JP2017206587A - Resin sheet, laminate, molding, method for producing molding, vehicular exterior part and interior material fabricated with molding, and cabinet of household electrical appliance and the like - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molding having an excellent antifouling property.SOLUTION: A resin sheet contains polyolefin and a silicone-olefin copolymer. In the resin sheet, at least one of the front surface and the rear surface has an arithmetic mean roughness Ra of 0.15 μm or less and/or a coefficient of static friction of 0.5 or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin sheet, a laminate, a molded body, a method for manufacturing the molded body, and an exterior part for a saddle-ride type vehicle, an exterior part for a four-wheeled vehicle, an interior material for a vehicle, and a household appliance, The present invention relates to a case, a decorative steel plate, a decorative plate, a housing facility, and a case of an information communication device.

Transportation equipment such as two-wheeled vehicles and four-wheeled vehicles has a problem that dirt such as mud adheres to the exterior (molded body) during traveling. In particular, two-wheeled vehicles have a problem that mud adheres to the mud cover due to running in rainy weather, the weight increases, and the running performance deteriorates.
In order to suppress the adhesion of dirt, a method of applying oil to the surface of a molded body, a method of kneading a part formed in a resin and bleeding out, and the like have been studied. However, these methods have a problem that mud tends to adhere gradually because the active ingredients on the surface of the molded body are likely to fall off.

Patent Document 1 discloses a laminate in which the release layer contains at least a polyolefin resin and a silicone compound.
Patent Document 2 discloses a technique for a water-repellent film containing a silylated polyolefin.

JP 2008-80626 A Japanese Patent Laying-Open No. 2015-25051

  However, conventional molded articles still have insufficient antifouling properties. The objective of this invention is providing the molded object which is excellent in antifouling property.

As a result of earnest verification by the present inventors, it has been found that the smoothness of the surface of the molded product greatly affects the antifouling property. Based on this finding, the present inventors have found that if the surface of the molded body contains a silicone-olefin copolymer and is smooth, it is difficult for dirt to adhere, and excellent antifouling properties can be exhibited, thereby completing the present invention.
According to the present invention, the following resin sheets and the like are provided.
1. A resin sheet comprising a polyolefin and a silicone-olefin copolymer, wherein the arithmetic average roughness Ra of at least one of the front surface and the back surface is 0.15 μm or less.
2. A resin sheet comprising a polyolefin and a silicone-olefin copolymer, wherein the static friction coefficient of at least one of the front surface and the back surface is 0.4 or less.
A laminate including a first resin layer and a second resin layer made of the resin sheet described in 3.1,
The laminated body whose arithmetic mean roughness Ra of the surface on the opposite side to the said 2nd resin layer of the said 1st resin layer is 0.15 micrometer or less.
A laminate including the first resin layer and the second resin layer made of the resin sheet described in 4.2,
The laminated body whose static friction coefficient of the surface on the opposite side to the said 2nd resin layer of the said 1st resin layer is 0.4 or less.
5. The laminate according to 3 or 4, wherein the polyolefin contained in the first resin layer is polypropylene, polyethylene, or polypropylene and polyethylene.
6). The laminated body in any one of 3-5 in which a said 2nd resin layer contains polyolefin.
7). The laminate according to 6, wherein the polyolefin of the second resin layer is polypropylene, polyethylene, or polypropylene and polyethylene.
8). The second resin layer includes a third resin layer on a surface opposite to the first resin layer, and the third resin layer is selected from urethane resin, acrylic resin, polyolefin and polyester The laminated body in any one of 3-7 containing the above resin.
9. 9. The laminate according to 8, wherein the third resin layer includes a printing layer on a part of or the entire surface on the side opposite to the second resin layer.
10. 9. The laminate according to 8, wherein the third resin layer includes a metal layer made of a metal or a metal oxide on a surface opposite to the second resin layer.
11. 11. The laminate according to 10, wherein the metal or metal oxide includes one or more metals selected from tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, and zinc, or an oxide thereof.
12 The laminate according to 10 or 11, wherein the metal or metal oxide includes one or more metals selected from indium and aluminum or an oxide thereof.
13. The laminate according to any one of 10 to 12, wherein the metal layer includes a printed layer on a part of or the entire surface on the side opposite to the third resin layer.
14 A laminated body in any one of 3-7 including a printing layer in a part or whole surface of the said 2nd resin layer on the opposite side to the said 1st resin layer.
15. 15. The laminate according to 14, wherein the printed layer includes a metal layer made of a metal or a metal oxide on a surface opposite to the second resin layer.
16. 16. The laminate according to 15, wherein the metal or metal oxide includes one or more metals selected from tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, and zinc, or oxides thereof.
17. The laminate according to 15 or 16, wherein the metal or metal oxide includes one or more metals selected from indium and aluminum or an oxide thereof.
18. A molded body of the laminate according to any one of 1 to 17.
19. 19. The molded body according to 18, wherein the arithmetic average roughness Ra of the surface made of the first resin layer is 0.15 μm or less.
20. 19. The molded product according to 18, wherein the surface of the first resin layer has a static friction coefficient of 0.4 or less.
The manufacturing method of the molded object which shape | molds the laminated body in any one of 21.3-17, and obtains a molded object.
22. 22. The method for producing a molded body according to 21, wherein the molding is performed by attaching the laminated body to a mold and supplying and integrating a molding resin.
23. The manufacturing of the molded body according to 21, wherein the molding is performed by shaping the laminated body so as to match a mold, mounting the shaped laminated body on a mold, and supplying and integrating a molding resin. Method.
24. The molding,
A core material is arranged in the chamber box,
Arrange the laminated body above the core material,
Depressurizing the inside of the chamber box,
Heat softening the laminate,
The manufacturing method of the molded object of 21 which presses and coat | covers the said laminated body heat-softened to the said core material.
An exterior part for a saddle-ride type vehicle or an exterior part for a four-wheeled vehicle, which is created using the molded body according to any one of 25.18 to 20.
26. A vehicle interior material, a housing for home appliances, a decorative steel plate, a decorative board, a housing facility, or a housing for an information communication device, created using the molded body according to any one of 26.18 to 20.

  ADVANTAGE OF THE INVENTION According to this invention, the molded object which is excellent in antifouling property can be provided.

It is a schematic block diagram which shows an example of the manufacturing apparatus for manufacturing the laminated body of this invention. It is a figure which shows one Embodiment of the laminated body of this invention.

[Resin sheet]
The first resin sheet of the present invention contains a polyolefin and a silicone-olefin copolymer. The arithmetic average roughness Ra of at least one of the front and back surfaces of the resin sheet is 0.15 μm or less.

Examples of the polyolefin include polyethylene, polypropylene, and cyclic polyolefin resin. In particular, polypropylene is preferable from the viewpoint of heat resistance and hardness.
Polypropylene is a polymer containing at least a structural unit derived from propylene. Specific examples include homopolypropylene and copolymers of propylene and other olefins (such as ethylene). It is good also as a mixture with which polyolefin and copolymers, such as polyethylene, and polypropylene were mixed.
The polypropylene copolymer may be random polypropylene, block polypropylene, or a mixture thereof.
These may be used alone or in combination of two or more.

You may mix | blend an additive, such as a pigment, antioxidant, a stabilizer, a ultraviolet absorber, with a polypropylene as needed.
Further, polyolefins such as polypropylene and polyethylene are modified with a modifying compound such as maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, etc. You may mix | blend the modified polyolefin resin obtained by doing.

（式（１）中、Ｒ_１は、水素原子、ハロゲン原子、炭化水素基、酸素含有基又はケイ素含有基を表し、炭化水素基、酸素含有基、ケイ素含有基は１つ以上のヘテロ原子を含んでいてもよい。
Ｙ_１は、Ｏ、Ｓ又はＮＲ（Ｒは水素原子又は炭化水素基を表す）を表す。） The silicone-olefin copolymer is a copolymer of silicone (polymer compound having a siloxane bond) and olefin (or polyolefin).
Silicone preferably has a structural unit represented by the following formula (1).

(In the formula (1), R ₁ represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group or a silicon-containing group, and the hydrocarbon group, the oxygen-containing group and the silicon-containing group represent one or more heteroatoms. May be included.
Y ₁ represents O, S or NR (R represents a hydrogen atom or a hydrocarbon group). )

Examples of the halogen atom include fluorine, chlorine, bromine and iodine.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. Examples include linear or branched alkyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, norbornyl group; and arylalkyl groups such as benzyl group, phenylethyl group, and phenylpropyl group.

Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthryl group, phenanthryl group and the like.

Examples of the oxygen-containing group include an alkoxy group and an aryloxy group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, an octyloxy group, a benzyloxy group, and a 2-phenylethoxy group.
Examples of the aryloxy group include a phenoxy group, a tolyloxy group, a biphenyloxy group, and a naphthyloxy group.

  Silicon-containing groups include alkylsilyl groups, alkenylsilyl groups, arylsilyl groups, alkylsiloxy groups, alkenylsiloxy groups, arylsiloxy groups, alkoxysilyl groups, aryloxysilyl groups, alkoxysiloxy groups, aryloxysiloxy groups, polysiloxyls, etc. Is mentioned. The polysiloxyl group is a group having two or more siloxane repeating units, and may be linear or branched.

  The hydrocarbon group, oxygen-containing group, and silicon-containing group described above may contain one or more heteroatoms. Specifically, groups in which at least one hydrogen of these groups is substituted with a group containing a halogen atom, oxygen, nitrogen, silicon, phosphorus, or sulfur are included.

Polyolefin usually has a structure containing one or more vinyl groups.
The structure excluding the vinyl group is an ethylene homopolymer chain, a propylene homopolymer chain, or ethylene, propylene, butene, vinyl norbornene, a cyclic polyene having two or more double bonds, and a chain having two or more double bonds Preferably, it is a copolymer chain of two or more olefins selected from the group consisting of gaseous polyenes.

The silicone-olefin copolymer can be synthesized by a known method.
The proportion of the structural unit (1) in the silicone-olefin copolymer is not particularly limited as long as the objective function of the silicone-olefin copolymer is expressed, but is usually 5 to 99% by mass, preferably It is 10-95 mass%.

  A commercially available copolymer may be used for the silicone-olefin copolymer, and what was manufactured may be used for it. Examples of commercially available products include silicone-olefin copolymers “EXFORA” (trade name, manufactured by Mitsui Chemicals, Inc.). Further, dimethyl vinyl polysiloxane having a vinyl group content of 0 to 1 mol%, EPDM (ethylene-propylene rubber) and SBS (styrene-butadiene styrene block copolymer) having an unsaturated group content of 0 to 5% by mass. Or a partially crosslinked product with SIS (styrene-isoprene block copolymer), amino-modified silicone or carboxyl-modified silicone, and maleic anhydride-modified olefin polymer or oligomer (polypropylene, polyethylene, ethylene / propylene copolymer, etc.) A reactant may be used.

  In addition, pellets obtained by master batching these with resin, “X-22-2101”, “X-222-147” (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), “BY27-001S” (Toray Dow Corning) And “BY27-201” (trade name, manufactured by Toray Dow Corning Co., Ltd.), which is a pellet obtained by partial graft polymerization with a resin.

  Content of a silicone-olefin copolymer is 2-80 mass% normally in a 1st resin sheet, Preferably it is 5-30 mass%. Moreover, it is good also as 2-15 mass%, 3-10 mass%, or 4-8 mass%.

  The first resin sheet may consist essentially of a polyolefin and a silicone-olefin copolymer. In this case, inevitable impurities may be included. For example, 70% by mass or more, 80% by mass or more, 90% by mass or more, 98% by mass or more, 99% by mass or more, or 99.5% by mass or more of the first resin sheet is a polyolefin and a silicone-olefin copolymer. It may be. Further, the first resin sheet may be composed only of a polyolefin and a silicone-olefin copolymer.

The arithmetic average roughness Ra of at least one of the front surface and the back surface of the first resin sheet is 0.15 μm or less. When Ra exceeds 0.15 μm, the surface becomes unsmooth, so that the area where the surface is in contact with the mud increases, and the mud peelability may be impaired. The arithmetic average roughness Ra is preferably 0.1 μm or less, more preferably 0.8 μm or less.
The arithmetic average roughness Ra is measured using a 3D measurement laser microscope. Specifically, it is measured by the method described in the examples.

The second resin sheet of the present invention contains a polyolefin and a silicone-olefin copolymer. Further, the static friction coefficient of at least one of the front surface and the back surface of the second resin sheet is 0.4 or less.
The polyolefin, silicone-olefin copolymer, blending amount and the like are the same as those of the first resin sheet.

The static friction coefficient of at least one of the front surface and the back surface of the second resin sheet is 0.4 or less, preferably 0.38 or less, more preferably 0.35 or less. If the static friction coefficient exceeds 0.5, the attached mud will not slide out and the mud releasability may be impaired.
The static friction coefficient is measured by the method described in the examples.

  The thickness of the first to second resin sheets (hereinafter sometimes referred to as “the resin sheet of the present invention”) is usually 50 to 1000 μm, preferably 100 to 500 μm.

In the resin sheet of the present invention, the dynamic friction coefficient of at least one of the front surface and the back surface is preferably 0.5 or less, preferably 0.4 or less, more preferably 0.35 or less. If the dynamic friction coefficient exceeds 0.5, the resistance of the mud that has started to slide is large, and the releasability of the mud may be impaired.
The dynamic friction coefficient is measured by the method described in the examples.

  Since the resin sheet of the present invention contains a silicone-olefin copolymer and at least one surface has a specific property (arithmetic average roughness Ra or static friction coefficient), it is excellent in antifouling property and dirt such as mud. It can be set as the molded object which does not adhere easily.

Examples of the method for forming the resin sheet of the present invention include an extrusion method.
An example of the manufacturing apparatus for manufacturing the resin sheet of this invention is shown in FIG.
The manufacturing apparatus shown in FIG. 1 includes a T die 12 of an extruder, a first cooling roll 13, a second cooling roll 14, a third cooling roll 15, a fourth cooling roll 16, a metal endless belt 17, and a peeling roll 21. .
An example of a method for manufacturing the resin sheet 11 by rapid cooling using the manufacturing apparatus configured as described above will be described below.

  First, the surface temperature of the metal endless belt 17 and the fourth cooling roll 16 that directly contacts and cools the extruded molten resin is maintained at a dew point of 50 ° C. or less, preferably 30 ° C. or less. Temperature control of each cooling roll 13, 14, 15, 16 is performed in advance.

  Here, if the surface temperature of the fourth cooling roll 16 and the metal endless belt 17 is equal to or lower than the dew point, condensation may occur on the surface, and uniform film formation may be difficult. On the other hand, when the surface temperature is higher than 50 ° C., the transparency of the obtained sheet 11 is lowered, and α crystals are increased, which may make it difficult to perform thermoforming. Therefore, the surface temperature is 20 ° C., for example.

Next, the molten resin (excluding the nucleating agent) extruded from the T die 12 of the extruder is sandwiched between the metal endless belt 17 and the fourth cooling roll 16 on the first cooling roll 13. In this state, the molten resin is pressed by the first and fourth cooling rolls 13 and 16 and rapidly cooled at 20 ° C.
At this time, the elastic material 22 is compressed and elastically deformed by the pressing force between the first cooling roll 13 and the fourth cooling roll 16.
The rapidly cooled sheet is press-contacted by the cooling rolls 13 and 16 at the portion where the elastic material 22 is elastically deformed, that is, the arc portion corresponding to the central angle θ1 of the first cooling roll 13. The surface pressure at this time is usually 0.1 MPa or more and 20 MPa or less.

  The sheet press-contacted as described above and sandwiched between the fourth cooling roll 16 and the metal endless belt 17 continues with the metal endless belt 17 at an arc portion corresponding to the substantially lower half circumference of the fourth cooling roll 16. The sheet is sandwiched between the fourth cooling rolls 16 and pressed in a planar manner. The surface pressure at this time is usually 0.01 MPa or more and 0.5 MPa or less.

  After the sheet pressure contact and cooling by the fourth cooling roll 16 as described above, the sheet that is in close contact with the metal endless belt 17 is moved onto the second cooling roll 14 as the metal endless belt 17 rotates. Here, the sheet guided by the peeling roll 21 and pressed to the second cooling roll 14 side is pressed by the metal endless belt 17 at the arc portion corresponding to the substantially upper half circumference of the second cooling roll 14 as described above. And cooled again at a temperature of 30 ° C. or lower. The surface pressure at this time is usually 0.01 MPa or more and 0.5 MPa or less.

  The sheet cooled on the second cooling roll 14 is peeled off from the metal endless belt 17 by the peeling roll 21 and wound up at a predetermined speed by a winding roll (not shown).

[Laminate]
The laminate of the present invention includes a first resin layer and a second resin layer made of the resin sheet of the present invention.
The laminate of the present invention is shown in FIG. The laminate 1 has a laminated structure of a first resin layer 100 and a second resin layer 200, and the surface A of the first resin layer 100 on the side opposite to the second resin layer 200 is the above-described resin. Have specific properties of the sheet.
The laminate of the present invention is specifically the following first to second laminates.

The 1st laminated body of this invention consists of the 1st resin layer which consists of said 1st resin sheet, and a 2nd resin layer. The arithmetic average roughness Ra of the surface (surface A) opposite to the second resin layer of the first resin layer is 0.15 μm or less.
The first resin sheet and the arithmetic average roughness Ra are as described above.

  The second resin layer preferably contains polyolefin. The polyolefin is as described in the first resin sheet. The polyolefin is preferably polypropylene, polyethylene, or polypropylene and polyethylene.

The 2nd laminated body of this invention contains the 1st resin layer which consists of said 2nd resin sheet, and a 2nd resin layer. The static friction coefficient of the surface (surface A) opposite to the second resin layer of the first resin layer is 0.5 or less.
The second resin sheet and the static friction coefficient are as described above.
The second resin layer is the same as the second resin layer in the first laminate.

  In the laminate of the present invention, the coefficient of dynamic friction of the surface (surface A) on the side opposite to the second resin layer of the first resin layer is preferably 0.5 or less. The dynamic friction coefficient is as described above.

  In the laminate of the present invention, the thickness of the first resin layer is usually 5 to 200 μm, preferably 10 to 100 μm. The thickness of the second resin layer is usually 45 to 800 μm, preferably 90 to 400 μm.

(Third resin layer)
The laminate of the present invention may include a third resin layer on the surface of the second resin layer opposite to the first resin layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / third resin layer). “/” Indicates a laminated structure.

  The third resin layer includes one or more resins selected from, for example, urethane resin, acrylic resin, polyolefin, and polyester. In consideration of adhesion to the second resin layer and ink and moldability, urethane resin is preferable.

The urethane resin is preferably a reaction product of diisocyanate, high molecular weight polyol and chain extender. Examples of the high molecular weight polyol include polyether polyol and polycarbonate polyol.
Thereby, even if a laminated body is shape | molded in complicated non-planar shape, a 3rd layer follows a 1st layer and can form a favorable layer structure. Moreover, the crack and peeling of the metal layer mentioned later can be prevented.

The third resin layer preferably has a glass transition temperature of −50 ° C. or higher and 100 ° C. or lower. When the glass transition temperature is less than −50 ° C., the distortion of the third resin layer exceeds the followability of the metal layer and the printing layer described later, and thus there is a possibility that defects due to fine cracks may occur during long-term use. When the glass transition temperature exceeds 100 ° C., the softening temperature becomes high, so that the elongation at the time of preliminary shaping is deteriorated, the elongation unevenness of the stretched portion is generated, and there is a possibility that the metal thin film is finely cracked.
The glass transition temperature can be measured by a method based on JIS K7121.

The third resin layer preferably has a tensile elongation at break of 150% to 900%, more preferably 200% to 850%, and even more preferably 300% to 750%. If the tensile elongation at break is lower than 150%, the second resin layer cannot follow the elongation of the first resin layer at the time of thermoforming, and cracks may occur, resulting in cracks in the metal layer and print layer described later. There is a risk of peeling. If the tensile elongation at break exceeds 900%, the water resistance may deteriorate.
The tensile elongation at break is measured with a sample having a thickness of 150 μm by a method based on JIS K7311.

The softening temperature of the third resin layer is preferably 50 ° C. or higher and 180 ° C. or lower, preferably 90 ° C. or higher and 170 ° C. or lower, more preferably 100 ° C. or higher and 165 ° C. or lower. When the softening temperature is lower than 50 ° C., the strength of the third resin layer is insufficient at room temperature, and there is a possibility that the layer made of metal or metal oxide or the printed layer may crack or peel off. When the softening temperature is higher than 180 ° C., the softening cannot be sufficiently performed at the time of thermoforming, and the third resin layer is cracked, and there is a possibility that a metal layer and a printing layer described later are cracked or peeled off.
The softening temperature is measured by measuring the flow start temperature with a Koka flow tester.

  The thickness of the third resin layer is preferably 0.01 μm or more and 3 μm or less, more preferably 0.03 μm or more and 0.5 μm or less. When the thickness of the third layer is less than 0.01 μm, there is a possibility that sufficient ink adhesion cannot be obtained. On the other hand, if it is thicker than 3 μm, stickiness may occur and cause blocking.

  The third resin layer can be formed by, for example, applying a resin with a gravure coater, kiss coater, bar coater or the like and drying (for example, at 80 ° C. for 1 minute).

(Print layer)
The laminate of the present invention may include a printed layer on the surface of the third resin layer opposite to the second resin layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / third resin layer / printing layer).
The print layer may be formed on a part of the third resin layer or may be formed on the entire surface. The shape of the print layer is not particularly limited, and examples thereof include various shapes such as a solid shape, a carbon tone, and a woodgrain tone.

As a printing method, a general printing method such as a screen printing method, an offset printing method, a gravure printing method, a roll coating method, or a spray coating method can be used. In particular, the screen printing method is preferable because the ink film thickness can be increased, and therefore, ink cracking hardly occurs when the ink is formed into a complicated shape.
For example, in the case of screen printing, an ink excellent in elongation at the time of molding is preferable, and examples thereof include “FM3107 high density white” and “SIM3207 high density white” manufactured by Jujo Chemical Co., Ltd., but are not limited thereto.

(Metal layer)
The laminate of the present invention may include a metal layer made of a metal or a metal oxide on the surface of the third resin layer opposite to the second resin layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / third resin layer / metal layer).

In the metal layer, the metal or metal oxide is not particularly limited as long as it is a metal that can impart a metallic design to the laminate, but for example, tin, indium, chromium, aluminum, nickel, copper, silver, gold , Platinum, zinc, and alloys containing at least one of these. These metals and oxides thereof may be used alone or in combination of two or more.
Among these, indium and aluminum are preferable from the viewpoint of extensibility and excellent color tone. This makes it difficult for cracks to occur when the laminate is three-dimensionally formed.

  Moreover, you may have a printing layer in a part or whole surface of the upper surface of the said metal layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / third resin layer / metal layer / printing layer). The print layer is as described above.

  The thickness of the metal layer is preferably 5 nm to 80 nm, and more preferably 15 nm to 70 nm. If it is less than 5 nm, the desired metallic luster may not be obtained, while if it exceeds 80 nm, cracks may occur.

  The method for forming the metal layer is not particularly limited, but from the viewpoint of imparting a high-quality and high-quality metallic design to the laminate, for example, a vapor deposition method, a vacuum vapor deposition method, or a sputtering method using the above-described metal. An ion plating method or the like is preferable. In particular, the vacuum evaporation method is preferable because it is low cost and causes little damage to the object to be evaporated. The conditions for the vapor deposition may be appropriately set according to the melting temperature or the evaporation temperature of the metal to be used. Moreover, the method of coating the paste containing said metal, the plating method using said metal, etc. can be used.

A printing layer may be provided without providing the third resin layer. In this case, a printing layer is included on a part or the entire surface of the second resin layer on the side opposite to the first resin layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / printing layer). The print layer is as described above.
In the structure, a metal layer may be provided on the print layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / printing layer / metal layer). The metal layer is as described above.

A metal layer may be provided without providing the third resin layer. In this case, a metal layer is included on the surface of the second resin layer on the side opposite to the first resin layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / metal layer). The metal layer is as described above.
In the structure, a printed layer may be provided on a part or the entire upper surface of the metal layer. In this case, the laminate has a configuration of (first resin layer / second resin layer / metal layer / printing layer). The print layer is as described above.

  The laminated body of this invention can be manufactured by the method similar to the resin sheet of this invention.

[Molded body]
A molded body can be produced using the laminate of the present invention.
In the molded article of the present invention, the arithmetic average roughness Ra of the surface comprising the first resin layer is 0.15 μm or less and / or the static friction coefficient is 0.5 or less.
In the molded article of the present invention, the coefficient of dynamic friction of the surface made of the first resin layer is preferably 0.5 or less. These properties are as described above.

[Method for producing molded article]
Examples of the molding method include in-mold molding, insert molding, and coating molding.

In-mold molding is a method in which a laminate is placed in a mold and molded into a desired shape with the pressure of a molding resin supplied into the mold to obtain a molded body.
The in-mold molding is preferably performed by mounting the laminate on a mold and supplying and integrating a molding resin.

Insert molding is a method of obtaining a molded body by preliminarily shaping a shaped body to be installed in a mold and filling the shape with a molding resin. More complicated shapes can be produced.
The insert molding is preferably performed by forming the laminated body so as to match the mold, mounting the shaped laminated body on the mold, and supplying and integrating the molding resin.
The attachment (preliminary attachment) that matches the mold is preferably performed by vacuum forming, pressure forming, vacuum / pressure forming, press forming, plug assist forming, or the like.

The molding resin is preferably a moldable thermoplastic resin. Specific examples include polypropylene, polyethylene, polycarbonate, acetylene-styrene-butadiene copolymer, and acrylic polymer, but are not limited thereto. Inorganic fillers such as fiber and talc may be added.
The supply is preferably performed by injection, and the pressure is preferably 5 MPa or more and 120 MPa or less.
The mold temperature is preferably 20 ° C. or higher and 90 ° C. or lower.

As covering molding, a core material is arranged in a chamber box, a laminate is arranged above the core material, the inside of the chamber box is decompressed, the laminate is heated and softened, and the laminate is placed on the upper surface of the core material. It is preferable that the laminated body that has been brought into contact and softened by heating is pressed against the core material to be coated.
After heat softening, it is preferable to bring the laminate into contact with the upper surface of the core material.
In the pressing, it is preferable to pressurize the opposite side of the core of the laminate while reducing the pressure of the side of the laminate that contacts the core in the chamber box.

  The core material may be convex or concave, and examples thereof include a resin having a three-dimensional curved surface, metal, and ceramic. Examples of the resin include the same resins as those used for the molding described above.

Specifically, it is preferable to use a chamber box composed of two upper and lower molding chambers that can be separated from each other.
First, a core material is placed and set on a table in the lower molding chamber. The laminate of the present invention, which is a molding object, is fixed to the upper surface of the lower molding chamber with a clamp. At this time, the upper and lower molding chambers are at atmospheric pressure.
Next, the upper molding chamber is lowered, the upper and lower molding chambers are joined, and the inside of the chamber box is closed. Both the upper and lower molding chambers are brought into the vacuum suction state from the atmospheric pressure state by the vacuum tank.
After the upper and lower molding chambers are evacuated, the heater is turned on and the decorative sheet is heated. Next, the table in the lower molding chamber is raised while the upper and lower molding chambers are in a vacuum state.
Next, by releasing the vacuum in the upper molding chamber and applying atmospheric pressure, the laminate of the present invention, which is a molding object, is pressed against the core material and overlaid (molded). In addition, by supplying compressed air into the upper molding chamber, the laminate of the present invention, which is a molding object, can be brought into close contact with the core material with a greater force.
After the overlay is completed, the heater is turned off, the vacuum in the lower molding chamber is released to return to atmospheric pressure, the upper molding chamber is raised, and the product with the decorative printed laminate coated as the skin material is taken out. .

[Uses for molded products]
The laminate and molded body of the present invention can be suitably used as an exterior part for a saddle-ride type vehicle or an exterior part for a four-wheeled vehicle.
When running on rainy or unpaved roads, mud rolled up by the vehicle's wheels and other vehicles becomes dirty and adheres to the exterior parts. On an unpaved road that contains moisture, mud accumulates on the exterior parts, increasing the vehicle weight. Since the laminate and molded body (for example, mud cover) of the present invention contain a silicone-olefin copolymer on the outermost surface and have a small surface energy, they do not adhere even if mud adheres. Furthermore, since the surface is smooth, the contact area between the molded product and the mud is small, and mud easily falls off the sliding molded body due to vibration during traveling. Since mud does not accumulate, it is possible to prevent a decrease in running performance due to an increase in mass.

  The laminated body and molded body of the present invention, in addition to exterior components for saddle riding type vehicles and four-wheeled vehicles, include vehicle interior materials, housings for home appliances, decorative steel plates, decorative plates, housing equipment, and housings for information and communication devices. It is suitable for parts such as the body where dirt may adhere.

Example 1
[Manufacture of laminates]
Using the manufacturing apparatus shown in FIG. 1, a laminate composed of the first resin layer and the second resin layer was manufactured as follows.
Polyolefin (trade name: Prime Polypro F-133A, manufactured by Prime Polymer Co., Ltd. (melt flow index 3 g / 10 min, homopolypropylene)) (95% by mass), and silicone-olefin copolymer (trade name: EXFORA, Mitsui Chemicals) (Made by Co., Ltd.) (5% by mass) was charged into an extruder (not shown) for the first resin layer.
Polyolefin (trade name: Prime Polypro F-133A, manufactured by Prime Polymer Co., Ltd. (melt flow index 3 g / 10 min, homopolypropylene)) was charged into an extruder (not shown) for the second resin layer.

While kneading, extrusion was performed under the following conditions to obtain a laminate.
Diameter of extruder for first resin layer: 65 mm
Diameter of extruder for second resin layer: 75 mm
T die width: 900mm
Take-up speed of laminated sheet: 6 m / min Surface temperature of cooling roll and metal endless belt: 20 ° C
Arithmetic average roughness Ra of the cooling roll: 0.032 μm
Cooling rate: 10,800 ° C./min. First resin layer thickness: 50 μm
Second resin layer thickness: 150 μm

[Measurement of arithmetic average roughness Ra]
About the surface which consists of a 1st resin layer in the obtained laminated body, arithmetic mean roughness Ra was measured with the following measuring devices and measurement conditions.
Measurement device: Olympus 3D measurement laser microscope (EXT4000LS)
Measurement conditions Objective lens: 20 × zoom: 1 × measurement pitch: 0.06 μm
Measurement Operation mode: X, Y, Z high-precision color measurement area: Surface measurement quality: High-precision analysis length: 642 μm

[Measurement of static friction coefficient and dynamic friction coefficient]
About the surface which consists of a 1st resin layer in the obtained laminated body, the static friction coefficient and the dynamic friction coefficient were measured with the following measuring apparatuses, measurement conditions, and the calculation method.
-Measuring device: Autograph AGSX-1kN manufactured by Shimadzu Corporation
-Measurement condition Shape of moving side test piece: 80 mm (flow direction) x 70 mm (width direction)
Fixed-side specimen shape: 170 mm (flow direction) x 110 mm (width direction)
Mass of moving weight: 324.6g
Crosshead speed: 300 mm / min Travel distance: 50 mm
-Static friction coefficient calculation method The static friction coefficient was calculated from the following equation using the test force at the first peak point and the mass of the moving moving weight.
Static friction coefficient = Peak point test force / Movement weight mass and dynamic friction coefficient calculation method The dynamic friction coefficient is calculated from the following equation using the average test force between the strokes of 10mm and 40mm and the mass of the movement weight. did.
Coefficient of dynamic friction = average test force with a stroke of 10 mm to 40 mm / mass of moving weight

[Evaluation of mud adhesion characteristics]
The obtained laminate was mounted on a flat plate mold having a thickness of 2 mm, a short side of 65 mm, and a long side of 150 mm, and primed polypro J- using a hydraulic injection molding machine IS-80EPN (manufactured by Toshiba Machine Co., Ltd.). 705UG (manufactured by Prime Polymer Co., Ltd., melt flow index 9 g / 10 min, block polypropylene) was supplied into the mold and integrated to produce a molded body for evaluating mud adhesion characteristics.

  The yellow soil was dried at 60 ° C. for 4 hours to remove moisture, and ion exchange water was mixed with this to 35% by mass to obtain mud for evaluating mud adhesion characteristics.

20 g of mud for evaluating mud adhesion characteristics was placed on the first resin layer of the molded body for evaluating mud adhesion characteristics, and the molded body was tilted 40 ° from the ground to slide mud. The mud adhesion characteristics were evaluated based on the following criteria. The results are shown in Table 1.
○: Mud slides down △: Mud slides, but a small amount of mud adheres after sliding ×: Mud does not slip, or much mud adheres after sliding

Example 2
A laminate was produced and evaluated in the same manner as in Example 1 except that the arithmetic average roughness Ra of the cooling roll surface of the production apparatus was changed to 0.02 μm. The results are shown in Table 1.

Comparative Example 1
A laminate was produced and evaluated in the same manner as in Example 1 except that the first resin layer was formed without using the silicone-olefin copolymer. The results are shown in Table 1.

Comparative Example 2
A laminate was produced and evaluated in the same manner as in Example 1 except that the arithmetic average roughness Ra of the surface of the cooling roll of the production apparatus was changed to 0.50 μm. The results are shown in Table 1.

From Table 1, it is confirmed that the molded product (laminate) of the present invention having specific surface characteristics has superior anti-slip properties compared to the molded product of Comparative Example 2 having no specific surface characteristics. did.
Further, the molded product (laminate) of the present invention having a silicone-olefin copolymer in the first resin layer is compared with the molded product of Comparative Example 1 having no silicone-olefin copolymer in the first resin layer. It was confirmed that there was an excellent mud-proof property.

DESCRIPTION OF SYMBOLS 1 Laminated body 11 Sheet | seat 12 T die 13 1st cooling roll 14 2nd cooling roll 15 3rd cooling roll 16 4th cooling roll 17 Metal endless belt 22 Elastic material 100 1st resin sheet 200 2nd resin sheet

Claims (26)

  A resin sheet comprising a polyolefin and a silicone-olefin copolymer, wherein the arithmetic average roughness Ra of at least one of the front surface and the back surface is 0.15 μm or less.   A resin sheet comprising a polyolefin and a silicone-olefin copolymer, wherein the static friction coefficient of at least one of the front surface and the back surface is 0.4 or less. A laminate comprising a first resin layer comprising the resin sheet according to claim 1 and a second resin layer,
The laminated body whose arithmetic mean roughness Ra of the surface on the opposite side to the said 2nd resin layer of the said 1st resin layer is 0.15 micrometer or less. A laminate comprising a first resin layer comprising the resin sheet according to claim 2 and a second resin layer,
The laminated body whose static friction coefficient of the surface on the opposite side to the said 2nd resin layer of the said 1st resin layer is 0.4 or less.   The laminate according to claim 3 or 4, wherein the polyolefin contained in the first resin layer is polypropylene, polyethylene, or polypropylene and polyethylene.   The laminate according to any one of claims 3 to 5, wherein the second resin layer contains a polyolefin.   The laminate according to claim 6, wherein the polyolefin of the second resin layer is polypropylene, polyethylene, or polypropylene and polyethylene.   The second resin layer includes a third resin layer on a surface opposite to the first resin layer, and the third resin layer is selected from urethane resin, acrylic resin, polyolefin and polyester The laminated body in any one of Claims 3-7 containing the above resin.   The laminate according to claim 8, wherein the third resin layer includes a printing layer on a part or the entire surface of the surface opposite to the second resin layer.   The laminate according to claim 8, comprising a metal layer made of a metal or a metal oxide on a surface of the third resin layer opposite to the second resin layer.   The laminate according to claim 10, wherein the metal or metal oxide includes one or more metals selected from tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, and zinc, or an oxide thereof.   The laminate according to claim 10 or 11, wherein the metal or metal oxide includes one or more metals selected from indium and aluminum or an oxide thereof.   The laminate according to any one of claims 10 to 12, wherein a printed layer is included on a part or the entire surface of the metal layer on the side opposite to the third resin layer.   The laminate according to any one of claims 3 to 7, wherein a printed layer is included on a part or the entire surface of the second resin layer on the side opposite to the first resin layer.   The laminate according to claim 14, wherein the printed layer includes a metal layer made of a metal or a metal oxide on a surface opposite to the second resin layer.   The laminate according to claim 15, wherein the metal or metal oxide includes one or more metals selected from tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, and zinc, or an oxide thereof.   The laminate according to claim 15 or 16, wherein the metal or metal oxide includes one or more metals selected from indium and aluminum or an oxide thereof.   A molded body of the laminate according to any one of claims 3 to 17.   The molded body according to claim 18, wherein the arithmetic average roughness Ra of the surface made of the first resin layer is 0.15 μm or less.   The molded product according to claim 18, wherein a coefficient of static friction of a surface formed of the first resin layer is 0.4 or less.   The manufacturing method of the molded object which shape | molds the laminated body in any one of Claims 3-17, and obtains a molded object.   The method for producing a molded body according to claim 21, wherein the molding is performed by mounting the laminated body on a mold and supplying and integrating a molding resin.   The molded body according to claim 21, wherein the molding is performed by forming the laminated body so as to match a mold, mounting the shaped laminated body on the mold, and supplying and integrating a molding resin. Manufacturing method. The molding,
A core material is arranged in the chamber box,
Arrange the laminated body above the core material,
Depressurizing the inside of the chamber box,
Heat softening the laminate,
The manufacturing method of the molded object of Claim 21 which presses and coat | covers the said laminated body heat-softened to the said core material.   An exterior part for a saddle-ride type vehicle or an exterior part for a four-wheeled vehicle, produced using the molded body according to any one of claims 18 to 20.   A vehicle interior material, a housing for home appliances, a decorative steel plate, a decorative board, a housing facility, or a housing for an information communication device, produced using the molded body according to any one of claims 18 to 20.

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