JP2012213894A - Decorative film for vacuum forming, decorative molding, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film for vacuum forming which is excellent in vacuum forming processability, adhesive strength, and durability as a decorative molding when the decorative molding is produced by a vacuum forming method.SOLUTION: The decorative film for vacuum forming has a base material layer, a decorative layer, and an adhesive layer containing an acrylic pressure sensitive adhesive and a tackifier having a softening point of 90-180°C in this order. The decorative film for vacuum forming, when the decorative molding is produced by the vacuum forming method, is excellent in vacuum forming processability such as malleability, foldabilty, and shape followability and durabilty as the decorative molding.

Description

  The present invention relates to a decorative film for vacuum forming, a decorative molded product, and a manufacturing method thereof.

  Conventionally, in various fields such as household appliances, automobile interior parts, and miscellaneous goods, by decorating the surface of the molded body that is the adherend with white, black, and color inks, High functionality and design have been developed. In particular, a vacuum molding method or an injection molding method has been used for decorating a molded body having a complicated surface shape such as a three-dimensional curved surface.

  The above vacuum forming method means that the decorative film is stretched while being softened by heating, the space on the adherend side of the decorative film is depressurized, and the space on the opposite side is pressurized as necessary to cover the decorative film. It is a method of sticking and laminating while forming along the three-dimensional solid shape of the surface of the adherend.

  Conventionally, a vinyl chloride resin sheet has been widely used as a base material layer of a decorative film used for vacuum forming, but recently, a non-vinyl chloride resin sheet such as a polyolefin resin sheet is used instead. It has become like this. However, when a polyolefin resin is used as the base material layer, when the decorative film is laminated by the vacuum forming method, the three-dimensional shape followability of the decorative film becomes insufficient, or the appropriate condition width of the thermoforming process is limited. There has been a problem that the vacuum forming processability is not sufficient, such as the occurrence of necking in the portion where the decorative film is extended or the uneven extension of the decorative film. In order to solve such a problem, it has been proposed to use an amorphous polyester resin as a base material layer of a decorative film (see, for example, Patent Document 1).

  Moreover, since the decorative film of the molded object which has a three-dimensional solid shape is used for uses, such as a household appliance housing | casing and a notebook PC, a weather resistance and durability are requested | required besides adhesive strength. The decorative film has a structure of base material layer / decoration layer / adhesive layer / adhesive body (molded body) from the surface after lamination to the molded product. Therefore, it is necessary to provide a highly transparent resin layer on the outermost surface base material layer.

  Therefore, the development of a decorative film for vacuum forming that is excellent in vacuum forming processability and adhesive strength and has excellent durability as a decorative molded product when manufacturing a decorative molded product by a vacuum forming method is desired. .

JP 2002-67242 A

  As a result of examining the above-mentioned background art, the present inventors have found that when an acrylic resin film having excellent transparency and moldability is used as the base material layer, the acrylic resin has a large stress on stretching, and therefore, according to a weather resistance test. It was found that the substrate layer tends to shrink. Then, although the method of providing the layer which consists of an acrylonitrile butadiene styrene copolymer (ABS resin) between a base material layer and an adhesion layer was devised, since material and a manufacturing process increased, cost increased. . Moreover, when a resin film with a small shrinkage tendency is used as the base material layer, the moldability is poor and the resin film may be cut during stretching. Furthermore, if a hot-melt adhesive that resists shrinkage and has high cohesive strength is used as the adhesive layer, a large amount of heat is required when laminating the decorative film to a molded product, and the heat resistance of the decorative film is insufficient. There was a problem of increased costs. Moreover, when the silicone type adhesive excellent in a weather resistance was used, adhesive strength was inadequate.

  The present invention has been made in view of the above-mentioned background art and these newly discovered problems. The purpose of the present invention is to produce vacuum molded workability and coverage when a decorative molded product is produced by a vacuum forming method. It is providing the decorating film excellent in the adhesiveness to a kimono.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by forming a pressure-sensitive adhesive layer of a decorative film for vacuum forming in combination with a specific pressure-sensitive adhesive and a tackifier. As a result, the present invention has been completed.

That is, according to one aspect of the present invention,
A base material layer;
A decorative layer,
There is provided a decorative film for vacuum forming comprising an acrylic pressure-sensitive adhesive and a pressure-sensitive adhesive layer comprising a tackifier having a softening point of 90 to 180 ° C. in this order.

  In the embodiment of the present invention, the tackifier preferably comprises a rosin resin and / or a terpene phenol resin.

  In the aspect of the present invention, it is preferable that the pressure-sensitive adhesive layer contains 0.1 to 10% by mass of a tackifier with respect to the acrylic pressure-sensitive adhesive.

  In the aspect of the present invention, it is preferable that the base material layer includes an acrylic resin.

  In the embodiment of the present invention, it is preferable that a release layer is further provided on the adhesive layer.

According to another aspect of the present invention,
There is provided a decorative molded product comprising a molded body and a decorative layer decorated with the above-described decorative film for vacuum molding on the molded body.

According to another aspect of the present invention,
There is provided a method for producing a decorative molded product, comprising a step of decorating a decorative body with a decorative layer using the vacuum forming decorative film.

  The decorative film for vacuum forming of the present invention is excellent in vacuum forming processability such as spreadability, bendability, and shape followability, and adhesive strength when a decorative molded product is produced by a vacuum forming method. Excellent durability as a decorative molded product. Moreover, the decorative molded body of this invention can express high functionality and designability by using such a decorative film for vacuum forming.

It is a schematic cross section which shows an example of the decorative film for vacuum forming by this invention. It is a schematic cross section which shows the other example of the decorative film for vacuum forming by this invention. It is a schematic cross section which shows an example of the decorative molded product by this invention.

Decorative film for vacuum forming The decorative film for vacuum forming of the present invention comprises a base layer, a decorative layer, and an adhesive layer in this order, and further has a release layer on the adhesive layer. May be. Hereinafter, the structure of the decorative film for vacuum forming of the present invention will be described with reference to the drawings.

  According to one aspect of the present invention, there is provided a decorative film having a base material layer, a decorative layer, and an adhesive layer in this order. Specifically, FIG. 1 shows a schematic cross-sectional view of an example of a decorative film for vacuum forming according to the present invention. The decorative film 10 shown in FIG. 1 has a decorative layer 12 formed on a base material layer 11 and an adhesive layer 13 formed on the decorative layer 12.

  According to the other aspect of this invention, the decoration film which has a base material layer, a decoration layer, an adhesion layer, and a peeling layer in this order is provided. Specifically, FIG. 2 shows a schematic cross-sectional view of another example of the decorative film for vacuum forming according to the present invention. The decorative film 20 shown in FIG. 2 has a decorative layer 22 formed on a base material layer 21, an adhesive layer 23 formed on the decorative layer 22, and a release layer 24 formed on the adhesive layer 23. It has been made. Hereinafter, each layer which comprises the decorative film for vacuum forming is demonstrated.

Base material layer The base material layer in the present invention is usually a resin layer made of a thermoplastic resin, and preferably contains an acrylic resin. By forming a base material layer using an acrylic resin, the vacuum forming processability such as spreadability, bendability, and shape followability required when producing decorative molded products by the vacuum forming method is achieved. Can be excellent.

  The base material layer made of an acrylic resin can be formed using a polymer having an ionizing radiation curable functional group. Ionizing radiation curable is one having an energy quantum that can crosslink and polymerize molecules in electromagnetic waves or charged particle beams, that is, it is crosslinked by causing polymerization reaction by being excited by irradiation with ultraviolet rays or electron beams. It is the ability to cure. The ionizing radiation curable functional group is a functional group capable of expressing the ionizing radiation curable property. In the present invention, ethylenically unsaturated groups such as vinyl group, (meth) acryloyl group, and allyl group are used. A functional group having a bond and an epoxy group.

  Examples of the polymer having an ionizing radiation-curable functional group include those obtained by polymerizing monomers such as acrylic (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate, those obtained by copolymerization of these monomers, polyester (meta ) Acrylates, and polymers such as polyether (meth) acrylates. In the present invention, these polymers may be used alone or in combination of two or more.

  The base material layer in the present invention is positioned in the outermost layer of the decorative molded product after the decorative film is decorated on the molded body, and functions as a protective layer for the decorative molded product. By forming the base material layer with an acrylic resin, it is possible to make it excellent in durability such as wear resistance, chemical resistance, and weather resistance.

  The base material layer in the present invention may be colorless and transparent, or may be colored and transparent. In order to color the base material layer, a known colorant as described in the decoration layer below may be added to the resin.

  Usually, the thickness of a base material layer becomes like this. Preferably it is 25 micrometers-300 micrometers, More preferably, they are 50 micrometers-200 micrometers. When the thickness of the base material layer is within the above range, when the decorative molded product is produced by the vacuum forming method, the processability, the shape followability, and the handleability are improved.

Decoration layer The decoration layer in this invention is a layer provided in order to provide the designability of a decoration film, and is a pattern layer expressing a pattern, a character, a pattern-like picture, etc. Examples of the pattern include wood grain, stone grain, cloth grain, sand grain, geometric pattern, character, stripe pattern and gradation pattern.

  The pattern layer can be usually formed by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, and ink jet printing with a printing ink. The thickness of the handle layer can be appropriately adjusted according to the shape of the handle.

  Ink binders used to form the pattern layer include chlorinated polyester resins, urethane resins, acrylic resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, cellulose resins, chlorinated polyethylene, chlorinated polypropylene, etc. A polyolefin resin etc. can be used 1 type or in mixture of 2 or more types. In addition to the binders made of the above-mentioned various resins, the ink used is appropriately mixed with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents.

  Colorants used in the above inks include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone yellow, hansa yellow A, quinacridone red, permanent Red 4R, organic pigments (including dyes) such as phthalocyanine blue, indanthrene blue RS, aniline black, metal pigments made of metal powders such as aluminum and brass, titanium dioxide-coated mica, foil powders such as basic lead carbonate A pearl luster (pearl) pigment, a fluorescent pigment, or the like made of can be used alone or in combination of two or more.

  The handle layer may be a metal thin film layer or the like. The metal thin film layer is formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum deposition or sputtering. Alternatively, a combination thereof may be used. The metal thin film layer may be provided on the entire surface or partially in a pattern.

  The decorative layer may be one in which a masking layer is further provided on the handle layer. The concealing layer is provided for the purpose of concealing the pattern and coloring of the ground (molded product) after the decorative film is laminated on the decorative molded product. For this reason, the layer structure after lamination on the molded body is preferably (surface side) base material layer / decoration layer (pattern layer / shielding layer) / adhesive layer (molded body side). The shielding layer is usually formed as a full-color or partially solid colored layer without a pattern. In some cases, the handle layer also functions as a solid layer (shielding effect). In this case, the shielding layer may not be formed. The shielding layer can be formed using an ink containing a coloring pigment similar to the pattern layer.

  In the present invention, the decorative film may be embossed. Since the temperature at the time of vacuum forming can be kept low, embossing with stable quality can be maintained.

  Usually, the thickness of a decoration layer becomes like this. Preferably it is 5-40 micrometers, More preferably, it is 5-30 micrometers. When the thickness of the decoration layer is within the above range, a sufficient thickness can be secured to express a complicated design such as gradation.

Adhesive layer The adhesive layer in the present invention is a layer for adhering the decorative layer to the molded article. In the present invention, the pressure-sensitive adhesive layer comprises an acrylic pressure-sensitive adhesive and a tackifier having a softening point of 90 to 180 ° C. The adhesive and tackifier will be described in detail below. The pressure-sensitive adhesive layer of the present invention can suppress softening at high temperatures by containing a tackifier having a high softening point. Therefore, when producing a decorative molded product by a vacuum forming method, there is little shrinkage of the decorative film caused by heat load, particularly shrinkage at the corners of the three-dimensional shape, and the weather resistance of the decorative molded product can be improved. . An acrylic pressure-sensitive adhesive has high adhesive strength, and when a tackifier is added, the initial adhesion of the pressure-sensitive adhesive increases. Therefore, a decrease in adhesive strength can be suppressed.

  The pressure-sensitive adhesive layer in the present invention is preferably 0.1 to 10% by weight, more preferably 0.2 to 8% by weight, and still more preferably 0.5 to 5% by weight, based on the acrylic pressure-sensitive adhesive. Is included. When the content of the tackifier is within the above range, both adhesive strength and weather resistance can be achieved.

Adhesive In the present invention, an acrylic adhesive is used as the adhesive. The acrylic pressure-sensitive adhesive is mainly composed of an acrylic pressure-sensitive adhesive resin, and the pressure-sensitive adhesive performance of the pressure-sensitive adhesive can be improved by adding the following tackifier. Furthermore, you may add a crosslinking agent as needed. In the present invention, by using an acrylic pressure-sensitive adhesive, the adhesive strength of the pressure-sensitive adhesive layer increases, and when the following tackifier is added, the initial adhesion of the pressure-sensitive adhesive layer increases. Therefore, a decrease in adhesive strength can be suppressed.

  Said acrylic adhesive resin has as a main component an acrylic copolymer resin obtained by copolymerizing an acrylic acid alkyl ester or methacrylic acid alkyl ester, another monomer and a functional monomer.

  The alkyl acrylate ester preferably has an alkyl group having 4 to 15 carbon atoms. Examples of such alkyl acrylates include n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, and isononyl acrylate. These alkyl acrylates may be used alone or in combination.

  The methacrylic acid alkyl ester preferably has an alkyl group having 4 to 15 carbon atoms, more preferably 10 to 12 carbon atoms. Examples of such methacrylic acid acrylic esters include methacrylic acid-n-hexyl and 2-ethylhexyl methacrylate. These methacrylic acid alkyl esters may be used alone or in combination.

  Examples of the other monomer include butyl acrylate, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, and vinyl acetate. These other monomers may be used alone or in combination of two or more.

  Examples of the functional monomer include acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl acrylate, hydroxylethyl methacrylate, propylene glycol acrylate, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, and methacrylic acid. Examples thereof include dimethylaminoethyl and tert-butylaminoethyl methacrylate. These functional monomers may be used alone or in combination of two or more.

  The composition ratio (mass%) of the acrylic acid alkyl ester and methacrylic acid alkyl ester, other monomers, and functional monomers in the acrylic copolymer resin is preferably 60 to 99: 0 to 30: 0 to 20, preferably. Is 70-95: 0-25: 0-15.

  For example, the weight average molecular weight of the acrylic copolymer resin is preferably in the range of 50,000 to 2.5 million, and more preferably in the range of 100,000 to 1.5 million.

  In the present invention, a commercially available acrylic pressure-sensitive adhesive can also be used. For example, SK dyne 2950, SK dyne 2953, and SK dyne 2943H (above, manufactured by Soken Chemical Co., Ltd.), Coponel 8711, and Coponil N-2411TF (above, manufactured by Nippon Synthetic Chemical Co., Ltd.) can be used. .

Tackifier In the present invention, a tackifier is an amorphous oligomer having a molecular weight of several hundred to several thousand, and imparts fluidity and tack by mixing with an elastomer (main component of the adhesive). It improves the adhesive strength.

  The tackifier in this invention has a softening point of 90-180 degreeC, Preferably it is 95-175 degreeC, More preferably, it is 100-170 degreeC, More preferably, it is 110-165 degreeC. When the tackifier has a softening point in the above range, softening of the adhesive layer at a high temperature can be further suppressed.

  There are roughly two types of tackifiers: natural resin and synthetic resin. In the present invention, a natural resin type is preferable, and among them, a resin comprising a rosin type resin and / or a terpene type viscous resin is preferable. Examples of rosins include rosin and rosin derivatives such as hydrogenated rosin, disproportionated rosin, polymerized rosin, and esterified rosin. Examples of the terpene series include terpene series resins, terpene phenol series resins, aromatic modified terpene series resins, and hydrogenated terpene series resins. These rosin resins and terpene resins may be used alone or in combination of two or more.

  In the present invention, a commercially available tackifier can also be used. For example, Haritac FK100, Haritac PCJ, and Haritac 28JA (above, manufactured by Harima Chemicals Co., Ltd.), YS Polystar N-125, Mighty Ace G-150, and YS Polystar T-160 (above, Yashara Chemical Co., Ltd.), Superester A-125 and Pencel D-125 (above, manufactured by Arakawa Chemical Co., Ltd.) can be used.

Cross-linking agent The above-mentioned cross-linking agent improves the cohesive force of the pressure-sensitive adhesive, and examples of such a cross-linking agent include a room temperature cross-linking type cross-linking agent or a heat cross-linking type cross-linking agent.

  The room temperature crosslinking type crosslinking agent is a crosslinking agent that crosslinks the pressure-sensitive adhesive by an aging treatment under room temperature conditions. Examples of such room temperature crosslinking type crosslinking agents include, for example, crosslinking agents using isocyanate compounds, polyfunctional epoxy compounds, metal chelates such as aluminum and titanium, and among them, isocyanate compounds Alternatively, it is preferable to use a polyfunctional epoxy compound. These compounds may be used alone or in combination of two or more.

  Examples of the isocyanate compound include a polyisocyanate compound, a trimer of a polyisocyanate compound, a urethane prepolymer having an isocyanate group at a terminal obtained by reacting a polyisocyanate compound and a polyol compound, or such a urethane prepolymer. And polymer trimers. The polyisocyanate compound is not particularly limited, and 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'- Examples thereof include diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, and lysine isocyanate.

  The polyfunctional epoxy-based compound is not particularly limited, but sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, Examples thereof include neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and polybutadiene diglycidyl ether.

  The heat crosslinking type crosslinking agent is a crosslinking agent that crosslinks the pressure-sensitive adhesive by an aging treatment under heating. As such a heat-crosslinking type crosslinking agent, a methylol group-containing compound obtained by reacting formaldehyde with melamine, benzoguanamine, urea, or the like, or a part or all of the methylol groups of the methylol group-containing compound is aliphatic. Examples include compounds etherified with alcohol.

  The addition amount of a crosslinking agent can be suitably set according to the kind of acrylic adhesive and crosslinking agent to be used. For example, the addition amount of the crosslinking agent is preferably 0.005 to 3.5% by mass and more preferably 0.01 to 2% by mass with respect to the acrylic pressure-sensitive adhesive.

  The pressure-sensitive adhesive layer in the present invention is an ink prepared by dissolving or dispersing an additive obtained by adding an additive such as a crosslinking agent to the above pressure-sensitive adhesive and tackifier, gravure coating method, roll coating method, It can be formed by applying and drying by known means such as a comma coating method, a gravure printing method, a screen printing method, and a gravure reverse roll coating method.

  Usually, the thickness of the adhesive layer is preferably 5 to 100 μm, more preferably 10 to 50 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, sufficient adhesive strength can be maintained when producing a decorative molded product by a vacuum forming method.

Release layer The release layer in the present invention is a layer for protecting the adhesive layer of the decorative film. The release layer can be easily peeled from the adhesive layer when a decorative molded product is produced by a vacuum forming method. A release agent is used for the release layer in order to improve the peelability. Release agents include melamine resin release agents, silicone release agents, fluororesin release agents, cellulose resin release agents, urea resin release agents, polyolefin resin release agents, paraffin release agents. Release agents such as mold agents, acrylic resin release agents, and composite release agents thereof are preferred. Of these, silicone release agents are particularly preferred.

  The release layer in the present invention can be formed using the above release agent and a binder resin. As the binder resin, it is preferable to use a thermoplastic resin. For example, acrylic resin, polyester resin, cellulose derivative resin, polyvinyl acetal resin, polyvinyl butyral resin, vinyl chloride-vinyl acetate copolymer, and chlorinated polyolefin resin. Etc. The release layer is prepared by dissolving or dispersing the above-mentioned release agent and binder resin with the necessary additives in an appropriate solvent. Gravure coating method, roll coating method, comma coating method, gravure printing It can be formed by applying and drying by a known means such as a method, a screen printing method, and a gravure reverse roll coating method.

  In this invention, you may use the peeling film which provided the release layer containing said release agent on the single side | surface of well-known resin films, such as a polyester film, as a release layer.

Manufacturing method of decorative film for vacuum forming The manufacturing method of the decorative film for vacuum forming of this invention will not be specifically limited if a decorative film has said each layer structure, It manufactures by a conventionally well-known method. be able to. For example, a decorative layer coating solution containing a colorant is applied onto the base material layer to form a decorative layer. Next, a decorative film can be produced by applying a pressure-sensitive adhesive layer coating solution containing the pressure-sensitive adhesive and the tackifier on the decorative layer to form the pressure-sensitive adhesive layer. In the case of providing a release layer, after applying the adhesive layer coating liquid on the release sheet to be the release layer to form an adhesive layer, the base material decoration layer and the release sheet adhesive layer are The decorative film may be manufactured by laminating.

  Moreover, when laminating | stacking each layer of the decorative film for vacuum forming of this invention, you may laminate | stack by providing the adhesive layer which consists of a conventionally well-known adhesive agent between each layer. As an adhesive for laminating, for example, one or two-component cured or non-cured vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, Other adhesives such as solvent type, aqueous type, and emulsion type can be used.

Examples of the coating method for the adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, and other methods. As the coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry state) position are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry state) position is more preferred.

Decorative molded product The decorative molded product of the present invention comprises a molded body and a decorative layer decorated on the molded body by the decorative film for vacuum forming of the present invention. The decorative molded product of the present invention can exhibit high functionality and design by using the vacuum forming decorative film of the present invention. Hereinafter, the structure of the decorative molded product of the present invention will be described with reference to the drawings.

  According to the aspect of the present invention, there is provided a decorative molded product having an adhesive layer, a decorative layer, and a protective layer in this order on the molded body. Specifically, FIG. 3 shows a schematic cross-sectional view of an example of a decorative molded product according to the present invention. The decorative molded product 30 shown in FIG. 3 is formed by bonding a molded body 35 and a decorative layer 32 via an adhesive layer 33 and further forming a protective layer 31 on the decorative layer 32. It is. Hereinafter, each layer which comprises a decorative molded product is demonstrated.

Molded body The molded body in the present invention is an adherend of the decorative film for vacuum molding of the present invention, and may be any one that can be laminated by a vacuum molding method. For example, the molded body is a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, a sheet (or film), and the like. More specifically, various materials include wood veneer, wood plywood, particle board, wood fiber board such as MDF (medium density fiber board), metal materials such as iron and aluminum, ceramics such as glass and ceramics, plaster, etc. Non-cement ceramic materials, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates, acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS resins, polycarbonate resins, phenolic resins And resin materials such as vinyl chloride resin, cellulose resin and rubber.

Protective layer After the decorative film for vacuum forming of the present invention is laminated, the base layer of the decorative film becomes the outermost layer of the decorative molded product. That is, the protective layer corresponds to the base material layer of the decorative film. About the detail of a protective layer, it is the same as that of the base material layer of the decorating film for vacuum forming demonstrated above. By forming the protective layer with the resin as described above, it can be made excellent in durability such as wear resistance, chemical resistance, and weather resistance.

  The pressure-sensitive adhesive layer and the decorative layer of the decorative molded product are the same as the pressure-sensitive adhesive layer and the decorative layer of the vacuum forming decorative film described above.

Manufacturing method of decorative molded product The manufacturing method of the decorative molded product of the present invention includes a step of decorating a decorative layer on a molded body using the decorative film for vacuum forming of the present invention. As a vacuum forming method for laminating a decorative film on a molded body that is an adherend, a TOM (Three Dimension Over Method) method is preferably used. With the TOM method, for example, the inside of the apparatus where the decorative film fixed to the fixed frame is divided is sucked in both spaces with a vacuum pump or the like, and the inside of the apparatus is evacuated. At the same time, it is heated with an infrared heater until a predetermined temperature at which the decorative film softens, and at the timing when the decorative film is heated and softened, the atmosphere is sent to only one side of the internal space of the apparatus, thereby The decorative film is firmly adhered to the three-dimensional shape of the molded body that is the wearing body. If necessary, compressed air pressing from the silicone rubber sheet side may be used in combination. After the decorative film adheres to the molded body, the silicone rubber sheet is released from the decorative film, and then the decorative film formed from the fixed frame is removed to obtain a decorative molded product. Vacuum forming is usually performed at 80 to 150 ° C, preferably about 110 to 140 ° C.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not construed as being limited to the contents of the following examples.

Example 1
A rosin-based tackifier (softening point: 96 to 102 ° C., manufactured by Harima Chemical Co., Ltd., trade name: Haritac FK100) was dissolved in 10 parts by mass of ethyl acetate to prepare a tackifier solution. 100 parts by mass of acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 2953: composition below) and cross-linking agent (epoxy, trade name: E-5XM, 0.46) 0.46 The tackifier solution was added to and massed with 10 parts by mass of the diluent solvent (ethyl acetate) to prepare an adhesive layer coating solution.
Composition of SK Dyne 2953 (mixing ratio)
-Acrylic acid ester copolymer: 30-40 parts by mass- Methacrylic acid ester copolymer: 30-40 parts by mass- Methyl ethyl ketone: 30-40 parts by mass- Ethyl acetate: 20-30 parts by mass- Toluene: 1-10 masses Parts / Butyl acrylate: 1 to 10 parts by mass

  Next, a release sheet that is a peelable protective film layer (a polyester film having a release treatment with a silicone release agent on one side, a film thickness: 38 μm, manufactured by Tosero Co., Ltd., trade name: SP-PET) On the release treatment surface, the adhesive layer coating solution was applied with an applicator so that the film thickness after drying was 20 to 30 μm, and then dried at 80 to 100 ° C. for 3 to 5 minutes in a drying oven. .

  On the other hand, on one surface of an acrylic resin film (high moldability PMMA film, film thickness: 125 μm, manufactured by Kaneka Corp., trade name: Sandulen SD015NAH) as a base material layer, printing ink (manufactured by Showa Ink Co., Ltd.) Product name: EX5000 (NT)) was applied to form a decorative layer (pattern, thickness: 5 μm). Then, after pasting the decoration layer of a PMMA film and the adhesion layer of the said peeling sheet, it aged 72 hours in 40 degreeC oven, and obtained the decorating film of Example 1. FIG. This decorative film had a layer structure as shown in FIG.

Example 2
Decorating in the same manner as in Example 1 except that the tackifier was changed to 1 part by mass of a rosin tackifier (softening point 118 to 128 ° C., manufactured by Harima Chemical Co., Ltd., trade name: Haritac PCJ). A film was obtained.

Example 3
Except for changing the tackifier to 0.5 parts by mass of a rosin-based tackifier (softening point 130 to 140 ° C., manufactured by Harima Chemical Co., Ltd., trade name: Haritac 28JA), in the same manner as in Example 1, A decorative film was obtained.

Example 4
Decorating in the same manner as in Example 1 except that the tackifier was changed to 1 part by mass of a terpene tackifier (softening point 125 ° C., manufactured by Yasuhara Chemical Co., Ltd., trade name: YS Polystar N-125). A film was obtained.

Example 5
Except for changing the tackifier to 0.5 parts by mass of a rosin tackifier (softening point 160 ° C., manufactured by Yasuhara Chemical Co., Ltd., trade name: YS Polystar T-160), the same as in Example 1, A decorative film was obtained.

Comparative Example 1
A decorative film in the same manner as in Example 1 except that the tackifier was changed to 5 parts by mass of a rosin-based tackifier (softening point 78 to 87 ° C., manufactured by Harima Chemicals Co., Ltd., trade name: SE10). Got.

Comparative Example 2
A decorative film was obtained in the same manner as in Example 1 except that the tackifier was not added.

Comparative Example 3
97.5 parts by mass of acrylic resin (Kuraray Co., Ltd., trade name: LA polymer LA410L triblock elastomer) and acrylic resin (Kuraray Co., Ltd., trade name: LA polymer LA4285 triblock elastomer) 2.5 Parts by mass, 0.5 parts by mass of a heat stabilizer (BASF Corporation, trade name: IRGANOX 1726), and a diluent solvent (MEK: toluene = 1: 1, manufactured by DIC Graphics Corporation, trade name: KT) -11) A decorative film was obtained in the same manner as in Comparative Example 2 except that the acrylic pressure-sensitive adhesive A obtained by mixing 150 parts by mass was used.

Comparative Example 4
An acrylic pressure-sensitive adhesive obtained in the same manner as in Comparative Example 3 except that 5 parts by mass of an epoxy resin (trade name: Epicoat 1001 manufactured by Japan Epoxy Resin Co., Ltd.) was added instead of 0.5 parts by mass of the heat stabilizer. A decorative film was obtained in the same manner as Comparative Example 2 except that B was used.

Comparative Example 5
A decorative film was obtained in the same manner as in Example 1 except that the addition amount of the tackifier was changed to 30 parts by mass.

Performance evaluation of decorative film for vacuum forming About the decorative film for vacuum forming produced in said Example and comparative example, (1) heat resistance and (2) adhesive strength were evaluated.

(1) Heat resistance test The decorative film obtained above was stretched to 200% with Tensilon heated to 130 ° C., and adhered to the ABS resin molded body with a roller. Then, a 10 mm square crosscut was put, and it was put into a cycle tester under the condition of (−20 × 2 hours → 1 hour → 70 ° C. × 2 hours) × 7 cycles and stored. Thereafter, the shrinkage ratio of the crosscut portion was measured.

(2) Adhesive strength test The decorative film obtained above was heat sealed with an ABS resin plate with a heat sealer heated to 110 ° C. Then, it cut | disconnected to 15 mm width and measured the adhesive strength at the time of 90 mm peeling | exfoliation by 50 mm / min with Tensilon (Orientec Co., Ltd. make, brand name: RTA-1T).

The results of the above evaluations are shown in Table 1. The pressure-sensitive adhesive layer comprising the acrylic pressure-sensitive adhesive and the rosin-based tackifier or terpene-based tackifier having a high softening point has improved durability while maintaining the adhesive strength before the addition of the tackifier. I understood.

DESCRIPTION OF SYMBOLS 10 Decorative film 11 Base material layer 12 Decorative layer 13 Adhesive layer 20 Decorative film 21 Base material layer 22 Decorative layer 23 Adhesive layer 24 Release layer 30 Decorative molded product 31 Protective layer 32 Decorative layer 33 Adhesive layer 35 Molded body

Claims (7)

A base material layer;
A decorative layer,
A decorative film for vacuum forming, comprising an acrylic adhesive and an adhesive layer comprising a tackifier having a softening point of 90 to 180 ° C in this order.   The decorative film for vacuum forming according to claim 1, wherein the tackifier comprises a rosin resin and / or a terpene phenol resin.   The decorative film for vacuum forming according to claim 1 or 2, wherein the adhesive layer comprises 0.1 to 10% by mass of the tackifier with respect to the acrylic adhesive.   The decorative film for vacuum forming according to any one of claims 1 to 3, wherein the base material layer comprises an acrylic resin.   The decorative film for vacuum formation as described in any one of Claims 1-4 which further has a peeling layer on the said adhesion layer.   The decorative molded product which has a molded object and the decoration layer decorated with the decorative film for vacuum forming as described in any one of Claims 1-5 on the said molded object.   The manufacturing method of the decoration molded product which includes the process of decorating a decoration layer to a molded object using the decorating film for vacuum forming as described in any one of Claims 1-5.

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