JP2022086252A - Resin composition, resin sheet, laminate, molding, and method for producing molding - Google Patents

Abstract

To provide a resin composition that can produce a resin sheet having excellent flaw resistance.SOLUTION: A resin composition contains polypropylene and an organic laminar inorganic compound, with the content of the organic laminar inorganic compound being 6 mass% or more, and the polypropylene having an isotactic pentad fraction of 85 mol% or more.SELECTED DRAWING: None

Description

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

In the industrial field such as automobiles and housing equipment, it is possible to reduce the environmental load and give a new design that has never been seen before, instead of the conventional methods such as painting and plating as a technique for giving a design to a molded product. As a method that can be used, a method using a decorative sheet is attracting attention. The decorative sheet is a resin sheet that has been printed or surface-treated in advance to give it a design, and by integrating it with the resin molded body, it is possible to give the molded body a design.

Polypropylene has excellent moldability and chemical resistance, and can be reduced in weight, so that it is expected to be applied as a decorative sheet. However, some polypropylene sheets are easily scratched on the surface, and when applied as a decorative sheet for interior or exterior of automobiles, for example, scratch resistance at a level that can withstand practical use cannot always be obtained. There's a problem.

As a technique for improving scratch resistance, for example, Patent Document 1 describes that a glass filler is blended for the purpose of improving the scratch resistance of a decorative sheet containing polypropylene. Further, Patent Document 2 describes that an inorganic filler and an oil are blended for the purpose of improving the scratch resistance of a molded product containing a propylene-based polymer.

Japanese Unexamined Patent Publication No. 2016-215379 Japanese Unexamined Patent Publication No. 2013-256670

However, in the technique of Patent Document 1, depending on the aspect ratio and the orientation state of the glass filler, surface irregularities may be remarkably developed due to the difference in shrinkage ratio between polypropylene and the glass filler. Further, in the technique of Patent Document 2, bleed-out may occur depending on the molding conditions and the usage environment. That is, there is a problem that the conventional method cannot sufficiently obtain the effect of improving the scratch resistance.

An object of the present invention is to provide a resin composition capable of producing a resin sheet having excellent scratch resistance.

According to the present invention, the following resin compositions and the like are provided.
1. 1. Containing polypropylene and organic layered inorganic compounds,
The content of the organic layered inorganic compound is 6% by mass or more, and the content is 6% by mass or more.
A resin composition having an isotactic pentad fraction of polypropylene of 85 mol% or more.
2. 2. The resin composition according to 1, wherein the organic layered inorganic compound has an average particle size of 2 to 20 μm.
3. 3. The resin composition according to 1 or 2, wherein the content of the organic layered inorganic compound is 6 to 25% by mass.
4. The resin composition according to any one of 1 to 3, wherein the organic layered inorganic compound is an organic modified product of the layered inorganic compound.
5. The resin composition according to any one of 1 to 4, wherein the organic layered inorganic compound is a compound that carries an organic cation between layers of the layered inorganic compound.
6. 4. The resin composition according to 4 or 5, wherein the average interlayer distance of the (001) plane of the layered inorganic compound is 1.5 nm or more when measured by a wide-angle X-ray diffraction method.
7. The resin composition according to any one of 1 to 6, which comprises one or more components selected from the group consisting of a neutralizing agent and an antioxidant.
8. 7. The resin composition according to 7, wherein the content of the neutralizing agent is 0.3% by mass or more.
9. 7. The resin composition according to 7 or 8, wherein the content of the antioxidant is 0.3% by mass or more.
A resin sheet prepared by using the resin composition according to any one of 10.1 to 9.
11. The resin sheet according to 10, wherein the crystallization rate of polypropylene contained in the resin sheet at 130 ° C. is 2.5 min ^-1 or less.
12. The resin sheet according to 10 or 11, which has an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak in the curve obtained by differential scanning calorimetry.
13. The resin sheet according to any one of 10 to 12, wherein the polypropylene of the resin sheet contains smetica crystals.
14. A laminate containing the resin sheet according to any one of 10.10 to 13.
15. A laminate comprising the resin sheet according to any one of 10 to 13 and an easy-adhesive layer.
16. 15. The laminate according to 15, wherein the easy-adhesive layer contains one or more resins selected from the group consisting of urethane, acrylic, polyolefin and polyester.
17. 15. The laminate according to 15 or 16, which has a printed layer on the surface of the easy-adhesive layer opposite to the resin sheet.
18. A molded product containing the resin sheet according to any one of 10 to 13 or the laminate according to any one of 14 to 17.
19. A method for producing a molded body by molding the resin sheet according to any one of 10 to 13 or the laminated body according to any one of 14 to 17 to obtain a molded body.
20. 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. 19. The method for producing a molded product according to 19, which comprises integrating the molding resin with the resin sheet or the laminated body while shaping the molded product.
21. 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. 19. The method for producing a molded product according to 19, comprising integrating the resin with the shaped resin sheet or the shaped laminate.
22. 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. 19. The method for producing a molded product according to 19.
23. The core material is arranged in the chamber box, the resin sheet or the laminate is arranged above the core material, the resin sheet or the laminate is heated and softened, and the inside of the chamber box is depressurized and the heat softened. 19. The method for producing a molded body according to 19, wherein the resin sheet or the heat-softened laminate is pressed against the core material to cover the core material.
Vehicle interior materials, vehicle exterior materials, saddle-type vehicle exterior covers, home appliance housings, decorative steel plates, decorative plates, housing equipment, or information and communications created using the molded body described in 24.18. Equipment housing.

According to the present invention, it is possible to provide a resin composition capable of producing a resin sheet having excellent scratch resistance.

It is a schematic block diagram of an example of the manufacturing apparatus for manufacturing the resin sheet of this invention.

Hereinafter, the resin composition, the resin sheet, the laminated body, the molded body, and the 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 Composition The resin composition according to one aspect of the present invention contains polypropylene and an organic layered inorganic compound. The content of the organic layered inorganic compound in the resin composition is 6% by mass or more, and the isotactic pentad fraction of polypropylene is 85 mol%.
As will be described later, the organic layered inorganic compound used in the above resin composition is composed of a layered inorganic compound, and polypropylene can penetrate between the layers. That is, since the organic layered inorganic compound has a high affinity for polypropylene, the resin sheet obtained from the above resin composition can uniformly disperse the organic layered inorganic compound throughout the resin sheet. As a result, the mechanical properties of the entire resin sheet are enhanced, and excellent scratch resistance can be realized.
In the present specification, the scratch resistance refers to the resistance to scratches when the surface of a sheet or a molded product is rubbed with a cloth, a brush, or the like, and is specifically evaluated by the method described in Examples.
Hereinafter, each component used in the above resin composition will be described.

(polypropylene)
Polypropylene is a polymer containing at least propylene. Specific examples thereof include homopolypropylene, a copolymer of propylene and an olefin, and the like. In particular, homopolypropylene is preferable because of its heat resistance and hardness.

The polypropylene used in the resin composition according to one aspect of the present invention has an isotactic pentad fraction of 85 mol% or more.
When the isotactic pentad fraction is 85 mol% or more, sufficient rigidity can be obtained when the resin sheet is used, and excellent scratch resistance can be obtained.
The isotactic pentad fraction of polypropylene is preferably 95 mol% or more, more preferably 96 mol% or more, and preferably 99 mol% or less, and 98.5 mol% or less. Is more preferable.
When the isotactic pentad fraction is 85 mol% or more and 99 mol% or less, excellent scratch resistance and sufficient transparency can be obtained when the resin sheet is used, which is good when the molded product is used. You can get a nice decoration.
The isotactic pentad fraction is preferably 85 mol% or more and 99 mol% or less, more preferably 95 mol% or more and 99 mol% or less, and 96 mol% or more and 98.5 mol% or less. Is more preferable.

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 copolymer of propylene and olefin can be a block copolymer or a random copolymer as long as the isotactic pentad fraction is 85 mol% or more (preferably 85 to 99 mol%). It may be a mixture thereof.
Examples of the olefin include ethylene, butylene, cycloolefin and the like.

The melt flow rate of polypropylene (hereinafter, may be referred to as “MFR”) is preferably in the range of 0.5 to 10 g / 10 minutes. Within this range, the formability into a film shape or a sheet shape is excellent. The polypropylene MFR is measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with JIS-K7210.

The content of polypropylene in the resin composition is usually 75% by mass or more, preferably 80% by mass or more, and more preferably 87% by mass or more. Further, it is usually 99% by mass or less, preferably 95% by mass or less.

(Organized layered inorganic compound)
The organic layered inorganic compound is an organic modified form of the layered inorganic compound. The organic layered inorganic compound is preferably a compound in which an organic cation is carried (intercalated) between layers of the layered inorganic compound. Intercalation usually means that an electron donor or an electron acceptor is inserted between layers of a layered material by a charge transfer force.

The content of the organic layered inorganic compound in the resin composition according to one aspect of the present invention is 6% by mass or more. When the content of the organic layered inorganic compound is 6% by mass or more, excellent scratch resistance can be obtained when the resin sheet is used.
The content of the organic layered inorganic compound in the resin composition is preferably 7% by mass or more, more preferably 8% by mass or more, further preferably 9% by mass or more, and 11% by mass or more. Is even more preferable, and 12% by mass or more is particularly preferable. Further, it is preferably 25% by mass or less, more preferably 20% by mass or less, further preferably 19% by mass or less, further preferably 18% by mass or less, and particularly preferably 17% by mass or less. .. When the content of the organic layered inorganic compound is 6% by mass or more and 25% by mass or less, the film formation of the resin sheet can be carried out without any problem, and excellent scratch resistance can be exhibited. Further, when the content of the organic layered inorganic compound is 11% by mass or more and 19% by mass or less, more preferably 12% by mass or more and 16% by mass or less, in addition to excellent scratch resistance, it is even better. It is possible to realize a resin sheet that also has surface smoothness.

Examples of the layered inorganic compound of the organic layered inorganic compound include clay minerals. Specific examples thereof include silicate minerals having a layered structure, and a large number of sheets (for example, a tetrahedral sheet composed of silicic acid, an octahedral sheet composed of silicic acid containing Al, Mg, etc.). Etc.) is an inorganic compound having a layered structure in which it is laminated.

Examples of the layered inorganic compound include montmorillonite, saponite, hectorite, pidelite, stepnsite, nontronite, vermiculite, halloysite, mica, kaolinite, pyrophyllite and the like. Further, as the layered inorganic compound, zirconium phosphate, fluorinated swelling mica (fluorinated mica) or the like may be used.
The layered inorganic compound may be a natural product or a synthetic product.

Among the above, montmorillonite, saponite, hectorite, and fluorinated swelling mica are preferable, and montmorillonite and fluorinated swelling mica are more preferable.
The layered inorganic compound may be used alone or in combination of two or more.

Examples of the organic cation include cations of organic compounds having a molecular weight of 10 to 1,000,000, for example, cations of compounds having functional groups compatible with the surface of layered inorganic compounds, metal cations, cations of onium salts, and the like. Examples thereof include cations of water-soluble polymers.

The cationic functional group of the compound having a functional group compatible with the surface of the layered inorganic compound includes a halogen atom, an acid anhydride group, a carboxylic acid group, a hydroxyl group, a thiol group, an epoxy group, an ester group, an amide group and a urea group. , Urethane group, ether group, thioether group, sulfonic acid group, phosphonic acid group, nitro group, amino group, oxazoline group, imide group, cyano group, isocyanate group and the like.
Examples of the functional group include aromatic ring groups such as a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, and a thiophene ring.

Examples of the metal of the metal cation include sodium, potassium, calcium, magnesium, aluminum and the like.

Examples of the onium salt cation include dialkyl (for example, 10 to 20 carbon atoms, preferably 14 to 18 carbon atoms) dimethylammonium cation, trialkyl (for example, 10 to 20 carbon atoms) monomethylammonium cation, and other tetraalkylammonium cations. Examples thereof include ammonium cations such as octyl ammonium cations, dodecyl ammonium cations, octadecyl ammonium cations, aminododecanoic acid cations, and phosphonium cations.
The cation of the onium salt is preferably a tetraalkylammonium cation, more preferably a dialkyldimethylammonium cation, a dialkyldiethylammonium cation, or a trialkylmonomethylammonium cation. Examples of the alkyl group (for example, 1 to 4, 10 to 22, 12 to 20 carbon atoms) include a dodecyl group having 12 carbon atoms, a tetradecyl group having 14 carbon atoms, a hexadecyl group having 16 carbon atoms, an octadecyl group having 18 carbon atoms, and the like. Can be mentioned.

Examples of the cation of the water-soluble polymer include polyoxyalkylene ethers such as polyethylene glycol and polypropylene glycol, polyoxyalkylene aryl ethers such as polyoxyethylene phenyl ether, polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose and the like. Examples thereof include cellulose derivatives, lignin derivatives such as lignin sulfonic acid, chitosan derivatives such as chitosan hydrochloride, and cations such as polyvinyl sulfonic acid, polyvinyl benzyl sulfonic acid, polyvinyl phosphonic acid, polyvinyl benzyl phosphonic acid, and polyacrylic acid.
The organic cation may be used alone or in combination of two or more.

For the layered inorganic compound, the average interlayer distance of the (001) plane of the layered inorganic compound as measured by the wide-angle X-ray diffraction method is preferably 1.5 nm or more, more preferably 2.0 nm or more. When it is 1.5 nm or more, polypropylene can more easily enter the layers, and it is easy to obtain a state in which the organic layered inorganic compound is uniformly dispersed in polypropylene.
The upper limit is not particularly limited, but is usually 100 nm.

The average interlayer distance of the (001) plane of the layered inorganic compound can be specifically measured by using Xpert PRO (manufactured by Spectris Co., Ltd.) or the like. Specifically, the measurement is performed as follows.
The resin composition is prepared as a flat plate sample having a thickness of 2 mm, a short side of 65 mm, and a long side of 150 mm by using a hydraulic injection molding machine IS-80EPN (manufactured by Toshiba Machine Co., Ltd.).
The obtained sample is subjected to X-ray diffraction measurement under the following conditions, and the average interlayer distance of the organic layered inorganic compound is calculated from the peak position derived from the (001) plane according to Bragg's conditioned formula.
Equipment: Xpert PRO (manufactured by Spectris Co., Ltd.)
Anode material: Cu
Anti-scatter slit: 1/8 °
Scan range: 1.5-6 °
Scan step size: 0.0167113 °
Time per step: Approximately 10
Bragg's conditional expression: λ = 2dsin (2θ / 2)
λ (incident X-ray wavelength): 1.541874 2θ: Measurement angle

The average particle size of the organic layered inorganic compound is preferably 2 μm or more, more preferably 5 μm or more, preferably 20 μm or less, and more preferably 15 μm or less.
When the average particle size of the organic layered inorganic compound is 2 μm or more, excellent scratch resistance can be obtained in the resin sheet. Further, when the average particle size of the organic layered inorganic compound is 20 μm or less, crushing of the organic layered inorganic compound during kneading with polypropylene can be suppressed, and excellent scratch resistance can be obtained in the resin sheet.

The average particle size of the organic layered inorganic compound is measured as follows.
That is, 100 particles having a particle size of 0.5 μm to 30 μm in a region of 9 mm ² were visually indiscriminately selected using a photograph taken with an electron microscope (manufactured by JEOL Ltd., product name: JSM-6010PLUS / LA). , A simple average (arithmetic average) of the particle sizes of the 100 particles is obtained. For the particle size, the major axis of the particles is used.

The organic layered inorganic compound is a layered inorganic compound having an organic substance between layers by mixing, for example, a dispersion medium containing water or a proton donor, an organic agent (for example, including an organic cation) and the layered inorganic compound. It can be prepared by preparing a compound-containing liquid (organic modification) and then detreating the excess dispersion medium.

The organic layered inorganic compound may be used alone or in combination of two or more.

(Neutralizer, Antioxidant)
In one embodiment, the resin composition further comprises one or more components selected from the group consisting of neutralizers and antioxidants. By including such a component, the heat-resistant discoloration property and the weather resistance of the resin sheet obtained by using the resin composition can be improved.

The respective effects when the neutralizing agent and the antioxidant are contained in the resin composition will be described below.
When an organic layered inorganic compound is used in the resin composition, the resin sheet may be discolored or the mechanical properties may be deteriorated due to a temperature change or the like due to the components leached from the organic layered inorganic compound. By containing one or more components selected from the group consisting of a neutralizing agent and an antioxidant in the resin composition, the occurrence of these defects can be suppressed.

Specifically, when the organic layered inorganic compound and polypropylene are kneaded, polypropylene invades between the layers of the layered inorganic compound, and the components such as chlorine and fluorine intercalated between the layers are released into the kneaded resin. May be done. Due to such a component, the weather resistance and the heat-resistant discoloration property may be lowered when the resin sheet is formed. In particular, when an antioxidant function is previously imparted to a resin composition containing polypropylene by a component having an antioxidant function, the antioxidant function may be impaired by the above-mentioned components such as chlorine and fluorine.
When a neutralizing agent is added to the resin composition, components such as chlorine and fluorine released from the layered inorganic compound into the kneaded resin can be captured by the neutralizing agent. Therefore, when a resin sheet is used, discoloration due to temperature changes and deterioration of mechanical properties can be suppressed, and deterioration of weather resistance and heat-resistant discoloration can be suppressed.
Further, when the resin composition contains an antioxidant, even if the originally imparted antioxidant function is slightly deteriorated, the lost antioxidant function can be restored by the antioxidant.

In the resin composition according to one aspect of the present invention, either one of the neutralizing agent and the antioxidant may be added, or both may be added.

Examples of the neutralizing agent include stearic acid-based neutralizing agents (compounds containing stearic acid), hydrotalcite-based neutralizing agents (compounds containing hydrotalcite), epoxy-based neutralizing agents (compounds containing epoxy), and the like. Can be mentioned. These may be used alone, or two or more kinds may be mixed and used.
Among these, a stearic acid-based neutralizer is preferable from the viewpoint of compatibility with the resin and suppression of bleed-out.
Specific examples of the stearic acid-based neutralizing agent include calcium stearate, calcium 12 hydroxystearate, magnesium 12 hydroxystearate and the like.

The content of the neutralizing agent in the resin composition according to one aspect of the present invention is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and 1% by mass or less. It is preferably 0.8% by mass or less, and more preferably 0.8% by mass or less.
When the content of the neutralizing agent is 0.2% by mass or more, excellent heat-resistant discoloration and weather resistance can be obtained when the resin sheet is used. Further, when the content of the neutralizing agent is 1% by mass or less, the occurrence of bleed-out can be suppressed.

Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, and the like. As the antioxidant, these may be used alone, or two or more kinds may be mixed and used.
Among these, phosphorus-based antioxidants are preferable from the viewpoint of stability of antioxidant performance.
Specific examples of the phosphorus-based antioxidant include "Irgafos 168 (trade name)" manufactured by BASF Japan Ltd. and "HOSTANOX P-EPQ (trade name)" manufactured by Clariant Chemicals Co., Ltd.

The content of the antioxidant in the resin composition according to one aspect of the present invention is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and 1% by mass or less. It is preferably 0.8% by mass or less, and more preferably 0.8% by mass or less.
When the content of the antioxidant is 0.2% by mass or more, excellent heat-resistant discoloration and weather resistance can be obtained when the resin sheet is used. Further, when the content of the antioxidant is 1% by mass or less, the occurrence of bleed-out can be suppressed.

A metal deactivator may be added to the resin composition according to one aspect of the present invention.
The metal deactivating agent is a substance that suppresses the diffusion of metal and / or metal ions. By containing a metal deactivator in the resin composition, it is possible to suppress the movement of not only metals and metal ions but also chlorine and fluorine ions. Deterioration can be suppressed, and deterioration of weather resistance and heat-resistant discoloration can be suppressed.
The content of the metal inactivating agent in the resin composition according to one aspect of the present invention is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and 1% by mass. It is preferably less than or equal to, and more preferably 0.8% by mass or less.

However, depending on the metal inactivating agent, the transparency (haze value) of the obtained resin sheet may be impaired. Therefore, when the transparency is prioritized, the content of the metal inactivating agent in the resin composition is, for example. , 0.3% by mass or less, 0.1% by mass or less, or 0% by mass.

The resin composition according to one aspect of the present invention may contain additives such as a colorant, a stabilizer, and an ultraviolet absorber, if necessary, in addition to the various components described above.

In the resin composition according to one aspect of the present invention, 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. 99.5% by mass or more, 99.8% by mass or more, 99.9% by mass or more, or 100% by mass.
Polypropylene and organic layered inorganic compounds;
Polypropylene, organic layered inorganic compounds, and neutralizers;
Polypropylene, organic layered inorganic compounds, and antioxidants;
Polypropylene, organic layered inorganic compounds, neutralizers and antioxidants;
Polypropylene, organic layered inorganic compounds, neutralizers, antioxidants, and metal deactivators; or polypropylene, organic layered inorganic compounds, neutralizers, antioxidants, metal deactivators, and any of the above components. One or more components selected from.

2. 2. Resin Sheet The resin sheet according to one aspect of the present invention is prepared by using the above-mentioned resin composition of the present invention, and can be said to include the resin composition. In principle, the composition of the resin composition of the present invention described above is directly reflected on the resin sheet. That is, the resin sheet according to one aspect of the present invention contains polypropylene and an organic layered inorganic compound, and the content of the organic layered inorganic compound is 6% by mass or more, and the isotropic pen of the polypropylene. The tad fraction is 85 mol% or more.

Since the resin sheet according to one aspect of the present invention can have the organic layered inorganic compound uniformly dispersed throughout the resin sheet, the mechanical properties of the entire resin sheet are enhanced and excellent scratch resistance is obtained. realizable.

The type, content, and other conditions of each component in the resin sheet according to one aspect of the present invention are the same as those described in "1. Resin composition".

The surface arithmetic mean roughness Ra of the resin sheet according to one aspect of the present invention is preferably 2.1 μm or less, more preferably 1.7 μm or less, and further preferably 1.4 μm or less. The lower limit is not particularly limited, but is, for example, 0 μm, and is preferably 0.01 μm or more in consideration of peelability.
A specific method for measuring the surface arithmetic mean roughness Ra is as described in Examples described later.

From the viewpoint of moldability, the crystallization rate of polypropylene contained in the resin sheet at 130 ° C. is preferably 2.5 min ^-1 or less, and 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, preferably 0.6 min ^-1 or more, more preferably 0.8 min ^-1 or more, still more preferably 0.9 min ^-1 or more, and 1.0 min. ^-1 or more is more preferable, and 1.2 min ^-1 or more is particularly preferable.
The specific method for measuring the crystallization rate is as described in Examples described later.

The polypropylene contained in 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 a polypropylene sheet with an isotactic pentad fraction of 85 mol% or more and 99 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 product 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 product. If the polypropylene has an isotactic pentad fraction of 85 mol% or more and 99 mol% or less and the crystallization rate of polypropylene is 2.5 min ^-1 or less, it can be said that the polypropylene is 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 preferably has an exothermic peak of 1 J / g or 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. (Also referred to as "low temperature side heat generation 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 thickness of the resin sheet according to one aspect of the present invention is usually 10 to 800 μm, preferably 20 to 600 μm. Within the above range, even if the resin sheet is thin, a certain degree of scratch resistance is exhibited. On the other hand, the larger the thickness, the higher the scratch resistance performance.

3. 3. 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 extrusion method includes cooling of the melt (hereinafter referred to as molten resin) of the resin composition of the present invention described above, and the cooling is preferably performed at a cooling rate of 80 ° C./sec or higher, and the inside of the resin sheet is cooled. Continue until the temperature drops below 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.
The specific manufacturing method will be described in detail in Examples.

4. Laminated body The resin sheet according to one aspect of the present invention may be a laminated body in which other layers are laminated.
That is, the laminate according to one aspect of the present invention includes the above-mentioned resin sheet of the present invention, and another layer is laminated on the resin sheet.

For example, the resin sheet according to one aspect of the present invention may be a laminated body by laminating another resin layer made of a resin component. The resin used for the other resin layer is not particularly limited, but the same resin (polypropylene) as the resin used for the resin sheet according to one aspect of the present invention is preferable. The polypropylene used for the other resin layer is as described in the above resin composition and resin sheet.
By providing such a resin layer, the thickness of the resin sheet as the outermost layer can be reduced, that is, the amount of the organic layered inorganic compound used can be suppressed. As described above, even if the thickness of the outermost resin sheet is reduced to some extent, a certain degree of scratch resistance is ensured.

The thickness of the other resin layer is usually 20 to 790 μm, preferably 50 to 590 μm.

When the other resin layer is provided, a desired laminate can be produced by coextruding the resin sheet and each material of the other resin layer and then performing the above cooling treatment. The specific manufacturing method will be described in detail in Examples.

In addition, layers for imparting various functions and designs may be laminated. Examples of such a layer include an easy-adhesion layer, an undercoat layer, a metal layer, a printing layer and the like.

In one embodiment, the laminate comprises a resin sheet and an easy-adhesive layer.
In one embodiment, the laminate comprises a resin sheet and an easy-adhesive layer, and has a printed layer on the surface of the easy-adhesive layer opposite to the resin sheet.
Hereinafter, each of the above-mentioned layers will be described.

(Easy adhesive layer)
The easy-adhesive 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-adhesion 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 polypropylene that can be contained in the resin sheet or the main body of the molded body.

The tensile elongation at break of the easy-adhesion layer is, for example, 150% or more and 900% or less, preferably 200% or more and 850%, and more preferably 300% or more and 750% or less.
When the tensile elongation at break of the easy-adhesive layer is 150% or more, the easy-adhesive layer can follow the elongation of the resin sheet during thermal molding without any problem, so that the easy-adhesive layer is cracked and the metal layer or the printed layer is cracked. And peeling can be suppressed. When the tensile elongation at break is 900% or less, the water resistance is good.

For the tensile elongation at break of the easy-adhesive layer, for example, a resin (composition) having the same composition as that used for forming the easy-adhesive layer is applied on a glass substrate with a bar coater and dried at 80 ° C. for 1 minute. After that, a sample having a thickness of 150 μm is prepared by separation, and the sample can be evaluated by measuring by a method according to JIS K7311: 1995.

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 is preferably 0.01 μm or more and 3 μm or less, and more preferably 0.03 μm or more and 0.5 μm or less.
The thickness of the easy-adhesion layer may be 0.01 μm or more, 0.03 μm or more, 3 μm or less, or 0.5 μm or less.
When the thickness of the easy-adhesion layer is 0.01 μm or more, sufficient ink adhesion can be obtained. Further, when the thickness of the easy-adhesive layer is 3 μm or less, blocking between the laminated bodies due to stickiness can be suppressed.

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, a curing agent may be used in combination with the above-mentioned resin component (main 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.

5. Molded body The resin sheet according to one aspect of the present invention described above can be used for manufacturing a molded body. That is, the molded product includes the resin sheet according to one aspect of the present invention described above.
In addition, instead of the resin sheet, the laminated body according to one aspect of the present invention may be used, and when the term "resin sheet" is used in "6. Method for manufacturing a molded body" described later, the resin sheet or the laminated body is used. Is shown.

6. Method for manufacturing a molded product In the method for producing a molded product according to one aspect of the present invention, the above-mentioned resin sheet of the present invention is molded to obtain a molded product. The molding method for obtaining a molded product is not particularly limited, and examples thereof include in-mold molding, insert molding, and coating molding. 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.

(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, pressure 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 molding resin used for in-mold molding, insert molding and the like is preferably a moldable thermoplastic resin. Specific examples of such a thermoplastic resin include, but are not limited to, polypropylene, polyethylene, polycarbonate, acrylonitrile-styrene-butadiene copolymer, acrylic polymer and the like. Inorganic fillers such as fiber and talc may be added to the thermoplastic resin.
The molding resin is preferably supplied by injection, preferably at a pressure of 5 MPa or more and 120 MPa or less.
The mold temperature is preferably 20 ° C. or higher and 90 ° C. or lower.

(Coating molding)
The manufacturing method of the molded product by coating molding is to dispose the core material in the chamber box, arrange the resin sheet above the core material in the chamber box, reduce the pressure in the chamber box, and heat the resin sheet. It is preferable to include softening and pressing the heat-softened resin sheet against the core material to cover the core material with the resin sheet.
At this time, it is preferable to bring the resin sheet into contact with the upper surface of the core material after heating and softening.
For pressing, it is preferable to pressurize the opposite side of the core material of the resin sheet while depressurizing the side of the resin sheet in contact with the core material in the chamber box.
The core material may be convex or concave, and examples thereof include resins, metals, and ceramics having a three-dimensional curved surface. Examples of the resin include the same as those described as the molding resin.

The chamber box used for coating molding is preferably provided with, for example, two upper and lower molding chambers (upper molding chamber and lower molding chamber) that can be separated from each other. An example of coating molding using such a chamber box will be described below.
First, the core material is placed on the table in the lower molding chamber and set. The resin sheet to be molded is fixed to the upper surface of the lower molding chamber with a clamp. At this time, the pressure inside the upper and lower molding chambers is 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 changed from the atmospheric pressure state to the vacuum suction state by the vacuum tank.
After the upper and lower molding chambers are in a vacuum suction state, the heater is turned on to heat the resin sheet.
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 sheet or laminate to be molded is pressed against the core material and overlaid (molded).
By supplying compressed air to the upper molding chamber, it is possible to bring the sheet or laminate into close contact with the core material with a larger force. After the overlay is completed, the heater is turned off, the vacuum in the lower molding chamber is released to return to the atmospheric pressure state, the upper molding chamber is raised, and the product covered with the decorative printed resin sheet as the skin material is taken out. be able to.

(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 is a vehicle interior material, a vehicle exterior material, a saddle-mounted vehicle exterior cover, a housing of a home appliance, a decorative steel plate, a decorative plate, a housing equipment, a housing of an information communication device, or the like. Can be used for.

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

Example 1
(1) Preparation of Resin Composition The following polypropylene, organic layered inorganic compound, neutralizing agent, antioxidant, and metal deactivating agent are mixed in the blending amount (% by mass) shown in Table 1 to prepare a resin composition. Was prepared.
Polypropylene: "Prime Polypro F133A" manufactured by Prime Polymer Co., Ltd., MFR: 3 g / 10 minutes, hereinafter may be referred to as "PP-1".
Organic layered inorganic compound: "Somasif MAE" manufactured by Katakura Corp. Agri Co., Ltd. (Layered inorganic compound: montmorillonite, organic cation: dialkyl (carbon number 14-18) dimethylammonium ion) Average particle size: 10 μm, average interlayer distance: 3. 5 nm)
Neutralizer: "Calcium stearate" manufactured by Kanto Chemical Co., Inc.
Antioxidant: "Irgafos 168" manufactured by BASF Japan Ltd.
Metal deactivating agent: "CDA-6" manufactured by ADEKA CORPORATION

(2) Manufacture of a laminated body Using the apparatus shown in FIG. 1, a laminated body having a two-layer laminated structure of a first layer (resin sheet, thickness 40 μm) and a second layer (thickness 260 μm) is manufactured. did.
The materials for each layer are as follows.
First layer (resin sheet): Resin composition obtained above Second layer: PP-1

The operation of the apparatus shown in FIG. 1 will be described.
A melt of the resin composition extruded from the T-die 52 of the extruder (hereinafter, simply referred to as a molten resin) 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. Similar to the above, the resin sheet is surface-pressed by a metal endless belt 57 at an 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 laminated body are as follows.
-Diameter of the extruder of the first layer (resin sheet): 50 mm
-Diameter of second layer extruder: 75 mm
-Width of T-die 52: 900 mm
-Thickness of the laminated body after molding: 300 μm
-Pick-up speed of polypropylene sheet 51: 5 m / min-Surface temperature of the fourth cooling roll 56 and the metal endless belt 57: 17 ° C.
-Cooling rate: 10,800 ° C / min

(3) Evaluation of the laminated body The following evaluation was performed on the obtained laminated body. The results are shown in Table 1.
-Isotactic pentat fraction The isotactic pentat fraction was measured by evaluating the ¹³ C-NMR spectrum of polypropylene (PP-1) used in the laminate. 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. The results are shown in Table 1.
(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 pentat 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

Crystallization rate The crystallization rate of polypropylene (PP-1) used in the laminate was measured using a differential scanning calorimetry device (DSC) (“Diamond DSC” manufactured by PerkinElmer). Specifically, polypropylene is heated 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 to 130 ° C. It was retained and crystallized. 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.

-Crystal structure The crystal structure of the laminate polypropylene (PP-1) was measured by using an X-ray generator ("model ultra X 18HB" manufactured by Rigaku Co., Ltd.) to measure the scattering pattern of wide-angle X-rays under the following measurement conditions. , Identified. As a result, it was confirmed that the Sumechika crystals were present in the laminate because the peaks of the Sumechika crystal type were observed even after the peaks were separated.
(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.

-Low temperature side heat generation peak The polypropylene (PP-1) used in the laminate was measured using the same differential scanning calorimetry device as in the measurement of the crystallization rate. Specifically, the temperature of polypropylene is raised from 50 ° C. to 230 ° C. at 10 ° C./min to observe the endothermic peak and the exothermic peak, and if the exothermic peak is observed, the calorific value (J / g) is determined. It was calculated according to the transition heat calculation method described in JIS-K-7122: 2012 (transition heat measurement method).

-Surface smoothness The surface arithmetic mean roughness Ra of the first layer (outermost layer) of the laminated body was determined by a 3D laser microscope ("LEXT4000LS" manufactured by Olympus Corporation) under the following conditions.
Objective lens: 20x zoom: 1x measurement pitch: 0.06μm
Scanning mode: X, Y, Z High-precision color analysis Length: 642 μm

-Scratch resistance The scratch resistance of the first layer (outermost layer) of the laminated body was evaluated by the rate of change in glossiness before and after the Gakushin wear test represented by the following formula.
Gloss change rate = (Glossiness before Gakushin wear test-Glossiness after Gakushin wear test) / Glossiness before Gakushin wear test (Glossy wear test)
Test equipment: Gakushin wear tester manufactured by Toyo Seiki Co., Ltd. (Model D)
Load: 300g
Number of round trips: 10 Round trip wearer: R20, 20 mm x 20 mm
Tester: Steel wool # 0000
(Gloss measurement)
Test equipment: "VG7000" manufactured by Nippon Denshoku Industries Co., Ltd.
Measurement angle: 20 °
The glossiness was measured according to JIS-K-7105.

-Transparency The transparency of the laminate was measured using a haze measuring machine (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS-K-7136.

-Heat-resistant discoloration After measuring the laminated body with a colorimeter, it was allowed to stand in a dryer at 100 ° C. for 1 week. Even after 200 hours had passed, the heat-resistant discoloration property was evaluated by measuring the laminated body with a colorimeter and calculating the color difference in the same manner.
Equipment used (colorimeter): "CM-2600d" manufactured by Konica Minolta Co., Ltd.
Measurement mode: L ^* a ^* b ^*
Light source system: D65 (UV100%)
Observation field of view: 10 °

-Weather resistance The weather resistance of the laminate was evaluated with a super xenon weather meter. Each sample was evaluated by measuring the color difference before and after the test.
Equipment used (weather resistance test): SX-75 manufactured by Suga Test Instruments
Irradiance on the sample surface: 180 W / m ² (300-400 nm)
BP temperature: 63 ± 3 ° C
Humidity: 50 ± 5% RH
Rainfall: 18 minutes out of 120 minutes Total irradiation time: 2000 hours Equipment used (colorimeter): "CM-2600d" manufactured by Konica Minolta Co., Ltd.
Measurement mode: L ^* a ^* b ^*
Light source system: D65 (UV100%)
Observation field of view: 10 °

Examples 2 to 7, Comparative Examples 1 and 2
The resin composition and the laminate were produced and evaluated by the same method as in Example 1 except that the composition of the resin composition used for the first layer (resin sheet) was changed as shown in Table 1. The results are shown in Table 1.

Example 8, Comparative Example 3
The composition of the resin composition used for the first layer (resin sheet) was changed as shown in Table 1, and the resin composition and the resin sheet were prepared in the same manner as in Example 1 except that the second layer was not provided. Manufactured and evaluated. The results are shown in Table 1. The thickness of the sheet was set to 300 μm only for the first layer.

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.

51 Resin sheet 52 T-die 53 1st cooling roll 54 2nd cooling roll 56 4th cooling roll 57 Metal endless belt 62 Elastic material

Claims (24)

Containing polypropylene and organic layered inorganic compounds,
The content of the organic layered inorganic compound is 6% by mass or more, and the content is 6% by mass or more.
A resin composition having an isotactic pentad fraction of polypropylene of 85 mol% or more. The resin composition according to claim 1, wherein the organic layered inorganic compound has an average particle size of 2 to 20 μm. The resin composition according to claim 1 or 2, wherein the content of the organic layered inorganic compound is 6 to 25% by mass. The resin composition according to any one of claims 1 to 3, wherein the organic layered inorganic compound is an organic modified product of the layered inorganic compound. The resin composition according to any one of claims 1 to 4, wherein the organic layered inorganic compound is a compound that carries an organic cation between layers of the layered inorganic compound. The resin composition according to claim 4 or 5, wherein the average interlayer distance of the (001) plane of the layered inorganic compound is 1.5 nm or more when measured by a wide-angle X-ray diffraction method. The resin composition according to any one of claims 1 to 6, which comprises one or more components selected from the group consisting of a neutralizing agent and an antioxidant. The resin composition according to claim 7, wherein the content of the neutralizing agent is 0.3% by mass or more. The resin composition according to claim 7 or 8, wherein the content of the antioxidant is 0.3% by mass or more. A resin sheet prepared by using the resin composition according to any one of claims 1 to 9. The resin sheet according to claim 10, wherein the crystallization rate of polypropylene contained in the resin sheet at 130 ° C. is 2.5 min ^-1 or less. The resin sheet according to claim 10 or 11, which has an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak in the curve obtained by differential scanning calorimetry. The resin sheet according to any one of claims 10 to 12, wherein the polypropylene of the resin sheet contains smetica crystals. A laminate containing the resin sheet according to any one of claims 10 to 13. A laminate comprising the resin sheet according to any one of claims 10 to 13 and an easy-adhesive layer. The laminate according to claim 15, wherein the easy-adhesive layer contains one or more resins selected from the group consisting of urethane, acrylic, polyolefin, and polyester. The laminate according to claim 15 or 16, which has a printed layer on the surface of the easy-adhesive layer opposite to the resin sheet. A molded product containing the resin sheet according to any one of claims 10 to 13 or the laminate according to any one of claims 14 to 17. A method for producing a molded body by molding the resin sheet according to any one of claims 10 to 13 or the laminated body according to any one of claims 14 to 17 to obtain a molded body. 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 19, which comprises integrating the molding resin with the resin sheet or the laminated body while shaping the molded product. 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 19, which comprises integrating the resin with the shaped resin sheet or the shaped laminate. 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. 19. The method for producing a molded product according to claim 19. The core material is arranged in the chamber box, the resin sheet or the laminate is arranged above the core material, the resin sheet or the laminate is heated and softened, and the inside of the chamber box is depressurized and the heat softened. The method for producing a molded body according to claim 19, wherein the resin sheet or the heat-softened laminate is pressed against the core material to cover the core material. Vehicle interior materials, vehicle exterior materials, saddle-mounted vehicle exterior covers, home appliance housings, decorative steel plates, decorative plates, housing equipment, or information and communications created using the molded body according to claim 18. Equipment housing.

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