JP2014148151A - Composite colored sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve problems, owing to proliferations of members having convoluted shapes among made-of-plastic decorative moldings used for automotive interior members such as door trims, etc., not only of color tone differences of monotone-colored deep-drawn molding members but also of the expression of a deep texture and to provide an inexpensive decorative molding member imparting a deeper clear texture without recourse to coating.SOLUTION: The provided composite colored sheet is obtained by forming a protective coating film by coating a specified urethane-modified acrylic coating material on the surface of the first layer of a piano black bilayer colored sheet formulated by integrating, based on a bilayer extrusion molding method, a first layer consisting of a colored polymer obtained by coloring, in piano black, a mixed polymer of a methacrylic resin and an acrylic rubber-containing polymer with a mixed coloring agent of a dye and a pigment and a second layer consisting of a pigment-colored acrylonitrile butadiene styrene (ABS) black colored polymer.

Description

  The present invention mainly relates to a surface layer material of a plastic three-dimensional molded product for automobile interior such as door rim.

  In recent years, in the plastic three-dimensional molding used for automobile interior materials such as door rim, innovation in manufacturing technology has been remarkably advanced with the progress of diversification of interior design. Corresponding to this need, product surface decoration technology is rapidly progressing.

  From the past, door rims, center panels, etc. are parts that are strongly required to be designed among automotive interior parts, and because there are many products with complex shapes, the water transfer method is often used to express the design of the surface layer. I came.

  However, the water transfer method requires the use of a large amount of water and painting to protect the decorated ink layer, and several coatings are required to improve the texture, so a large amount of solvent is used. In recent years, the need for a dry decorating method without paint has rapidly increased due to environmental issues.

  As a conventional typical dry decoration method, there is an injection molding simultaneous decoration method as a first prescription. In this formulation, a release decorative film in which a release layer, a protective layer, a pattern layer, and an adhesive layer are formed on a release biaxially stretched PET film is inserted into a predetermined mold inner surface and clamped, and then inside the cavity In the decoration method, a predetermined resin is melted to create an injection molded product, and then the release PET film is peeled off to create a decorative molded product. (For example, Patent Document 1)

  The above injection molding simultaneous decorating method has the following problems. First, the release biaxially stretched PET film is simultaneously molded, and the PET film is not suitable for a molded member having a complicated shape, and it is difficult to deep draw 100% or more. Secondly, because the decoration is performed by gravure printing, the ink layer thickness is as thin as 10 microns at the maximum, and color tone differences are likely to occur at deep drawing sites. Third, since the protective layer on the surface is a photocurable or electron beam curable resin layer, it is difficult to uniformly cure at the deep drawing portion. For this reason, it is difficult to apply to plastic molded members for automobile interiors that need to support various shape members.

  Next, as a second decorative molding method, a composite film in which a decorative layer is formed mainly by gravure printing on the back surface of the acrylic film, and a photocurable and electron beam curable protective layer is formed on the surface of the acrylic film. As a first layer, an ABS resin sheet or the like is used as a backup layer for the second layer, and a decorative sheet is prepared by dry lamination via an adhesive. Next, the decorative sheet is inserted into a predetermined mold and vacuum molded to trim unnecessary parts, and then inserted into an injection mold and ABS resin is backed up by injection molding to create a decorative molded product. There is a molding method. (For example, Patent Document 2 and Patent Document 3)

  On the other hand, the following problems are pointed out in the decoration method by the insert molding method. First, in the insert molding method, the decorative sheet based on the dry laminate prescription described above is often used, but most of the decorative sheet is applied by gravure printing, so the ink layer is thin and piano black or the like is used. In the case of monotone design, there is a problem of color difference at a deep drawing member and a problem that it is difficult to express a deep color tone. Secondly, in order to clear various physical properties as an automobile interior member, it is necessary to form a photo-curing or electron beam-curing protective layer on the surface layer as described in item 7. Although it is necessary to pass the molded product through a curing process after the molding process, it is difficult to uniformly cure the surface of a member having a complicated shape. Thirdly, the cost increases as the number of man-hours increases.

JP 2010-234769 A JP 2010-028771 A JP 2010-163576 A Japanese Patent Laid-Open No. 11-5278

  The conventional methods for producing decorative molded parts for automobile interiors as described above have problems in terms of environmental measures, adaptability to complicated shapes such as deep-drawn parts, and cost performance aspects. Is required.

  The first problem of the present invention relates to a decorative molded member for automobile interior, and in a monotone design member, particularly a piano black member, there is no color tone difference with respect to a deep drawing member of 300% or more regardless of printing prescription. Moreover, it is to provide a decorative sheet for a decorative molded member having a deep texture.

  Next, the second problem of the present invention is that it is paint-free from the viewpoint of environmental measures, and without using a functional film such as an acrylic film on the surface layer, light resistance, stain resistance, alcohol resistance, scratch resistance, surface hardness, etc. It is to provide a decorative sheet for a decorative molded member for automobile interior having characteristics excellent in various physical properties.

  The third object of the present invention is to provide a decorative sheet for a decorative molded member for automobile interior at low cost by improving productivity by shortening the production process.

  In the decorative sheet for the existing dry decorative molded product described above, most of the prescriptions that give decoration are colored by gravure printing prescription. Coloring by gravure printing has a maximum color layer thickness of 10 microns as described in Section 6. In the case of giving a monotone color such as piano black, a so-called solid printing is adopted, but the thickness of the solid color layer is limited to 10 microns even in two-plate printing.

  As already mentioned, some automotive interior parts require molded parts that require a deep drawing of about 300%. However, with a color layer of about 10 microns, the thickness of the color layer at the maximum extension is about 3 microns. There is a problem that a color difference in an object is likely to occur.

  Furthermore, the piano black color required for true jetness cannot be obtained with a color layer of about 10 microns, and black ink for gravure printing tends to be reddish or bluish black, and it is difficult to express true jet black. There are challenges.

  In the present invention, as means for solving the problems 15 and 16, the present invention focuses on polymer coloring and solves it by forming a raw material-colored polymer into a sheet by an extrusion molding method.

  In selecting the polymer raw material to be colored here, in the present invention, the surface hardness is H or higher, the transparency is high, the light resistance, the stain resistance, the chemical resistance and the like are excellent, and the deep drawability of 300% or more is excellent. We focused on adopting a proven mixed polymer of methacrylic resin and acrylic rubber-containing polymer. The mixing ratio of the mixed polymer is suitably 60 to 80% methacrylic resin and 40 to 20% by weight of an acrylic rubber-containing polymer in consideration of the processability and sheet physical properties of the extruded sheet.

  In addition, as a means to cope with the problem of cost reduction, the above acrylic resin colored polymer is used as the first layer as a surface layer, and the two layers are extruded simultaneously by using a colored ABS polymer in the second layer. It is possible to provide a decorative sheet for a decorative molded product of monotone design such as piano black at a low cost. Here, the composition ratio of the first layer and the second layer is the second layer (3 to 4) with respect to the first layer (1) in consideration of cost and processability as a decorative sheet for a decorative molded product. ) Is preferred. The total thickness of the two-layer sheet is preferably 300 to 500 μm.

  Next, when coloring the acrylic resin used in the first layer as a means to solve the problem of developing the true jetness, pay attention to coloring with dyes, compared to the pigment coloring often used in traditional raw colored polymers. did. Since the acrylic resin used in the first layer is also excellent in dyeability, it can be colored with a clear color tone that cannot be obtained with other resins. Further, in the present invention, it is possible to express deep jetness with excellent concealability by adopting a prescription for preparing a colored polymer by mixing a special carbon pigment with black dye.

  In addition, in the production of colored ABS polymer used for the second layer, it is colored using a black masterbatch for ABS in consideration of cost, and the above-mentioned acrylic colored polymer is used as the first layer for simultaneous two-layer extrusion molding. By making a composite colored sheet, it was possible to provide a decorative sheet for a piano black decorative molded product having true jetness at low cost.

  Next, in the characteristics of the acrylic resin used in the first layer described in item 18 as a means for clearing various physical properties as automobile interior members, the alcohol resistance and scratch resistance, which are the disadvantages of the acrylic resin, are improved. Therefore, in the present invention, on the surface of the colored acrylic resin layer of the first layer, a composite sheet obtained by applying a primary thermosetting by applying a two-stage thermosetting urethane-modified acrylic resin is insert-molded. Alcohol resistance and scratch resistance can be improved by secondary curing by heating. The composite sheet was also confirmed to follow a 3000% deep drawing process.

  The surface of the protective coating after the primary thermosetting formed on the surface of the first layer by the above formulation is non-tacky and has excellent handleability such as winding workability after coating and excellent transparency. As a result, it has become possible to provide a molded product having a deep jetness.

  Furthermore, the acrylic resin described in item 18 is used for the first layer without coloring the raw material by making use of the original high transparency, and the two layers are formed using an ABS polymer colored in a predetermined color tone for the second layer. By creating an extruded sheet, it has become possible to provide a decorative sheet having a clear layer with a deeper texture that is difficult to obtain by painting instead of clear painting.

  In addition, various metallic pigments, hologram pigments, etc. are mixed in the coloring agent of the colored ABS polymer used in the second layer, and the composite sheet is prepared according to the above-mentioned formulation. It became possible to provide.

  As described above, the composite colored sheet prepared according to the present invention has 300% deep-drawing moldability, and since the color layer is thick, there is no color tone difference in the deep-drawing part, and molding for automobile interiors of any shape. In addition to providing a product with a uniform color tone in the member, it also provides a product with a deeper texture.

  In addition, the surface layer is an acrylic resin layer, and the surface is coated with a thermosetting resin coating having 300% heat extensibility, thereby providing various properties for automobile interiors with excellent alcohol resistance and scratch resistance. It came to provide a decorative sheet for a clear decorative molded product.

  Furthermore, by adopting a processing prescription with high productivity by shortening the processing process, the effect of providing a decorative sheet for decorative molding with low cost and high function was exhibited.

It is sectional drawing which shows the composite coloring sheet concerning this invention. It is sectional drawing of the composite coloring sheet | seat concerning Claim 3 of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Here, FIG. 1 is a cross-sectional view of a piano black composite colored sheet A used for a decorative molded product for automobile interior according to the present embodiment. FIG. 2 is a cross-sectional view of a composite colored sheet B used for a decorative molded product for automobile interior according to an embodiment of claim 3 of the present invention.

  In creating the piano black composite colored sheet A according to this embodiment, a colored polymer used for the piano black colored acrylic resin layer (1) used for the first layer was prepared according to the following formulation.

  First, a mixed acrylic polymer was prepared by polymer-alloying 70% methacrylic resin and 30% by weight of an acrylic rubber-containing polymer.

  The mixed acrylic polymer is excellent in extrudability, and the extruded sheet made from the polymer is flexible and difficult to break, and it is difficult to form a sheet with a common acrylic resin. Production of thin sheets of 0, 1 mm to 0.5 mm Is possible. This sheet is highly transparent and has a surface hardness as high as H or more, and is excellent in stain resistance and weather resistance, and these characteristics are about the same level as ordinary acrylic resin plates, and are thin sheets. For this reason, it is suitable for post-processing and handling when making a composite sheet. Further, as a result of confirming moldability, it was found that 300% or more deep drawing can be performed. Furthermore, the sheet has already been commercialized as a paint replacement sheet. For example, “JP 11-5278” (Patent Document 4)

  Next, in creating the piano black composite coloring sheet A according to the present embodiment, as a means for obtaining a piano black sheet having true jetness, a color obtained by mixing a special black dye for acrylic resin with a fine carbon black pigment An agent was prepared, melt-kneaded into the acrylic polymer described in 32, and pelletized to prepare an acrylic piano black polymer.

  Next, the above-mentioned acrylic piano black polymer is used as a raw material for the first black piano colored acrylic resin layer (1), and the ABS black masterbatch is mixed with the ABS polymer to prepare a second colored black colored ABS resin layer (2) raw material. A piano black two-layer colored sheet I having a total thickness of 400 microns was prepared by a two-layer extrusion molding method with the first layer thickness set to 90 microns and the second layer thickness set to 310 microns. In the preparation of the piano black two-layer colored sheet I, the first layer of the piano black-colored acrylic resin layer (1) and the second layer of the black-colored ABS resin layer (2) have the following thickness structure: It is desirable that the thickness is 50 μ to 150 μ and the second layer is 400 μ to 200 μ. Further, by adopting transparent ABS as the ABS polymer used here, it is possible to create a piano black two-layer colored sheet with higher jetness.

  Next, in order to clear the various physical properties of the decorative molded article for automobile interiors, the two-layer piano black composite is used as a form for improving the alcohol resistance and scratch resistance, which were the drawbacks of acrylic resin. The surface of sheet I was coated with a protective coating layer (3) by applying a two-stage thermosetting urethane-modified acrylic paint.

The two-stage thermosetting paint is primarily cured by heat treatment after coating, so that the sheet surface is non-adhesive and can be processed into a roll without blocking problems, and a post-processing step There is no problem in handling. Moreover, it is possible to completely cross-link and harden the surface by secondary curing by heating during the molding process. By this action, the effect of improving the surface physical properties of the decorative molded product at the same time as molding is obtained. Further, this prescription has the effect that deep drawing can be performed because the coating film on the sheet surface is not completely cured in the heat treatment process in the primary stage.

As the two-stage thermosetting paint used in the above-mentioned form, a paint prepared by diluting a urethane-modified acrylic polymer of 90 to 70 parts of acrylic with a nonvolatile content of 20% to 40% with respect to 10 to 30 parts of urethane is appropriate. It is. An isocyanate-based curing agent is added to the paint and gravure-coated to form a protective film having a size of 3 to 8 microns. The dilution solvent used here is preferably a mixed solvent of MEK (methyl ethyl ketone) and IPA (isopropyl alcohol), and the mixing ratio of the solvent is preferably 40 to 60 parts of MEK and 60 to 40 parts of IPA.

  Next, in providing a colored sheet with a deeper texture that takes advantage of the clear texture of paint replacement, the acrylic polymer described in item 32/33 used for the first layer is extruded without coloring and transparent acrylic resin An effective prescription is to form a single-layer colored bilayer sheet II by forming the layer (4) and coloring the ABS polymer used for the second layer to form the colored ABS resin layer (5). The acrylic polymer used for the first layer in this embodiment has a light transmittance of 93%, a cloud value of 0.5% and high transparency, and forms a thick clear layer that is difficult to obtain with a coating of 50 to 200 microns. Therefore, the color tone of the second layer becomes a deeper texture.

  The ABS polymer used for the second layer may be a general grade, but it is preferable to use transparent ABS in order to express a clearer color tone. Transparent ABS polymers that can be used here include Toyolac 920 manufactured by Toray Industries, Ltd., TE20S manufactured by Denki Kagaku Kogyo Co., Ltd., Techno H814 manufactured by Technopolymer Co., Ltd., and Clarastic ST600 manufactured by Nippon A & L Co., Ltd.

  Further, by adding a metallic pigment or a hologram pigment to the ABS colored polymer used for the second layer in addition to the monotone pigment, it is possible to provide a decorative sheet having a high design tone.

  Subsequently, the urethane-modified acrylic paint described in the item 36 was applied to the surface of the single-layer colored bilayer sheet II to form a protective coating layer (3), thereby preparing a composite colored sheet B.

  The composite colored sheet B created in the form according to the above prescription can be decorated simultaneously with the sheet creation without using printing means, and a deep clear surface layer can be obtained without using a clear film such as an acrylic film. As a result, it has become possible to provide a decorative sheet for decorative molded products that is an alternative to painting at low cost.

  The piano black composite colored sheet A and composite colored sheet B produced by the above embodiment also have the effect of improving the alcohol resistance and scratch resistance of the surface, and are used in decorative molded products for automobile interiors. As a decorative sheet, products with sufficient physical properties and moldability are provided at low cost.

  First, in preparing the piano black composite colored sheet A, the acrylic resin polymer used for the first layer was prepared by mixing 70% methacrylic resin and 30% acrylic rubber-containing polymer, and the polymer was treated with fine carbon black pigment and acrylic. A colorant mixed with a special dye for resin was mixed and pelletized to prepare a piano black acrylic polymer for the piano black colored acrylic resin layer (1) of the first layer.

  Next, a black masterbatch for ABS resin is mixed with general-purpose ABS resin manufactured by Denki Kagaku Kogyo Co., Ltd. to prepare a black colored polymer for the second colored black colored ABS resin layer (2). A piano black two-layer colored sheet I was prepared by extruding two layers at a weight ratio of 1: 4 with the first layer and the second layer as the first layer with the polymer as the first layer and the black-colored ABS polymer as the second layer. .

  Next, an isocyanate-based curing agent is added to a predetermined two-stage thermosetting urethane-modified acrylic paint on the surface of the piano black two-layer colored sheet I and diluted with a diluent of 50 parts of IPA and 50 parts of IPA. After the microgravure coating, a dry heat treatment at 90 ° C. for 80 seconds was performed to cover the protective coating layer (3) to prepare a piano black composite colored sheet A.

  Next, the colored ABS polymer prepared by mixing the silver metallic pigment prepared in advance is used for the second colored ABS resin layer (5), and the acrylic polymer described in the item 32 is used as the first transparent acrylic resin layer (4). For the purpose, a single layer colored bilayer sheet II was prepared by extruding two layers at a weight ratio of 1 to 3 with the extrusion ratio of the first layer and the second layer.

  A composite colored sheet B was prepared by coating the surface of the single-layer colored bilayer sheet II with the protective coating layer (3) according to the formulation described in 47.

  The product of Example 1 made according to the present invention has a true jet blackness with a depth, and even for a molded product having a complicated shape that requires 300% deep drawing, It was possible to provide a decorative sheet for piano black moldings with no difference in color. Furthermore, it has become possible to provide a decorative sheet for a three-dimensional decorative molded article that has cleared various physical properties as an automobile interior material such as alcohol resistance and scratch resistance at low cost. In addition, the product of Example 2 can provide a decorative sheet for a decorative molded article for a metallic interior with a paint-less and deep transparent texture at a low cost. It became a deep contribution.

(1) Piano black colored acrylic resin layer (2) Black colored ABS resin layer (3) Protective coating layer (4) Transparent acrylic resin layer (5) Colored ABS resin layer I Piano black bilayer colored sheet II Single layer colored two Layer sheet A Piano black composite colored sheet B Composite colored sheet

Claims (3)

  The first layer is a colored hard acrylic resin layer having a thickness of 50 μm to 150 μm obtained by polymer-coloring a mixed polymer of methacrylic resin 60% to 80% by weight and acrylic rubber-containing polymer 40% to 20% by weight, and acrylonitrile / butadiene / styrene. In a colored sheet having a thickness of 250 μm to 550 μm, in which a colored resin layer having a thickness of 200 μm to 400 μm obtained by polymerizing a resin (hereinafter referred to as ABS resin) is used as a second layer, the surface of the first layer is 100% to 300%. A composite colored sheet produced by coating a three-dimensional moldable urethane-modified acrylic resin coating film having a heating elongation ratio of   2. The composite colored sheet according to claim 1, wherein the first layer and the second layer are integrally formed by a two-layer extrusion molding method.   3. The composite colored sheet according to claim 1, wherein the first layer is made of a transparent acrylic resin layer.

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