CN107636099B

CN107636099B - Adhesive film, laminate, and decorative molded article

Info

Publication number: CN107636099B
Application number: CN201680033342.0A
Authority: CN
Inventors: 太田喜宽; 锦织义治
Original assignee: Oji Holdings Corp
Current assignee: Oji Holdings Corp
Priority date: 2015-06-15
Filing date: 2016-06-13
Publication date: 2021-06-22
Anticipated expiration: 2036-06-13
Also published as: WO2016203304A1; KR20180002830A; KR102255602B1; CN107636099A; TW201706130A; JP6601494B2; JPWO2016203304A1; TWI608939B

Abstract

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

Description

Adhesive film, laminate, and decorative molded article

Technical Field

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

This application claims priority based on Japanese patent application No. 2015-120042 filed on 15/6/2015 and the contents of which are incorporated herein.

Background

Conventionally, when the surface of an automobile interior and exterior part, a household electrical appliance part, a building material part, or the like is protected or decorated (decorated), a molded body is processed by injection molding, vacuum molding, or the like, and then a coating material is applied to the surface of the molded body by spray coating or the like, followed by drying and heat curing. However, such coating has problems that the discharge of the volatile organic solvent deteriorates the working environment, and that the coating requires a working process and production equipment for each molded part and coating of the coating material is repeated, so that the finished product rate of the coating material is poor and the productivity is low.

In recent years, the use of resin molded articles as molded articles has been advanced for the purpose of reducing the weight of automobile interior and exterior parts, household electrical appliances, building material parts, and the like. In many cases, the decoration (decoration) of the resin molded product is not suitable for spray coating, and various methods have been developed for decorating the surface of the resin molded product. Among them, the method of obtaining a decorative molded article by decorating the outermost surface of the molded article with a decorative film has advantages of high degree of freedom in design and excellent productivity as compared with a method of coating or printing the surface with a paint or the like. In addition, a decoration method using a decorative film can decorate the surface of a molded article having three-dimensional irregularities, and thus is used for various applications.

As a method for decorating the surface of a molded article having three-dimensional unevenness with a decorative film, there is a method of three-dimensional overmolding (TOM molding) (patent document 1). TOM molding is a molding method under vacuum conditions or reduced pressure conditions, and is a method of obtaining a decorative molded article by pressure-bonding a decorative film to a molded article. In the TOM molding, decoration can be performed regardless of the material of the molded body. Further, the reverse tapered portion and the terminal clamping portion can be overmolded without providing a vacuum hole in the molded body.

Some decorative films used for TOM molding include adhesive films in which an adhesive layer or an adhesive layer is laminated on a decorative layer. When a decorative molded article 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 that can obtain adhesiveness by heating at the time of TOM molding. In addition, 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.

As the adhesive constituting the adhesive layer, a solvent-based adhesive is generally used, but the use of an ultraviolet-curable adhesive is also studied. For example, patent document 2 discloses a decorative sheet having a decorative layer and an ionizing radiation-curable adhesive layer. Here, the ionizing radiation-curable pressure-sensitive adhesive layer has a property of being capable of temporary adhesion for a certain period of time, and the polymerization reaction of the monomer component constituting the pressure-sensitive adhesive is performed over time.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 3733564

Patent document 2: japanese patent laid-open publication No. 2004-142107

Disclosure of Invention

Technical problem to be solved by the invention

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 for the adhesive layer. However, when a solvent-based adhesive is used, the adhesive layer is liable to foam, which is a problem.

Further, patent document 2 has studied on the use of an ultraviolet-curable adhesive for an adhesive layer, but it has been found by the study of the inventors of the present invention that when the decorative film of patent document 2 is used for TOM molding, the decorative film is likely to foam after temporary adhesion, and the yield of a decorative molded article and the like are deteriorated.

Therefore, the present inventors have made studies to solve the above-mentioned problems of the prior art and have an object of providing an adhesive film in which foaming from an adhesive layer is suppressed when TOM molding is performed.

Means for solving the problems

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found that foaming during TOM molding can be suppressed by setting the volatile component contained in the adhesive layer to a certain level or less in an adhesive film having a decorative layer and an adhesive layer.

Specifically, the present invention has the following configuration.

[1] An adhesive film characterized by comprising an adhesive layer and a decorative layer laminated on one surface side of the adhesive layer, wherein 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 at least 1 selected from a monomer as a constituent of an adhesive constituting the adhesive layer and an oligomer as a constituent of an adhesive constituting the adhesive layer.

[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 decorative layer has a thickness of 75 μm or more.

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

[8] A laminate, comprising: an adhesive layer, a decorative layer laminated on one surface side of the adhesive layer, and a separation layer laminated on the other surface side of the adhesive layer, the other surface side being the opposite surface side to the surface on which the decorative layer is laminated; characterized in that the volatile substance contained in the adhesive layer is less than 50 ppm.

[9]According to [8]The laminate, wherein at least one of the adhesive layer, the decorative layer and the isolation layer has a surface resistance of 1 × 10⁵～1×10¹²Omega/□.

[10]According to [8]Or [9 ]]The laminate, wherein the separator has a surface resistance of 1 × 10⁵～1×10¹²Omega/□.

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

[12] A method of manufacturing a decorative molding, comprising: laminating the adhesive film on the molded body under vacuum or reduced pressure; a step of pressing the adhesive film to the molded body by utilizing the air pressure difference; 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.

Effects of the invention

According to the present invention, an adhesive film in which foaming from an adhesive layer is suppressed at the time of TOM molding can be obtained. 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 having excellent design properties can be obtained.

Drawings

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

Fig. 2 is a sectional view illustrating the structure of the laminate of the present invention.

Fig. 3 is a sectional view illustrating the structure of the decorative molded article of the present invention.

FIG. 4 is a diagram illustrating molded bodies used in examples and comparative examples. Fig. 4(a) is a plan view, fig. 4(b) is a right side view, and fig. 4(c) is a bottom view.

Detailed Description

The present invention will be described in detail below. In the following description of the constituent elements, the description may be based on a representative embodiment and a specific example, but the present invention is not limited to such an embodiment. In the present specification, the numerical range expressed by "to" means a range including numerical values before and after "to" as a lower limit value and an upper limit value.

(adhesive film)

The adhesive film of the present invention includes an adhesive layer and a decorative layer laminated on one surface side of the adhesive layer. The volatile substance contained in the adhesive layer is less than 50 ppm. The volatile substance contained in the adhesive layer is preferably less than 30ppm, more preferably 15ppm or less, and particularly preferably 5ppm or less. Here, the volatile substance means a substance which is volatilized under vacuum at 150 ℃. The adhesive film of the present invention is a film before TOM molding which is bonded to an object to be bonded (molded body), and is characterized in that the content of volatile substances in the adhesive film before bonding is within the above range.

Examples of the volatile substance include at least 1 selected from a solvent, a monomer that is a constituent of an adhesive constituting the adhesive layer, and an oligomer that is a constituent of an adhesive constituting the adhesive layer. The oligomer as a component of the adhesive is obtained by polymerizing 2 to 5 monomers as a component of the adhesive.

Since the adhesive film of the present invention has the above structure, when molding is performed under vacuum conditions or under reduced pressure conditions (TOM molding), foaming in the adhesive layer can be suppressed. The adhesive film of the present invention can exhibit excellent adhesive force to a molded article to be adhered, and therefore is preferably used as an adhesive film for molding under vacuum conditions or under reduced pressure conditions.

Fig. 1 is a cross-sectional view showing an example of the structure of the 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 surface side of the decorative layer 22. In such an adhesive film 20, the adhesive layer 24 is attached to the surface of a molded body to be adhered, thereby decorating the molded body.

In the adhesive film of the present invention, the thickness of the adhesive agent layer is preferably 20 μm or more, more preferably 35 μm or more, still more preferably 70 μm or more, and particularly preferably 150 μm or more. In the present invention, by setting the thickness of the adhesive agent layer within the above range, even when the adhesive agent layer bites in a foreign substance, the foreign substance can be prevented from coming off to the surface of the decorative molded body. Therefore, if the foreign matter or the air bubbles are fine, the foreign matter or the air bubbles are not affected by the biting.

The thickness of the decorative layer is preferably 50 μm or more, more preferably 100 μm or more, and still more preferably 180 μm or more. In the present invention, by setting the thickness of the decorative layer within the above range, even when the adhesive layer bites in a foreign substance, the foreign substance can be prevented from coming off to 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. Examples of the ultraviolet-curable adhesive include solvent-free adhesives 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, "unit" refers to a repeating unit (monomer unit) constituting a polymer. Further, "(meth) acrylic acid" is meant to include both "acrylic acid" and "methacrylic acid".

Examples of the (meth) acrylate ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, lauryl (meth) acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isopropyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and the like. These (meth) acrylate monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among them, at least 1 selected from methyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is preferably used.

Further, the following components may be contained as necessary. Examples thereof include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 6-hexanediol diacrylate, polytetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and the like. Further examples include: a component having a carboxyl group, preferably acrylic acid, methacrylic acid, maleic acid, crotonic acid, β -carboxyethyl acrylate; and/or a component having a hydroxyl group, preferably 2-hydroxyethyl (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 components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile, macromonomers. The component having a carboxyl group, the component having a hydroxyl group, and the copolymerizable component are preferably contained in an amount of 0.1 to 30% by mass, preferably 1 to 10% by mass, based on the acrylic polymer.

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

In addition to the acrylic polymer, the adhesive constituting the adhesive layer may contain 0 to 40 mass%, more preferably 10 to 25 mass% of an aliphatic (C5) -based petroleum resin, an aromatic (C9) -based petroleum resin, a copolymerized (C5/C9) -based petroleum resin, a dicyclopentadiene (DCPD) -based petroleum resin, a coumarone-indene resin, a styrene-based resin containing an α -methylstyrene-based resin, a rosin ester resin, a terpene-based resin, an aromatic modified terpene resin, a terpene-based resin, a hydrogenated resin thereof, or the like, in the adhesive.

The adhesive constituting the adhesive layer preferably contains 0.1 to 10% by mass, more preferably 0.5 to 5% by mass of a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator. Examples of the polymerization initiator include acetophenone type initiators, benzoin ether type initiators, benzophenone type initiators, hydroxyalkyl benzophenone type initiators, thioxanthone type initiators, amine type initiators, and acylphosphine oxide type initiators.

Specific examples of the acetophenone initiator include diethoxyacetophenone and benzildimethylketal.

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

Specific examples of the benzophenone initiator include benzophenone and methyl benzoylbenzoate.

Specific examples of the hydroxyalkyl phenone 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 initiator include triethanolamine and ethyl 4-dimethylbenzoate.

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

The adhesive agent layer may contain, as necessary, a crosslinking agent, a chain transfer agent, a sensitizer, a light stabilizer, a filler, a pigment, a thickener, a viscosity modifier, a wetting agent, a leveling agent, a defoaming agent, an antiseptic, a dispersant, an antioxidant, an antifreezing agent, a flame retardant, and the like, which are known additives, in a range where the effects of the present invention are not impaired.

The average molecular weight of the acrylic polymer constituting the adhesive layer is preferably 1 to 500 ten thousand, more preferably 30 to 300 ten thousand, and particularly preferably 70 to 250 ten thousand. By setting the average molecular weight of the acrylic polymer within the above range, when molding is performed under vacuum conditions or under reduced pressure conditions (TOM molding), the following property to the molded article can be improved, and a molded article having a complicated shape can be decorated. The acrylic polymer preferably has a molecular weight distribution (Mw/Mn) of 1 to 30, more preferably 1 to 20, and particularly preferably 1 to 6. In order to obtain a desired molecular weight distribution, 2 or more kinds of polymers having different average molecular weights may be used in combination.

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

The surface resistance of the adhesive layer is preferably 1X 10⁵～1×10¹²Omega/□, more preferably 1X 10⁶～1×10¹²Omega/□. Particularly, the surface resistance of the isolation layer is not 1X 10⁵～1×10¹²When the ratio Ω/□ is within the range, the surface resistance of the adhesive layer is preferably within the above range. The surface resistance of the adhesive layer may be in the above range on either side.

In order to set the surface resistance of the adhesive layer to 1X 10⁵～1×10¹²Omega/□, the adhesive layer preferably contains an antistatic agent. Particularly, the surface resistance of the isolation layer is not 1X 10⁵～1×10¹²In the case where the ratio is in the range of Ω/□, the adhesive layer preferably contains an antistatic agent. The antistatic agent contained in the adhesive layer may be the same as that contained in the barrier layer described later, and preferred antistatic agents are also the same.

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

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% by mass, and still more preferably 1 to 5% by mass, based on the total mass of the adhesive layer.

The adhesive force of the adhesive layer is preferably 10 to 200N/25mm, more preferably 25 to 100N/25mm, as measured according to JIS Z0237.

(decorative layer)

The laminate of the present invention contains a decorative layer. The decorative layer may have a single-layer structure, but is preferably a layer having a surface protective layer containing an ultraviolet absorber and a colored layer. In addition, the colored layer preferably contains a pigment, a dye, 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, an evaporated or sputtered layer formed of a pigment, a dye, a metal, or a metal oxide, or a layer formed by printing an ink layer containing a pigment, a dye, a metal, or a metal oxide on the decorative layer. In this case, the printed 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 relief printing, offset printing, flexographic printing, gravure printing, and inkjet printing. Examples of the printing ink used for these printings include oxidative polymerization type oil-based ink, soybean oil ink, vegetable oil ink, ultraviolet ray-curable UV ink, LED-UV ink, gravure ink, flexographic ink, screen printing ink, and the like, and gravure ink, screen printing ink, and inkjet ink are particularly preferable. If necessary, additives such as pigment dispersants, antifoaming agents, ultraviolet absorbers, antioxidants, antistatic agents, abrasion inhibitors, and antiblocking agents may be added to the printing ink.

Further, when the colored layer is a resin layer containing a pigment, a dye, a metal, and a metal oxide, the resin layer is preferably made of a thermoplastic resin. Specifically, ABS resins (copolymers of acrylonitrile, butadiene and styrene), AS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acrylic acid and styrene), acrylic resins, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resins, urea resins, melamine resins, liquid crystal polymers, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyether sulfone, polyacetal, polyether ether ketone, polyphenylene sulfide, polyether imide, polyamide imide, polycarbonate, polyethylene, polypropylene, polystyrene, polyurethane resins, vinylidene chloride, vinyl chloride and the like are preferable.

Examples of pigments that can be included in the colored layer include inorganic pigments (alumina white, titanium oxide, zinc oxide, black iron oxide, micaceous iron oxide, white lead, white carbon black, molybdenum white, carbon black, lead monoxide, lithopone, barite, cadmium red, cadmium mercury red, red iron oxide, molybdenum red, red lead, chrome yellow, cadmium yellow, barium yellow, strontium yellow, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chromium green, ultramarine, prussian blue, cobalt blue, cyan blue, manganese violet, cobalt violet, etc.) and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyed lakes, etc.); or insoluble azo pigments such as toluidine red, toluidine mauve, Hansa yellow (Hansa yellow), benzidine yellow, and pyrazolone red; soluble azo pigments such as lisoshir red, elio jujube red (Helio Bordeaux), scarlet pigment, permanent red 2B, and the like; derivatives such as alizarin, indanthrone, thioindigo maroon, etc.; 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-based pigments such as pyranthrone red and pyranthrone orange; thioindigo pigments; a condensed azo pigment; pyrrolopyrrole dione type pigments; and (3) yellow (flavanthrone yellow), amide yellow, quinophthalone yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinone red, dioxazine violet, and other pigments. The present invention is not limited to these dyes, and any known pigment may be used.

Examples of the dye that the colored layer may have include an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, and an edible pigment. Any known dye may be used in the present invention, and is not limited thereto. Among these dyes, azo dyes and phthalocyanine dyes are particularly preferable, and acid dyes, direct dyes, reactive dyes, food dyes, 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 a layer constituting the outermost surface in the decorative molded article. In particular, when a member requiring strength, such as an automobile interior or exterior member, is decorated, the surface protective layer is required to have scratch resistance, strength, and the like. The pencil hardness of the surface protective layer of the present invention is preferably B or more, and more preferably F or more.

The surface protective layer is preferably a resin layer. Specifically, ABS resins (copolymers of acrylonitrile, butadiene and styrene), AS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acrylic acid and styrene), acrylic resins, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resins, urea resins, melamine resins, liquid crystal polymers, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacetal, polyether ether ketone, polyphenylene sulfide, polyetherimide, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, polyurethane resins, vinylidene chloride resins, vinyl chloride resins, and the like are preferably listed. Acrylic resins are more preferable because of their excellent scratch resistance. Further, the surface protective layer of the present invention may be an ionizing radiation curable resin. The ionizing radiation curable resin refers to a resin that is cured by irradiation with an electron beam, ultraviolet light, or the like. 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 resistance of the decorative layer is preferably 1X 10⁵～1×10¹²Omega/□, more preferably 1X 10⁶～1×10¹²Omega/□. In particular, the surface resistance of the release layer and the adhesive layer is not 1X 10⁵～1×10¹²When the Ω/□ is in the range, the surface resistance of the decorative layer is preferably in the above range. The surface resistance of the decorative layer may be within the above range.

When the surface resistance of the decorative layer is in the above range, an antistatic agent may be contained between the surface protection layer and the colored layer. In this case, the same antistatic agents as those listed in the item of the release layer described later can be used as the antistatic agent.

The surface resistance of the decorative layer was measured by using Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Analyticech Co., Ltd., measurement method: constant voltage application/leakage current measurement method).

(laminated body)

The present invention relates to a laminate having: the adhesive layer, the decorative layer laminated on one surface side of the adhesive layer, and the isolation layer laminated on the other surface side of the adhesive layer, the other surface side being the opposite surface side to the surface on which the decorative layer is laminated. Here, the volatile substance 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 laminate of the present invention. As shown in fig. 2(a), the laminate 30 of the present invention includes: the adhesive layer 24, the decorative layer 22 laminated on one surface side of the adhesive layer 24, and the spacer layer 26 laminated on the other surface side of the adhesive layer 24, which is the opposite surface side from the surface on which the decorative layer 22 is laminated. Since the laminate 30 has the separator 26, it is possible to prevent foreign matter such as dirt from adhering to the surface of the adhesive layer 24 during storage of the laminate 30. When the laminate 30 of the present invention is used, the separator 26 is peeled off to expose the adhesive layer 24. Then, the adhesive layer 24 is attached to a molded article as an adherend. In this specification, the laminate from which the separator 26 has been peeled off is referred to as an adhesive film 20.

Fig. 2(b) is a cross-sectional view showing a preferred structure of the laminate of the present invention. In the laminate 30 of the present invention, the decorative layer 22 is preferably a layer including the surface protective layer 32 and the colored layer 34. The separator 26 preferably includes a base layer 42, a release agent layer 44, and an antistatic layer 46. The laminate 30 of the present invention may have a layer other than the above-described layers, may have a structure in which the decorative layer 22 further has an antistatic layer, and may have a structure in which the adhesive layer has a colored layer and/or an antistatic layer.

In the laminate 30 shown in fig. 2(b), the separator 26 is peeled off to form the adhesive film 20.

The laminate of the present invention may be in the form of a sheet or may be wound in a roll form because of the above-described structure. When wound in a roll shape, the separator is preferably wound so as to be disposed on the mandrel side.

(isolation layer)

The laminate of the present invention contains a separator. The spacer layer is preferably a resin layer that does not include a paper base. By using such a separator, foreign matter such as dirt from paper is not sandwiched between the laminate and the molded body, and biting of foreign matter can be effectively suppressed.

The surface resistance of the isolation layer is preferably 1 × 10⁵～1×10¹²Omega/□, more preferably 1X 10⁶～1×10¹²Omega/□. In the laminate, foreign matter tends to be easily attached to the adhesive layer due to electrostatic interaction when the separator 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, and particularly, when molding is performed under vacuum conditions or under reduced pressure conditions (TOM molding), biting of foreign matter can be more effectively suppressed. The surface resistance of the spacer layer may be in the above range.

The separator has a single-layer structure, and the surface resistance of the single layer may be in the above range, but it is preferable that the separator has a layer having a surface resistance in the above range. Specifically, the isolation layer preferably has: the antistatic layer is laminated on the other surface side of the base layer, and the other surface side is the surface side opposite to the surface on which the release agent layer is laminated. Wherein the surface resistance of the antistatic layer is preferably 1 × 10⁵～1×10¹²Ω/□。

In the present invention, it is preferable that the release layer contains an antistatic agent, and it is preferable that the adhesive film composed of the decorative layer and the adhesive layer does not contain an antistatic agent. In the present invention, when the laminate is used, the separator is peeled off from the laminate to form an adhesive film composed of the decorative layer and the adhesive layer. The adhesive film is then attached to a molded article as an adherend. That is, when only the barrier layer contains the antistatic agent, the decorative molded article does not contain the antistatic agent, and the durability of the whole decorative molded article can be further improved.

The surface resistance of the separator was measured by using Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical analytical Co., Ltd., measurement method: applied constant voltage/leakage current measurement method).

As shown in fig. 2(b), the separation layer 26 is preferably a layer containing a base layer 42, a release agent layer 44, and an antistatic layer 46, and the antistatic layer 46 preferably contains an antistatic agent. The antistatic agent is preferably at least 1 selected from ionic antistatic agents, organic antistatic agents and inorganic antistatic agents, more preferably at least 1 selected from organic antistatic agents and inorganic antistatic agents, and particularly preferably an inorganic antistatic agent. The organic antistatic agent is more preferably a pi-conjugated conductive polymer antistatic agent. By using at least 1 kind selected from the group consisting of pi conjugated conductive polymer antistatic agents and inorganic antistatic agents as the antistatic agent, the humidity dependence of antistatic performance can be suppressed. That is, the antistatic performance can be exhibited in all humidity bands. In particular, inorganic antistatic agents can exhibit excellent antistatic performance even in a low humidity environment. In addition, since the ionic antistatic agent is relatively 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 preferable examples thereof include glyceric acid fatty acid ester, polyglyceric fatty acid ester, sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, alkylsulfonate, alkylbenzenesulfonate, tetraalkylammonium salt, trialkylbenzylammonium salt, monoglyceride stearate, N-bis (2-hydroxyethyl) alkylamine, N-bis (2-hydroxyethyl) alkylamide, fatty acid ester of polyoxyethylene alkylamine, alkyl sulfate, alkyl phosphate, alkylbetaine, sodium polystyrene sulfonate, polyethylene glycol methacrylate copolymer, polyether ester amide and the like.

As the organic antistatic agent, a pi conjugated conductive polymer antistatic agent is preferably used. As the pi-conjugated conductive polymer antistatic agent, any known pi-conjugated conductive polymer antistatic agent can be used in the present invention, but polythiophene, polypyrrole, polyaniline, and the like can be preferably used, and polythiophene is particularly preferable.

As the inorganic antistatic agent, any known inorganic antistatic agent can be used in the present invention, and ITO filler, silver nanofiller, antimony oxide-doped tin oxide-coated titanium oxide, and the like can be preferably used, and particularly silver nanofiller is preferable.

When the antistatic layer contains an antistatic agent, the content of the antistatic agent is preferably 2 to 100% by mass, more preferably 50 to 100% by mass, relative to the total mass of the antistatic layer. Further, the coating amount of the antistatic layer after drying is preferably 0.001 to 1g/m²Particularly preferably 0.01 to 0.2g/m²。

The base layer constituting the separator is preferably a resin layer, and the resin layer is preferably made of a thermoplastic resin. Specifically, examples of the base layer include a polyolefin film, a polyvinyl chloride film, a polyvinyl alcohol film, a polyester film, a polycarbonate film, a polystyrene film, and a polyacrylonitrile film. Among them, a polyester film is preferably used, and a polyethylene terephthalate (PET) film is particularly preferably used. In addition, a film subjected to embossing such as a lens film, a prism film, or a hologram film may be used as the base layer.

The release agent layer contains a release agent. As the release agent, for example, a general-purpose addition type or condensation type silicone-based release agent can be used. In particular, addition silicone-based release agents having high reactivity are preferably used. Specific examples of the silicone-based release agent include BY24-162 and SD-7234 manufactured BY Dow Corning Toray Co., Ltd, KS-3600, KS-774 and X62-2600 manufactured BY Shin-Etsu Chemical Co., Ltd. Further, the silicone-based release agent preferably contains SiO₂Unit, (CH)₃)₃SiO_1/2Unit or CH₂＝CH(CH₃)SiO_1/2A silicone resin as the organosilicon compound. Specific examples of the silicone resin include BY24-843, SD-7292, and SHR-1404 manufactured BY Dow Corning Toray Co., Ltd, andKS-3800, X92-183, and the like, manufactured by Shin-Etsu chemical Co., Ltd.

Auxiliary additives such as a catalyst and an adhesion improver may be added to the release agent layer. The catalyst is preferably a platinum-based or tin-based catalyst. The adhesion improver may be any adhesion improver as long as adhesion is improved, and a silane coupling agent is preferably used.

The coating amount of the release agent layer after drying is preferably 0.01-1 g/m²Particularly preferably 0.05 to 0.2g/m²。

The release layer may be formed by coating a release agent-containing solution and an antistatic agent-containing solution on the base material layer and drying them. For coating each solution, a size press coater (size press coater), a gate roll coater (gate roll coater), a bar coater, a roll coater, an air knife coater, a blade coater, a rod blade coater (rod blade coater), a curtain coater, a gravure coater, or the like can be used. Among them, a double head coater that can coat both the front and back surfaces at a time is preferably used, and a double head coater that has a Gravure head (Gravure head) that can control a small amount of coating and can coat both the front and back surfaces is particularly preferable. Therefore, the functional layers can be simultaneously formed on the two surfaces of the substrate layer, and the production efficiency of the isolation layer can be improved.

(method of producing laminate)

In the step of producing the laminate of the present invention, it is preferable that the decorative layer, the adhesive layer, and the separator layer are laminated to have the above-described structure, and then irradiated with light (ultraviolet rays or electron beams). Alternatively, the above structure may be formed by laminating the separator, the adhesive layer, and the separator, irradiating light (ultraviolet rays or electron beams) thereto, and bonding the laminate to the decorative layer. When the structure including the decorative layer is irradiated with light, it is preferable to irradiate light (ultraviolet rays or electron beams) from the side of the separator.

In the step of irradiating with light (ultraviolet rays), it is preferable that at least the illumination intensity with a wavelength of 200 to 400nm is 50mW/cm²The ultraviolet ray is preferably 70 to 3000mW/cm²Particularly preferably ultraviolet rays ofIrradiating 100-1000 mW/cm²Ultraviolet rays of (1). The cumulative light amount is preferably 100 to 10000mJ/cm²Particularly preferably 300 to 3000mJ/cm². As the irradiator for performing such irradiation, at least 1 selected from a high-pressure mercury ultraviolet irradiator, a metal halogen ultraviolet irradiator, and an electrodeless ultraviolet irradiator is preferably used. The illumination intensity of the wavelength range of 200-400 nm is 50mW/cm²The above ultraviolet irradiation conditions are set in the above range, and the amount of the monomer component remaining in the adhesive layer can be reduced. Further, by setting the irradiation conditions in the above range, yellowing of the decorative layer due to ultraviolet rays can be suppressed.

In the present invention, the illumination intensity is 50mW/cm except for using the wavelength of 200-400 nm²In addition to the step of irradiating ultraviolet rays, it is preferable to use an illumination intensity of 20mW/cm in a wavelength range of 200 to 400nm²The following ultraviolet rays were irradiated. More preferably, the illumination intensity of the wavelength of 200-400 nm is 1-10 mW/cm²Particularly preferably, the illumination intensity is 2-5 mW/cm²Is irradiated with ultraviolet rays. As an irradiator for performing such irradiation, at least 1 selected from a chemical lamp and/or black light is preferably used. By using these irradiators, the irradiation is preferably carried out for 0.01 to 30 minutes, particularly preferably for 0.1 to 20 minutes, and the cumulative light amount is preferably set to 10 to 1000mJ/cm²More preferably 40 to 600mJ/cm²Particularly preferably 100 to 400mJ/cm². The illumination intensity of the used wavelength range of 200-400 nm is 20mW/cm²The following ultraviolet irradiation conditions are set to the above ranges, and the following properties of the adhesive layer can be improved at the time of TOM molding.

In the invention, the illumination intensity of the used wavelength range of 200-400 nm is 20mW/cm²When the ultraviolet rays are irradiated, the illuminance is preferably 50mW/cm in the wavelength range of 200 to 400nm²The step of irradiating ultraviolet rays is performed before.

In the present invention, by irradiating ultraviolet rays under the conditions as described above, the polymerization degree of the monomer can be increased, and the proportion of the volatile substance contained in the adhesive agent layer can be set to a predetermined value or less.

(shaping under vacuum or reduced pressure (TOM shaping))

The laminate of the present invention is preferably used for molding under vacuum or reduced pressure. When the laminate of the present invention is molded under vacuum or reduced pressure, the laminate can prevent foreign matter such as dirt from being caught between the adhesive agent layer and the molded article. In this manner, the laminate of the present invention can exhibit its effects when used for molding under vacuum conditions or under reduced pressure conditions.

In the present specification, molding under vacuum or reduced pressure refers to a molding method called TOM molding. The TOM forming method comprises the following steps: laminating the adhesive film on the molded body under vacuum or reduced pressure; and a step of pressing the adhesive film to the molded body by utilizing the air pressure difference. In the present specification, the molding under vacuum or reduced pressure does not include a method of adhering an adhesive film to a molded article by using a molded article having a vacuum hole in the molded article. Specifically, molding under vacuum or reduced pressure can be performed by using a "vacuum molding apparatus" described in japanese patent No. 3733564.

The invention also relates to a process for the production of a decorative shaped body as described above. Specifically, the method for producing a decorative molded article of the present invention comprises: laminating the adhesive film on the molded body under vacuum or reduced pressure; and a step of pressing the adhesive film to the molded body by utilizing a difference in air pressure under a compressed air condition. In the method for producing a decorative molded article of the present invention, it is preferable that the method further comprises a step of heating the surface of the laminate to 100 to 180 ℃ after the step of pressing the adhesive film to the molded article. In this case, an infrared heater is preferably used for heating the surface of the laminate.

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

(decorative molding)

The invention also relates to a decorative shaped body comprising: an adhesive film comprising the decorative layer and the adhesive layer of the laminate, and a molded article decorated with the adhesive film. The decorative molded article is obtained by adhering an adhesive film to a part or the entire surface of the molded article. That is, in the decorative molded body, the decorative layer is laminated via the adhesive layer.

Fig. 3 is a sectional view illustrating the structure of the decorative molded body 100. Fig. 3 shows a molded article 50 having a concave portion on the surface thereof decorated with an adhesive film 20. As shown in fig. 3, in the molding under vacuum or reduced pressure, even if the vacuum hole is not provided in the molded body 50, the reverse tapered portion and the terminal clamping portion can be over-molded. In addition, the decoration can be performed regardless of the material of the product. This also allows the surface of the molded article having complicated three-dimensional irregularities to be decorated, thereby obtaining a decorated molded article 100 having high design properties.

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. For example, ABS resin (a copolymer of acrylonitrile, butadiene and styrene), AS resin (a copolymer of acrylonitrile and styrene), AAS resin (a copolymer of acrylonitrile, acrylic acid and styrene), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene ether, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyether sulfone, polyacetal, polyether ether ketone, polyphenylene sulfide, polyether imide, polyamide imide, polycarbonate, polyethylene, polypropylene, polystyrene, polyurethane resin, vinylidene chloride resin, vinyl chloride resin, and the like can be preferably used. These resins may also be blended. For example, polycarbonate-containing resins and the like are preferably exemplified. As the polycarbonate-containing resin, a resin blended with polycarbonate and polybutylene terephthalate (PC · PBT), a resin blended with polycarbonate and ABS resin (PC · ABS), a resin blended with polycarbonate and PET (PC · PET), and the like can be particularly preferably used. As the polyolefin resin, polypropylene (PP) can be particularly preferably used.

Specifically, ABS resins (copolymers of acrylonitrile, butadiene and styrene), AS resins (copolymers of acrylonitrile and styrene), AAS resins (copolymers of acrylonitrile, acrylic acid and styrene), acrylic resins, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resins, urea resins, melamine resins, liquid crystal polymers, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacetal, polyether ether ketone, polyphenylene sulfide, polyetherimide, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, polyurethane resins, and the like are preferably listed.

The molded article obtained by the present invention can be used for, for example, parts for automobiles (for example, parts such as a vehicle body, a bumper, a spoiler, a mirror, a wheel, and an interior material, and parts of various materials), parts for motorcycles, road materials (for example, a traffic sign and a sound-proof wall), tunnel materials (for example, a side wall panel), railway vehicles, furniture, musical instruments, home electric appliances, building materials, containers, office supplies, sporting goods, toys, and the like.

Examples

The features of the present invention will be described in further detail below with reference to examples and comparative examples. The materials, the amounts used, the ratios, the contents of the treatments, the procedures of the treatments, and the like shown in the following examples can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited to the specific examples shown below.

(example 1)

< decorative layer 1 >

A black ink (TRC 1268, manufactured by DIC CORPORATION) layer (colored layer) was provided on one surface of an acrylic film (manufactured by Mitsubishi Rayon co., ltd., acrylen HBA001P, pencil hardness 2H, thickness 125 μm) by a gravure press so as to have a thickness of 5 μm on the entire surface, and a decorative layer 1 was obtained.

< isolation layer 1 >

In 38 μm thick PET (Toray Industries, I)nc. is manufactured by the method that the adhesive tape is used for adhering,

t60) was applied to one side of the substrate in an amount of 0.07g/m²The method of (1) coating an organic conductive material containing a pi-conjugated system: DENATRON P-502S (manufactured by Nagase ChemteX Corporation) of poly (3, 4-ethylenedioxythiophene) was treated with a dryer at 130 ℃ for 30 seconds. Thereby forming an antistatic layer.

Then, on the opposite side, the weight after drying was 0.1g/m²In the embodiment, a release agent composed of 100 parts by mass of a thermosetting silicone (LTC 300B, manufactured by Dow Corning Toray co., ltd.) and 1 part by mass of a catalyst (SRX 212, manufactured by Dow Corning Toray co., ltd.) was applied to form a release agent layer. Then, treatment was performed at 130 ℃ for 60 seconds by a dryer, and the separator 1 was obtained.

< adhesive 1 >

To a reaction vessel containing a nitrogen atmosphere, 95 parts by mass of 2-ethylhexyl acrylate and 5 parts by mass of acrylic acid were added, and polymerization was carried out using 0.01 part by mass of an initiator (2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile)), whereby adhesive 1 having a polymer concentration of 9% and a weight average molecular weight Mw of 150 ten thousand was obtained.

< laminate 1 >

To 100 parts by mass of the adhesive 1, 0.1 part by mass of hexanediol diacrylate and 1 part by mass of benzildimethyl ketal were added, nitrogen gas was purged to completely remove dissolved oxygen, and the adhesive 1 was applied (wet-laminated) so that the thickness of the adhesive layer was 50 μm between the release layer side of the release layer 1 and the ink layer side of the 130 μm decorative layer 1. Then, using a chemical lamp, the illuminance of ultraviolet light having a wavelength of 365nm was 4mW/cm²The cumulative light amount was 300mJ/cm²The ultraviolet light was irradiated from the side of the separator 1, and then irradiated by a high-pressure mercury lamp at an illuminance of 100mW/cm with an ultraviolet ray having a wavelength of 365nm²The cumulative light amount became 2000mJ/cm²The irradiation was performed in the manner as described above, and a laminate 1 was obtained. Volatile substances contained in the adhesive agent layer of the laminate 1 were measured by gas chromatography,the result was 5 ppm.

< method for producing decorative molded article >

The separator 1 was peeled off from the laminate 1 to form the adhesive film 1. The adhesive film 1 was mounted on a TOM molding machine. An incoming-line rain cover (product number: WP9171, manufactured by Panasonic Corporation) was attached to a TOM molding machine (manufactured by Fu-se Vacuum Forming ltd., NGF molding machine) so that the outer surface (convex surface) side of the cover faced the adhesive layer of the adhesive film 1. The adhesive film 1 was laminated on the molded body at 130 ℃ by using a TOM molding machine, thereby obtaining a decorative molded body 1. In the same manner, 10 decorative molded bodies 1 were produced.

Fig. 4(a) to (c) show the shapes of the incoming rain covers. When the inlet rain cover shown in fig. 4(a) to (c) is viewed from above as shown in fig. 4(a), the length in the longitudinal direction (vertical axis) is 90mm, and the length in the width direction (horizontal axis) is 60 mm.

(example 2)

Except that the thickness of the adhesive layer 1 was set to 75 μm, the separator 1 was changed to the separator 2, and the ultraviolet irradiation was set to 300mW/cm in illuminance of ultraviolet light having a wavelength of 365nm using only a high-pressure mercury lamp²The cumulative light amount was set to 3000mJ/cm²A decorative molded article 2 was obtained in the same manner as in example 1 except that the laminate 2 was obtained under the conditions of (1). The volatile matter contained in the adhesive agent layer was measured, and the result was 23 ppm.

< isolation layer 2 >

The coating was applied to a substrate made of PET (manufactured by Toray Industries, inc.),

t60) was applied to one side of the substrate in an amount of 0.15g/m after drying²The coating was applied with glycerol monostearate, and the treatment was carried out with a dryer at 130 ℃ for 30 seconds. Thereby forming an antistatic layer.

Then, on the opposite side, the weight after drying was 0.1g/m²The coating composition is prepared by coating 100 parts by mass of a thermosetting silicone (LTC 300B, manufactured by Dow Corning Toray co., ltd.) and a catalyst(SRX 212, manufactured by Dow Corning Toray co., ltd.) 1 part by mass, thereby forming a release agent layer. Then, treatment was performed at 130 ℃ for 60 seconds by a dryer, and the separator 2 was obtained.

(example 3)

Except that the adhesive 3 was used in place of the adhesive 1 to form an adhesive layer 3 having a thickness of 25 μm and a chemical lamp was used, the illuminance of ultraviolet light having a wavelength of 365nm was 4mW/cm²The cumulative light amount became 100mJ/cm²The ultraviolet light was irradiated from the side of the separator 2, and then the illuminance of ultraviolet light having a wavelength of 365nm was 100mW/cm using a high-pressure mercury lamp²The cumulative light amount became 2000mJ/cm²A decorative molded body 3 was obtained in the same manner as in example 2, except that the irradiation was performed in the manner as described above, and the laminated body 3 was obtained. The volatile substance contained in the adhesive layer of the laminate 3 was measured, and the result was 3 ppm.

< adhesive 3 >

To a reaction vessel under a nitrogen atmosphere, 90 parts by mass of 2-ethylhexyl acrylate, 5 parts by mass of acrylic acid, and 5 parts by mass of isobornyl acrylate were charged, and polymerization was carried out using 0.01 part by mass of an initiator (2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile)), whereby adhesive 3 having a polymer concentration of 8% and a weight average molecular weight Mw of 200 ten thousand was obtained.

(example 4)

An adhesive layer 4 was formed by replacing the adhesive 1 with an adhesive 4, the decorative layer 1 was replaced with a spacer layer 3, and a metal halogen lamp was used instead of a high-pressure mercury lamp, so that the illuminance of ultraviolet light having a wavelength of 365nm was 100mW/cm²The cumulative light amount became 2000mJ/cm²A decorative molded body 4 was obtained in the same manner as in example 1 except that the structure of the separator 1/the adhesive layer 4/the separator 3 was manufactured by irradiation, the separator 1 was peeled off, and the decorative layer 1 was bonded to the exposed adhesive layer 4 by a roll bonding machine to obtain a laminate 4. The volatile matter contained in the adhesive agent layer of the laminate 4 was measured, and the result was 14 ppm.

< adhesive 4 >

Into a reaction vessel having a nitrogen atmosphere, 95 parts by mass of butyl acrylate and 5 parts by mass of 2-hydroxymethyl acrylate were charged, and polymerization was carried out using 0.01 part by mass of an initiator (2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile)), whereby a solution 4 having a polymer concentration of 11% and a weight average molecular weight Mw of 100 ten thousand was obtained. To this solution 4, 15 parts by mass of a rosin-based tackifier (KE 311, manufactured by Arakawa Chemical Industries, ltd.) was added and stirred to obtain an adhesive 4.

< isolation layer 3 >

Silver nanowires (CST-NW-S40, manufactured by Cold stores) and a polyester-based binder (TAKAMATSU OIL)&FAT co, LTD, PESRESIN A-645GH), was blended so that the weight after drying became 20:80, and was coated on PET (Toray Industries, inc., manufactured,

t60) on one side. The coating weight after drying was 0.01g/m²The coating amount was set and coating was performed in a clean room (1000 stages). Then, a treatment was performed at 130 ℃ for 30 seconds using a dryer, and an antistatic layer D was formed.

Next, in a clean room (class 1000), the weight after drying was 0.1g/m²In the embodiment, a release agent composed of 100 parts by mass of a thermosetting silicone (LTC 300B, manufactured by Dow Corning Toray co., ltd.) and 1 part by mass of a catalyst (SRX 212, manufactured by Dow Corning Toray co., ltd.) was coated on the opposite surface to form a release agent layer. Then, treatment was performed at 130 ℃ for 60 seconds by a dryer, and the separator 3 was obtained.

(example 5)

A laminate 5 was produced in the same manner as in example 4 except that the adhesive 5 was used instead of the adhesive 1 and the thickness of the adhesive layer 5 was set to 25 μm, to obtain a decorative molded article 5.

The volatile matter contained in the adhesive agent layer of the laminate 5 was measured, and the result was 4 ppm.

< adhesive 5 >

To a reaction vessel containing a nitrogen atmosphere, 90 parts by mass of 2-ethylhexyl acrylate and 10 parts by mass of acrylic acid were added, and polymerization was carried out using 0.01 part by mass of an initiator (2,2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile)), whereby a solution 5 having a polymer concentration of 11% and a weight average molecular weight Mw of 150 ten thousand was obtained. To this solution 5, 10 parts by mass of a terpene tackifier (YASUHARA CHEMICAL co., ltd., manufactured by TH130) and an aliphatic hydrocarbon tackifier (arakawa CHEMICAL Industries, manufactured by ltd., ARKON M100) were added and stirred to obtain an adhesive 5.

(example 6)

A laminate 6 was produced in the same manner as in example 2 except that the thickness of the adhesive layer was set to 200 μm and the separator 2 was replaced with the separator 4, to obtain a decorative molded article 6. The volatile matter contained in the adhesive agent layer of the laminate 6 was measured, and the result was 30 ppm.

< isolation layer 4 >

t60) on one side, the weight after drying was 0.1g/m²In the embodiment, a release agent composed of 100 parts by mass of a thermosetting silicone (LTC 300B, manufactured by Dow Corning Toray co., ltd.) and 1 part by mass of a catalyst (SRX 212, manufactured by Dow Corning Toray co., ltd.) was applied to form a release agent layer. Then, treatment was performed at 130 ℃ for 60 seconds by a dryer, and the separator 4 was obtained.

Comparative example 1

The decorative molded body 11 was obtained by using the adhesive film 11 from which the separator 4 was peeled off from the laminate 11, but when the processing was performed at 130 ℃ using a TOM molding machine, the adhesive layer was foamed, and a good decorative molded body could not be obtained. The volatile substance contained in the adhesive layer of the laminate 11 was measured, and the result was 80 ppm.

< laminate 11 >

An adhesive 11 was applied to the release agent layer of the separator 4 so that the thickness after drying became 25 μm, and after drying at 90 ℃ for 10 minutes, the decorative layer 1 was bonded by a roll laminator to obtain a laminate 11.

< adhesive 11 >

Butyl acrylate 65 parts by mass, methyl acrylate 30 parts by mass, and acrylic acid 5 parts by mass were put into a reaction vessel (equipped with a temperature controller, a stirrer, and a reflux apparatus) in a nitrogen atmosphere, and 200 parts by mass of ethyl acetate and 0.1 part by mass of azobisisobutyronitrile were added to conduct polymerization reaction, thereby obtaining a polymer a. The weight average molecular weight Mw of the resulting polymer A was 80 ten thousand. The obtained polymer a, poly α -methylstyrene (molecular weight Mw 850,000, Tg 105 ℃, manufactured by Wako Pure Chemical Industries, ltd.), and a crosslinking agent (MITSUBISHI GAS CHEMICAL COMPANY, manufactured by inc., tetra-X) were blended in such a manner that the dry weight ratio became 98:10:2, to obtain an adhesive 11.

Comparative example 2

The decorative molded body 12 is obtained by using the adhesive film 12 from which the separator 2 has been peeled off from the laminate 12, but when the processing is performed at 130 ℃ using a TOM molding machine, the adhesive layer is foamed, and a good decorative molded body cannot be obtained. The volatile substance contained in the adhesive agent layer of the laminate 12 was measured, and the result was 140 ppm.

< laminate 12 >

A 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 2 so that the thickness after drying became 75 μm.

< 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 put into a reaction vessel (equipped with a temperature controller, a stirrer and a reflux apparatus) in a nitrogen atmosphere, 200 parts by mass of ethyl acetate and 0.1 part by mass of azobisisobutyronitrile were added thereto, and a polymerization reaction was carried out, thereby obtaining a polymer B. The weight average molecular weight Mw of the resulting polymer B was 80 ten thousand.

The resulting polymer B, a crosslinking agent (MITSUBISHI GAS CHEMICAL COMPANY, inc., ltrad-X), and bistrifluoromethanesulfonimide were blended in a dry weight ratio of 96:2:2 to obtain an adhesive 12.

Comparative example 3

The decorative molded body 13 was obtained by using the adhesive film 13 from which the separator 1 was peeled off from the laminate 13, but when the processing was performed at 130 ℃ using a TOM molding machine, the adhesive layer was foamed, and a good decorative molded body could not be obtained.

< laminate 13 >

The illuminance of ultraviolet light having a wavelength of 365nm was set to 100mW/cm except for using a high-pressure mercury lamp²The cumulative light amount was set to 50mJ/cm²Except for this, a laminate 13 was obtained in the same manner as in example 1. The volatile matter contained in the adhesive layer of the laminate 13 was measured, and the result was 610 ppm.

Comparative example 4

The decorative molded article 14 was obtained by using the adhesive film 14 from which the separator 1 was peeled off from the laminate 14, but when the processing was performed at 130 ℃ using a TOM molding machine, the adhesive layer was foamed, and a good decorative molded article could not be obtained.

< laminate 14 >

Except for using a metal halogen lamp, the illuminance of ultraviolet light with a wavelength of 365nm is 100mW/cm²The cumulative light amount became 50mJ/cm²A structure of a separator 1/an adhesive layer 4/a separator 3 was produced in the same manner as in example 4 except that irradiation was performed, the separator 1 was then peeled off, and the decorative layer 1 was bonded to the exposed adhesive layer 4 by a roll bonding machine, thereby obtaining a laminate 14. The volatile substance contained in the adhesive agent layer of the laminate 14 was measured, and the result was 310 ppm.

(evaluation)

(measurement of surface resistance value)

After the laminate was left to stand for 1 day under a humidity-controlled atmosphere at 23 ℃ and 50% RH, the surface resistance was measured by Hiresta UX MCP-HT800 (manufactured by Mitsubishi Chemical Analyticech Co., Ltd.).

(TOM Molding Property)

The adhesive films of examples 1 to 6 and comparative examples 1 to 4 were evaluated as having good moldability (. smallcircle.) when they were molded without occurrence of blisters. The case where foaming was found at the time of film molding was evaluated as poor moldability (x). The results are shown in Table 1.

(number of defects)

The surface of a decorative molded article using a laminate (adhesive film) cured at 23 ℃ and a relative humidity of 50% was observed, and the number of defects whose surface was expanded in a convex shape was counted. The upper surfaces (regions corresponding to the upper surfaces in fig. 4 (a)) of the decorative molded bodies obtained in the respective examples and comparative examples were observed with a laser microscope (VK-X100, KEYENCE co., Ltd), and the number of defects was counted with the upper surface having a height of 3 μm or more being regarded as a defect. The number of defects was an average value of the number of defects in the same region of 10 decorative molded articles produced in the same manner in each example and each comparative example.

(number of defects in Low humidity Environment)

In the same manner as described above, the surface of a decorative molded article using a laminate (adhesive film) cured at 15 ℃ and a relative humidity of 30% was observed, and the number of defects was counted to obtain an average value.

(adhesive force)

A test piece of 25X 50mm was attached to an ABS plate, pressure-bonding (2kg roller, 1 pass) and heat treatment (130 ℃ C., 1 minute) were carried out, and after standing for 24 hours, the force required for peeling the test piece under conditions of a peeling speed of 300 mm/minute, a peeling angle of 180 degrees, a measurement temperature of 23 ℃ and a measurement humidity of 50% was measured using a tensile tester.

(durability (cross-cut adhesion test))

The decorative molded article was left to stand at 80 ℃ for 500 hours, and after standing at room temperature, 11 longitudinal and transverse cutting marks were made on the surface of the film at intervals of 2mm, thereby obtaining 100 checkerboards. The number of squares remaining without peeling when the transparent tape was adhered to the surface thereof and peeled off at once.

[ Table 1]

When TOM molding was performed using the adhesive film obtained in the examples, TOM moldability was good. On the other hand, when TOM molding was performed using the adhesive film obtained in the comparative example, foaming occurred from the adhesive layer.

In addition, the laminate obtained in the examples had a small number of defects and exhibited good adhesion to the molded article. Further, the decorative molded article obtained in the examples was found to have excellent durability.

Description of the reference numerals

20: an adhesive film; 22: a decorative layer; 24: an adhesive layer; 26: an isolation layer; 30: a laminate; 32: a surface protection layer; 34: a colored layer; 42: a substrate layer; 44: a release agent layer; 46: an antistatic layer; 50: a shaped body; 100: decorating the molded body.

Claims

1. An adhesive film comprising an adhesive layer and a decorative layer laminated on one surface side of the adhesive layer,

the adhesive constituting the adhesive layer is an ultraviolet-curable adhesive containing an acrylic polymer and a photopolymerization initiator,

the adhesive constituting the adhesive layer contains a monomer unit of (meth) acrylate, a monomer unit having a carboxyl group or a monomer unit having a hydroxyl group, and a monomer unit selected from the group consisting of ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 6-hexanediol diacrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate as a monomer unit constituting the acrylic polymer The number of the element,

the average molecular weight Mw of the acrylic polymer is 70 to 500 ten thousand, the molecular weight distribution Mw/Mn is 1 to 6,

the photopolymerization initiator is at least 1 selected from the group consisting of acetophenone initiators, benzoin ether initiators, benzophenone initiators, hydroxyalkyl phenone initiators, thioxanthone initiators, amine initiators and acylphosphine oxide initiators,

volatile substances which are volatilized under a vacuum condition of 150 ℃ and are contained in the adhesive layer are less than 50 ppm.

2. The adhesive film according to claim 1, wherein the volatile substance is at least 1 selected from a solvent, a monomer as a constituent of an adhesive constituting the adhesive layer, and an oligomer as a constituent of an adhesive constituting the adhesive layer.

3. The adhesive film according to claim 1 or 2, wherein the thickness of the adhesive layer is 20 μm or more.

4. The adhesive film according to claim 1 or 2, wherein the decorative layer has a thickness of 75 μm or more.

5. The adhesive film according to claim 1 or 2, which is used for molding under vacuum conditions or under reduced pressure conditions.

6. A laminate, comprising: an adhesive layer, a decorative layer laminated on one surface side of the adhesive layer, and a separator laminated on the other surface side of the adhesive layer, the other surface side being the opposite surface side to the surface on which the decorative layer is laminated; it is characterized in that the preparation method is characterized in that,

7. The laminate according to claim 6, wherein at least one of the adhesive layer, the decorative layer and the separator has a surface resistance of 1 x10⁵～1×10¹²Omega/□.

8. The laminate according to claim 6 or 7, wherein the separator has a surface resistance of 1 x10⁵～1×10¹²Omega/□.

9. A decorative molded article comprising the adhesive film according to any one of claims 1 to 5 and a molded article decorated with the adhesive film.

10. A method of manufacturing a decorative molding, comprising: a step of laminating the adhesive film on the molded body under vacuum or reduced pressure,

A step of pressing the adhesive film to the molded body by using a difference in air pressure;

the adhesive film comprises an adhesive layer and a decorative layer laminated on one surface side of the adhesive layer, wherein the adhesive constituting the adhesive layer is an ultraviolet-curable adhesive comprising an acrylic polymer and a photopolymerization initiator, and the adhesive constituting the adhesive layer comprises a (meth) acrylate monomer unit, a monomer unit having a carboxyl group or a monomer unit having a hydroxyl group, and a monomer unit selected from the group consisting of ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 6-hexanediol diacrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and mixtures thereof, The acrylic polymer is composed of a monomer unit selected from the group consisting of tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate, the acrylic polymer has an average molecular weight Mw of 70 to 500 ten thousand and a molecular weight distribution Mw/Mn of 1 to 6, the photopolymerization initiator is at least 1 selected from the group consisting of acetophenone initiators, benzoin ether initiators, benzophenone initiators, hydroxyalkyl benzophenone initiators, thioxanthone initiators, amine initiators, and acylphosphine oxide initiators, and a volatile substance contained in the adhesive layer and volatilized under a vacuum condition of 150 ℃ is less than 50 ppm.