JP4151906B2 - Decorating resin laminate - Google Patents

Description

  The present invention relates to a decorative resin laminate suitable for decoration with a metallic surface, a manufacturing method thereof, a resin molded article having a metallic appearance composed of the decorative resin laminate, and a manufacturing method thereof.

  Conventionally, as a metallic-like resin molded product, a resin molded body composed of a single decorative layer or two layers of a decorative layer and a colored layer is generally known. The decorative layer forms an elegant appearance by blending a pearl pigment exhibiting a decorative effect of metallic tone or pearly luster tone. Based on this structure, a multilayer structure molded body having three or more layers composed of a coating layer provided in close contact with the outer side of the decoration layer for improving the finished feeling has been devised.

For example, a design sheet having a mirror-finished surface made of a thermoplastic resin in which a pearl pigment coated with titanium oxide is dispersed on the surface of fine flaky mica is described (see Patent Document 1). However, in the production of this sheet, there is a problem that wrinkles are generated on the surface of the metal roll due to the pigment exposed on the surface of the sheet when a sheet obtained by extruding a resin containing a pigment is pressed with a metal roll for mirror finishing. .
A resin film containing a luster pigment or a film in which the resin film and a colored resin film are laminated is described (see Patent Document 2). And after apply | coating the raw material which mix | blended the glossy pigment with the liquid resin composition containing a solvent to the resin film containing a gloss pigment on a base material, this solvent is volatilized and a resin coating film is obtained, and this coating film Describes a process for peeling off the substrate from the substrate. It is described that this is for preventing the glossy pigment from cracking and facilitating orientation during film formation.
In addition, a polyolefin resin mixed with a predetermined amount of a luster pigment is used as a core layer, a colored polyolefin resin is used as a colored layer, and a transparent thermoplastic resin is used as a coating layer, and each extruded layer is laminated to form a cylindrical bottle shape. A multilayer structure molded article is described (for example, see Patent Document 3). However, for this multilayer structure molded article with a glossy color, it is described in the specification that a coextruded sheet is sandwiched between rolls and laminated. Not listed. Although this structure molded article has a certain level of glitter, it cannot be said that it has sufficient glitter because the coating layer on the outside of the molded article does not contain a luster pigment.
Japanese Patent Laid-Open No. 3-173626 JP 2001-226500 A JP 2001-341240 A

  In the present invention, in order to exhibit the overall glitter of a molded article having at least a three-layer structure, a part of the gloss pigment dispersed in the vicinity of the surface of the molded article, that is, the core layer is disposed on one or both sides of the core layer. By transferring to a skin layer and dispersing and containing a luster pigment, a decorative resin laminate having a deep and strong luster and gloss, a resin molded product comprising the laminate, and a decorating resin It aims at providing the manufacturing method of a laminated body.

As a result of intensive studies to solve the above problems, the inventors of the present invention pressed the glossy pigment dispersed in the core layer on one side of the core layer or by pressing with a metal roll while laminating the sheets of the extruded layers. The present inventors have found that it can be dispersed in the skin layers on both sides and have completed the present invention.
That is,
The decorative resin laminate of the present invention is a laminate comprising at least three layers of a core layer and a skin layer sandwiching the layer, and has an average thickness of 20 μm or less and an average particle diameter of 10 to 300 μm. A molten resin composition that becomes a core layer having a metallic pigment whose surface is coated with a metal or metal oxide layer and a molten resin that becomes a skin layer that does not contain the pigment are combined in layers to form a sheet with a T-die. The laminate obtained by extruding and transferring at least a part of the pigment to the skin layer is press- cooled and molded with a metal roll, has surface specularity, has a sense of depth, and exhibits a strong glitter .
Furthermore, the present invention is a laminate comprising at least three layers of a core layer and a skin layer sandwiching the layer, and the surface of the flaky glass having an average thickness of 20 μm or less and an average particle size of 10 to 300 μm is made of metal or A molten resin composition to be a core layer having a metallic pigment coated with a metal oxide layer and a molten resin to be a skin layer not containing the pigment are combined in layers and extruded into a sheet shape with a T-die, 1 part of the pigment contained in the molten resin composition comprising is shifted in the skin layer, by pressing cooled molded with metal rolls has a surface specularity, there is sense of depth, for that Teisu strong glittering decoration It is a manufacturing method of a resin laminated body.
In addition, a resin molded product obtained by vacuum / pressure forming the decorative resin laminate is also included in the present invention.

The decorative resin laminate of the present invention causes wrinkles on the surface of the metal roll by dispersing the glossy pigment contained in the core layer in the skin layer and not exposing it to the surface of the skin layer. However, it can be easily manufactured by a normal molding machine.
And since the gloss pigment can be dispersed in the skin layer on the surface of the decorative resin laminate, the amount added to the core layer of the expensive gloss pigment has a sense of depth and luxury, effectively exhibits a strong glitter. From this laminate, it is possible to easily obtain a glossy resin molded product that is remarkably excellent in cosmetics, excellent in eye catching at the time of display, and glossy.

The present invention is described in detail below.
The decorative resin laminate of the present invention has a structure in which the skin layer has surface glossiness, improved mechanical strength, and other glitter such as adhesion, and the core layer has functions such as glitter. . A colorant other than the luster pigment can be dispersed in one skin layer to provide functions such as concealment and light shielding properties.
The thickness of the decorative resin laminate of the present invention can be appropriately selected according to the type of resin used and the use of the laminate, but is usually 200 to 500 μm. If it is this range, a favorable laminated body can be shape | molded, the stable production is attained, and secondary processing of a favorable resin molded product etc. is realizable.
And the thickness of each layer which comprises a laminated body is the range which can be laminated | stacked by coextrusion, Usually, a core layer has a thickness of 30-400 micrometers in order to reflect the shining light effectively from the disperse gloss pigment. Is preferred. The skin layer preferably has a thickness of 30 to 100 μm in a state in which the glossy pigment is dispersed and is not exposed on the surface of the skin layer.

  The resin used in this laminate is mainly a thermoplastic resin, and the type thereof is not particularly limited. For example, typical resins include polyolefin resins such as polyethylene resin, polypropylene resin, and polymethylene pentene resin. And their copolymers, or modified products added with unsaturated carboxylic acids, vinyl chloride resin, polystyrene resin, ABS resin, AS resin, PET resin, PBT resin, polyamide resin, polycarbonate resin, acrylic resin, methacrylic resin, Examples thereof include biodegradable resins such as ethylene-vinyl acetate resin, ethylene-vinyl alcohol copolymer, and polylactic acid.

The resin used for the core layer is preferably a resin having a transparent or translucent property. More preferably, it is a transparent resin. Examples thereof include biodegradable resins such as polyethylene resin, polypropylene resin, vinyl chloride resin, polystyrene resin, ABS resin, AS resin, acrylic resin, methacrylic resin, polycarbonate resin, PET resin, and polylactic acid.
In addition, specific functions required for the sheet to be each layer include, for example, PET resin, PBT resin, polyamide resin and ethylene-vinyl acetate in order to improve the mechanical strength of the skin layer and increase the surface gloss. It is preferable to use a saponified copolymer or the like.
The resin used as the core layer and skin layer preferably has the functions and characteristics required for each layer, is rich in co-extrusion and co-workability, and has good adhesiveness. , Each may be of a different type.

Glossy pigments used to impart glittering properties include metal powders such as aluminum powder and brass powder, pearl pigments and metallic pigments of titanium dioxide-coated mica, but the added resin surface has a three-dimensional effect and is excellent It is preferable to use a metallic pigment because it has excellent glitter and extremely good transparency.
The metallic pigment is characterized by scaly particles in which the surface of flaky glass is coated with a metal or metal oxide layer. Examples of the metal used for coating the flaky glass include gold, silver, brass, titanium, nickel, or alloys thereof. Examples of the metal oxide used for coating include titanium dioxide, zirconium oxide, and iron oxide. As the metallic pigment, scale-like particles in which the surface of the flaky glass is coated with a metal oxide having a refractive index higher than the refractive index of the flaky glass are preferred because they emit extremely strong reflected light.

The metallic pigment preferably has a larger surface area in order to obtain a higher brightness. The flaky glass before coating with metal or metal oxide preferably has a thickness of 20 μm or less and an average particle size of 10 to 300 μm. The aspect ratio (average particle diameter / average thickness) is preferably at least 15.
Furthermore, in order to improve the adhesion between the metallic pigment and the resin component, the coated surface of the luster pigment may be treated with a surface treatment agent such as a coupling agent, if necessary.

  In order to effectively reflect light from the gloss pigment dispersed in the core layer and the skin layer, and to have a brilliant and elegant appearance, the gloss pigment is added to the core layer resin composition in an amount of 0.01 to 0.5. It is preferable to add by weight. If it is less than 0.01% by weight, a glittering shine cannot be obtained, and if it exceeds 0.5% by weight, the smoothness of the skin layer is reduced, and the glitter is not improved and economically undesirable. .

  A compounding agent generally used, for example, a stabilizer, an ultraviolet absorber, a lubricant, or the like can be added to the decorative resin laminate of the present invention as necessary. In particular, it is preferable to add an ultraviolet absorber for imparting weather resistance and protecting the laminate. The decorative resin laminate of the present invention may contain various known color pigments in order to impart metallic textures having various textures to the obtained resin molded product.

The sheet to be each layer of the resin laminate can be produced by a melt casting method such as a melt casting method, a T die method, an inflation method, a calendar method, etc., but from the viewpoint of economy, a T die and cooling are used. It is preferable to manufacture with an extrusion molding machine equipped with a roll and a winder.
As a method for producing the decorative resin laminate of the present invention, a sheet to be a core layer and a sheet to be a skin layer on both sides of the core layer are each extruded from a T-die and then heated to heat melt the boundary surface. Lamination method for laminating by adhesion, laminating method for laminating by providing an adhesive layer on the boundary surface, or a method for laminating by directly contacting the molten sheet co-extruded from 3 layers and coming out from a 3 layer die There is.

In addition, there is a molding method in which molten resin to be a core layer and a skin layer are merged and combined into a layer before being extruded from a T die, and then extruded from a feed block type multilayer T die into a sheet. This method is preferable because it is easy to disperse the luster pigment of the core layer in the skin layer. The extruded sheet-like molten laminate can be molded by pressing with a cooling roll. Examples of the cooling method include a method in which a melt-laminated laminate is sandwiched between metal rolls and molded.
By pressing with a cooling roll, the skin layer has surface glossiness, and a laminate having a deep and strong glitter is obtained.

The reason why some glossy pigments dispersed in the core layer are dispersed in the skin layer is not clear, but when molding with a multilayer T-die, from the time when the resin that becomes the core layer and the skin layer in the molten state merges, Until the time of extrusion, it is presumed that the molten resin in each layer flows and the gloss pigment in the core layer moves to the skin layer and is dispersed accordingly.
And in the combination of the resins to be extruded, for example, the gloss that shifts from the core layer to the skin layer by making a difference between the viscosity of the resin composition of the molten core layer and the viscosity of the resin composition of each skin layer The amount of pigment can be varied, so that the luster pigment can be dispersed in the skin layers on both sides of the core layer or in the skin layer on only one side.

In order to obtain a mirror surface and a sense of depth on the surface of the laminated decorative resin laminate, it can be formed by being sandwiched between a plurality of metal rolls or belts. By molding so that the area is in contact with the roll, the mirror surface and depth of the sheet surface can be obtained.
Moreover, a resin molded product can be obtained by vacuum / pressure forming the resin laminate of the present invention.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist.
A resin composition containing polyester (manufactured by Hualon) and a luster pigment (manufactured by Nippon Sheet Glass Co., Ltd., trade name “Metashine” (metal coat series (MC5090PS)), the content of the luster pigment being 0.3% by weight; Polyester (manufactured by Hualon) was extruded from a twin-screw kneading extruder (manufactured by Nippon Steel Works, trade name “TEX”) and supplied to a co-extruded three-layer T-die fitted with a feed block.
In the feed block, the polyester was divided into two parts, and the two polyesters were combined to form a layer by sandwiching the resin composition between the two polyesters.
The obtained laminated body was cooled with a cooling roll and wound up to obtain a decorative resin laminated body having a core layer of 300 μm, each skin layer of 50 μm, and a thickness of 400 μm.
As a result of observing the cross section of the obtained decorative resin laminate with an electron microscope, the glossy pigment was contained in both skin layers. In FIG. 1, sectional drawing of the resin laminated body for decorating is shown.
Further, the surface of the decorative resin laminate was visually observed, and the dispersibility of the glossy pigment was good, the gold color by strong reflected light was exhibited, the depth feeling was excellent, and a sparkling appearance was obtained. Further, no die line was generated by the T-die on the surfaces of both skin layers, and no exposure of the glossy pigment was observed.

  The decorative resin laminate obtained in Example 1 was vacuum molded using a vacuum molding machine equipped with a mold having a cavity having a length of about 20 cm, a width of about 15 cm, and a depth of about 4 cm, and a resin molded product Was made. The mold temperature was about 55 ° C. By visually observing the surface of the resin molded product, the dispersibility of the glossy pigment was good, it exhibited a gold color by strong reflected light, an excellent depth feeling, and a sparkling appearance. In FIG. 2, the schematic of the resin molded product by vacuum forming is shown.

  As a decorative resin laminate and its resin molded product, mainly for decoration, for example, for building materials such as wall materials and flooring materials, for displays such as advertisements, signboards, guide boards, miscellaneous goods, stationery supplies, blister cases, It can be used for various purposes such as lighting parts or gifts such as cartons, boxes, and wrapping.

It is sectional drawing of the resin laminated body for decorating. It is the schematic of the resin molded product by vacuum forming.

Explanation of symbols

A: Decorating resin laminate B: Resin molded product 1: Core layer 2: Skin layer 3: Glossy pigment

Claims (3)

A laminate comprising at least three layers of a core layer and a skin layer sandwiching the layer, and the surface of the flaky glass having an average thickness of 20 μm or less and an average particle size of 10 to 300 μm is a metal or metal oxide layer A molten resin composition serving as a core layer having a coated metallic pigment and a molten resin serving as a skin layer not containing the pigment are combined in a layer form and extruded into a sheet shape by a T-die, and at least a part of the pigment is a skin layer. A decorative resin laminate that has been subjected to pressure cooling molding with a metal roll, has a surface specularity, has a sense of depth, and exhibits strong glitter . A laminate comprising at least three layers of a core layer and a skin layer sandwiching the layer, and the surface of the flaky glass having an average thickness of 20 μm or less and an average particle size of 10 to 300 μm is a metal or metal oxide layer A molten resin composition to be a core layer having a coated metallic pigment and a molten resin to be a skin layer not containing the pigment are combined in a layer form and extruded into a sheet shape with a T-die to obtain a molten resin composition to be a core layer A method for producing a decorative resin laminate, wherein a part of the pigment contained is transferred to a skin layer, press-cooled and molded with a metal roll, has surface specularity, has a sense of depth, and exhibits strong glitter .   A resin molded product obtained by vacuum / pressure forming of the decorative resin laminate according to claim 1.

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