JP2007223203A - Manufacturing method of insert moldings - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of insert moldings having a desired partly decorated portion at a desired position. <P>SOLUTION: The manufacturing method of the insert moldings with the partly decorated part comprises a process of heat forming a laminated sheet 3 which is made by laminating a releasable film 1 capable of heat forming and a partly decorated sheet 2, a process of insert molding by mounting the laminated sheet 3 heat formed in a mold for insert forming and a process of peeling the releasable film 1 capable of heat forming after the insert forming. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an insert molded body capable of partially decorating a surface.

As a method for decorating a resin molded body such as an injection molded body, a method of kneading a pigment in a resin and coloring the resin itself to perform injection molding, or a method of spray coating the surface layer of a molded body after injection molding Etc. In particular, when decoration of a metallic design is required, the metallic design is often applied by painting or plating after molding because it is difficult to uniformly disperse the metal pigment in the resin. .
However, in recent years, from the viewpoint of protection of the working environment against the discharge of chemical substances and protection of the external environment, there is a demand for an alternative to the coating or plating method. Therefore, attempts have been made to use water-based paints, powder paints, and the like as methods for imparting decorations to metal designs, but this is difficult at present.

  On the other hand, for the purpose of providing decoration, a decorative sheet that can be formed into a desired shape by heat is thermoformed in advance to the same shape as the concave mold of injection molding, and the decorative sheet after thermoforming is injection molded. An insert molding method is known in which a resin mold is placed in contact with a concave mold, and an injection resin is filled on the back side of the decorative sheet after the thermoforming. In this method, if a decorating sheet imparting a metal design is used as the decorating sheet, it is possible to decorate the metal design on a resin molded product such as an injection molded product without using a solvent.

  In these insert molding methods, it is necessary to thermoform the decorative sheet in advance to the same shape as the concave mold for injection molding. Therefore, when decorating the entire surface of the injection-molded body, problems such as alignment do not occur, but when partially decorating the desired position on the surface of the injection-molded body, depending on the shape of the mold, It is difficult to accurately align the decorative sheet with a desired position in the mold, and a deviation may occur during injection molding. Moreover, the injection resin wraps around between the partially decorated sheet and the mold at the time of injection molding, and the boundary between the decoration and the base resin of the obtained injection molded body is not clear, and the desired part In some cases, decoration could not be obtained.

On the other hand, after thermoforming in a state where the decorative sheet is covered with a temporary adhesive protective sheet in advance, the temporary adhesive protective sheet is peeled off, and at the time of injection molding, the decorative sheet after thermoforming without the temporary adhesive protective sheet is used. A method of performing insert molding is known (see, for example, Patent Document 1). This method uses a temporary adhesive protective sheet for the purpose of protecting the surface of the decorative sheet, and is performed by removing the temporary adhesive protective sheet during insert molding.
JP 2004-17508 A

  The subject of this invention provides the manufacturing method of an insert molded object which has a desired partial decoration in a desired position.

The present inventors previously thermoformed a laminate sheet of a peelable film and a partially decorated sheet, affixing a thermoformable peelable film to the surface that is to be decorated on the partially decorated sheet, The subject of the present invention was solved by a method of performing insert molding using the laminated sheet after thermoforming and peeling the peelable film from the obtained injection-molded product.
The peelable film serves as a support for the partially decorated sheet during injection molding. Accordingly, the partially decorated sheet is fixed in the mold, and the positional deviation is eliminated. In addition, after the injection molding, the peelable film can be peeled and removed, and when removing, the injection resin that goes around between the mold and the peelable film can be removed at the same time, so that a desired partial decoration can be obtained. .

  That is, the present invention is equipped with a laminated sheet obtained by laminating a peelable film that can be thermoformed and a partially decorated sheet, a thermoforming step 1, and a laminated sheet that is thermoformed in an insert molding die. There is provided a method for producing an insert-molded body having a partial decoration, which includes a step 2 for insert molding and a step 3 for peeling a thermoformable peelable film after insert molding.

According to the present invention, an injection molded article having a desired partial decoration at a desired position can be obtained.
For example, when using a mold that easily shifts the position of the partially decorated sheet, the size of the peelable film is at least large enough to cover the entire inner surface of the recessed mold of the insert molding mold. By attaching a partially decorated sheet to a part of the peelable film that is possible, it is possible to prevent misalignment during injection molding. Furthermore, since the injection resin covers up to the end face of the partially decorated sheet, there is no step between the injection resin and the partially decorated sheet after removing the peelable film after insert molding.
Also, for example, when the partially decorated sheet and the peelable film are all the same size, by laminating the partially decorated sheet and the peelable film without any gaps, the mold is wrapped around the mold side during injection molding. The injection resin can be removed together with the peelable film, and a desired partial decoration can be obtained.
Moreover, for example, when post-coating the obtained injection-molded product, a peelable film can be used for masking purposes. In this case, it is sufficient that a part or all of the decorative sheet is covered with a peelable film, and the post-coating is performed after the injection molding by setting the shape of the peelable film to a desired partially decorated shape, and then peeling By peeling the adhesive film, an injection molded body having a part of the decorative sheet on the surface in the shape of the peelable film can be obtained.
In any case, an insert molded body having excellent appearance quality can be obtained without causing scratches or dust on the surface of the partially decorated sheet.

  In addition, hereinafter, in the decorative sheet used for the purpose of decoration at the time of insert molding, the laminated sheet before thermoforming in which the peelable film and the decorative sheet are laminated is referred to as “sheet A”, and the peelable film and the decorative sheet. The laminated sheet after thermoforming is referred to as “sheet B”.

(Peelable film that can be thermoformed)
As the thermoformable peelable film used in the present invention, a known film can be used. Usually, a thermoplastic film having an adhesive layer on one side is used.
Specifically, stretched or unstretched polypropylene resin film, polyethylene resin film such as high density polyethylene, low density polyethylene, linear low density polyethylene, polyester (PET, PBT) resin film, polyvinyl alcohol (PVA) resin Film, polyamide resin film such as nylon 6 and nylon 66, ABS (acrylonitrile butadiene styrene) resin film, PC (polycarbonate) resin film, PMMA (polymethyl methacrylate) resin film, ionomer resin film, polyvinyl chloride and polyvinyl chloride A chlorine resin film such as vinylidene, a fluororesin film such as polyvinyl fluoride or polyvinylidene fluoride, or the like can be used. Also, for the purpose of imparting flexibility to polypropylene resin film, high density polyethylene, low density polyethylene, linear low density polyethylene, styrene-ethylene-butadiene-styrene copolymer, and styrene-ethylene-propylene-styrene copolymer A blend of styrene elastomer such as coalescence, olefin elastomer such as ethylene-propylene copolymer and ethylene-propylene-diene copolymer can also be used. The resin used for the adhesive layer of the masking film includes ethylene-vinyl acetate copolymer resin (EVA), low-density polyethylene, linear low-density polyethylene, styrene-ethylene-butadiene-styrene copolymer, and styrene. Styrene elastomers such as ethylene-propylene-styrene copolymers, ethylene-propylene copolymers, and olefin elastomers such as ethylene-propylene-diene copolymers, soft vinyl chloride resins, acrylonitrile-butadiene copolymers, acrylic rubber And natural rubber.
It is also possible to use a peelable film in which these resin layers are a single layer or a laminate.

(Partial decoration sheet)
If the partial decorating sheet used by this invention is used as a decorating sheet for insert molding, it will not specifically limit, A well-known decorating sheet can be used. Among these, a laminated sheet in which a thermoplastic resin film layer, a decorative layer, and a supporting base resin layer are laminated in this order is preferable because of excellent balance of spreading ratio and strength during thermoforming. Also,
Hereinafter, as a preferred embodiment of the present invention, a laminated sheet in which a thermoplastic resin film layer, a decorative layer, and a supporting base resin layer are laminated in this order will be described in detail.

(Partial decorative sheet thermoplastic resin film layer)
The thermoplastic film layer used in the present invention is a transparent or translucent single layer or multilayer film, may contain a colorant such as a pigment or dye, and a film exhibiting malleability by heating is used. The method for producing the thermoplastic film is not particularly limited, and the film may be used by a conventional method. Further, the thermoplastic film may be stretched uniaxially or biaxially as long as it does not impair the extensibility during thermoforming.
Although there is no restriction | limiting in particular in the thickness of a thermoplastic film, The range of 30-2000 micrometers is preferable from the applicability | paintability and thermoformability of a metallic luster ink layer, More preferably, it is 50-500 micrometers.

In order to perform a heat forming process such as vacuum forming, a film mainly composed of a thermoplastic resin having a softening point in the range of 30 to 300 ° C is preferable, and a more preferable softening point is in the range of 50 to 250 ° C. Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, acrylic resins such as polymethyl methacrylate and polyethyl methacrylate, ionomer resins, polystyrene, polyacrylonitrile and acrylonitrile. -Styrene resin, methyl methacrylate-styrene resin, polyacrylonitrile, polyamide resin such as nylon 6 and nylon 66, ethylene-vinyl acetate, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene-vinyl alcohol resin, polyvinyl chloride, Chlorine resin such as polyvinylidene chloride, fluorine resin such as polyvinyl fluoride and polyvinylidene fluoride, polycarbonate resin, cyclic polyolefin Fin, modified polyphenylene ether resins, methylpentene resins, cellulose resins are preferably used. Among these thermoplastic resins, a film mainly composed of at least one selected from the group of acrylic resins, polyester resins, polycarbonate resins, and cyclic polyolefin resins because of excellent thermoformability and expression of metal design. preferable.
Moreover, these blends and polymer alloys can be used as long as the transparency of the film is not impaired. These may be used in a single layer or multiple layers.
In addition, these thermoplastic resin films may be modified with rubber as long as transparency is not hindered. There is no particular limitation on the method of making the rubber modified, but a method of copolymerizing by adding a rubber component monomer such as butadiene at the time of polymerization of each resin, and hot melting of each resin and synthetic rubber or thermoplastic elastomer. The method of blending is mentioned.
In addition, conventional additives may be added to these thermoplastic resin films as long as transparency and moldability are not hindered. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), Antioxidants, antiozonants, activators, antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, difficulty You may mix | blend additives, such as a flame retardant and a vortex accelerator and a accelerating accelerator. These additives may be used alone or in combination of two or more.

(Partial decoration sheet decoration layer)
The decoration layer used in the present invention is not particularly limited. For example, ink or paint is spread on a thermoplastic resin film layer by a conventional method, or a metal thin film is formed by a vacuum deposition method, a sputtering method, a plating method, or the like. A decorative layer can be used.

The colorant contained in the ink or paint is preferably a pigment from the viewpoint of weather resistance. The pigment to be used is not particularly limited, and known and commonly used pigments such as colored pigments, metallic pigments, interference color pigments, fluorescent pigments, extender pigments and rust preventive pigments can be used.
Examples of the color pigment include quinacridone series such as quinacridone red, azo series such as pigment red, phthalocyanine series organic pigments such as phthalocyanine blue, phthalocyanine green and perylene red; and inorganic pigments such as titanium oxide and carbon black. Examples of the metallic pigment include aluminum powder, nickel powder, copper powder, brass powder, and chromium powder.
Examples of interference color pigments include pearlescent pearl mica powder and pearlescent colored pearl mica powder, and fluorescent pigments include quinacridone, anthraquinone, perylene, perinone, and diketopyrrolopyrrole. , Isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine Organic pigments such as nickel, phthalocyanine and indanthrone; metal complexes such as nickel dioxin yellow and copper azomethine yellow; metal oxides such as titanium oxide, iron oxide and zinc oxide; metal salts such as barium sulfate and calcium carbonate; And carbon black, aluminum and And inorganic pigments such as mother.

Moreover, when giving a metallic design, the metallic luster ink containing a metal powder is used. As the metal powder, metal powder usually used in metallic ink, metal thin film strips, and the like are used. In particular, metallic glossy inks using metal thin film strips cannot be obtained with conventional metal powders as a result of the metal thin film strips being oriented parallel to the surface of the object when the ink is printed or applied. A glossy surface with high brightness and a high metallic tone is particularly preferable.
As metals, aluminum, chromium, nickel, gold, platinum, silver, copper, germanium, brass, titanium, indium, molybdenum, tungsten, palladium, iridium, silicon, tantalum, nickel chromium, stainless steel, chromium copper, aluminum silcon A metal, an alloy, or a compound such as zinc oxide or tin oxide is used. As the metal thin film strip, a metal thin film strip obtained from these vapor-deposited metal thin films is preferably used. The thickness of the metal thin film is in the range of 0.01 to 0.1 μm, preferably 0.015 to 0.08 μm, and more preferably 0.018 to 0.045 μm. The average particle size of the metal thin film strips dispersed in the ink is in the range of 5 to 25 μm, preferably 10 to 15 μm. In addition, the content of the metal thin film strip with respect to the nonvolatile content in the ink is preferably in the range of 3 to 60% by mass, more preferably in the range of 10 to 60% by mass, and further preferably 20 to 45% by mass. preferable.
In order to obtain a higher-brightness mirror-like metallic luster, the thickness of the ink layer is preferably 0.05 to 3.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.5 to 2. 0.0 μm. When setting this film thickness to less than 1 micrometer, it is preferable to make content of the metal thin film strip in a film into 20-60 mass%.

  As the binder resin contained in the ink or paint, conventional gravure inks, flexographic inks, screen inks, or resins usually used for paints can be used. Specific examples include acrylic resin, polyurethane resin, polyamide resin, urea resin, polyester resin, vinyl chloride resin, vinylidene chloride resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, olefin resin, chlorination. Olefin resins, epoxy resins, petroleum resins, cellulose derivative resins and the like are used. These resins may be used in combination or in combination with those obtained by chemically bonding polar groups such as carboxylic acid groups, phosphoric acid groups, sulfonic acid groups, amino groups, and quaternary ammonium bases.

  As long as it does not impair the design and moldability of the ink constituting the decorative layer, various additives usually used in conventional gravure ink, flexo ink, screen ink, paint, etc. are used as necessary. You can also. Various organic solvents can also be used for the purpose of adjusting the viscosity and the like.

When the decoration layer is obtained as a metal vapor deposition layer, the metal used is a metal, alloy, or compound such as aluminum, chromium, nickel, gold, silver, copper, germanium, zinc oxide, or tin oxide. The metal vapor deposition layer is formed on the thermoplastic resin film layer by vacuum vapor deposition, sputtering, ion plating, plating, or the like.
The metal vapor deposition layer may be implemented on the entire surface, or may be partially implemented by masking and patterned in combination with color ink.

  Examples of a method for spreading the ink or paint used for the decorative layer on the thermoplastic resin film layer include printing methods such as gravure printing, flexographic printing, and screen printing; and gravure coaters, gravure reverse coaters, flexographic coaters, and blankets. Coating methods such as a coater, roll coater, knife coater, air knife coater, kiss touch coater, kiss touch reverse coater, comma coater, comma reverse coater, and micro gravure coater can be used.

  The thickness of the decorative layer is not particularly limited, but is preferably 0.1 to 5 μm, particularly preferably 0 when using an ink or paint because it is excellent in concealment and design properties and hardly causes color unevenness during thermoforming. 0.5-3 μm. Moreover, when forming a metal thin film layer, 0.01-0.50 micrometer is preferable, Most preferably, it is 0.02-0.10 micrometer. Further, for the purpose of controlling the adhesion between the thermoplastic resin film layer and the decorative layer, the surface of the thermoplastic resin film layer may be subjected to a surface treatment such as corona treatment or primer coating.

(Ink protective layer)
When the ink constituting the decoration layer is a metallic glossy ink using metal thin film strips, between the decoration layer and the thermoplastic resin film layer, heat resistance, solvent resistance, design, weather resistance, etc. One or more ink protective layers may be provided for the purpose of improving the quality. Especially, since the ink solvent resistance and the heat resistance at the time of shaping | molding are favorable, the ink protective layer which consists of a thermosetting composition is preferable.
The type of resin that can be used for the ink protective layer is not particularly limited as long as it does not impair the moldability. However, acrylic resin can be used from the viewpoints of easy adjustment of the crosslink density, weather resistance, and adhesion to the thermoplastic resin film layer. Based resins are preferred. There are no particular restrictions on the crosslinking mechanism, and in the case of acrylic resins, UV curing, EB curing, hydroxyl group-containing vinyl copolymer / isocyanate curing, silanol / water curing, epoxy / amine curing, etc. can be used. From the viewpoints of easiness, weather resistance, reaction rate, presence or absence of reaction byproducts, production cost, etc., hydroxyl group-containing vinyl copolymer / isocyanate curing is preferable.
The ink protective layer can also be a colored layer in order to impart design properties. In this case, the amount of the colorant added is preferably 20% or more of the total light transmittance of the colorant and the target color tone or the protective layer, and the total light transmittance is particularly preferably 40% or more. More preferred.
A pigment is preferred as the colorant. The pigment to be used is not particularly limited, and known pigments such as colored pigments, metallic pigments, interference color pigments, fluorescent pigments, extender pigments and rust preventive pigments can be used.
Examples of the color pigment include quinacridone series such as quinacridone red, azo series such as pigment red, phthalocyanine series organic pigments such as phthalocyanine blue, phthalocyanine green, and perylene red; and inorganic pigments such as titanium oxide and carbon black. Examples of metallic pigments include aluminum powder, nickel powder, copper powder, brass powder, and chromium powder.
Examples of interference color pigments include pearlescent pearl mica powder and pearlescent colored pearl mica powder, and fluorescent pigments include quinacridone, anthraquinone, perylene, perinone, and diketopyrrolopyrrole. , Isoindolinone, condensed azo, benzimidazolone, monoazo, insoluble azo, naphthol, flavanthrone, anthrapyrimidine, quinophthalone, pyranthrone, pyrazolone, thioindigo, anthanthrone, dioxazine , Phthalocyanine and indanthrone organic pigments, metal complexes such as nickel dioxin yellow and copper azomethine yellow, metal oxides such as titanium oxide, iron oxide and zinc oxide, barium sulfate and calcium carbonate, etc. Metal salts, carbon black, aluminum and And inorganic pigments such as mica.

(Partial decorative sheet support base resin layer)
After the decoration layer is formed on the thermoplastic film layer, a supporting base resin layer can be further laminated. For this layer, a thermoplastic film is used, and a thermoplastic resin having a softening point in the range of 30 to 300 ° C is preferred, and a more preferable softening point is in the range of 50 to 250 ° C. Specific examples include ABS (acrylonitrile butadiene styrene) resin, ABS polymer alloy, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, PC (polycarbonate) / ABS resin. , PBT (polybutylene terephthalate) / ABS resin, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic acid Ester / styrene resin, PC (polycarbonate) resin, PMMA (polymethyl methacrylate) resin, PMMA / ABS / AS resin, polyolefin resin such as polyethylene and polypropylene, polyethylene terephthalate and polybutylene terf Polyester resin such as rate, acrylic resin such as polymethyl methacrylate and polyethyl methacrylate, ionomer resin, polyamide resin such as nylon 6 and nylon 66, ethylene-vinyl acetate, ethylene-acrylic acid resin, ethylene-ethyl acrylate resin, ethylene- Vinyl alcohol resins, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, fluororesins such as polyvinyl fluoride and polyvinylidene fluoride, etc. are preferably used. Among these thermoplastic resins, polypropylene resins, polyethylene resins, blends thereof, and films mainly composed of ABS resins and AAS resins are preferable among these thermoplastic resins.
For the purpose of improving impact strength, these resins have ethylene propylene rubber (EPR), styrene / butadiene / styrene (SBS) resin, styrene / isoprene / butadiene / styrene (SIBS) resin, styrene / ethylene / butadiene / A rubber-based modifier such as styrene (SIBS) resin may be added. These blends and polymer alloys can be used as long as the transparency of the film is not impaired. These may be used in a single layer or multiple layers. The thickness of the support base resin layer is not particularly limited, but is preferably 10 to 3000 μm, for example.
In addition, conventional additives may be added to these supporting base resin layers as long as the moldability is not inhibited. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants Agents, antiozonants, activators, antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants and You may mix | blend additives, such as a flow promoter and a flow promoter. These additives may be used alone or in combination of two or more.
As a method for laminating the supporting base resin layer, a co-extrusion method by heat melting is preferable because a film forming cost is low and an efficient sheet with little thickness unevenness can be obtained.

  The laminated sheet is made into a three-dimensional decorative sheet by thermoforming. At this time, if the molding shrinkage of the thermoplastic resin used for the supporting base resin layer and the thermoplastic resin film layer is different, the molded body is deformed. It is difficult to maintain a good shape. In order to improve this, an inorganic filler can be mix | blended in a support base resin layer. The kind of the inorganic filler is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, and silica. The added amount of the inorganic filler is preferably 5 to 60% by mass. The particle size is not particularly limited, but if it is too large, irregularities may occur on the surface of the supporting base resin layer, which may adversely affect the appearance and gloss of the laminated sheet. Therefore, the average particle size of the inorganic filler in the support base resin layer is preferably 8 μm or less, and more preferably 4 μm or less.

When a colorant is contained in the supporting base resin layer, the concealability of the decorative sheet base is improved, and it is more preferable because the design of the transfer object can be unified. The colorant is not particularly limited, and similarly to the colorant used for the thermoplastic resin of the base material, conventional inorganic pigments and organic pigments used for coloring general thermoplastic resins according to the intended design. And dyes can be used. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, complex oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo Pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. In addition, it is preferable to use one or two dyes mainly selected from the group of oil-soluble dyes.
The blending amount of the colorant varies depending on the type and the thickness and color tone of the supporting base resin sheet, but in order to secure the hue and concealment and maintain the impact strength, the resin constituting the supporting base resin layer is used. The mass percentage is preferably in the range of 0.1 to 20 mass%, more preferably in the range of 0.5 to 15 mass%.

(Partial decorative sheet adhesive layer)
After the decorative layer is formed on the thermoplastic film layer, the support base resin layer can be further laminated via an adhesive layer. As an adhesion method, lamination can be performed by a dry lamination method, a wet lamination method, a hot melt lamination method, or the like using a conventional solvent-type adhesive.

Components constituting the adhesive include conventional phenol resin adhesives, resorcinol resin adhesives, phenol-resorcinol resin adhesives, epoxy resin adhesives, urea resin adhesives, polyurethane adhesives, and polyaromatics. Thermosetting resin adhesives such as tic adhesives and reactive adhesives using ethylene unsaturated carboxylic acid, vinyl acetate resin, acrylic resin, ethylene vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal, vinyl chloride, nylon, And thermoplastic resin adhesives such as cyanoacrylate resins, chloroprene adhesives, nitrile rubber adhesives, SBR adhesives, and rubber adhesives such as natural rubber adhesives.
As the coating method of these adhesives, a gravure coater, a gravure reverse coater, a flexo coater, a blanket coater, a roll coater, a knife coater, a kiss touch coater, a comma coater, or the like can be used.
The coating amount of the adhesive for a better satisfactory dry adhesion strength is preferably in the range of 0.1 to 30 g / ^{m 2,} particularly preferably 2 to 10 g / ^{m 2.} When it is less than 2 g / m ² , the adhesive strength is weakened, and when it is more than 10 g / m ² , the drying property is lowered.
The thickness of the adhesive layer is preferably in the range of 0.1 to 30 μm, more preferably 1 to 20 μm, and particularly preferably 2 to 10 μm.
In addition, the adhesive surface of the supporting base resin layer is surface treatment such as plasma treatment, corona treatment, flame treatment, electron beam irradiation treatment, sanding treatment, ozone treatment, or vacuum for the purpose of improving the affinity with the adhesive. Dry plating treatment such as vapor deposition, sputtering, or ion plating may be performed.
Moreover, it can replace with an adhesive bond layer and can also provide an adhesive layer. As the adhesive, acrylic, rubber, polyalkyl silicon, urethane, polyester, and the like are preferably used.

(Partial decorative sheet surface protective layer)
The partially decorated sheet used in the present invention has performance such as designability, abrasion resistance, scratch resistance, weather resistance, contamination resistance, water resistance, chemical resistance, heat resistance, etc. on the surface side during thermoforming. In order to give, you may have a surface protective layer in the surface layer of a thermoplastic resin film. As the surface protective layer, a lacquer type, a thermal crosslinking type with an isocyanate, an epoxy, or the like, a UV crosslinking type, or an EB crosslinking type is preferably used as long as the thermoformability is not impaired.

(Lamination method of thermoformable peelable film and partially decorative sheet)
In order to obtain the sheet A by laminating the thermoformable peelable film and the sheet for partial decorating, the partially decorated sheet already prepared and the peelable film may be bonded to each other, or the peelable film may be peeled off. The process of manufacturing the film, the partially decorated sheet, and the process of laminating the peelable film may be manufactured in one line.
As a method of pasting the former partially decorated sheet and peelable film, use a laminator that has been surface-treated with fluorine coating or the like so that the peelable film does not adhere to the laminar roll. Alternatively, pressure bonding may be performed using a laminar roll such as a gravure coater, a gravure reverse coater, a flexo coater, a blanket coater, a roll coater, a knife coater, a kiss touch coater, or a comma coater that is also subjected to the same surface treatment.
Moreover, in order to manufacture the peelable film, the step of producing the partially decorated sheet, and the step of laminating the peelable film in one line, known printing, coating, or laminating methods can be combined. For example, in the case of the sheet A having a layer structure of peelable film / thermoplastic resin film layer / ink protective layer / decorative ink layer / adhesive layer / support base resin layer, the peelable film and the thermoplastic resin film layer are laminated. After that, an ink protective layer and a decorative ink layer were printed or applied in this order on the thermoplastic resin film layer, and finally a support base resin layer provided with an adhesive layer was applied to the adhesive layer and the decorative ink. It can be obtained by laminating so that the layers overlap.
In the case of the sheet A having a layer structure of peelable film / decorative ink layer / adhesive layer / support base resin layer, the ink protective layer and the decorative ink layer are printed or applied in this order on the peelable film, and finally A support base resin layer provided with an adhesive layer by coating may be laminated so that the adhesive layer and the decorative ink layer overlap.

(Sheet A)
There is no limitation in particular in the shape of the said sheet | seat A, It can be set as arbitrary shapes according to the objective. For example, when using a mold that easily shifts the position of the partially decorated sheet, as shown in FIG. 1, cover the entire inner surface of the concave mold of the mold for insert molding as shown in FIG. The sheet A is trimmed to a desired shape and laminated on a part of the peelable film, and a misalignment during injection molding is prevented. be able to.
For example, as shown in FIG. 2, you may use a peelable film and a decorating sheet | seat by laminating | stacking by the exact same dimension. If necessary, the obtained sheet A can be trimmed to a desired shape and used. In sheet A, the peelable film and the decorative sheet are laminated without any gaps, so that the injection resin that wraps around the mold side can be removed together with the peelable film at the time of injection molding. Can be obtained.
Moreover, what is necessary is just to laminate | stack and use the peeling film trimmed to the desired shape dimension with the decoration sheet of a full dimension, when post-coating is shown in FIG.
In either case, an insert molded body having excellent appearance quality can be obtained without causing scratches or dust on the surface of the partially decorated sheet.

(Step 1 Thermoforming method of sheet A)
Specifically, the process 1 for thermoforming the sheet A includes a hot plate forming method, a vacuum forming method, an ultra-high pressure forming method, a pressure forming method, a pressure forming method, a match mold forming method, a press forming method, and a vacuum lamination press. It can be molded by an existing thermoforming method such as a molding method. Further, if necessary, a straight method using a plug, a drape method, a plug assist method, an air slip method, a method, a snapback method and the like may be used in combination. As the heating method, either an indirect heating method such as radiant heat or dielectric heating, or a direct heating method in which heating is performed in contact with a hot plate or the like may be used.
As the thermoforming method, it is preferable to use a match mold forming method or a compressed air vacuum forming method, which is high in mass productivity and easily obtains good mold reproducibility even at low temperature forming.

(Pressurized vacuum forming method)
The compressed air vacuum forming method is a forming method in which a male mold or a female mold is pressed against a sheet heated in a heating zone, and the sheet is shaped using compressed air and vacuum pressure. The molding conditions are not particularly limited, but when a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 2 to 30 seconds, and heating is performed until the sheet reaches a desired temperature. To do. The mold temperature needs to be determined while confirming the appearance and the degree of shrinkage of the resulting decorative sheet, but is preferably 20 to 80 ° C. and the cooling time by the mold is preferably 1 to 60 seconds. The molding pressure is preferably 0.1 to 1 MPa, but 0.3 to 0.7 MPa is more preferably used in terms of mold reproducibility and equipment investment. In the case of the ultra-high pressure molding method, molding is performed by applying a molding pressure of about 30 MPa, so that good mold reproducibility can be obtained even at low temperatures.

(Match mold molding method)
The match mold molding method is characterized in that a male mold and a female mold are matched and molded so as to sandwich a sheet heated in a heating zone. The mold used here is usually provided with a vacuum hole as an air escape path in the mold. However, vacuum suction may be supplementarily performed using this hole. Since the molding pressure can use the power of servo motor, hydraulic pressure, etc., the force is about 10 to 1000 times that of normal pressure forming, so that sufficient mold reproducibility can be obtained unless the sheet is torn. I can do it. Further, molding at a lower temperature is possible, and in the case of match molding, when the sheet A uses a metallic gloss ink, it can be used as a decorative sheet while maintaining its surface gloss. Although there is no particular limitation on the molding conditions, when a far infrared heater is used, the heater temperature is 200 to 500 ° C., the indirect heating time is 2 to 30 seconds, and the sheet is heated until it reaches a desired temperature. . The mold temperature needs to be determined while confirming the appearance and the degree of shrinkage of the resulting decorative sheet, but is preferably 20 to 100 ° C. and the cooling time by the mold is preferably 10 to 5 minutes. Moreover, it is more preferable to cool the decorative sheet obtained after completion of molding with air or the like because deformation that easily occurs during mold release can be prevented.

(Process 2 Insert molding)
The sheet B obtained by the above method can be mounted in an injection mold and molded by an insert molding method to obtain a transfer object.

(Insert molding)
The resin used for insert molding is preferably selected depending on the compatibility with the peelable film or the decorative sheet. Specifically, a resin used for the peelable film or a resin of the same system as the supporting base resin layer of the laminated sheet for thermoforming is preferable. For example, when the resin used for the peelable film or the supporting base resin layer of the laminated sheet for thermoforming is ABS (acrylonitrile butadiene styrene) resin, the base material resin for injection is preferably ABS resin, PVC (polyvinyl chloride) / ABS resin, PA (polyamide) / ABS resin, PC (polycarbonate) / ABS resin, PBT (which is an ABS polymer alloy if the adhesion to the supporting base resin layer is sufficient. (Polybutylene terephthalate) / ABS resin may be used. Similarly, if the adhesion is good, AAS (acrylonitrile / acrylic rubber / styrene) resin, AS (acrylonitrile / styrene) resin, AES (acrylonitrile / ethylene rubber / styrene) resin, MS ((meth) acrylic ester / styrene) It may be a different resin such as resin, PC resin, PMMA (polymethyl methacrylate) resin, PMMA / ABS / AS resin.

  When the resin used for the peelable film or the supporting base resin layer of the laminated sheet for thermoforming is a polypropylene resin, the base material resin for injection is preferably a polypropylene resin, and the laminated sheet is supported. From the viewpoint of adhesion to the base resin layer, it is preferable that the injection resin contains 40% by mass or more of polypropylene. Other components may include a resin component that can be melt-mixed with polypropylene. Polypropylene resins and meltable resins include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, styrene-ethylene-propylene-styrene copolymers, and styrene-based copolymers such as styrene-ethylene-propylene-styrene copolymers Examples thereof include olefin elastomers such as elastomers, ethylene-propylene copolymers, and ethylene-propylene-diene copolymers.

In addition, an inorganic filler can be added to the injection resin in order to prevent deformation during or after molding. The inorganic filler is not particularly limited, and examples thereof include talc, calcium carbonate, clay, diatomaceous earth, mica, magnesium silicate, silica and the like.
Furthermore, conventional additives may be added as long as the moldability is not inhibited. For example, plasticizers, light-resistant additives (ultraviolet absorbers, stabilizers, etc.), antioxidants, ozonization inhibitors, activators , Antistatic agents, lubricants, antifriction agents, surface conditioners (leveling agents, antifoaming agents, antiblocking agents, etc.), antifungal agents, antibacterial agents, dispersants, flame retardants and wake accelerators You may mix | blend additives, such as an agent. These additives may be used alone or in combination of two or more.

Further, a colorant may be added to the injection resin in accordance with the color or pattern of the hydraulic transfer film to be used. Although the addition amount of a coloring agent changes with kinds of coloring agent and the target color tone, it is preferable that it is 30 mass parts or less with respect to 100 mass parts of injection resin, More preferably, it is 20 mass parts or less.
The colorant to be used is not particularly limited, and conventional inorganic pigments, organic pigments and dyes used for coloring general thermoplastic resins can be used according to the intended design. For example, inorganic pigments such as titanium oxide, titanium yellow, iron oxide, complex oxide pigments, ultramarine, cobalt blue, chromium oxide, bismuth vanadate, carbon black, zinc oxide, calcium carbonate, barium sulfate, silica, talc; azo Pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, anthraquinone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, quinophthalone pigments, thioindigo pigments and diketopyrrolo Organic pigments such as pyrrole pigments; metal complex pigments and the like. In addition, it is preferable to use one or two dyes mainly selected from the group of oil-soluble dyes.

The insert molding conditions are not particularly limited. The injection conditions and the mold temperature may be set according to the injection resin, but if the injection resin temperature or the mold temperature is too low, the supporting base resin layer and the injection resin However, if the injection resin temperature or the mold temperature is too high, the injection resin may wash away the supporting base resin layer near the gate. For this reason, for example, in the case of polypropylene resin, the filling temperature is preferably 180 to 270 ° C, and more preferably 190 to 260 ° C. In the case of ABS resin, 190-290 degreeC is preferable and 200-270 degreeC is more preferable.
The mold temperature may be controlled by water cooling to about 100 ° C for both cavity side mold and core side mold in polypropylene resin and ABS resin insert molding, but warpage may occur depending on the shape of the transferred material after insert molding. In such a case, mold temperature control may be performed by providing a temperature difference between the cavity side mold and the core side mold. In addition, in order to warm the decorative sheet inserted in the mold to the mold temperature before filling with the injection resin, an injection delay time for holding the decorative sheet in the range of 1 to 100 seconds in the mold clamped may be set. good.

(Process 3 peels the peelable film)
The peelable film is peeled from the obtained injection-molded product. The peeling method is not particularly limited. For example, the boundary end face may be lifted and peeled off. When it is difficult to lift the boundary end face, an adhesive tape or the like may be attached to make a peeling end and then peeled off.

  Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified, “part” and “%” are based on mass. The measurement method and determination method used are described below.

(Manufacture of partially decorated sheets)
(Ink adjustment for decoration layer Aluminum thin film manufacturing method)
Nitrocellulose (HIG7) was dissolved in a mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4 to make a 6% solution. The solution was applied onto a polyester film with a gravure plate having a screen line number of 175 lines / inch and a cell depth of 25 μm to form a release layer. After sufficiently drying, aluminum is vapor-deposited on the release layer to a thickness of 0.04 μm, and the same nitrocellulose solution as that used for the release layer is applied to the deposited film surface under the same conditions as in the release layer. The top coat layer was formed by coating.
After peeling the aluminum vapor-deposited film from the polyester film immersed in the mixed solvent of ethyl acetate: isopropyl alcohol = 6: 4, the aluminum vapor-deposited film was pulverized with a stirrer so as to have a size of about 150 μm, An aluminum thin film strip was prepared.

(Adjustment of aluminum thin film slurry)
Aluminum thin film strip 10 parts Ethyl acetate 35 parts Methyl ethyl ketone 30 parts
30 parts of isopropyl alcohol The above was mixed, and 5 parts of a nitrocellulose solution having the following composition was added while stirring.
Nitrocellulose (HIG 1/4) 25%
Ethyl acetate: isopropyl alcohol = 6: 4 mixed solvent 75%
While maintaining the temperature at 35 ° C. or lower, the above mixture was stirred using a turbo mixer until the size of the aluminum thin film pieces became 5 to 25 μm, thereby adjusting the aluminum thin film piece slurry (nonvolatile content 10%). did.

(Adjustment of decorative layer ink)
Aluminum thin film slurry (non-volatile content 10%) 30 parts Binder resin Carboxylic acid-containing vinyl acetate resin 3 parts
("Vinylite VMCH" manufactured by UCC)
Carboxylic acid-containing urethane resin 7 parts
(Dai Nippon Ink Chemical Co., Ltd. “Tyforce NT810-45” nonvolatile content 45%)
Ethyl acetate 23 parts Methyl ethyl ketone 26 parts Isopropanol 10 parts
The above was mixed to prepare an ink having an aluminum thin film strip concentration of 35 mass% in the nonvolatile content.

(Adjustment of thermoplastic resin film)
As the transparent or translucent thermoplastic resin film layer, a rubber-modified PMMA film (trade name “Technoloy S-001”, manufactured by Sumitomo Chemical Co., Ltd.) having a haze of 0.1% and a thickness of 125 μm was used.

(Surface protective layer and ink protective layer)
850 parts of butyl acetate and 1 part of perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) are added to a reaction vessel equipped with a temperature controller, a nitrogen introducing tube, a dropping device (2 units), and a stirring device. After charging and nitrogen substitution, the temperature was raised to 110 ° C. over 1.5 hours.
Separately, 660 parts of methyl methacrylate, 150 parts of t-butyl methacrylate and 190 parts of 2-hydroxyethyl methacrylate (hereinafter referred to as monomer solution), 200 parts of isobutyl acetate, and perbutyl O (trade name, manufactured by NOF Corporation) , T-butyl peroxy-2-ethylhexanoate) 9 parts, perbutyl Z (trade name, manufactured by NOF Corporation, t-butyl peroxybenzoate) 2 parts well stirred solution (hereinafter referred to as catalyst solution) Each was charged into a dropping device and immediately purged with nitrogen.
The above monomer solution and catalyst solution were dropped in a reaction vessel under a nitrogen atmosphere over 5 hours while monitoring the reaction temperature so as not to increase rapidly. As a result of continuing stirring for about 15 hours after completion of the dropping, a hydroxyl group-containing copolymer having a solid content of 60% was obtained. The weight average molecular weight of the obtained resin was 100,000, the hydroxyl value of the solid content was 79 KOHmg / g, and Tg was 95 ° C.
The hydroxyl group-containing copolymer and the polyisocyanate compound “BURNOCK DN-981” (trade name, manufactured by Dainippon Ink & Chemicals, Inc., isocyanurate ring-containing polyisocyanate, number average molecular weight of about 1000, non-volatile content 75% (solvent: Ethyl acetate), 3 functional groups, and 13 to 14% NCO concentration) were blended and mixed at a solid content ratio of 1: 1 to prepare an ink protective layer solution.

  (Here, the weight average molecular weight is a polystyrene equivalent value of the GPC measurement result. In addition, the solid content was measured by taking 1 g of a sample on an aluminum dish and spreading it thinly and uniformly with toluene, followed by air drying and further at 108 ° C. It was dried for 1 hour in a hot air dryer and calculated from the weight after drying.The hydroxyl value was calculated as a KOH neutralized amount from the monomer charge composition, the polymer Tg was DSC, and the acid value was 0.05 mol · dm−. (Measured by titration with 3 potassium hydroxide-toluene solution.)

(adhesive)
A two-component polyester urethane adhesive (a two-component mixed adhesive of “LX-630PX” and “KR-90” manufactured by Dainippon Ink and Chemicals, Inc.) is mixed at a ratio of 30: 1 and adhesive D is added. It was adjusted.

(Supporting base resin layer)
Two types of supporting base resin layers were used.
As support base resin layer S-1, ABS (Clarastic MTH-2) manufactured by Nippon A & L Co., Ltd. was introduced from an extruder hopper, extruded from a T die at a processing temperature of 240 ° C., and heated to 100 ° C. After passing through a cast roll, an unstretched original sheet having a thickness of 200 μm obtained by winding was used.
Also, random PP (Noblen FS3611) manufactured by Sumitomo Chemical Co., Ltd. was introduced from the extruder hopper as the support base resin layer S-2, extruded from a T-die at a processing temperature of 200 ° C., and heated to 40 ° C. After passing through the roll, an unstretched original fabric sheet having a thickness of 200 μm obtained by winding was used.

(Peelable film)
As the peelable film, a polyolefin-based surface protective film P-1 made by Sumilon Co., Ltd. having a thickness of 50 μm (trade name “EC700”, a protective film P-2 made by Nitto Denko Co., Ltd. having a thickness of 80 μm) (trade name “SPV -AL-300 ") were used.

(Manufacturing method of sheet A1)
On the thermoplastic resin film, the ink protective layer solution was applied using a micro gravure coater so as to have a dry film thickness of 2 μm, and then subjected to aging treatment at 40 ° C. for 3 days. Next, the decorative layer ink was printed on the ink protective layer using a micro gravure coater so that the dry film thickness was 1 μm.
Next, the adhesive surface of the support base resin layer S-2 was subjected to corona treatment, and an adhesive was applied using a gravure coater so as to have a dry film thickness of 5 μm, and then applied onto the thermoplastic resin film. The decorative layer ink was bonded, and then an aging treatment was performed at 40 ° C. for 3 days to obtain a decorative sheet 1.
The obtained decorative sheet 1 and the peelable film P-2 are laminated by a thermal laminator, and the peelable film P-2 / thermoplastic resin film layer / decorative ink layer / adhesive layer / support base resin layer. A sheet A1 having a layer configuration of S-2 was obtained. The shape of the stack was the shape shown in FIG.

(Manufacturing method of sheet A2)
The ink protective layer solution was applied onto the peelable film P-1 using a microgravure coater so as to have a dry film thickness of 2 μm, and then subjected to an aging treatment at 40 ° C. for 3 days. Next, the decorative layer ink was printed on the ink protective layer using a micro gravure coater so that the dry film thickness was 1 μm.
Next, a corona treatment is applied to the adhesive surface of the supporting base resin layer S-1, an adhesive is applied using a gravure coater so as to have a dry film thickness of 5 μm, and the decoration applied on the peelable film. A sheet having a layer structure of peelable film P-1, decorative ink layer / adhesive layer / support base resin layer S-1, which is laminated with layer ink and then subjected to aging treatment at 40 ° C. for 3 days. A2 was obtained. The shape of the stack was the shape shown in FIG.

(Thermoforming of sheets A1 and A2)
The obtained sheets A1 to A2 were heated using a PLAVAC vacuum forming machine manufactured by Sanwa Kogyo Co., Ltd., and an aluminum mold coated with a fluororesin on the surface. Compressed air vacuum forming was performed at a temperature of 300 ° C. to obtain a three-dimensional thermoformed body. Hereinafter, a sheet B1 is formed by thermoforming the sheet A1, and a sheet B2 is formed by thermoforming the sheet A2.

(trimming)
Sheet B2 was set on a Thomson blade and cut with a press to perform trimming of a predetermined shape.

(Insert molding of sheets B1 and B2)
Insert molding after mounting the release film side of the sheets B1 to B2 on the mold cavity side to the injection mold having the same shape as that obtained by thermoforming the sheets A1 to A2. A three-dimensional decorative molded body made of a peelable film / decorative sheet / injection molded resin was obtained.
As the resin for injection molding, ABS resin C-1 (trade name “Polylac PA-756”) manufactured by Kitami Jitsugyo Co., Ltd. and polypropylene resin C-2 (trade name “TX1868H5”) manufactured by Novatec Co., Ltd. were used.
As the injection molding machine, Sumitomo Nestal C160 manufactured by Sumitomo Heavy Industries, Ltd. was used. The mold has a structure in which an injection resin having a thickness of 2.5 mm can be filled on the supporting base layer side with respect to a three-dimensional thermoformed body.

Example 1
A sheet B1 obtained by thermoforming the sheet A1 by a compressed air vacuum forming method was trimmed into a predetermined partially decorated shape with a Thomson blade and mounted on an injection mold. The layer structure of the laminated sheet at this time is peelable film P-2 / thermoplastic resin film layer / decorative ink layer / adhesive layer / support base resin layer S-2.
An insert molded article having a good appearance was obtained using the injection resin C-2 at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C. This molded product had a good appearance even when the masking film was peeled off.

(Example 2)
A sheet B2 obtained by thermoforming the sheet A2 by a compressed air vacuum forming method was mounted on an injection mold. At this time, the layer structure of the laminated sheet is peelable film P-1 / decorative ink layer / adhesive layer / support base resin layer S-1.
An insert molded article having a good appearance was obtained using the injection resin C-1 at a mold temperature of 60 ° C. and a cylinder temperature of 230 ° C. This molded product had a good appearance even when the masking film was peeled off.

(Comparative Example 1)
Without using a peelable film, a sheet obtained by thermoforming only a partially decorated sheet was mounted on an injection mold and subjected to insert molding. The layer structure of the laminated sheet at this time was thermoplastic resin film layer / decorative ink layer / adhesive layer / support base resin layer S-2, and the injection resin C-2 at a mold temperature of 40 ° C. and a cylinder temperature of 220 ° C. It was used. The obtained insert-molded product was misaligned, and the injection-molded resin turned around to the front side of the laminated sheet, impairing the design.

It is an example of the specific aspect of the lamination sheet (sheet | seat A) which laminated | stacked the peelable film which can be thermoformed, and the sheet | seat for partial decorations used by this invention. It is an example of the specific aspect of the lamination sheet (sheet | seat A) which laminated | stacked the peelable film which can be thermoformed, and the sheet | seat for partial decorations used by this invention. It is an example of the specific aspect of the lamination sheet (sheet | seat A) which laminated | stacked the peelable film which can be thermoformed, and the sheet | seat for partial decorations used by this invention.

Explanation of symbols

1: Thermoformable peelable film 2: Partial decorating sheet 3: Laminated sheet (sheet A)

Claims (2)

Step 1 for thermoforming a laminated sheet obtained by laminating a thermoformable peelable film and a partially decorated sheet, and a step for inserting and molding the laminated sheet thermoformed in an insert molding die 2 and the process 3 which peels the peelable film which can be thermoformed after insert molding, The manufacturing method of the insert molded object which has a partial decoration characterized by the above-mentioned. The manufacturing method of the insert molded object which has the partial decoration of Claim 1 in which the said partial decorating sheet | seat has a metallic gloss ink layer containing a metal thin film strip and binder resin.

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