorative molded object. Particularly, when a member requiring strength such as automobile interior and exterior parts is embossed, it is required that the surface protective layer has damage hardness and strength. The surface protective layer in the present invention preferably has a pencil hardness of B or more, more preferably F or more.

The surface protection layer is preferably a resin layer. Specific examples include ABS resins (copolymers of acrylonitrile, butadiene and styrene), AS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acryl and styrene), acrylic resins, But are not limited to, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, There may be preferably mentioned polyacetal, polyether ether ketone, polyphenylene sulfide, polyether imide, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, vinylidene chloride resin and vinyl chloride resin. More preferably, it is an acrylic resin in view of excellent scratch resistance. The surface protective layer of the present invention may be an ionizing radiation curable resin. An ionizing radiation curing resin is a resin which is cured by irradiation with 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, an acrylic ultraviolet curable resin is preferably used.

The surface electric resistance of the decorative layer is preferably 1 x 10 ^{5 to} 1 x 10 ¹² Ω / square, more preferably 1 × 10 ^{6 to} 1 × 10 ¹² Ω / square. In particular, when the surface electrical resistivity of the separator layer and the pressure-sensitive adhesive layer described below is not within the range of 1 10 ^{5 to} 1 10 ¹² ? / □, it is preferable that the surface electric resistance of the decorative layer is in the above range. Here, the surface electrical resistance of the decorative layer may be such that the surface electrical resistance of one surface is within the above range.

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

On the other hand, the surface electrical resistance of the decorative layer can be measured by means of Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Corporation, measurement method: constant voltage application / leakage current measurement method).

(Laminate)

The present invention relates to a laminate having a pressure-sensitive adhesive layer, a decorative layer laminated on one surface side of the pressure-sensitive adhesive layer, and a separator layer laminated on the surface side opposite to the surface on which the decorative layer is laminated as the other surface side of the pressure- It is also. Here, the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm.

2 (a) is a cross-sectional view showing an example of the structure of the laminate of the present invention. 2 (a), the laminate 30 of the present invention comprises a pressure-sensitive adhesive layer 24, a decorative layer 22 laminated on one surface side of the pressure-sensitive adhesive layer 24, a pressure-sensitive adhesive layer 24, And a separator layer 26 laminated on the surface opposite to the surface on which the decorative layer 22 is laminated. Since the laminate 30 has the separator layer 26, adhesion of foreign matter such as dust to the surface of the pressure-sensitive adhesive layer 24 at the time of storing the laminate 30 or the like is suppressed. When using the laminate 30 of the present invention, the separator layer 26 is peeled off to expose the pressure-sensitive adhesive layer 24. Then, the pressure-sensitive adhesive layer 24 is adhered to the molded body as the adherend. In the present specification, the laminate in which the separator layer 26 is peeled off is referred to as an adhesive film 20.

2 (b) is a cross-sectional view showing a preferable structure of the laminate of the present invention. In the layered product 30 of the present invention, the decorative layer 22 is preferably a layer including the surface protective layer 32 and the colored layer 34. [ It is preferable that the separator layer 26 is a layer including the base layer 42, the release agent layer 44, and the antistatic layer 46. The laminate 30 of the present invention may have a layer other than the above-mentioned layer, the decorative layer 22 may further have an antistatic layer, and the pressure-sensitive adhesive layer may have a colored layer and / or an antistatic layer .

Also in the laminate 30 as shown in Fig. 2 (b), after the separator layer 26 is peeled off, it becomes the adhesive film 20.

Since the laminate of the present invention has the above-described structure, it may be in a sheet form or wound in a roll form. In the case of being rolled up, it is preferable that the separator layer is wound so as to be disposed on the side of the core shaft.

(Separator layer)

The laminate of the present invention includes a separator layer. The separator layer is preferably made of resin and is preferably a layer not including a paper substrate. By using such a separator layer, it is possible to effectively prevent the foreign matter such as dust from being trapped between the laminate and the molded body from mixing with foreign matter.

The surface electrical resistance of the separator layer is preferably 1 x 10 ^{5 to} 1 x 10 ¹² Ω / □, more preferably 1 × 10 ^{6 to} 1 × 10 ¹² Ω / □. In the laminate, foreign matter tends to adhere to the pressure-sensitive adhesive layer due to electrostatic interaction between the separator layer and the separator layer. However, in the present invention, the surface electrical resistance of the separator layer within the above-described range can suppress the adhesion of foreign matter, and more effectively suppress the ingress of foreign matter in the molding (under TOM molding) under a vacuum condition or a reduced pressure condition . On the other hand, the surface electrical resistance of the separator layer may be such that the surface electrical resistance of one surface is within the above range.

The separator layer has a single layer structure, and the surface electrical resistance of the single layer may be within the above-mentioned range, but it is preferable that the separator layer has a surface electric resistance within the above range. Specifically, the separator layer has a base layer, a release agent layer laminated on one surface 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 surface side of the base layer . Among them, it is preferable that the surface electric resistance of the antistatic layer is 1 × 10 ^{5 to} 1 × 10 ¹² Ω / □.

In the present invention, it is preferable that the separator layer contains an antistatic agent, and the pressure-sensitive adhesive film composed of the decorative layer and the pressure-sensitive adhesive layer preferably contains no antistatic agent. In the present invention, when the laminate is used, the separator layer is peeled off from the laminate, resulting in an adhesive film composed of a decorative layer and a pressure-sensitive adhesive layer. Then, the pressure-sensitive adhesive film is adhered to the formed article as the adherend. That is, when only the separator layer contains an antistatic agent, the decorative molded object does not contain an antistatic agent, so that the durability of the decorative molded object as a whole becomes higher.

On the other hand, the surface electrical resistance of the separator layer can be measured by Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Engineering Co., Ltd., measurement method: constant voltage application / leakage current measurement method).

2B, the separator layer 26 is preferably a layer including a base layer 42, a stripping agent layer 44, and an antistatic layer 46, and the antistatic layer 46 is preferably a It is preferable to contain an inhibitor. The antistatic agent is preferably at least one selected from an ionic antistatic agent, an organic antistatic agent and an inorganic antistatic agent, more preferably at least one selected from an organic antistatic agent and an inorganic antistatic agent, particularly preferably an inorganic antistatic agent Do. It is more preferable that the organic antistatic agent is a π conjugated system conductive high molecular weight antistatic agent. As the antistatic agent, the humidity dependency of the antistatic performance can be suppressed by using at least one selected from the group consisting of a π-conjugated conductive polymeric antistatic agent and an inorganic antistatic agent. That is, in all humidity zones, antistatic performance can be exhibited. In particular, the inorganic antistatic agent can exhibit excellent antistatic performance even in a low humidity environment. Further, since the ionic antistatic agent is comparatively inexpensive, the production 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 it is preferable to use an ionic antistatic agent such as glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, N-bis (2-hydroxyethyl) alkylamine, N, N-bis (2-ethylhexyl) ethylamine, ethylene glycol fatty alcohol ether, alkylsulfonate, alkylbenzenesulfonate, tetraalkylammonium salt, trialkylbenzylammonium salt, stearic acid monoglyceride -Hydroxyethyl) alkylamides, fatty acid esters of polyoxyethylene alkylamines, alkyl sulfates, alkyl phosphates, alkyl betaines, sodium polystyrene sulfonate, polyethylene glycol methacrylate copolymers and polyether ester amides.

As the organic antistatic agent, it is preferable to use a π conjugated system conductive antistatic agent. As the? -conjugated conductive high molecular weight antistatic agent, any known? -conjugated conductive high molecular weight antistatic agent may be used in the present invention, and preferred examples thereof include polythiophene, polypyrrole, polyaniline and the like, Lt; / RTI >

As the inorganic antistatic agent, any of known inorganic antistatic agents can be used in the present invention, and preferable examples thereof include ITO filler, silver nano filler, titanium oxide coated with antimony oxide doped tin oxide, and particularly preferably silver nano- It is a filler.

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

The base layer constituting the separator layer is preferably a resin layer, and the resin layer is preferably composed of a thermoplastic resin. Specifically, the base layer may 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 particularly preferably used. The substrate layer may be a film having concave-convex processing such as a lens film, a prism film, and a holographic film.

The release agent layer includes a release agent. As the releasing agent, for example, general-purpose addition type or condensation type silicone type releasing agent is used. Particularly, an addition-type silicone based release agent having high reactivity is preferably used. Specific examples of silicone release agents include BY24-162 and SD-7234 manufactured by Toray Dow Corning Silicone Co., and KS-3600, KS-774 and X62-2600 manufactured by Shin-Etsu Chemical Co., . Also as, 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 units. Specific examples of the silicone resin include BY24-843, SD-7292 and SHR-1404 manufactured by Toray Dow Corning Silicone Co., Ltd. and KS-3800 and X92-183 manufactured by Shin-Etsu Chemical Co.,

An auxiliary additive such as a catalyst or adhesion improver may be added to the release agent layer. As the catalyst, a platinum-based or tin-based catalyst is preferably used. The adhesion-improving agent may be any kind as long as adhesion is improved, and preferably a silane coupling agent can be used.

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

The separator layer can be formed by applying a releasing agent-containing liquid and an antistatic agent-containing liquid to the substrate layer and drying the same. When each solution is applied, 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 and the like can be used. Among them, it is preferable to use a two-head coater capable of coating one back and forth, and a two-head coater capable of coating a front and back having a gravure head capable of controlling a small amount of coating is particularly preferable. This makes it possible to simultaneously form functional layers on both sides of the substrate layer, and to improve the production efficiency of the separator layer.

(Method for producing laminate)

In the step of producing the laminate of the present invention, it is preferable to irradiate light (ultraviolet ray or electron beam) after laminating the edible layer, the pressure-sensitive adhesive layer and the separator layer so as to have the above-described constitution. Further, it is also possible to form the above-described structure by irradiating a light (ultraviolet ray or electron beam) after laminating the separator layer, the pressure-sensitive adhesive layer and the separator layer, and bonding the decorative layer and the decorative layer. In the case of irradiating a light beam with a configuration including a decorative layer, it is preferable to irradiate a light ray (ultraviolet ray or electron beam) from the side of the separator layer.

The step of irradiating a light ray (ultraviolet ray) is preferably carried out using ultraviolet rays having an illuminance of at least 50 mW / cm < 2 > in a wavelength range of 200 to 400 nm, more preferably irradiated with ultraviolet rays of 70 to 3000 mW / It is particularly preferable to irradiate ultraviolet rays of 100 to 1000 mW / cm 2. The accumulated light quantity is preferably 100 to 10000 mJ / cm 2, and particularly preferably 300 to 3000 mJ / cm 2. As the irradiator for performing such irradiation, it is preferable to use at least one selected from a high-pressure mercury ultraviolet irradiator, a metal halide ultraviolet irradiator, and an electrodeless ultraviolet irradiator. By setting the irradiation conditions of ultraviolet rays having an illuminance of 50 mW / cm < 2 > or more in the wavelength range of 200 to 400 nm within the above-described range, the amount of the monomer component remaining in the pressure- Further, by setting the irradiation conditions in the above range, it is possible to suppress yellowing of the decorative layer by ultraviolet rays.

In the present invention, in addition to the irradiation step using ultraviolet rays having an illuminance of 50 mW / cm 2 or more in the wavelength range of 200 to 400 nm, it is preferable to perform irradiation using ultraviolet rays having an illuminance of 20 mW / cm 2 or less in the wavelength range of 200 to 400 nm . More preferably, irradiation with ultraviolet light having a wavelength in the range of 200 to 400 nm of 1 to 10 mW / cm 2, particularly preferably 2 to 5 mW / cm 2 is performed. As the irradiator for performing such irradiation, it is preferable to use at least one kind selected from a chemical lamp and / or a black light. It is preferable to set the amount of accumulated light to 10 to 1000 mJ / cm 2, more preferably to 40 to 600 mJ / cm 2 by irradiation with 0.01 to 30 minutes, particularly preferably 0.1 to 20 minutes, , And particularly preferably 100 to 400 mJ / cm 2. By setting the irradiation conditions using ultraviolet rays having an illuminance of 20 mW / cm 2 or less in the wavelength range of 200 to 400 nm within the above-mentioned range, the followability of the pressure-sensitive adhesive layer in the TOM molding can be improved.

In the present invention, in the case of irradiating with ultraviolet rays having an illuminance of 20 mW / cm 2 or less in a wavelength range of 200 to 400 nm, it is preferable to carry out irradiation with ultraviolet rays having an illuminance of 50 mW / cm 2 or more in a wavelength range of 200 to 400 nm desirable.

In the present invention, by irradiating ultraviolet rays under the above-described conditions, the proportion of volatile substances contained in the pressure-sensitive adhesive layer can be lowered to a predetermined value or lower while increasing the polymerization degree of the monomer.

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

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, foreign matter such as dust can be prevented from being mixed between the pressure-sensitive adhesive layer and the molded body under vacuum or under reduced pressure. As described above, the laminate of the present invention can be used for molding under a vacuum condition or under a reduced pressure condition, so that the effect can be exerted.

In this specification, the molding under a vacuum condition or a reduced pressure condition is so-called TOM molding. The TOM molding method includes a step of laminating a pressure-sensitive adhesive film on a molded article under a vacuum condition or a reduced pressure condition, and a step of pressing the pressure-sensitive adhesive film to a molded article by a pressure difference. On the other hand, in the present specification, the molding under a vacuum condition or under a reduced pressure condition does not include a method in which a vacuum hole is formed in a molded body, and a method for bringing the adhesive film and the molded body into close contact with each other. Specifically, molding under a vacuum condition or under a reduced pressure condition can be carried out by using a "vacuum molding apparatus" described in Japanese Patent No. 3733564.

The present invention relates to a method of manufacturing an edible molded article as described above. Specifically, the method for producing an edible molded article of the present invention includes a step of laminating an adhesive film on a molded article under vacuum or reduced pressure conditions, and a step of pressing the adhesive film onto the molded article under a pressure difference under pressure condition. Further, in the method for producing a decorated molded article of the present invention, it is preferable to include a step of heating the surface of the layered product to 100 to 180 캜 after the step of pressing the adhesive film onto the formed product. In this case, an infrared heater is preferably used for heating the surface of the laminate.

Further, the pressure-sensitive adhesive film used in the method for producing an edible molded article of the present invention is the above-mentioned pressure-sensitive adhesive film, and the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm.

(Decorative molded article)

The present invention also relates to a decorative molded article comprising a pressure-sensitive adhesive film composed of a decorative layer and a pressure-sensitive adhesive layer of the laminate as described above and a molded article edited with an adhesive film. The decorative molded object is obtained by adhering an adhesive film to a part or the entire surface of a molded article. That is, in the decorative molded object, the decorative layer is laminated via the pressure-sensitive adhesive layer.

3 is a sectional view for explaining the constitution of the decorative molded object 100. Fig. Fig. 3 shows a state in which the molded body 50 having a concave portion on the surface is edited with the adhesive film 20. Fig. As shown in Fig. 3, in the case of molding under a vacuum condition or under a reduced pressure condition, the reverse tapered portion and the end curled portion can be formed by coating without forming a vacuum hole in the formed body 50. [ Also, regardless of the material of the product, it can be edible. As a result, the decorative molded object 100 having high complexity can be obtained even on the surface of the molded body having complicated three-dimensional unevenness.

The molded body 50 may be a metal material such as an ED steel plate, a Mg alloy, stainless steel (SUS), or an aluminum alloy, or a resin molded body, but is preferably a resin molded body. (Copolymers of acrylonitrile, acrylonitrile and styrene), ABS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acrylic and styrene), acrylic resins, But are not limited to, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, A polyetherimide, a polycarbonate, a polyethylene, a polypropylene, a polystyrene, a urethane resin, a vinylidene chloride resin, a vinyl chloride resin and the like can be preferably used. These resins may be blended. For example, a polycarbonate-containing resin and the like can be preferably exemplified. Examples of the polycarbonate-containing resin include a resin (PC · PBT) in which polycarbonate and polybutylene terephthalate are blended, a resin in which polycarbonate and ABS resin are blended (PC · ABS), a resin in which polycarbonate and PET are blended PET) and the like can be particularly preferably used. As the polyolefin resin, polypropylene (PP) can be particularly preferably used.

Specific examples include ABS resins (copolymers of acrylonitrile, butadiene and styrene), AS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acryl and styrene), acrylic resins, But are not limited to, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, Polyacetal, polyether ether ketone, polyphenylene sulfide, polyetherimide, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin and the like.

The decorative molded object obtained by the present invention can be applied to various parts such as automobile parts (such as body parts, bumpers, spoilers, mirrors, wheels, interior parts, and the like), motorcycle parts, road materials It can be used for, for example, traffic signs, soundproof walls, etc., materials for tunnels (eg, side wall plates), railway vehicles, furniture, musical instruments, household appliances, building materials, containers, office supplies, sporting goods, .

Example

Hereinafter, the features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be suitably changed as long as they do not depart from the gist of the present invention. Accordingly, the scope of the present invention should not be construed as being limited by the following specific examples.

(Example 1)

≪ Edging layer (1) >

(TRIC1268) layer (colored layer) was formed on one surface of an acrylic film (Acryprene HBA001P, pencil hardness 2H, thickness of 125 m, manufactured by Mitsubishi Rayon Co., Ltd.) To obtain a decorative layer (1).

≪ Separator layer (1) >

On one surface of a 38 탆 thick PET (Lumirror T60, manufactured by Toray Industries, Inc.), Denatron P-502S (manufactured by Nagase Chemtech Co., Ltd.) containing a π conjugated organic conductive material: poly (3,4-ethylenedioxythiophene) ) Was coated so as to have a coating amount after drying of 0.07 g / m 2, and treated at 130 캜 for 30 seconds by a dryer. Thus, an antistatic layer was formed.

Next, on the opposite surface, a releasing agent consisting of 100 parts by mass of a thermosetting silicone (LTC300B, manufactured by Toray-Dow Corning Toray Co., Ltd.) and 1 part by mass of a catalyst (SRX212, manufactured by Dow Corning Toray Co., Ltd.) And a release agent layer was formed. Thereafter, treatment was carried out at 130 DEG C for 60 seconds in a dryer to obtain a separator layer (1).

<Adhesive (1)>

95 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were placed in a reaction vessel in a nitrogen atmosphere and 0.01 mass parts of an initiator (2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) To obtain a pressure-sensitive adhesive (1) having a polymer concentration of 9% and a weight average molecular weight Mw of 1.5 million.

&Lt; Layered product (1) &gt;

0.1 part by mass of hexanediol diacrylate and 1 part by mass of benzyldimethyl ketal were added to 100 parts by mass of the pressure-sensitive adhesive (1), and nitrogen gas was purged to completely remove dissolved oxygen, and the release agent layer side of the separator layer (1) (Wet lamination) of the pressure-sensitive adhesive 1 so that the thickness of the pressure-sensitive adhesive layer became 50 占 퐉 between the side of the ink layer of the decorative layer 1 of 占 퐉. Thereafter, irradiation was performed using a chemical lamp from the side of the separator layer 1 so that the illuminance of the ultraviolet ray having a wavelength of 365 nm was 4 mW / cm 2 and the accumulated light amount was 300 mJ / cm 2. Next, To an illuminance of 100 mW / cm &lt; 2 &gt; and an accumulated light quantity of 2000 mJ / cm &lt; 2 &gt; The volatile substance contained in the pressure-sensitive adhesive layer of the layered product (1) was measured by gas chromatography and found to be 5 ppm.

&Lt; Preparation method of edged molded article &gt;

The separator layer 1 was peeled from the layered product 1 to obtain an adhesive film 1. The adhesive film (1) was set in a TOM molding machine. (NGF molding machine manufactured by Fuze Vacuum Co., Ltd.) so that the outer surface (convex surface) side of the cover and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film 1 are opposed to each other with a rain-proof liner cover (manufactured by Panasonic Corporation, product number: WP9171) did. The adhesive film (1) was laminated to the above molded body at 130 占 폚 using a TOM molding machine to obtain a decorative molded article (1). In the same manner, ten decorative molded objects 1 were produced.

Figs. 4 (a) to 4 (c) show the shape of the rain-fed lane cover. 4 (a) to 4 (c), when viewed from above as shown in Fig. 4 (a), the length of the cover in the length (longitudinal direction) is 90 mm and the length in the width .

(Example 2)

The thickness of the pressure-sensitive adhesive layer 1 was changed to 75 占 퐉, the separator layer 1 was changed to the separator layer 2 and the ultraviolet irradiation was performed with a high-pressure mercury lamp at an intensity of ultraviolet light of 365 nm wavelength of 300 mW / (2) was obtained in the same manner as in Example 1, except that the layered product (2) was obtained only at 3000 mJ / cm 2. The volatile substance contained in the pressure-sensitive adhesive layer was measured and found to be 23 ppm.

&Lt; Separator Layer (2) &gt;

Glycerin monostearate was coated on one side of 50 탆 thick PET (Lumirror T60, manufactured by Toray Industries, Inc.) so that the coating amount after drying was 0.15 g / m 2 and treated at 130 캜 for 30 seconds by a dryer. Thus, an antistatic layer was formed.

Next, on the opposite surface, a releasing agent consisting of 100 parts by mass of a thermosetting silicone (LTC300B, manufactured by Toray-Dow Corning) and 1 part by mass of a catalyst (SRX212, manufactured by Dow Corning Toray Co., Ltd.) was dried at 0.1 g / So as to form a release agent layer. Thereafter, treatment was carried out at 130 DEG C for 60 seconds by a dryer to obtain a separator layer (2).

(Example 3)

The pressure sensitive adhesive layer 1 was changed to the pressure sensitive adhesive 3 to form a pressure sensitive adhesive layer 3 having a thickness of 25 占 퐉 and an ultraviolet light having a wavelength of 365 nm was irradiated from the side of the separator layer 2 with a chemical lamp at an intensity of 4 mW / Except that the laminate 3 was irradiated so that the light quantity was 100 mJ / cm 2 and then irradiated with a high pressure mercury lamp so that the illuminance of the ultraviolet ray having a wavelength of 365 nm was 100 mW / cm 2 and the accumulated light quantity was 2000 mJ / The decorative molded object 3 was obtained in the same manner as in Example 2. The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 3 was measured and found to be 3 ppm.

<Adhesive (3)>

90 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of acrylic acid and 5 parts by mass of isobornyl acrylate were placed in a reaction vessel in a nitrogen atmosphere and an initiator (2,2'-azobis (4-methoxy- Dimethylvaleronitrile)) as a polymerization initiator to obtain a pressure-sensitive adhesive (3) having a polymer concentration of 8% and a weight average molecular weight Mw of 2,000.

(Example 4)

The pressure sensitive adhesive 1 is replaced with the pressure sensitive adhesive 4 to form the pressure sensitive adhesive layer 4 and a separator layer 3 is used instead of the decorative layer 1 and a metal halide lamp is used instead of the high pressure mercury lamp at a wavelength 365 Sensitive adhesive layer (4) / separator layer (3) were prepared in such a manner that the illuminance of the ultraviolet light of 100 nm / ㎚ and the accumulated light amount of 2000 mJ / Except that the decorative layer 1 was peeled off and the decorative layer 1 was applied to the exposed pressure-sensitive adhesive layer 4 using a roll coater to obtain the layered product 4, 4). The volatile substance contained in the pressure-sensitive adhesive layer of the layered product (4) was measured and found to be 14 ppm.

<Adhesive (4)>

95 parts by mass of butyl acrylate and 5 parts by mass of 2-hydroxymethyl acrylate were placed in a reaction vessel in a nitrogen atmosphere, and an initiator (2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ) To obtain a solution (4) having a polymer concentration of 11% and a weight average molecular weight Mw of 1,000,000. To this solution (4), 15 parts by mass of a rosin-based tackifier (KE311 manufactured by Arakawa Chemical Industries, Ltd.) was added and stirred to obtain a pressure-sensitive adhesive (4).

&Lt; Separator Layer (3) &gt;

(CST-NW-S40, manufactured by Cold stones, CST-NW-S40) and a polyester binder (PESRESIN A-645GH manufactured by Takamatsu KK) were blended so as to have a dry weight of 20:80, Manufactured by Toray Industries, Inc., Lumirror T60). The coating amount was such that the coating amount after drying was 0.01 g / m 2, and the coating was performed in a clean room (class 1000). Thereafter, treatment was carried out at 130 DEG C for 30 seconds in a dryer to form an antistatic layer (D).

Next, on the opposite surface, a releasing agent consisting of 100 parts by mass of a thermosetting silicone (LTC300B, manufactured by Toray-Dow Corning) and 1 part by mass of a catalyst (SRX212, manufactured by Dow Corning Toray Co., Ltd.) was dried at 0.1 g / So as to form a release agent layer in a clean room (class 1000). Thereafter, the separator layer 3 was treated by a dryer at 130 DEG C for 60 seconds.

(Example 5)

A laminated body 5 was produced in the same manner as in Example 4 except that the pressure-sensitive adhesive 1 was changed to the pressure-sensitive adhesive 5 to make the thickness of the pressure-sensitive adhesive layer 5 25 m, and a decorative molded article 5 was obtained.

The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 5 was measured and found to be 4 ppm.

<Adhesive 5>

90 parts by mass of 2-ethylhexyl acrylate and 10 parts by mass of acrylic acid were placed in a reaction vessel in a nitrogen atmosphere, and 0.01 mass parts of an initiator (2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) To obtain a solution (5) having a polymer concentration of 11% and a weight average molecular weight Mw of 1.5 million. 10 parts by mass of a terpene-based tackifier (TH130, produced by Yasuhara Chemical Co., Ltd.) and an aliphatic hydrocarbon-based tackifier (Alcon M100 manufactured by Arakawa Chemical Industries, Ltd.) were added to this solution 5 and stirred. .

(Example 6)

The decorative article 6 was obtained in the same manner as in Example 2 except that the thickness of the pressure-sensitive adhesive layer was changed to 200 탆 and the separator layer 2 was replaced with the separator layer 4. The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 6 was measured and found to be 30 ppm.

&Lt; Separator Layer (4) &gt;

100 parts by mass of a thermosetting silicone (LTC300B, manufactured by Dow Corning Toray Co., Ltd.) and 1 part by mass of a catalyst (SRX212, manufactured by Dow Corning Toray Co., Ltd.) were laminated on one surface of a 38 탆 thick PET (Lumirror T60, Was applied so as to have a dry weight of 0.1 g / m &lt; 2 &gt; to form a release agent layer. Thereafter, the separator layer 4 was treated at 130 캜 for 60 seconds in a dryer.

(Comparative Example 1)

It was tried to obtain the decorative molded object 11 by using the adhesive film 11 from which the separator layer 4 was peeled off from the layered product 11. However, when the TOM type molding machine was used to perform the processing at 130 占 폚, A good decorated molded article could not be obtained. The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 11 was measured and found to be 80 ppm.

&Lt; Layered product (11) &gt;

The pressure-sensitive adhesive 11 was coated on the release agent layer of the separator layer 4 so that the thickness after drying was 25 占 퐉 and dried at 90 占 폚 for 10 minutes and then the decorative layer 1 was laminated with a roll coater, (11).

&Lt; Adhesive (11) &gt;

65 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate and 5 parts by mass of acrylic acid were placed in a reaction vessel (temperature controller, stirrer and reflux condenser) in a nitrogen atmosphere, and 200 parts by mass of ethyl acetate and 0.1 parts by mass of azobisisobutyronitrile Mass part was added to carry out a polymerization reaction to obtain a polymer A. The weight average molecular weight Mw of the obtained polymer A was 800,000. The resulting polymer A was mixed with poly (alpha methylstyrene) (molecular weight Mw = 850,000, Tg = 105 ° C, manufactured by Wako Pure Chemical Industries, Ltd.) and a crosslinking agent (Tetrad X manufactured by Mitsubishi Gas Chemical Company, To obtain a pressure-sensitive adhesive (11).

(Comparative Example 2)

It was tried to obtain the decorative molded article 12 by using the adhesive film 12 from which the separator layer 2 was peeled from the layered product 12. However, when the pressure-sensitive adhesive layer was foamed at 130 占 폚 using a TOM molding machine, A good decorated molded article could not be obtained. The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 12 was measured and found to be 140 ppm.

&Lt; Layered product (12) &gt;

A layered product (12) was obtained in the same manner as in Comparative Example 1 except that the pressure-sensitive adhesive (12) was applied on the release agent layer of the separator layer (2) so that the thickness after drying was 75 占 퐉.

<Adhesive (12)>

65 parts by mass of butyl acrylate, 30 parts by mass of methyl acrylate and 5 parts by mass of 2-hydroxyethyl acrylate were placed in a reaction vessel (temperature controller, stirrer and reflux condenser) in a nitrogen atmosphere, 200 parts by mass of ethyl acetate, And 0.1 parts by mass of azobisisobutyronitrile were added to carry out a polymerization reaction to obtain a polymer B. [ The weight average molecular weight Mw of the obtained polymer B was 800,000.

A pressure-sensitive adhesive (12) was obtained by blending the obtained polymer B, a cross-linking agent (Tetrad X) manufactured by Mitsubishi Gas Chemical Company, and bistrifluoromethane sulfonimide in a dry weight ratio of 96: 2: 2.

(Comparative Example 3)

It was tried to obtain the decorative molded article 13 by using the adhesive film 13 from which the separator layer 1 was peeled off from the layered product 13. However, when the pressure-sensitive adhesive layer was foamed at 130 占 폚 using a TOM molding machine, A good decorated molded article could not be obtained.

&Lt; Layered product (13) &gt;

A layered product (13) was obtained in the same manner as in Example 1 except that the high-pressure mercury lamp was used to adjust the intensity of ultraviolet rays at a wavelength of 365 nm to 100 mW / cm2 and the accumulated light quantity to 50 mJ / cm2. The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 13 was measured and found to be 610 ppm.

(Comparative Example 4)

The decorative molded body 14 is obtained by using the adhesive film 14 obtained by peeling the separator layer 1 from the laminated body 14. However, A good decorated molded article could not be obtained.

&Lt; Layered product (14) &gt;

The separator layer 1 / the pressure-sensitive adhesive layer 4 / the separator 4 were formed in the same manner as in Example 4 except that the metal halide lamp was irradiated with ultraviolet light having a wavelength of 365 nm so as to have an illuminance of 100 mW / cm 2 and an integrated light quantity of 50 mJ / The laminate 14 is formed by peeling the separator layer 1 and then peeling off the exposed adhesive layer 4 with the decorative layer 1 using a roll coater, . The volatile substance contained in the pressure-sensitive adhesive layer of the layered product 14 was measured and found to be 310 ppm.

(evaluation)

(Measurement of Surface Electrical Resistance Value)

The surface electrical resistance was measured by means of Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Engineering Co., Ltd.) after allowing the laminate to humidify and stand for one day under an environment of 23 캜 and 50% RH.

(TOM moldability)

When the pressure-sensitive adhesive films of Examples 1 to 6 and Comparative Examples 1 to 4 were molded, evaluation of moldability was evaluated as good (?). When the film was formed, it was evaluated that the foamed material was observed as poor in moldability (X). The results are shown in Table 1.

(Number of defects)

The surface of the decorated molded article obtained by using the laminate (adhesive film) obtained by aging in an environment of 23 캜 and a relative humidity of 50% was observed, and the number of defects on the bulged surface in a convex shape was measured. The upper surface (the area corresponding to the upper surface in Fig. 4 (a)) of the decorative molded object obtained in each of the examples and the comparative examples was observed with a laser microscope (VK-X100, manufactured by Keans) Respectively. Here, the number of defects is an average value of the number of defects in the copper area of the ten decorated molded articles produced in each of the examples and comparative examples.

(Number of defects under low humidity environment)

The surface of the decorated molded product obtained by using the laminate (adhesive film) obtained by aging under the environment of 15 캜 and a relative humidity of 30% was observed in the same manner as above to measure the number of defects and obtain an average value.

(adhesiveness)

A test piece of 25 x 50 mm was affixed to the ABS plate and subjected to compression bonding (2 kg roller, one reciprocation) and heat treatment (130 캜, 1 min.) And left for 24 hours. Then, using a tensile tester, The force required to peel the test piece when the test piece was peeled off under conditions of a peeling speed of mm / min, a peeling angle of 180 degrees, a measurement temperature of 23 占 폚, and a measurement humidity of 50% was measured.

(Durability (crosscut test))

The decorated molded article was allowed to stand for 500 hours under an environment of 80 DEG C, and after left standing, 11 cuts were made on the surface of the film at intervals of 2 mm at room temperature to make 100 checkerboard scales. After the cellophane tape was brought into close contact with the surface of the cellophane tape, the number of scales remaining without being peeled off at one time was displayed.

When the TOM was molded using the adhesive film obtained in the examples, the TOM moldability was good. On the other hand, when TOM molding was carried out using the adhesive film obtained in the comparative example, foaming occurred from the pressure-sensitive adhesive layer.

In addition, the laminate obtained in the examples has a small number of defects and exhibits good adhesion to the molded article. Further, it can be seen that the decorative molded object obtained in the examples is excellent in durability.

20 adhesive film
22 The decorative layer
24 pressure-sensitive adhesive layer
26 Separator layer
30 laminate
32 surface protective layer
34 colored layer
42 base layer
44 Release material layer
46 antistatic layer
50 shaped body
100

Claims (12)

A pressure-sensitive adhesive sheet comprising: a pressure-sensitive adhesive layer; and a decorative layer laminated on one side of the pressure-
Wherein the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm. The method according to claim 1,
The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer is an ultraviolet curable pressure-sensitive adhesive. 3. The method according to claim 1 or 2,
Wherein the volatile substance is at least one selected from a solvent, an oligomer which is a component of a monomer constituting the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, and an adhesive constituting the pressure-sensitive adhesive layer. 4. The method according to any one of claims 1 to 3,
Wherein the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer comprises a (meth) acrylic acid ester monomer unit. 5. The method according to any one of claims 1 to 4,
Wherein the pressure-sensitive adhesive layer has a thickness of 20 占 퐉 or more. 6. The method according to any one of claims 1 to 5,
Wherein the decorative layer has a thickness of 75 占 퐉 or more. 7. The method according to any one of claims 1 to 6,
An adhesive film used for forming under vacuum or under reduced pressure. 1. A laminate having a pressure-sensitive adhesive layer, a decorative layer laminated on one surface side of the pressure-sensitive adhesive layer, and a separator layer laminated on the surface side opposite to the surface on which the decorative layer is laminated as another surface side of the pressure-
And the volatile substance contained in the pressure-sensitive adhesive layer is less than 50 ppm. 9. The method of claim 8,
Wherein at least one of the pressure-sensitive adhesive layer, the decorative layer and the separator layer has a layer having a surface electrical resistance of 1 x 10 ^{5 to} 1 x 10 ¹² ? / ?. 10. The method according to claim 8 or 9,
Wherein the separator layer has a layer having a surface electrical resistance of 1 x 10 &lt; ⁵ &gt; to 1 x 10 &lt; ¹² &gt; A decorative molded article comprising the adhesive film of any one of claims 1 to 7 and a molded article edged with the adhesive film. A step of laminating the pressure-sensitive adhesive film on a molded article under a vacuum condition or under a reduced pressure condition,
And pressing the pressure-sensitive adhesive film against the molded body by an air pressure difference,
Wherein the pressure sensitive adhesive film has a pressure sensitive adhesive layer and a decorative layer laminated on one surface side of the pressure sensitive adhesive layer, and the volatile substance contained in the pressure sensitive adhesive layer is less than 50 ppm.

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