WO2022080084A1 - Resin sheet, laminate, molded body, and method for producing molded body - Google Patents

Abstract

A resin sheet having a storage modulus of 1500 MPa or less at 80°C and a frequency of 1 Hz and a storage modulus of 100 MPa or more at 120°C and a frequency of 1 Hz.

Description

Resin sheet, laminated body, molded body, and method for manufacturing the molded body

The present invention relates to a resin sheet, a laminated body, a molded body, and a method for manufacturing the molded body.

In various fields such as automobiles, home appliances, building materials, daily necessities, information and communication equipment, decorative sheets are used as a technology that can reduce the environmental load instead of the conventional painting as a technology to improve the design of the appearance. The method is attracting attention.
The decorative sheet is a resin sheet that has been printed or vapor-deposited in advance, or the resin sheet itself is colored to give it a design. By providing it on the surface of the molded product, the design of the molded product is improved. can do.

In recent years, improvement of design by giving a texture or a specific texture to the surface of the molded product to create a three-dimensional effect has also been studied. As a method of imparting a three-dimensional shape to the surface of the decorative sheet, a method of softening the decorative sheet with the heat of an injection resin (molding resin) and transferring the shape imparted to the surface of the mold cavity by the pressure of the resin is used. It is common.

Japanese Unexamined Patent Publication No. 2009-262511 International Publication No. 2010/053142

However, depending on the decorative sheet, there is a problem that the heat and pressure of the injection resin do not sufficiently soften the sheet, the transfer of the shape becomes loose, and the intended design cannot be obtained. Therefore, it has been studied to sufficiently soften the decorative sheet and improve the transferability by using a rapid heating / rapid cooling mold that heats the mold at the time of resin filling and cools after the filling is completed. For example, in Patent Documents 1 and 2, by using a mold capable of heating and cooling as a mold for injection molding, the mold itself is heated to soften a laminated sheet or a multilayer film, and a molding resin is used. By cooling the mold after injecting the mold, we are trying to transfer the mold shape to a laminated sheet or a multilayer film. However, the rapid heating / rapid cooling mold is complicated and very expensive, and has problems such as time and effort for controlling the temperature of the mold.
Further, in the method of softening the decorative sheet with the heat of the injection resin to transfer the three-dimensional shape, it is required that the decorative sheet has heat resistance that can maintain the shape even if it is exposed to a certain high temperature during molding.

An object of the present invention is to provide a resin sheet having excellent transferability of a mold shape and excellent heat resistance.

According to the present invention, the following resin sheets and the like are provided.
A resin sheet having a storage elastic modulus of 1500 MPa or less at 1.80 ° C. and a frequency of 1 Hz, and a storage elastic modulus of 100 MPa or more at 120 ° C. and a frequency of 1 Hz.
2. 2. The resin sheet according to 1, wherein the resin sheet contains polyolefin.
3. 3. The resin sheet according to 1 or 2, wherein the resin sheet contains polypropylene.
4. 3. The resin sheet according to 3, wherein the polypropylene contained in the resin sheet has an isotactic pentad fraction of 80 mol% or more and 98% mol or less.
5. 3. The resin sheet according to 3 or 4, wherein the polypropylene contained in the resin sheet has a crystallization rate of 2.5 min ^-1 or less at 130 ° C.
6. The resin sheet according to any one of 1 to 5, which has a two-layer or three-layer laminated structure.
7. 6. The resin sheet according to 6, wherein all the layers in the two-layer or three-layer laminated structure contain polypropylene.
A laminated body having the resin sheet according to any one of 8.1 to 7 on the surface.
9. The molded body containing the thermoplastic resin and
A molded product comprising the resin sheet according to any one of 1 to 7 or the laminated body according to 8, which covers at least a part of the surface of the molded product body.
10. 9. The molded product according to 9, which has irregularities on the surface of the resin sheet.
The resin sheet according to any one of 11.1 to 7 or the laminate according to 8 is mounted on a mold, and a molding resin is supplied to integrally mold the resin sheet or the laminate and the molding resin. A method for manufacturing a molded product.
12. By arranging the resin sheet or the laminate on the mold and supplying the molding resin toward the resin sheet or the laminate, the resin sheet or the laminate is matched with the mold. 11. The method for producing a molded product according to 11, which comprises integrating the molding resin with the resin sheet or the laminated body while shaping the molded product.
13. For molding by shaping the resin sheet or the laminated body so as to match the mold, and supplying the molding resin toward the shaped resin sheet or the shaped laminated body. 11. The method for producing a molded product according to 11, comprising integrating the resin with the shaped resin sheet or the shaped laminate.
14. The resin sheet or the laminate is heated and placed on the cavity surface of the mold, the resin sheet or the laminate is shaped so as to match the shape of the mold, and the molding resin is used. To integrate the molding resin with the shaped resin sheet or the shaped laminate by supplying the shaped resin sheet or the shaped laminate. 11. The method for producing a molded product according to 11.
15. The method for producing a molded product according to any one of 11 to 14, wherein the mold temperature when the molding resin is supplied is 20 ° C. or higher and 90 ° C. or lower.
16. The method for producing a molded product according to any one of 11 to 15, wherein the temperature of the molding resin supplied to the mold is 190 ° C. or higher and 240 ° C. or lower.
17. The method for producing a molded product according to any one of 11 to 16, wherein the injection pressure of the molding resin is 5 MPa or more and 120 MPa or less.

According to the present invention, it is possible to provide a resin sheet having excellent transferability of a mold shape and excellent heat resistance.

It is schematic sectional drawing of the molded article which concerns on 1st Embodiment of this invention. It is a schematic block diagram of an example of the manufacturing apparatus for manufacturing the resin sheet of this invention.

Hereinafter, a sheet, a laminated body, a molded body, and a method for manufacturing the molded body according to the present invention will be described. In the present specification, "x to y" represents a numerical range of "x or more and y or less". Regarding one technical matter, when there are multiple lower limit values such as "x or more" or when there are multiple upper limit values such as "y or less", the upper limit value and the lower limit value can be arbitrarily selected and combined. It shall be possible.

1. 1. Resin sheet The resin sheet according to one aspect of the present invention has a storage elastic modulus of 1500 MPa or less at 80 ° C. and a frequency of 1 Hz, and a storage elastic modulus of 100 MPa or more at 120 ° C. and a frequency of 1 Hz.

When a molded product is manufactured by injection molding using a resin sheet, when the resin sheet is placed in the cavity of the mold and the molding resin is injected into the mold, the temperature of the surface side of the mold cavity of the resin sheet is changed. Usually, the temperature rises to 80 ° C. or higher. Here, when the storage elastic modulus of the resin sheet at 80 ° C. and a frequency of 1 Hz is 1500 MPa or less, the surface shape (concave and convex shape, three-dimensional shape) of the mold is caused by the heat and pressure of the molding resin supplied into the mold. The shape) can be sufficiently transferred to the surface of the resin sheet with high reproducibility. This makes it possible to freely apply the intended design to the surface of the molded product, and it is possible to manufacture a molded product having excellent designability.
Further, according to the resin sheet according to one aspect of the present invention, the resin sheet is appropriately softened by the heat and pressure of the molding resin supplied into the mold, so that it is a special type such as a rapid heating / rapid cooling mold. Good transferability can be achieved without using a simple mold.

The storage elastic modulus of the resin sheet at 80 ° C. and a frequency of 1 Hz is preferably 150 MPa or more. When the storage elastic modulus is 150 MPa or more, the rigidity can be further increased while maintaining high transferability, so that the possibility of wrinkling or tearing of the decorative sheet can be reduced.

The storage elastic modulus at 80 ° C. and a frequency of 1 Hz is preferably 1000 MPa or less, more preferably 500 MPa or less. Further, it is preferably 200 MPa or more, and more preferably 250 MPa or more.

Next, regarding the storage elastic modulus of the resin sheet at 120 ° C. and a frequency of 1 Hz, if the storage elastic modulus is 100 MPa or more, the resin sheet can be obtained to exhibit excellent heat resistance during molding or printing. .. If the storage elastic modulus is less than 100 MPa, the rigidity of the resin sheet may decrease, making processing difficult.

The storage elastic modulus of the resin sheet at 120 ° C. and a frequency of 1 Hz is preferably 500 MPa or less. When the storage elastic modulus is 500 MPa or less, the sheet is sufficiently softened during molding, so that the shape of the mold can be transferred.

The storage elastic modulus at 120 ° C. and a frequency of 1 Hz is preferably 120 MPa or more, more preferably 150 MPa or more. Further, it is preferably 500 MPa or less, and more preferably 350 MPa or less.

The resin sheet according to one aspect of the present invention has a storage elastic modulus at 80 ° C. and a frequency of 1 Hz, and a storage elastic modulus at 120 ° C. and a frequency of 1 Hz, respectively, within the above-mentioned ranges. Even if a special mold such as a mold is not used, good transferability can be realized by a general mold, and further, excellent heat resistance at the time of molding or printing can be exhibited. ..

The storage elastic modulus (G') will be described below.
A viscoelastic body such as a resin has both viscosity and elasticity. In the case of an ideal elastic body, stress and strain are observed in phase. On the other hand, in the case of an ideal liquid, the strain phase is delayed by 90 degrees with respect to the stress phase. The viscoelastic body exhibits an intermediate behavior, and the phase difference is a value between 0 degrees and 90 degrees.
The elastic modulus can be expressed as the following mathematical formula (F1) as a complex elastic modulus G * by a complex number as a ratio of stress (σ *) and strain (γ *).
G * = σ * / γ * = (σ0 / γ0) eiδ = (σ0 / γ0) (cosδ + isinδ) ・ ・ ・ (F1)
The complex elastic modulus G * can be expressed by the following mathematical formula (F2) by dividing it into a real number part and an imaginary number part.
G * = G'+ iG'' ・ ・ ・ (F2)
The real part G'represents the elastic part of the viscoelasticity, and the imaginary part G'' represents the viscous part because it is in a phase 90 degrees behind it. Here, G'is referred to as a storage elastic modulus and G'' is referred to as a loss elastic modulus, and in the present invention, the former storage elastic modulus G'is focused on.
By applying vibration deformation to the measurement sample and measuring the strain amplitude, the stress amplitude detected by the force gauge, and the phase difference between them, the contribution of elasticity and the contribution of viscosity in the viscoelastic body are evaluated. be able to.
A specific method for measuring the storage elastic modulus (G') is as described in Examples described later.

The storage elastic modulus of the resin sheet can be controlled to a desired value by changing the physical properties such as the crystallinity of the resin constituting the resin sheet and the degree of orientation of the crystalline region and the amorphous region.

(Resin used for resin sheet)
The resin used for the resin sheet according to one aspect of the present invention is not particularly limited, and is not particularly limited, and is an acrylic resin such as polyolefin, polycarbonate, polystyrene, polymethyl methacrylate (PMMA), acrylonitrile-butadiene-styrene copolymer, and acrylonitrile-styrene. Copolymers, polyamides such as polyvinyl chloride, nylon 6, nylon 66, polyacetal, polyphenylene ethers such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and other polyesters, liquid crystal polymers, polyphenylene sulfide, polyimide, polyamideimide , Polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyarylate, polyetherimide, fluororesin, polybutylene succinate, polylactic acid and the like.
These may be used alone or may be a blend resin or an alloy resin using two or more of them.
Among these resins, polyolefin, polycarbonate, and acrylic resins are preferable from the viewpoint of transparency and durability, and polyolefin is more preferable from the viewpoint of chemical resistance, durability, and moldability.

As the polyolefin, polyethylene, polypropylene, cyclic polyolefin and the like can be used.
The cyclic polyolefin is a polymer containing a structural unit derived from the cyclic olefin, and may be, for example, a copolymer with ethylene (cyclic polyolefin copolymer).
Modifications obtained by modifying polyolefins with modifying compounds such as maleic anhydride, dimethyl maleate, diethyl maleate, acrylic acid, methacrylic acid, tetrahydrophthalic acid, glycidyl methacrylate, hydroxyethyl methacrylate, and methyl methacrylate. Polyolefin resin may be contained in the resin sheet.
Among these resins, polypropylene is preferable from the viewpoint of chemical resistance, durability and moldability.

Polypropylene is a polymer containing at least propylene. Specific examples thereof include homopolypropylene, a copolymer of propylene and an olefin, and the like.
Homopolypropylene is preferred because of its heat resistance and hardness.
The copolymer of propylene and olefin may be a block copolymer, a random copolymer, or a mixture thereof.
Examples of the olefin include ethylene, butylene, cycloolefin and the like.

When polypropylene is contained in the resin sheet, the polypropylene preferably has an isotactic pentad fraction of 80 mol% or more, more preferably 86 mol% or more, and 91 mol% or more. Is more preferable, and it is more preferable that the content is 98 mol% or less.
The isotactic pentad fraction is preferably 80 mol% or more and 98 mol% or less, more preferably 86 mol% or more and 98 mol% or less, and 91 mol% or more and 98 mol% or less. Is more preferable.
When the isotactic pentad fraction is within the above range, high transparency of the resin sheet can be obtained, and good decorativeness can be obtained when the molded product is formed.

The isotactic pentad fraction is an isotactic fraction in a pentad unit (five consecutive isotactic bonds of five propylene monomers) in the molecular chain of the resin composition. As a method for measuring this fraction, for example, the method described in Macromoleculars, Vol. 8, p. 687 can be adopted, and the fraction can be measured by ¹³ C-NMR.
A specific method for measuring the isotactic pentad fraction is as described in Examples described later.

The polypropylene used for the resin sheet preferably has a crystallization rate of 2.5 min ^-1 or less at 130 ° C. from the viewpoint of moldability.
The crystallization rate of polypropylene is preferably 2.5 min ^-1 or less, more preferably 2.0 min ^-1 or less. When the crystallization rate is 2.5 min ^-1 or less, it is possible to suppress rapid hardening of the portion in contact with the mold, and it is possible to prevent deterioration of the design. The lower limit is not particularly limited, but is usually 0.1 min ^-1 or more.
The specific method for measuring the crystallization rate is as described in Examples described later.

The polypropylene used for the resin sheet preferably contains smetica crystals as a crystal structure. Smetica crystals are a metastable intermediate phase, and are preferable because each domain size is small and the transparency is excellent. Further, since the smetika crystal is in a metastable state, the sheet is softened with a lower amount of heat as compared with the α crystal in which crystallization has progressed, and thus the sheet is excellent in moldability, which is preferable.
The crystal structure of polypropylene may include other crystal forms such as α crystal, β crystal, γ crystal, and amorphous portion in addition to Smetika crystal.
For example, 30% by mass or more, 50% by mass or more, 70% by mass or more, or 90% by mass or more of polypropylene in the resin sheet may be Smetika crystals.
The specific method for confirming the crystal structure is as described in Examples described later.

The resin sheet preferably does not contain a nucleating agent.
Even when the resin sheet contains a nucleating agent, the content of the nucleating agent in the resin sheet is preferably small, for example, 1.0% by mass or less of the resin sheet, and preferably 0. It is 5% by mass or less.
Examples of the nucleating agent include sorbitol-based crystal nucleating agents, and examples of commercially available products include Gelol MD (Nihon Rikagaku Co., Ltd.) and Rikemaster FC-1 (RIKEN Vitamin Co., Ltd.).

In one embodiment, the resin sheet is used by setting the crystallization rate of polypropylene to 2.5 min ^-1 or less without adding a nucleating agent and cooling at 80 ° C./sec or more to form the above-mentioned Smetika crystals. It is possible to obtain excellent designability in the molded body. Further, as described in the production of the molded product described later, by heating and shaping the resin sheet, the resin sheet is transferred to α crystals while maintaining the fine structure derived from Smetika crystals. This transition can further improve the surface hardness and transparency of the resin sheet.

In order to obtain polypropylene with an isotactic pentad fraction of 80 mol% or more and 98 mol% or less and a polypropylene crystallization rate of 2.5 min ^-1 or less and excellent transparency and gloss, smetica crystals are usually used. It needs to be formed.
As will be described in the production of the molded body described later, by heating and shaping the resin sheet, polypropylene of the resin sheet is transferred to α crystals while maintaining the microstructure derived from Smetica crystals, but in the molded body If polypropylene has an isotactic pentad fraction of 80 mol% or more and 98 mol% or less and a crystallization rate of 2.5 min ^-1 or less, it can be said to be derived from Smetica crystals.

By calculating the scattering intensity distribution and the long period by the small-angle X-ray scattering analysis method, it is possible to determine whether the resin sheet is obtained by cooling at 80 ° C./sec or higher or not. That is, it is possible to determine whether or not the resin sheet has a fine structure derived from Smetika crystals by the above analysis. The measurement is performed under the following conditions.
-The X-ray generator uses ultraX 18HF (manufactured by Rigaku Co., Ltd.), and an imaging plate is used to detect scattering.
-Light source wavelength: 0.154 nm
-Voltage / current: 50kV / 250mA
・ Irradiation time: 60 minutes ・ Camera length: 1.085m
-Stack the sheets so that the sample thickness is 1.5 to 2.0 mm. Stack the sheets so that the film formation (MD) directions are aligned.
In order to shorten the measurement time, the sheets are stacked so as to be 1.5 to 2.0 mm, but if the measurement time is lengthened, even one sheet can be measured without stacking the sheets.

Polypropylene contained in the resin sheet is preferably 1.0 J / g or more, more preferably 1.5 J / g or more on the low temperature side of the maximum endothermic peak in the curve (DSC curve) obtained by differential scanning calorimetry (DSC) measurement. Has an endothermic peak (also referred to as "low temperature side exothermic peak"). The upper limit is not particularly limited, but is usually 10 J / g or less.
The specific measurement method described above is as described in Examples described later.

The resin sheet may contain additives such as a colorant, an antioxidant, a stabilizer, and an ultraviolet absorber, if necessary, in addition to the above-mentioned resin component.

In one embodiment, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99. 5% by mass or more, 99.8% by mass or more, 99.9% by mass or more or 100% by mass is a resin (for example, polypropylene) or is selected from the resin (for example, polypropylene) and each of the above optional components. It is one or more components.

In one embodiment, the resin sheet may be composed of a single layer, or may be a laminated structure in which other layers are laminated for the purpose of imparting design.

The resin sheet (also referred to as “laminated resin sheet”) which is a laminated structure is usually a laminated structure consisting of two or three layers, and the layer structure is, for example, a resin layer (first layer) composed of a resin component. ), And a two-layer structure consisting of a design-imparting layer (second layer) composed of a composition in which an additive such as a colorant is added to a resin component, a first layer, a second layer, and a resin component. Examples thereof include a three-layer structure composed of a resin layer (third layer).

As the first layer, a layer having the same structure as the resin sheet according to the above-described aspect of the present invention can be used.
As the resin component used for the second layer and the third layer, various resins described in the first layer can be used, but the same resin as the first layer (for example, polypropylene) is preferable.

The storage elastic modulus of the laminated resin sheet is a value for the entire laminated resin sheet. Further, various measurements of the isotactic pentad fraction, the crystallization rate, the crystal structure, and the heat generation peak in the differential scanning calorimetry are also the values measured for the entire laminated resin sheet.

The thickness of the resin sheet according to one aspect of the present invention (all thicknesses in the case of a laminated resin sheet) is usually 100 to 1000 μm, preferably 150 to 800 μm.

2. 2. Method for Producing Resin Sheet The method for producing the resin sheet of the present invention is not particularly limited, and examples thereof include an extrusion method.
The above-mentioned extrusion method includes cooling of the molten resin, and the cooling is preferably performed at a cooling rate of 80 ° C./sec or higher until the internal temperature of the resin sheet becomes equal to or lower than the crystallization temperature. As a result, the crystal structure of the polyolefin (particularly polypropylene) contained in the resin sheet can be made into the above-mentioned Smetika crystal. The cooling rate is more preferably 90 ° C./sec or higher, and even more preferably 150 ° C./sec or higher.
When the resin sheet is the above-mentioned laminated resin sheet, a desired laminated resin sheet can be produced by co-extruding each of the materials for two or three layers and then performing the above-mentioned cooling treatment.
The specific manufacturing method will be described in detail in Examples.

3. 3. Laminated body The resin sheet (or laminated resin sheet) according to one aspect of the present invention may be made into a laminated body by laminating layers for imparting various functions and designs. Examples of such a layer include an easy-adhesion layer, an undercoat layer, a metal layer, a printing layer and the like. Hereinafter, these layers will be described.

(Easy adhesive layer)
The easy-adhesion layer preferably contains one or more resins selected from the group consisting of urethane-based resins, acrylic-based resins, polyolefin-based resins, and polyester-based resins.
By providing such an easy-adhesive layer, even when the molded body described later is molded into a complicated non-planar shape, the easy-adhesive layer can follow the resin sheet to form a good layer structure and crack. And peeling can be prevented.

As the urethane-based resin, a urethane-based resin obtained by reacting a diisocyanate, a high molecular weight polyol, and a chain extender is preferable. The high molecular weight polyol may be a polyether polyol or a polycarbonate polyol. Examples of commercially available urethane-based resins include Hydran WLS-202 (manufactured by DIC Corporation).
Examples of the acrylic resin include Acryt 8UA-366 (manufactured by Taisei Fine Chemical Co., Ltd.) and the like.
Examples of the polyolefin resin include Arrow Base DA-1010 (manufactured by Unitika Ltd.) and the like.
Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate and the like.

As the easy-adhesive layer, the above-mentioned materials may be used alone or in combination of two or more.

Of the urethane-based resin, acrylic-based resin, polyolefin-based resin, and polyester-based resin contained in the easy-adhesion layer, urethane-based resin is preferable in consideration of adhesion to the metal layer and print layer described later and moldability.

When the easy-adhesive layer contains a polypropylene-based resin, the polypropylene-based resin contained in the easy-adhesive layer is usually different from the polypropylene that can be contained in the resin sheet or the main body of the molded product.

The easy-adhesion layer may be a single layer or a laminated structure of two or more layers.

The thickness of the easy-adhesion layer may be 35 nm or more and 3000 nm or less, 50 nm or more and 2000 nm or less, or 50 nm or more and 1000 nm or less.
The thickness of the easy-adhesive layer may be 35 nm or more, 50 nm or more, or 3000 nm or less, 2000 nm or less, or 1000 nm or less.

The easy-adhesive layer can be formed, for example, by applying the above-mentioned resin with a gravure coater, a kiss coater, a bar coater, or the like and drying at 40 to 100 ° C. for 10 seconds to 10 minutes.

Various coatings such as ink, hard coat, antireflection coat, and heat shield coat can be laminated on the easy-adhesion layer.
Further, in the resin sheet, another easy-adhesive layer may be provided on the surface opposite to the above-mentioned easy-adhesive layer (first easy-adhesive layer) (second easy-adhesive layer). By doing so, it is possible to impart functionality such as surface treatment and hard coating to the polyolefin resin layer that is the surface of the molded product.

(Undercoat layer)
The undercoat layer is a layer capable of bringing the easy-adhesive layer and the metal layer into close contact with each other. By providing the undercoat layer, innumerable extremely fine cracks can be generated in the metal layer even when stress is applied during thermoforming, and the occurrence of the rainbow phenomenon can be eliminated or reduced.
Examples of the material forming the undercoat layer include urethane resin, acrylic resin, polyolefin, polyester and the like.

Acrylic resin is preferable as the material for forming the undercoat layer from the viewpoint of whitening resistance during molding (difficulty of whitening phenomenon) and adhesion to the metal layer. For example, "DA-" manufactured by Arakawa Chemical Industries, Ltd. 105 ”can be used.

The above materials may be used alone or in combination of two or more.

In the undercoat layer, the above-mentioned resin component (main agent) may be used in combination with a curing agent. Examples of the curing agent include an aziridine compound, a blocked isocyanate compound, an epoxy compound, an oxazoline compound, a carbodiimide compound and the like, and for example, "CL102H" manufactured by Arakawa Chemical Industry Co., Ltd. can be used.

When a curing agent is used, the content ratio of the main agent and the curing agent in the undercoat layer is, for example, 35: 4 to 35:40, preferably 35: 4 to 35:32, and more, in terms of the mass ratio of the solid content. It is preferably 35:12 to 35:32. Further, it may be 35:12 to 35:20.
When the blending amount of the curing agent is 4 or more with respect to the main agent 35, the curing reaction proceeds without any problem, and the whitening resistance can be maintained. When it is 40 or less, the extensibility of the undercoat layer is good, and cracking during molding can be suppressed.

As a method for forming the undercoat layer, for example, the above-mentioned material is applied with a gravure coater, a kiss coater, a bar coater or the like, dried at 50 to 100 ° C. for 10 seconds to 10 minutes, and dried at 40 to 100 ° C. for 10 to 200. It can be formed by time aging.

The thickness of the undercoat layer may be 0.05 μm to 50 μm, 0.1 μm to 10 μm, or 0.5 μm to 5 μm.
The thickness of the undercoat layer may be 0.05 μm or more, 0.1 μm or more, or 0.5 μm or more, and may be 50 μm or less, 10 μm or less, or 5 μm or less.

(Metal layer)
The metal layer is a layer containing a metal or a metal oxide.
The metal forming the metal layer is not particularly limited as long as it is a metal that can give a metallic design to the laminate, and for example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum and zinc are used. An alloy containing at least one of these may be used.
Of the above, indium and aluminum are preferable because they are particularly excellent in extensibility and color tone. If the metal layer has excellent extensibility, cracks are less likely to occur when the laminated body is three-dimensionally formed.

The method for forming the metal layer is not particularly limited, but from the viewpoint of imparting a high-quality metallic design to the laminate, for example, a vacuum vapor deposition method, a sputtering method, or ion plating using the above-mentioned metal. A vapor deposition method such as a method can be used. In particular, the vacuum thin-film deposition method is low-cost and can reduce damage to the vapor-film-deposited body. The conditions of the vacuum vapor deposition method may be appropriately set according to the melting temperature or evaporation temperature of the metal to be used.

In addition to the above method, a method of applying a paste containing the above metal or a metal oxide, a plating method using the above metal, or the like can also be used.

The thickness of the metal layer may be 5 nm or more and 80 nm or less. When it is 5 nm or more, a desired metallic luster can be obtained without any problem, and when it is 80 nm or less, cracks are less likely to occur.

(Print layer)
The shape of the print layer is not particularly limited, and examples thereof include various shapes such as solid, carbon, and wood grain.
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, and a spray coating method can be used. In particular, since the screen printing method can increase the thickness of the ink, ink cracking is unlikely to occur when the ink is formed into a complicated shape.
For example, in the case of screen printing, an ink having excellent elongation during molding is preferable, and examples thereof include "FM3107 high density white" and "SIM3207 high density white" manufactured by Jujo Chemical Co., Ltd., but this is not the case.

4. Molded body The resin sheet (or laminated resin sheet) of the present invention described above can be used for manufacturing a molded body.
The molded body according to one aspect of the present invention includes a molded body body containing a thermoplastic resin and the above-mentioned resin sheet of the present invention, and the resin sheet covers at least a part of the surface of the molded body body.
In addition, instead of the resin sheet, the laminate according to one aspect of the present invention may be used, and when the term "resin sheet" is used in "4. Molded article", it means a resin sheet or a laminate. The same applies to "5. Method for manufacturing a molded product".

By using the above resin sheet on the surface of the molded body according to one aspect of the present invention, the uneven shape of the molding die can be transferred to the surface of the resin sheet with high reproducibility at the time of manufacturing the molded body. That is, the molded body according to one aspect of the present invention has an uneven shape corresponding to the uneven shape provided on the mold on the resin sheet on the surface.
The resin sheet may cover a part of the surface of the molded body, or may cover the entire surface (entire surface) of the molded body.

The molded body may include the molded body and the resin sheet. The shape of the molded body is not particularly limited, and may be, for example, a layered shape or a specific three-dimensional shape.

FIG. 1 shows a schematic cross-sectional view of a molded product according to one aspect of the present invention. In FIG. 1, the molded body 1 includes a molded body main body 2 and a resin sheet 3 that covers the molded body main body 2. Although not shown, the resin sheet 3 has an uneven shape corresponding to the uneven shape of the mold on the surface thereof.
In FIG. 1, the aspect ratio and the film thickness ratio are not always accurate.

The thermoplastic resin used for the molded body 2 is not particularly limited as long as it can be injection molded.
Examples of the thermoplastic resin contained in the molded body 2 include polypropylene, polyethylene, polycarbonate, acetylene-styrene-butadiene copolymer, acrylic polymer and the like. As the thermoplastic resin, these may be used alone, or two or more kinds may be mixed and used.

5. Method for Manufacturing a Molded Body As a method for manufacturing a molded product according to one aspect of the present invention, in-mold molding, insert molding and the like can be mentioned. Hereinafter, each manufacturing method will be described.

(In-mold molding)
In-mold molding is a method in which a resin sheet is placed in a mold and molded into a desired shape by the pressure of the molding resin supplied in the mold to obtain a molded product. Specifically, by arranging the resin sheet on the mold and supplying the molding resin toward the resin sheet, the resin sheet is shaped so as to match the mold for molding. It includes integrating the resin and the resin sheet.
Here, the molding resin is cooled on the resin sheet and solidified to form the molded body body.

(Insert molding)
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. Specifically, by shaping the resin sheet so as to match the mold and supplying the molding resin toward the shaped resin sheet, the molding resin and the shaped resin sheet are formed. And, including unifying. In insert molding, a molded body having a more complicated shape can be formed as compared with the above-mentioned in-mold molding.
The shaping (preliminary shaping) performed so as to match the mold can be performed by vacuum forming, compressed air forming, vacuum forming, press forming, plug assist forming or the like. The resin sheet can be heated in advance at the time of shaping.

(Insert molding that performs preliminary molding in the injection molding die)
Further, as a type of insert molding, there is also a method of performing preliminary shaping of a resin sheet in a mold for injection molding. Specifically, the resin sheet is heated and placed on the cavity surface of the mold, and the resin sheet is shaped so as to match the shape of the mold, and the resin sheet to which the molding resin is shaped is shaped. It includes integrating the molding resin and the shaped resin sheet by supplying the resin toward the above.
As a method of preforming the resin sheet, for example, the resin sheet is preheated with a heater or the like, the heated resin sheet is placed on the cavity surface of the injection molding die, and the inside of the cavity is sucked. , The resin sheet can be shaped to match the internal shape of the mold. After that, a molded product can be obtained by filling the molded resin with the shaped resin sheet installed in the cavity.
According to this method, a molded product having a more complicated shape can be formed by a simpler method.

The surface shape of the mold used in the above molding method is usually given by subjecting the cavity surface, which is the product surface of the mold, to laser processing, etching processing, cutting processing, or the like. Examples of the surface shape include those having a shallow shape such as grain and blast, and those having a specific shape such as hairline, carbon pattern, and wood grain.

In the above molding method, the mold temperature when the molding resin is supplied is preferably 20 ° C. or higher and 90 ° C. or lower. When the mold temperature is within the above range, the uneven shape of the mold can be satisfactorily transferred to the resin sheet.
The mold temperature when the molding resin is supplied is preferably 30 ° C. or higher and 70 ° C. or lower. Within this range, since the resin sheet is cooled, the concern about design changes and melting due to the heat of the molten resin can be reduced, and an excellent appearance can be obtained. In addition, the concern that the resin in the mold causes molding defects (insufficient filling) at the flow end due to supercooling can be reduced, and the moldability is excellent.

In the above molding method, the temperature of the molding resin supplied to the mold is preferably 190 ° C. or higher and 240 ° C. or lower. Within this range, the resin is easily filled up to the flow end portion in the mold, so that the moldability is excellent. Further, when the temperature is 240 ° C. or lower, the risk of the sheet melting due to the heat of the molding resin and damaging the design is reduced, which is also preferable in this respect.

The molding resin composition is preferably supplied to the mold by injection, and the injection pressure is preferably 5 MPa or more, more preferably 10 MPa or more. Further, it is preferably 120 MPa or less, and more preferably 110 MPa or less. Within this range, the resin sheet is strongly pressed against the mold by the molding resin, so that a molded product having an excellent transfer rate can be obtained.

(Use of molded product)
The use of the molded product described above is not particularly limited, and it can be used for various purposes. In one embodiment, the molded body can be used as an exterior part of a saddle-mounted vehicle or an exterior part of a four-wheeled vehicle. Further, the molded body can be used for interior materials and exterior materials of vehicles, housings of home appliances, decorative steel plates, decorative plates, housing equipment, housings of information and communication equipment, and the like.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
(1) Manufacture of resin sheet Resin sheet 1 was manufactured using the apparatus shown in FIG. Polypropylene (“Prime Polypro F-133A” manufactured by Prime Polymer Co., Ltd., MFR: 3 g / 10 minutes, homopolypropylene, hereinafter may be referred to as “PP-1”) was used as a raw material for the resin sheet 1. ..

The operation of the device will be described.
The polypropylene molten resin extruded from the T-die 52 of the extruder is sandwiched between the metal endless belt 57 and the fourth cooling roll 56 on the first cooling roll 53.
In this state, the molten resin is pressure-welded with the first and fourth cooling rolls 53 and 56 and rapidly cooled to obtain a resin sheet. Subsequently, the resin sheet is sandwiched between the metal endless belt 57 and the fourth cooling roll 56 at the arc portion corresponding to the substantially lower half circumference of the fourth cooling roll 56, and is surface-pressed. After surface pressure welding and cooling with the fourth cooling roll 56, the resin sheet in close contact with the metal endless belt 57 is moved onto the second cooling roll 54 with the rotation of the metal endless belt 57. As described above, the resin sheet is surface-pressed by the metal endless belt 57 at the arc portion corresponding to substantially the upper half circumference of the second cooling roll 54, and is cooled again. The resin sheet 51 cooled on the second cooling roll 54 is then peeled off from the metal endless belt 57. The surfaces of the first and second cooling rolls 53 and 54 are coated with an elastic material 62 made of nitrile-butadiene rubber (NBR).
The manufacturing conditions of the resin sheet 1 are as follows.
・ Diameter of extruder: 150mm
・ Width of T-die 52: 1400 mm
-Thickness of resin sheet after molding: 200 μm
-Pick-up speed of polypropylene sheet 51: 25 m / min-Surface temperature of the fourth cooling roll 56 and the metal endless belt 57: 17 ° C.
-Cooling rate: 10,800 ° C / min

(2) Evaluation of Resin Sheet The following evaluation was performed on the obtained resin sheet 1.
-The storage elastic modulus of the resin sheet 1 obtained in (1) was measured using a viscoelastic spectrometer (manufactured by Seiko Instruments Inc., product name "EXSTAR DMS6100"). Specifically, first, a measurement sample having a length of 40 mm, a width of 4.0 mm, and a thickness of 0.2 mm was prepared from the resin sheet 1. The distance between spans was set to 20 mm, and dynamic viscoelasticity was measured from 0 ° C to the melting point under the conditions of a temperature rise rate of 2 ° C / min and a frequency of 1 Hz in the TD direction (width direction) of the sample. From the measurement results obtained, storage elastic moduli at 80 ° C. and 120 ° C. were obtained.

Crystallization rate The crystallization rate of polypropylene used for the resin sheet 1 was measured using a differential scanning calorimetry device (DSC) (“Diamond DSC” manufactured by PerkinElmer Co., Ltd.). Specifically, polypropylene is used at 10 ° C / min from 50 ° C to 230.
The temperature was raised to ° C., held at 230 ° C. for 5 minutes, cooled from 230 ° C. to 130 ° C. at 80 ° C./min, and then held at 130 ° C. for crystallization. The measurement of the change in calorific value was started from the time when the temperature reached 130 ° C., and the DSC curve was obtained. From the obtained DSC curve, the crystallization rate was determined by the following procedures (i) to (iv).
(I) The baseline was the linear approximation of the change in calorific value from the time point 10 times the time from the start of measurement to the top of the maximum peak to the time point 20 times.
(Ii) The intersection of the tangent line having the slope at the inflection point of the peak and the baseline was obtained, and the crystallization start and end times were obtained.
(Iii) The time from the obtained crystallization start time to the peak top was measured as the crystallization time.
(Iv) The crystallization rate was determined from the reciprocal of the obtained crystallization time.
The crystallization rate of polypropylene used for the resin sheet 1 was 0.3 min ^-1 .

-Isotactic pentad fraction The isotactic pentad fraction was measured by evaluating the ¹³ C-NMR spectrum of the polypropylene used in the resin sheet 1. Specifically, according to the peak attribution proposed in "Macropolymers, 8, 687 (1975)" by A. Zambali et al., The following apparatus, conditions and calculation formulas were used.
(Device / conditions)
Equipment: ¹³ C-NMR equipment ("JNM-EX400" type manufactured by JEOL Ltd.)
Method: Proton complete decoupling method (concentration: 220 mg / ml)
Solvent: 90:10 (volume ratio) of 1,2,4-trichlorobenzene and heavy benzene Mixing solvent temperature: 130 ° C
Pulse width: 45 °
Pulse repetition time: 4 seconds integration: 10,000 times (calculation formula)
Isotactic pentad fraction [mmmm] = m / S × 100
Racemic pentad fraction [rrrr] = γ / S × 100
Racemic Meso Lasemi Mesopentad Fraction [rmrm] = Pββ + Pαβ + Pαγ
S: Signal intensity of side chain methyl carbon atom in total propylene unit Pββ: 19.8 to 22.5 ppm
Pαβ: 18.0 to 17.5 ppm
Pαγ: 17.5 to 17.1 ppm
γ: Racemic pentad chain: 20.7 to 20.3 ppm
m: Mesopentad chain: 21.7 to 22.5 ppm
The isotactic pentad fraction was 98 mol%.

-Crystal structure The polypropylene crystal structure of the resin sheet 1 was identified by measuring the scattering pattern of wide-angle X-rays using an X-ray generator (“model ultra X 18HB” manufactured by Rigaku Co., Ltd.) under the following measurement conditions. As a result, a smechka crystal type peak was observed even after peak separation, and it was confirmed that smechka crystals were present in the resin sheet 1.
(Measurement condition)
-Light source wavelength: 300 mA CuKα line (wavelength = 1.54 Å) monochromatic light-Radioactive source output Voltage / current: 50 kV / 250 mA
・ Irradiation time: 60 minutes ・ Camera length: 1.085m
-Stack the sheets so that the sample thickness is 1.5 to 2.0 mm. Stack the sheets so that the film formation (MD) directions are aligned.
In order to shorten the measurement time, the sheets are stacked so as to be 1.5 to 2.0 mm, but if the measurement time is lengthened, even one sheet can be measured without stacking the sheets.

-Measurement of differential scanning calorimetry The polypropylene used for the resin sheet 1 was measured using the same differential scanning calorimetry device as in the measurement of the crystallization rate. Specifically, polypropylene was heated at 10 ° C./min from 50 ° C. to 230 ° C., and an endothermic peak and an exothermic peak were observed. By observing the obtained endothermic exothermic peak, it was confirmed that the exothermic peak was 1.7 J / g on the low temperature side of the maximum endothermic peak.

(3) Manufacture of molded body The resin sheet 1 obtained in (1) has a trapezoidal shape (162 mm × 73 mm, height 13 mm) using a vacuum compressed air molding machine (“FH-3M / H” manufactured by Minos Co., Ltd.). ) Was preliminarily shaped. The preformed resin sheet is attached to the surface of the fixed side cavity of the mold, and the molding resin is supplied into the mold using a hydraulic injection molding machine (“IS-80EPN” manufactured by Toshiba Machine Co., Ltd.). And integrated to obtain a molded body 1 (insert molding).
As a mold for injection molding, a mold having a trapezoidal shape and having a wood grain tone and a hairline tone on the top surface was used. The molding conditions were such that the resin temperature of the molding resin supplied to the mold was 210 ° C. and the mold temperature was 40 ° C. The injection pressure of the molding resin was 33 MPa.

Block polypropylene ("Prime Polypropylene J705UG" manufactured by Prime Polymer Co., Ltd., MFR: 9.0 g / 10 minutes) was used as the molding resin (hereinafter, also referred to as "molding resin 1"). The MFR measurement condition of the molding resin 1 was measured at 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

(4) Evaluation of molded product The following evaluation was performed on the molded product 1. The results are shown in Table 1.
-Designability The designability of the molded product 1 was visually evaluated according to the following criteria.
◯: The mold shape is sufficiently transferred to the molded body 1, and the mold shape is highly reproducible.
Δ: The shape of the mold is reflected in the molded body 1, but the reproducibility of the shape is low.
X: The mold shape is hardly transferred to the molded body 1, and the shape is unclear.

-Of the uneven shape of the transferable mold surface, the portion where the height of the step is 152 μm is defined as the “reference step”, and the height of the step corresponding to the portion on the surface of the molded body 1 is measured. , The transferability (transcription rate) was evaluated by calculating these ratios. The height of the step was measured with a laser microscope (“OLS4100” manufactured by Olympus Corporation).
Transfer rate (%) = (height of step on the surface of molded body 1 / height of reference step) x 100

-A test piece of 5 cm x 5 cm was cut out from the heat-resistant molded product 1 and allowed to stand in a constant temperature bath at 120 ° C. for 60 minutes, and the change in shape was visually observed according to the following criteria.
◯: No change in the shape of the resin sheet in the molded body 1 Δ: The resin sheet in the molded body 1 has a change in shape such as warpage or deformation ×: The resin sheet in the molded body 1 is warped or deformed There is a significant change in shape such as

Example 2
(1) Manufacture of Resin Sheet Using the apparatus shown in FIG. 2, a three-layer stacking of a first layer (thickness 48 μm) / a second layer (thickness 217 μm) / a third layer (thickness 35 μm) A resin sheet 2 having a structure was manufactured.
The materials for each layer are as follows.
First layer: Polypropylene ("Prime Polypro F-300SP" manufactured by Prime Polymer Co., Ltd., MFR: 3 g / 10 minutes, homopolypropylene, hereinafter may be referred to as "PP-2").
Second layer: Mixture of polypropylene (PP-2) and white masterbatch (MB) (“PPM 1KB662 WHT-FD” manufactured by Toyo Color Co., Ltd.) (PP-2: 90% by mass, white masterbatch: 10% by mass) %)
Third layer: PP-2

The manufacturing conditions of the resin sheet 2 are as follows.
First layer extruder diameter: 65 mm
-Diameter of second layer extruder: 75 mm
-Diameter of third layer extruder: 50 mm
・ T-die width: 900 mm
・ Pick-up speed of laminated sheet: 3m / min ・ Surface temperature of cooling roll and metal endless belt 57: 20 ℃
-Cooling rate: 10,800 ° C / min

(2) Evaluation of Resin Sheet The obtained resin sheet 2 was evaluated in the same manner as in "(2) Evaluation of Resin Sheet" of Example 1. The results of the storage elastic modulus are shown in Table 1.
The crystallization rate of polypropylene (PP-2) used for the resin sheet 2 was 0.5 min ^-1 .
The isotactic pentad fraction of polypropylene (PP-2) used in the resin sheet 2 was 93 mol%.
It was confirmed that the polypropylene (PP-2) used for the resin sheet 2 had Smetica crystals.
As a result of measuring the differential scanning calorimetry of polypropylene (PP-2) used for the resin sheet 2, it was confirmed that the endothermic exothermic peak had an exothermic peak of 1.5 J / g on the lower temperature side than the maximum endothermic exothermic peak. rice field.

(3) Manufacture and evaluation of molded product As a molding resin, instead of molding resin 1, homopolypropylene ("Prime Polypro J105G" manufactured by Prime Polymer Co., Ltd., MFR: 9.0 g / 10 minutes, hereinafter "for molding" The molded body 2 is manufactured by the same method as in "(3) Manufacture of molded body" of Example 1 except that "resin 2")) is used, and the same method as in "(4) Evaluation of molded body". Evaluated in. The results are shown in Table 1.

Comparative Example 1
(1) Resin Sheet As the resin sheet, a biaxially stretched polyester (PET) sheet ("Cosmo Shine A4300" manufactured by Toyobo Co., Ltd., also referred to as "resin sheet 3", having a thickness of 188 μm) was used. The storage elastic modulus of the resin sheet 3 was measured by the same method as in Example 1 (the thickness of the measurement sample was 188 μm). The results are shown in Table 1.

(2) Manufacture / Evaluation of Molded Body (molded body 3) was manufactured and evaluated by the same method as in Example 1 except that the resin sheet 3 was used instead of the resin sheet 1. The results are shown in Table 1.

Comparative Example 2
(1) Resin sheet As the resin sheet, a polycarbonate sheet (PC) (also referred to as "Panlite" or "resin sheet 4" manufactured by Teijin Limited, 192 μm in thickness) was used. The storage elastic modulus of the resin sheet 4 was measured by the same method as in Example 1 (the thickness of the measurement sample was 192 μm). The results are shown in Table 1.

(2) Manufacture / Evaluation of Molded Body (molded body 3) was manufactured and evaluated by the same method as in Example 1 except that the resin sheet 4 was used instead of the resin sheet 1. The results are shown in Table 1.

Comparative Example 3
(1) Resin sheet As the resin sheet, an acrylic resin (PMMA) sheet (also called "Acryplene" or "resin sheet 5" manufactured by Mitsubishi Chemical Corporation, having a thickness of 75 μm) was used. The storage elastic modulus of the resin sheet 5 was measured by the same method as in Example 1 (the thickness of the measurement sample was 75 μm). The results are shown in Table 1.

(2) Manufacture / Evaluation of Molded Body (molded body 3) was manufactured and evaluated by the same method as in Example 1 except that the resin sheet 5 was used instead of the resin sheet 1. The results are shown in Table 1.

Comparative Example 4
(1) Resin Sheet As the resin sheet, an amorphous polyester (A-PET) sheet ((Mitsubishi Chemical Corporation "Novaclear AA025-M", also referred to as "resin sheet 6", thickness 300 μm)) was used. The storage elastic modulus of the resin sheet 6 was measured by the same method as in Example 1 (the thickness of the measurement sample was 300 μm). The results are shown in Table 1.

(2) Manufacture / Evaluation of Molded Body (molded body 3) was manufactured and evaluated by the same method as in Example 1 except that the resin sheet 6 was used instead of the resin sheet 1. The results are shown in Table 1.

The molded body obtained from the resin sheet and the laminated body of the present invention can be used for a wide variety of applications, for example, in a wide range of transportation equipment (automobiles, motorcycles, etc.), housing equipment, building materials, home appliances, and the like. It can be used as a decorative sheet to replace painting in the case of the field.

Although some embodiments and / or embodiments of the present invention have been described above in detail, those skilled in the art will appreciate these exemplary embodiments and / or embodiments without substantial departure from the novel teachings and effects of the present invention. It is easy to make many changes to the examples. Therefore, many of these modifications are within the scope of the invention.
All the documents described in this specification and the contents of the application underlying the priority under the Paris Convention of the present application are incorporated.

Claims (17)

1. A resin sheet having a storage elastic modulus of 1500 MPa or less at 80 ° C. and a frequency of 1 Hz, and a storage elastic modulus of 100 MPa or more at 120 ° C. and a frequency of 1 Hz.
2. The resin sheet according to claim 1, wherein the resin sheet contains polyolefin.
3. The resin sheet according to claim 1 or 2, wherein the resin sheet contains polypropylene.
4. The resin sheet according to claim 3, wherein the polypropylene isotactic pentad fraction contained in the resin sheet is 80 mol% or more and 98% mol or less.
5. The resin sheet according to claim 3 or 4, wherein the crystallization rate of the polypropylene contained in the resin sheet at 130 ° C. is 2.5 min ^-1 or less.
6. The resin sheet according to any one of claims 1 to 5, which has a two-layer or three-layer laminated structure.
7. The resin sheet according to claim 6, wherein all the layers in the two-layer or three-layer laminated structure contain polypropylene.
8. A laminated body having the resin sheet according to any one of claims 1 to 7 on the surface.
9. The molded body containing the thermoplastic resin and
   A molded product comprising the resin sheet according to any one of claims 1 to 7 or the laminated body according to claim 8, which covers at least a part of the surface of the molded product body.
10. The molded product according to claim 9, which has irregularities on the surface of the resin sheet.
11. The resin sheet according to any one of claims 1 to 7 or the laminate according to claim 8 is mounted on a mold, and a molding resin is supplied to combine the resin sheet or the laminate with the molding resin. A method for manufacturing a molded body that is integrally molded.
12. By arranging the resin sheet or the laminate on the mold and supplying the molding resin toward the resin sheet or the laminate, the resin sheet or the laminate is matched with the mold. The method for producing a molded product according to claim 11, which comprises integrating the molding resin with the resin sheet or the laminated body while shaping the molded product.
13. For molding by shaping the resin sheet or the laminated body so as to match the mold, and supplying the molding resin toward the shaped resin sheet or the shaped laminated body. The method for producing a molded product according to claim 11, which comprises integrating the resin with the shaped resin sheet or the shaped laminate.
14. The resin sheet or the laminate is heated and placed on the cavity surface of the mold, the resin sheet or the laminate is shaped so as to match the shape of the mold, and the molding resin is used. To integrate the molding resin with the shaped resin sheet or the shaped laminate by supplying the shaped resin sheet or the shaped laminate. 11. The method for producing a molded product according to claim 11.
15. The method for manufacturing a molded product according to any one of claims 11 to 14, wherein the mold temperature when the molding resin is supplied is 20 ° C. or higher and 90 ° C. or lower.
16. The method for manufacturing a molded product according to any one of claims 11 to 15, wherein the temperature of the molding resin supplied to the mold is 190 ° C. or higher and 240 ° C. or lower.
17. The method for manufacturing a molded product according to any one of claims 11 to 16, wherein the injection pressure of the molding resin is 5 MPa or more and 120 MPa or less.

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