JP2017149144A - Laminate, molding, and method for producing molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having a good appearance and excellent adhesion, and provide a molding and a method for producing the molding.SOLUTION: A laminate comprises a first resin layer comprising thermoplastic resin, a second resin layer, and a metal layer comprising metal or metal oxide, in the stated order. The second resin layer has a thickness of 35 nm or more and 70 nm or less, and the resin of the second resin layer and the resin of the first resin layer are not the same.SELECTED DRAWING: None

Description

  The present invention relates to a laminate, a molded body, and a method for manufacturing the molded body.

Conventionally, plating is used to impart a metallic design to a resin molded body. However, since plating generates a large amount of waste liquid and harmful substances, in recent years, alternative techniques for plating have been actively studied for the purpose of reducing the environmental load.
Among them, a method has been developed in which a metal thin film is formed on a plastic sheet by vapor deposition, and this is integrated with a housing by various decorative molding methods to give a metallic design instead of plating.

Patent Document 1 describes a method of using a primer layer having a thickness of about 0.5 to 3 μm (more preferably 1 to 2 μm) in order to adhere a plastic sheet and a metal thin film.
In Patent Document 2, an anchor coat layer having a thickness of 0.1 μm to 3.0 μm (preferably 0.3 μm to 1.0 μm) and a thickness of 0.3 μm to 5.0 μm are used in order to adhere the plastic sheet and the metal thin film. A method using a second anchor coat layer having a thickness of (more desirably 0.5 μm to 2.0 μm) is described.

JP 2014-208432 A Japanese Patent Laying-Open No. 2005-305786

When a resin layer such as the primer layer of Patent Document 1 or the anchor coat layer of Patent Document 2 is used, depending on the adhesion to the metal thin film and the magnitude of change of the resin layer with time and heat, the metal thin film may be fine. A rainbow phenomenon in which cracks occur and rainbow-colored luminance unevenness occurs, and luminance decreases due to whitening.
In particular, when polypropylene having low adhesion is used for the plastic sheet, fine cracks are likely to occur as compared with sheets of other materials.
The objective of this invention is providing the manufacturing method of the laminated body, molded object, and molded object which are excellent in an external appearance and adhesiveness.

As a result of diligent verification by the present inventors, it has been found that appearance defects such as cracks and rainbows are related to the thickness of the resin layer, leading to the present invention.
According to the present invention, the following laminate, molded body, and method for producing the molded body are provided.
1. A first resin layer comprising a thermoplastic resin;
A laminate including a second resin layer and a metal layer containing a metal or metal oxide in this order,
A laminate in which the thickness of the second resin layer is not less than 35 nm and not more than 70 nm, and the resin of the second resin layer and the resin of the first resin layer are not the same.
2. The laminate according to 1, wherein the second resin layer includes one or more resins selected from the group consisting of urethane resins, acrylic resins, polyolefins, and polyesters.
3. The laminate according to 1 or 2, wherein the first resin layer contains polypropylene.
4). Any of 1 to 3 wherein the metal or metal oxide is one or more metals or metal oxides selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum and zinc The laminated body of crab.
5. The laminate according to any one of 1 to 3, wherein the metal or metal oxide is one or more metals or metal oxides selected from the group consisting of indium and aluminum.
6). The laminate according to any one of 1 to 5, wherein a printed layer is partially or entirely provided on a surface of the metal layer opposite to a surface in contact with the second resin layer.
7). The laminated body in any one of 1-5 which contains a printing layer in part or the whole surface between the said metal layer and the said 2nd resin layer.
8). A third resin layer is included on the surface of the first resin layer opposite to the surface in contact with the second resin layer, and the resin of the third resin layer is the same as the resin of the second resin layer. The laminated body in any one of 1-7 which is the same.
A molded body of the laminate according to any one of 9.1 to 8.
10. The metal or metal oxide is indium or indium oxide, and the glossiness measured from the surface of the first resin layer opposite to the surface in contact with the second resin layer is 250% or more. Molded body.
11. 10. The metal or metal oxide is aluminum or aluminum oxide, and the glossiness measured from the surface of the first resin layer opposite to the surface in contact with the second resin layer is 380% or more. Molded body.
The manufacturing method of the molded object which shape | molds the laminated body in any one of 12.1-8, and obtains a molded object.
13. 13. The method for producing a molded body according to 12, wherein the molding is performed by mounting the laminated body on a mold and supplying and integrating a molding resin.
14 The manufacturing of the molded body according to 12, 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. Method.
15. The molding is
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,
13. The method for producing a molded body according to 12, wherein the core material is pressed and coated with the heat-softened laminate.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body, the molded object, and the molded object which are excellent in an external appearance and adhesiveness can be provided.

It is a schematic block diagram of an example of the manufacturing apparatus for manufacturing the 1st resin layer of the laminated body of this invention.

  The laminate of the present invention includes a first resin layer containing a thermoplastic resin, a second resin layer, and a metal layer containing a metal or metal oxide in this order, and the thickness of the second resin layer is 35 nm or more. It is 70 nm or less, and the resin of the second resin layer and the resin of the first resin layer are not the same.

The laminated body of this invention can contact | adhere a metal layer and a 1st resin layer by including a 2nd resin layer.
In addition, when the thickness of the second resin layer is 70 nm or less, even when the first resin layer is a resin that is easy to move (the volume is likely to fluctuate due to aging or heat), distortion during thermoforming or long-term storage may occur. Since it decreases and falls within a range in which the metal layer can follow, a fine crack is not generated, and a metal-like molded article having excellent luminance can be obtained.
On the other hand, when the thickness is 35 nm or more, the metal layer can be satisfactorily adhered.

  The thickness of the second resin layer is preferably 40 nm or more and 65 nm or less, and more preferably 45 nm or more and 60 nm or less.

  The thickness of the second resin layer can be measured, for example, by a reflection X-ray small angle scattering method. By this method, the thickness of the metal layer containing the metal or metal oxide of the laminate of the present invention can also be measured.

The resin of the second resin layer and the resin of the first resin layer are not the same. The second resin layer preferably contains one or more resins selected from the group consisting of urethane resins, acrylic resins, polyolefins, and polyesters. Among these, urethane resin is preferable in view of adhesion to the first resin layer and a printing layer described later and moldability.
Thereby, the 2nd resin layer can function as an easily bonding layer.

  The second resin layer is preferably one or more layers, and may be composed of a plurality of layers. One or two layers are preferred.

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 when a laminated body is shape | molded in a complicated non-planar shape, it can form favorably following a 1st resin layer. Moreover, the crack and peeling of a metal layer can be prevented.

  Examples of the urethane resin include Hydran WLS-202 (manufactured by DIC Corporation).

Examples of the acrylic resin include ACRYT 8UA-366 (manufactured by Taisei Fine Chemical Co., Ltd.).
Examples of the polyolefin include Arrow Base DA-1010 (manufactured by Unitika Ltd.).

  The tensile elongation at break of the second resin layer is preferably from 150% to 900%, more preferably from 200% to 850%, particularly preferably from 300% to 750%.

  When the tensile elongation at break of the second resin layer is less than 150%, the second resin layer cannot follow the elongation of the first resin layer during thermoforming, cracks occur, and the metal layer cracks. May occur or peel off. On the other hand, if the tensile elongation at break exceeds 900%, the water resistance may deteriorate.

  The tensile elongation at break can be measured with a sample having a thickness of 150 μm by a method based on, for example, JIS K7311.

  The softening temperature of the second resin layer is preferably 50 ° C. or higher and 180 ° C. or lower, more preferably 90 ° C. or higher and 170 ° C. or lower, and particularly preferably 100 ° C. or higher and 165 ° C. or lower.

When the softening temperature of the second resin layer is lower than 50 ° C., the strength of the second resin layer at room temperature is insufficient, and the metal layer may be cracked or peeled off. On the other hand, when it exceeds 180 ° C., it cannot be sufficiently softened during thermoforming, and the second resin layer may crack, and the metal layer may be cracked or peeled off.
The softening temperature can be determined, for example, by measuring the flow start temperature with a Koka flow tester.

The glass transition temperature of the second resin layer is preferably −60 ° C. or higher and 100 ° C. or lower, and more preferably −55 ° C. or higher and 80 ° C. or lower.
If the glass transition temperature is less than −60 ° C., the distortion of the second resin layer may exceed the followability of the metal layer, and a defect due to fine cracks may occur during long-term use. On the other hand, when the temperature exceeds 100 ° C., the softening temperature becomes high, so that there is a possibility that the elongation at the time of thermoforming is insufficient, and uneven elongation at the stretched portion occurs, which may cause fine cracks in the metal layer.

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

  The first resin layer includes a thermoplastic resin. Examples of the thermoplastic resin include polypropylene, polyolefin, modified polyolefin, polyethylene, and polyolefin-based elastomer. These may be used alone or in combination of two or more. In particular, polypropylene is preferable because of heat resistance and hardness.

Polypropylene is a polymer containing at least propylene. Specific examples include homopolypropylene and a copolymer of propylene and olefin. In particular, homopolypropylene is preferred for reasons of heat resistance and hardness.
The copolymer may be a block copolymer, a random copolymer, or a mixture thereof.
Examples of the olefin include ethylene, butylene, and cycloolefin.
Polypropylene may be used alone or in combination of two or more.

It is preferable that the isotactic pentad fraction of polypropylene is 80% or more and 98% or less. More preferably, they are 86% or more and 98% or less, More preferably, they are 91% or more and 98% or less.
If the isotactic pentad fraction is less than 80%, the molded sheet may have insufficient rigidity. On the other hand, if the isotactic pentad fraction exceeds 98%, the transparency may be lowered.
By being in the said range, transparency will be acquired and it will become easy to decorate favorably.

  The isotactic pentad fraction is an isotactic fraction in a pentad unit (one in which five propylene monomers are isotactically bonded) in a molecular chain of a resin composition. This method for measuring the fraction is described in, for example, Macromolecules, Vol. 8 (1975), p. 687, and can be measured by 13C-NMR.

  Polypropylene preferably has a melt flow rate (hereinafter referred to as MFR) of 0.5 g / 10 min or more and 5.0 g / 10 min or less. More preferably, it is 1.5 g / 10 minutes or more and 4.5 g / 10 minutes or less, More preferably, it is 2.0 g / 10 minutes or more and 4.0 g / 10 minutes or less.

When the MFR is less than 0.5 g / 10 minutes, the shear stress at the die slip portion during extrusion molding becomes strong, and crystallization may be promoted to reduce transparency. On the other hand, when MFR exceeds 5.0 g / 10 minutes, there is a possibility that drawdown becomes large at the time of thermoforming and moldability is lowered.
About the measurement of MFR, based on JIS-K7210, it can measure with a measurement temperature of 230 degreeC and a load of 2.16 kg, for example.

Polypropylene, from the viewpoint of moldability, preferably the crystallization rate at 130 ° C. is 2.5 min ^-1 or less, more preferably 2.0Min ^-1 or less. When the crystallization rate exceeds 2.5 min ⁻¹ , the laminate that is heated and softened at the time of molding is rapidly hardened at the part that first contacts the mold, the elongation becomes poor, and the part that is forcibly extended. There is a risk of whitening and deterioration in design.

The crystallization speed of polypropylene can be measured using, for example, a differential scanning calorimeter (DSC) (product name “Diamond DSC”, manufactured by PerkinElmer). Specifically, the temperature of polypropylene is raised from 50 ° C. to 230 ° C. at 10 ° C./min, held at 230 ° C. for 5 minutes, cooled from 230 ° C. to 130 ° C. at 80 ° C./min, and then raised to 130 ° C. Hold and crystallize. From the point of time when the temperature reaches 130 ° C., the measurement of the change in calorie is started, and the crystallization speed can be determined from the obtained DSC curve by the following procedures (i) to (iv).
(I) A baseline obtained by approximating a change in calorie from a time point 10 times the time from the start of measurement to the peak top point to a time point 20 times by a straight line is used as a baseline.
(Ii) The intersection of the tangent line having a slope at the inflection point of the peak and the baseline is obtained, and the crystallization start time and end time are obtained.
(Iii) The time from the obtained crystallization start time to the peak top is measured as the crystallization time.
(Iv) The crystallization rate is obtained from the reciprocal of the obtained crystallization time.

Examples of the polyolefin include polyethylene and olefin copolymers, and linear low density polyethylene is preferable.
Examples of the olefin include the same as those described above.

The modified polyolefin is a modified product of a compound for modifying an olefin polymer.
Examples of the olefin polymer include homopolypropylene, homopolyethylene, a copolymer of propylene and olefin, a copolymer of ethylene and olefin, and polycycloolefin. Examples of the olefin are the same as those described above.
The modified polyolefin may be used alone or in combination of two or more.

  Examples of the modifying compound include maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, and methyl methacrylate.

  You may mix | blend additives, such as a pigment, antioxidant, a stabilizer, a ultraviolet absorber, a nucleating agent, with a 1st resin layer as needed.

The crystal structure of the first resin layer preferably includes a smectic crystal.
Smectic crystals are preferred because they are metastable mesophases and each domain has a small size and is excellent in transparency. Further, since it is in a metastable state, the sheet is softened with a lower amount of heat compared to the α crystal that has been crystallized, so that it is excellent in formability, which is preferable.
In addition, other crystal forms such as β crystal, γ crystal, and amorphous part may be included.
30% or more, 50% or more, 70% or more, or 90% or more of the first resin layer may be smectic crystals.

  The thickness of the first resin layer is preferably 60 to 250 μm, and more preferably 75 to 220 μm.

  Examples of the method for forming the first resin layer include an extrusion method.

The cooling is preferably performed at 80 ° C./second or more until the internal temperature of the first resin layer becomes equal to or lower than the crystallization temperature.
Thereby, the crystal structure of the 1st resin layer can be made into the above-mentioned smectic crystal.
The cooling is more preferably 90 ° C./second or more, and further preferably 150 ° C./second or more.

An example of a manufacturing apparatus for manufacturing the first resin layer 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. .
A method for manufacturing the sheet (first resin layer) 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 planar 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. It is pressed 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).

  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 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.

  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 vapor deposition may be appropriately set according to the melting temperature or evaporation temperature of the metal used. Moreover, the method of coating the paste containing said metal, the plating method using said metal, etc. can be used.

The laminate of the present invention is obtained by laminating the above-described first resin layer, second resin layer, and metal layer in this order.
The first resin layer and the second resin layer may be in contact with each other. Further, the second resin layer and the metal layer may be in contact with each other.
The laminate of the present invention may include a printing layer, a third resin layer, a backing film, and the like.

The print layer is preferably formed on the surface of the metal layer opposite to the surface in contact with the second resin layer, or between the metal layer and the second resin layer.
The print layer may be formed on a part or the entire surface. The shape of the printing layer is not particularly limited, and various shapes such as a solid shape, a carbon tone, and a woodgrain tone are exemplified.

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 thickness of the ink can be increased, and therefore, ink cracking hardly occurs when the ink is molded into a complicated shape.
For example, in the case of screen printing, ink excellent in elongation at the time of molding is preferable, and FM3107 high density white, SIM3207 high density white, etc. manufactured by Jujo Chemical Co., Ltd. can be exemplified, but not limited thereto.

The third resin layer is preferably formed on the surface of the first resin layer opposite to the surface in contact with the second resin layer. The presence of the third resin layer makes it easier to form a print layer or a coating layer on the opposite side of the first resin layer from the metal layer.
Examples of the resin of the third resin layer include the same resins as those of the second resin layer. The resin of the third resin layer is preferably the same as the resin of the second resin layer.

  The thickness of the third resin layer is preferably 100 nm or more and 3000 nm or less. If the thickness of the third resin layer is less than 100 nm, ink adhesion during screen printing may not be obtained. If it exceeds 3000 nm, stickiness may occur and cause blocking.

  Various coating layers such as a printing layer, a hard coat, an antireflection coating, and a thermal barrier coating can be laminated on the surface of the third resin layer opposite to the surface in contact with the first resin layer, but this is not restrictive.

  In the method for producing a molded article of the present invention, the laminate can be molded to obtain the molded article of the present invention.

When the metal or metal oxide is indium or indium oxide, the molded article of the present invention preferably has a glossiness of 250% or more. More preferably, it is 300% or more, and particularly preferably 330% or more.
When the glossiness is 250% or more, a metallic luster is exhibited and an excellent metallic design can be imparted to the molded body.

Moreover, when the metal or metal oxide is aluminum or aluminum oxide, the molded article of the present invention preferably has a glossiness of 380% or more. More preferably, it is 400% or more, and particularly preferably 420% or more.
When the glossiness is 380% or more, a metallic luster is exhibited and an excellent metallic design can be imparted to the molded body.

About the measurement of glossiness, it can measure based on the measuring method of 60 degree specular glossiness of JISZ8741.
Specifically, an automatic colorimetric color difference meter (AUD-CH-2 type-45, 60, manufactured by Suga Test Instruments Co., Ltd.) was used, and the sheet was irradiated with light at an incident angle of 60 degrees. The reflected luminous flux ψs when the reflected light is received is measured, and the glossiness can be obtained by the following formula (1) based on the ratio with the reflected luminous flux ψ0s from the glass surface having a refractive index of 1.567.
Glossiness (Gs) = (ψs / ψ0s) * 100 (1)

  The glossiness is preferably measured from the surface of the first resin layer opposite to the surface in contact with the second resin layer.

  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. .

  The laminated body and molded body of the present invention, and the molded body obtained by the method of the present invention are computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electric or electronic devices, portable information terminals, home appliance parts, toilet seats. It can be used for automobile parts, motorcycle parts, industrial materials and building materials.

Example 1
(1) Manufacture of a laminated body The manufacturing apparatus shown in FIG. 1 was used. Polypropylene (Prime Polypro F-133A manufactured by Prime Polymer Co., Ltd. (melt flow index 3 g / 10 min, homopolypropylene)) was charged into the extruder and extruded under the following conditions to obtain a first resin layer.
Extruder diameter: 150mm
Width of T-die 12: 1400mm
Thickness: 200 μm
Take-up speed of sheet 11: 25 m / min Surface temperature of fourth cooling roll 16 and metal endless belt 17: 17 ° C.
Cooling rate: 10,800 ° C / min

  In addition, about the measurement of the melt flow index, it measured based on JIS-K7210.

  The obtained first resin layer was subjected to corona treatment, and a urethane resin (manufactured by Hydran WLS-202 DIC Corporation) was applied with a bar coater so that the thickness after drying was 49 nm. A second resin layer was formed by drying for a minute.

  Aluminum was deposited to a thickness of 50 nm on the surface of the obtained second resin layer opposite to the first resin layer to form a metal thin film (metal layer containing a metal or metal oxide) to obtain a laminate.

(2) Evaluation of laminated body The thickness of the 2nd resin layer of the obtained laminated body was measured by the reflection X-ray small angle scattering method.
Using SmartLab (manufactured by Rigaku Corporation), Cu-Kα ray, wavelength 1.5406 mm, output 200 kV, 45 mA X-ray, 2θ = 0.2 ° to 1.5 ° X-ray reflection intensity Was measured. From the obtained 2θ and X-ray reflection intensity curve, the thickness of the second resin layer was calculated.

About the obtained laminated body, 11 notches were made | formed at 1 mm intervals on the surface side opposite to the surface which contact | connects a 2nd resin layer of a metal layer using a cutter knife. In addition, 11 cuts were made at 1 mm intervals to make a 10 × 10 square so as to be perpendicular to the cuts.
A commercially available cellophane tape (CT-24 manufactured by Nichiban (width: 24 mm)) was pasted on the above-mentioned notch, and the cellophane tape was peeled off after closely contacting with the finger pad.
The number of remaining cells was expressed as a percentage, and the adhesion was evaluated. The results are shown in Table 1.

(3) Manufacture of a molded object About the obtained laminated body, it thermoformed by vacuum pressure forming using the vacuum pressure forming machine FM-3M / H (made by Minos Co., Ltd.), and obtained the molded object.

(4) Evaluation of molded body The appearance of the obtained molded body was evaluated.
Regarding the crack, the case where the metallic luster was developed was evaluated as ◎, the case where the metallic luster remained but decreased, the case where the metallic luster was lost, and the case where the metallic luster was lost were evaluated as x. The results are shown in Table 1.
With respect to the rainbow, the case where no rainbow was generated was evaluated as ○, and the case where the rainbow was generated was evaluated as visual. The results are shown in Table 1.

Moreover, based on the measuring method of 60 degree specular gloss of JIS Z8741, about the obtained molded object, an automatic colorimetric color difference meter (AUD-CH-2 type-45,60, made by Suga Test Instruments Co., Ltd.) Used to measure the reflected luminous flux ψs when the first resin layer is irradiated with light from the surface opposite to the surface in contact with the second resin layer at an incident angle of 60 degrees and the reflected light is received at 60 degrees. Then, the glossiness was determined by the following formula (1) based on the ratio to the reflected light beam ψ0s from the glass surface having a refractive index of 1.567. The results are shown in Table 1.
Glossiness (Gs) = (ψs / ψ0s) * 100 (1)

(5) Evaluation of resin of second resin layer For the tensile elongation at break of the second resin layer, the urethane resin was applied on a glass substrate with a bar coater and dried at 80 ° C. for 1 minute. Thereafter, the sample was separated to prepare a sample having a thickness of 150 μm and measured by a method in accordance with JIS K7311. The tensile elongation at break of the urethane resin of the second resin layer was 600%.
The softening temperature of the second resin layer was determined by measuring the flow start temperature using a Koka flow tester using a sample prepared in the same manner as described above. The softening temperature of the urethane resin of the second resin layer was 160 ° C.
About the 2nd resin layer, using the sample created similarly to the above, a differential scanning calorimeter DSC-7 (made by Perkin Elmer Japan Co., Ltd.) measured a differential scanning calorimetry curve on the following conditions, and glass transition I asked for a point. The glass transition point of the urethane resin of the second resin layer was −50 ° C.
Measurement start temperature: -90 ° C
Measurement end temperature: 220 ° C
Temperature rising temperature: 10 ° C / min

Example 2
A laminate and a molded body were produced and evaluated in the same manner as in Example 1 except that the thickness of the second resin layer was 55 nm. The results are shown in Table 1.

Example 3
A laminated body and a molded body were produced and evaluated in the same manner as in Example 1 except that indium was deposited by 30 nm in place of aluminum. The results are shown in Table 1.

Example 4
A laminate and a molded body were produced and evaluated in the same manner as in Example 3 except that the thickness of the second resin layer was 55 nm. The results are shown in Table 1.

Comparative Example 1
A laminate and a molded body were produced and evaluated in the same manner as in Example 1 except that the thickness of the second resin layer was 28 nm. The results are shown in Table 1.

Comparative Example 2
A laminate and a molded body were produced and evaluated in the same manner as in Example 1 except that the thickness of the second resin layer was 76 nm. The results are shown in Table 1.

Comparative Example 3
A laminate and a molded body were produced and evaluated in the same manner as in Example 1 except that the thickness of the second resin layer was 230 nm. The results are shown in Table 1.

Comparative Example 4
A laminate and a molded body were produced and evaluated in the same manner as in Example 3 except that the thickness of the second resin layer was 230 nm. The results are shown in Table 1.

  The laminated body and molded body of the present invention, and the molded body obtained by the method of the present invention are computer parts such as desktop personal computers and notebook personal computers, mobile phone parts, electric or electronic devices, portable information terminals, home appliance parts, automobiles. It can be used for parts, industrial materials and building materials.

DESCRIPTION OF SYMBOLS 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 21 Peeling roll 22 Elastic material

Claims (15)

A first resin layer comprising a thermoplastic resin;
A laminate including a second resin layer and a metal layer containing a metal or metal oxide in this order,
A laminate in which the thickness of the second resin layer is not less than 35 nm and not more than 70 nm, and the resin of the second resin layer and the resin of the first resin layer are not the same.   The laminate according to claim 1, wherein the second resin layer includes one or more resins selected from the group consisting of urethane resins, acrylic resins, polyolefins, and polyesters.   The laminate according to claim 1 or 2, wherein the first resin layer contains polypropylene.   The metal or metal oxide is one or more metals or metal oxides selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum and zinc. The laminated body in any one of.   The laminate according to any one of claims 1 to 3, wherein the metal or metal oxide is one or more metals or metal oxides selected from the group consisting of indium and aluminum.   The laminated body in any one of Claims 1-5 which includes a printing layer in the surface opposite to the surface which contact | connects the said 2nd resin layer of the said metal layer in part or the whole surface.   The laminate according to any one of claims 1 to 5, wherein a printed layer is partially or entirely disposed between the metal layer and the second resin layer.   A third resin layer is included on the surface of the first resin layer opposite to the surface in contact with the second resin layer, and the resin of the third resin layer is the same as the resin of the second resin layer. It is the same, The laminated body in any one of Claims 1-7.   The molded body of the laminate according to any one of claims 1 to 8.   The glossiness measured from the surface of the first resin layer opposite to the surface in contact with the second resin layer is 250% or more, wherein the metal or metal oxide is indium or indium oxide. The molded product according to 1.   The glossiness measured from the surface opposite to the surface in contact with the second resin layer of the first resin layer is 380% or more, wherein the metal or metal oxide is aluminum or aluminum oxide. The molded body described.   The manufacturing method of the molded object which shape | molds the laminated body in any one of Claims 1-8, and obtains a molded object.   The method for producing a molded body according to claim 12, 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 12, wherein the molding is performed by forming the laminated body so as to match a mold, mounting the shaped laminated body on a mold, and supplying and integrating a molding resin. Manufacturing method. The molding is
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 12 which presses and coat | covers the said laminated body heat-softened on the said core material.

Images