JP2016068337A - Laminate, molding, molded product, and production method of the product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which can be prevented from being damaged by blocking and even an irregular-shaped product of which can be decorative-molded excellently and to provide a molding, a molded product, and a production method of the molded product.SOLUTION: The laminate is produced by stacking a polyurethane layer 3B of a polyurethane resin, which has 150-900% tensile elongation at break and 50-180°C softening temperature and contains an inorganic particle, on a transparent polypropylene sheet obtained by rapidly cooling a molten polypropylene resin. A resin sheet is produced by stacking a printed layer 3C on the polyurethane layer 3B. The molded product having a non-planar molding 1 partially is produced by an insert molding method, which molding is obtained from a resin sheet. The laminate can be prevented from being damaged by blocking. Even when the laminate is molded into a complicated shape, the polypropylene sheet is not whitened and the printed layer 3C is neither cracked nor exfoliated.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate including a layer containing a polypropylene resin, a molded body, a molded product, and a method for manufacturing the molded product.

Conventionally, water pressure transfer, film insert molding, in-mold as exterior parts of various articles such as mobile communication terminals, home appliances, vehicles, etc. from the viewpoint of reducing environmental impact by painting and plating-less, and adding new design properties Molded products imparted with designability by decorative molding such as molding are known.
As such a molded product, a method of insert molding a molded product obtained by printing on a polypropylene sheet is known (see, for example, Patent Documents 1 to 3).

The thing of patent document 1 laminates | stacks the easily bonding layer which consists of acrylic polyol-type resin on a polypropylene sheet, and the laminated body by which printing was performed on this easy bonding layer is insert-molded.
However, in the thing of patent document 1, the phenomenon called what is called blocking arises by giving easy adhesiveness. Specifically, at the time of winding up the sheet-like laminate or at the time of rewinding the wound sheet-like film, the sheets adhere to each other and cannot be wound or rewound well, and the appearance is There exists a possibility that it may be impaired and easy-adhesiveness may be impaired.

The thing of patent document 2 is a laminated film which provided the coating layer which has as a main component the acrylic resin containing an inert inorganic particle in the polyester film, and improved handling property.
However, since the thing of patent document 2 uses the polyester film, the further moldability and chemical resistance are desired. That is, when decoratively molding the surface of a deformed object, it is not possible to provide a laminated film along the surface without impairing printing, and the laminated film may be whitened. . Moreover, the use of the decoratively molded article is limited from the viewpoint of chemical resistance, and versatility cannot be improved. Furthermore, there is a possibility that the ink may be repelled due to the charging of the laminated film, and the usable ink is limited, so that the versatility cannot be improved.

The thing of patent document 3 is the packaging film which gave the activation process which provides printability to the surface of the non-fogging layer of the stretched polystyrene film which provided the antifogging layer. As the activation treatment, an acrylic resin is used in addition to the corona discharge treatment.
However, since the thing of patent document 3 uses the stretched polystyrene film, it is difficult to carry out the decorative shaping | molding of the surface of a deformed thing, without impairing printing and whitening. Furthermore, since corona discharge treatment and an acrylic resin layer are provided for the activation of printability, there is still a risk of repelling the ink by charging of the stretched polystyrene film. Improves the performance.

JP 2007-307831 A Japanese Unexamined Patent Publication No. 1-182041 JP-A-6-171035

In the conventional laminate, it is difficult to decorate and mold the surface of a deformed object without causing printing damage or whitening, and the ink is repelled, and good printing cannot be obtained.
In view of these points, the present invention aims to provide a laminate, a molded product, a molded product, and a method for manufacturing the molded product that can prevent damage due to blocking and can be well-decorated even with a deformed product. To do.

The laminate of the present invention comprises a polypropylene layer (A) containing a polypropylene resin and a polyurethane layer (B) containing a polyurethane resin having a tensile breaking elongation of 150% to 900% and a softening temperature of 50 ° C to 180 ° C. And the polyurethane layer (B) contains inorganic particles.
In the present invention, the polypropylene layer (A) has a laminated structure having a polyurethane layer (B) containing a polyurethane resin having a tensile breaking elongation of 150% to 900% and a softening temperature of 50 ° C to 180 ° C and inorganic particles. . Thus, when the obtained laminate is wound or unwound, damage such as wrinkles due to blocking can be prevented, and there is no need to use a release sheet or the like for preventing blocking. And even if it is molded into a complicated shape, the elongation at the time of molding is absorbed by the polyurethane layer (B), and for example, the elongation at the time of molding becomes difficult to be transmitted to the printing layer provided in the polyurethane layer (B). There is no inconvenience of cracking or peeling. Furthermore, even if it shape | molds to a complicated shape, the polypropylene layer (A) excellent in a moldability does not whiten, can provide the outstanding designability, and can improve versatility by chemical resistance.

In the laminate of the present invention, when the average particle diameter of the inorganic particles is D and the layer thickness dimension of the polyurethane layer is d, the ratio (D / d) is 0.55 or more and 15.0 or less. It is preferable.
In this invention, when the ratio (D / d) is 0.55 or more and 15.0 or less, damage due to blocking can be prevented without impairing the adhesion of the printing layer provided on the polyurethane layer (B).

In the laminate of the present invention, the ratio (D / d) is preferably 0.55 or more and 1.1 or less.
In the present invention, in particular, damage such as peeling of the printed layer can be prevented even if it is molded into a complicated shape.

Furthermore, in the laminate of the present invention, the polyurethane layer (B) preferably contains a surfactant.
In this invention, the surfactant improves the wettability between the surface of the polyurethane layer (B) and the ink, prevents the ink from repelling and causing printing defects, and can use various inks. Can be improved.

Moreover, as for the laminated body of this invention, it is preferable that the said polyurethane layer (B) contains the polymer which has a sulfonate.
In this invention, conductivity is imparted by the polymer having a sulfonate, the surface of the polyurethane layer (B) becomes difficult to be charged, printing defects can be prevented, various inks can be used, and versatility can be improved.

And it is preferable that the laminated body of this invention is printed on at least one part of the surface on the opposite side to the side in which the said polypropylene layer (A) in the said polyurethane layer (B) was provided.
In this invention, even if it is formed in a complicated shape after printing on at least a part of the surface opposite to the polypropylene layer (A) in the polyurethane layer (B), the printing does not peel or crack, And whitening of a polypropylene layer (A) does not arise. For this reason, the design which was excellent also in the complicated shape can be provided.

The molded body of the present invention is characterized in that the laminate of the present invention is formed in a non-planar shape.
In this invention, since the laminate of the present invention is formed into a non-planar shape, for example, even if it is formed into a complicated shape after the printing layer is provided, the printing does not peel off or crack, and the polypropylene layer ( The whitening of A) does not occur, and an excellent design can be provided even with a complicated shape.

The molded product of the present invention is characterized in that the molded product of the present invention is provided on a part of a substrate by insert molding.
In this invention, even if it is molded into a complicated shape, for example, even if a printing layer is provided, the printing layer does not peel or crack, and the whitening of the polypropylene layer (A) does not occur. Even shaped molded articles can be satisfactorily molded and can provide excellent design properties with polypropylene resin.

The method for producing a molded article of the present invention comprises a mirror endless belt wound around a plurality of cooling rolls and a mirror cooling roll, and the surface temperatures of the mirror endless belt and the mirror cooling roll are kept at a dew point or higher and 50 ° C. or lower. A slanting device is used to introduce a molten resin containing polypropylene resin into a sheet by extruding between the mirror cooling roll and the mirror endless belt by a T-die extruder and press-contacting to form the sheet. A polypropylene sheet is rapidly cooled by spraying cooling water having a temperature lower than the surface temperature of the mirror endless belt, and a tensile elongation at break of 150% to 900% and a softening temperature of 50 ° C. is applied to the polypropylene sheet. A polyurethane layer containing polyurethane resin and inorganic particles at 180 ° C. or lower is stacked. A step of forming a laminate by, characterized in that the laminate implementing the steps of providing at least a portion of the substrate by insert molding, a.
In the present invention, a mirror endless belt wound around a plurality of cooling rolls and a mirror cooling roll are used, and an apparatus in which the surface temperatures of the mirror endless belt and the mirror cooling roll are kept at a dew point or higher and 50 ° C. or lower is used. Then, a molten resin containing polypropylene resin is introduced between a mirror surface cooling roll and a mirror surface endless belt by a T-die extruder, pressed into a sheet shape, and the surface temperature of the mirror surface endless belt is applied to the mirror surface endless belt. A clear polypropylene sheet is obtained by quenching by blowing cooling water at a lower temperature. A polyurethane layer containing polyurethane resin and inorganic particles having a tensile breaking elongation of 150% to 900% and a softening temperature of 50 ° C. to 180 ° C. is laminated on the obtained polypropylene sheet to form a laminate. The obtained laminate is provided on at least a part of the substrate by insert molding. For this reason, when winding up and unwinding the obtained laminated body, damage, such as wrinkles by blocking, can be prevented, and there is no need to use a release sheet or the like for preventing blocking. Even if the laminate is molded into a complicated shape, the elongation during molding is absorbed by the polyurethane layer, and for example, the printing layer provided in the polyurethane layer is difficult to transmit the elongation during molding, causing cracks in the printed layer. Or inconvenience of peeling. Furthermore, even if it is molded into a complicated shape, the polypropylene sheet can be prevented from whitening, and even a molded product having a complicated shape can be favorably decorated without impairing the appearance.

Sectional drawing which concerns on one Embodiment of the molded product of this invention. Explanatory drawing which shows the relationship between the layer thickness of the polyurethane layer which comprises the said molded object, and the average particle diameter of an inorganic particle. The schematic structure of the manufacturing apparatus which manufactures the polypropylene sheet which comprises the molded object provided in the said molded object.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the present embodiment, a configuration in which a molded product partially including the molded body of the present invention is insert-molded is illustrated, but the present invention is not limited thereto.

[Composition of molded product]
In FIG. 1, 1 is a molded body, and this molded body 1 is provided integrally with a part of a substrate (not shown) by insert molding. A molded product in which the molded body 1 is provided on a base material is used for exterior and interior products of various articles such as mobile communication terminals, home appliances, and vehicles.
Here, as the base material constituting the molded product, for example, a thermoplastic resin capable of insert molding is used.
Specific examples include polypropylene, polyethylene, polycarbonate, acetylene-styrene-butadiene copolymer, and acrylic polymer, but are not limited thereto.
In addition, what added inorganic fillers, such as a fiber and a talc, may be sufficient as the base material.

The molded body 1 is obtained by thermoforming a resin sheet (not shown) into a predetermined shape.
Here, the resin sheet includes a polypropylene layer 3A as a polypropylene layer (A) made of a transparent polypropylene sheet, a polyurethane layer 3B which is a polyurethane layer (B) provided on at least one surface of the polypropylene layer 3A, and the polyurethane layer. The layer 3B has a laminated structure in which the surface on which the polypropylene layer 3A is provided and the printed layer 3C provided on at least a part of the opposite surface are sequentially laminated. In addition, the laminated body of this invention is comprised by 3A of polypropylene layers and a polyurethane layer (B).

Although details will be described later, the polypropylene layer 3A is formed into a sheet by quenching a molten polypropylene resin.
Here, as the rapid cooling, details will be described later. For example, a mirror surface endless belt and a mirror surface cooling roll wound around a plurality of cooling rolls are provided, and the surface temperature of the mirror surface endless belt and the mirror surface cooling roll is not less than the dew point and not more than 50 ° C. Using a device maintained in the above, the resin is extruded by a T-die extruder between a mirror cooling roll and a mirror endless belt, and a molten resin made of polypropylene resin is introduced and rapidly cooled to form a sheet.

The polypropylene resin may be a polymer containing at least propylene, and may be a polypropylene, a copolymer of propylene and an olefin such as ethylene, or a mixture of polypropylene and a polyolefin or copolymer such as polyethylene. . In particular, polypropylene is preferable because of heat resistance and hardness.
In addition, the polypropylene is selected from any of four types of homopolypropylene, random polypropylene, block polypropylene, and mixtures thereof.
In addition, you may mix | blend additives, such as a pigment, antioxidant, a stabilizer, and an ultraviolet absorber, with a polypropylene resin as needed.

The polypropylene layer 3A molded under the rapid cooling condition has, for example, an average spherulite radius of 4 μm or less, an average spherulite number of the sheet cross section of 600 pieces / mm ² or less, a solid density of 0.896 g / cm ³ or less, The maximum endothermic peak of the differential scanning calorimetry (DSC) curve has a melting enthalpy ΔH of less than 90 J / g, a gloss of at least one side of 90% or more, and an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak. .
Here, the average spherulite radius is 4 μm or less, preferably 3 μm or less, particularly preferably 2 μm or less.
If the average spherulite radius is coarser than 4 μm, the internal haze becomes high, and the transparency is lowered, so that it becomes impossible to provide better design.
In addition, an average spherulite radius can be measured by observing the cross section of the obtained resin sheet with a polarizing microscope, for example. Moreover, since internal haze excludes the influence of sheet | seat surface roughness and measures the transparency inside a sheet | seat, a silicone is apply | coated to the sheet | seat surface and a haze is measured in the state which pinched both surfaces with the glass plate. By dividing the haze value of only glass from this haze value, the internal haze can be measured.

Further, the average number of spherulites in the sheet cross section is 600 pieces / mm ² or less, preferably 400 pieces / mm ² or less, particularly preferably 200 pieces / mm ² or less.
When the average number of spherulites in the sheet cross section is more than 600 / mm ² , the density is too high, that is, the crystallinity is too high, which is not preferable.
The average number of spherulites can be measured, for example, by observing the cross section of the obtained resin sheet with a polarizing microscope.

Furthermore, the solid density of 0.896 g / cm ³ or less, preferably 0.860 g / cm ³ or more 0.893 g / cm ³ or less, particularly preferably 0.885 g / cm ³ or more 0.890 g / cm ³ or less.
If the solid density is higher than 0.896 g / cm ³ , the density is too high, that is, the crystallinity is too high, which is not preferable. Incidentally, 0.860 g / cm ³ or less when it comes too rigidity of the seat low, since there is a danger that handling during fabrication is difficult, it is preferable to 0.860 g / cm ³ or more.
The solid density can be measured by a method based on JIS K7112.

The melting enthalpy ΔH of the maximum endothermic peak of the differential scanning calorimetry (DSC) curve is less than 90 J / g, preferably 55 J / g or more and 80 J / g or less, particularly preferably 60 J / g or more and 75 J / g or less.
When the melting enthalpy ΔH is 90 J / g or more, it is difficult to soften the sheet during thermoforming, which may make it difficult to form a complicated shape. In addition, when it becomes 55 J / g or less, for example, when heat treatment such as drying at the time of printing is performed, the sheet may be softened and handling may be difficult.
The melting enthalpy ΔH can be obtained from the area of the maximum endothermic peak in a differential scanning calorimetry curve measured under the following conditions using, for example, a differential scanning calorimeter (DSC-7 manufactured by Party Elmer Japan Co., Ltd.). it can.
-Measurement start temperature: 50 ° C
-Measurement end temperature: 220 ° C
・ Temperature rising temperature: 10 ℃ / min

The gloss of at least one surface, that is, the surface corresponding to the surface of the molded product is 90% or more, preferably 95% or more and 170% or less, and particularly preferably 120% or more and 160% or less.
If the gloss is less than 90%, light is reflected on the surface and thus does not pass, and transparency may be deteriorated.
In addition, glossiness uses, for example, an automatic colorimetric color difference meter (AUD-CH-2 type-45, 60, manufactured by Suga Test Instruments Co., Ltd.), and the sheet is irradiated with light at an incident angle of 60 degrees. The reflected light flux ψs when the reflected light was received was measured, and the ratio of the reflected light flux ψ0s from the glass surface with a refractive index of 1.567 was obtained by the following equation (1).
Surface glossiness (Gs) = (ψs / ψ0s) * 100 (1)

The exothermic peak on the low temperature side of the maximum endothermic peak is 1 J / g or more. This exothermic peak is an exotherm caused by heating at the time of DSC measurement, and when a part of the crystal transitions from smectic crystal to α crystal, the predetermined average spherulite radius, average spherulite number, solid density, differential scanning calorimetry, surface This phenomenon is unique to polypropylene sheets with glossy properties.
The exothermic peak was determined, for example, by checking whether or not an exothermic peak occurs on the lower temperature side than the temperature at which the maximum endothermic peak is given in the differential scanning calorimetry curve.

The polyurethane layer 3B is obtained by reacting a diisocyanate, a high molecular weight polyol and a chain extender, and has a structure containing a polyurethane resin in which the high molecular weight polyol is selected from polyether polyol or polycarbonate polyol, and inorganic particles.
In this invention, even if the resin sheet is formed into a complicated non-planar shape by forming the polyurethane layer 3B with a polyurethane resin obtained by reacting at least the above-described diisocyanate, high molecular weight polyol and chain extender, transparent polypropylene The layer structure can be well formed following the layer 3A. For example, even if the printing layer 3C is provided on the polyurethane layer 3B, it is possible to prevent the printing layer 3C from being cracked or peeled off.

The type of inorganic particles contained in the polyurethane layer 3B is not particularly limited. For example, talc, kaolin, calcium carbonate, titanium oxide, silicon oxide, calcium fluoride, lithium fluoride, aluminum oxide, barium sulfate, Zirconium oxide, mica and calcium phosphate can be used. In particular, silicon oxide which is widely distributed and easily available and whose average particle diameter is controlled is preferable.
As shown in FIG. 2, the inorganic particles preferably have a ratio (D / d) of 0.55 or more and 15.0 or less when the average particle diameter is D and the thickness of the polyurethane layer 3B is d. More preferably, it is not less than .55 and not more than 1.1.
Here, when the ratio (D / d) is smaller than 0.55, the average particle diameter D of the inorganic particles 31 is too small with respect to the layer thickness dimension d of the polyurethane layer 3B. When the sheet-like laminate is wound up or rewound into a roll shape, the laminates may adhere to each other and cause damage such as wrinkles. On the other hand, when the ratio (D / d) is larger than 15.0, the average particle diameter D of the inorganic particles 31 is too large with respect to the layer thickness dimension d of the polyurethane layer 3B, and the adhesion of the ink is lowered. In addition, there is a concern that the printed layer 3C may be inconveniently cracked or peeled off.
In addition, the average particle diameter D can be measured by a method based on JIS Z8823-2.

Further, the inorganic particles are preferably contained in an amount of 0.5% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and particularly preferably based on the total amount of the composition constituting the polyurethane layer 3B. It is 3 mass% or more and 7 mass% or less.
If the amount of inorganic particles is less than 0.5% by mass, damage due to blocking may occur. On the other hand, if it exceeds 15% by mass, the scattering of visible light by the inorganic particles increases, which may cause a disadvantage that the transparency is lowered.

The polyurethane layer 3B preferably contains a surfactant.
As the surfactant, an anionic or nonionic surfactant is used when the polyurethane resin is anionic, and a cationic or nonionic surfactant is used when the polyurethane resin is cationic.
Examples of the anionic surfactant include styrene sulfonates such as styrene sulfonic acid, sodium styrene sulfonate, lithium styrene sulfonate, ammonium styrene sulfonate; vinyl sulfonic acid, sodium vinyl sulfonate, lithium vinyl sulfonate, Vinyl sulfonates such as aluminum vinyl sulfonate; lauryl sulfonates such as sodium lauryl sulfonate and potassium lauryl sulfonate; stearin sulfonates such as sodium stearate sulfonate and potassium stearate sulfonate; and potassium lauryl benzene sulfonate Oleylbenzenesulfonates such as laurylbenzenesulfonate, sodium oleylbenzenesulfonate, potassium oleylbenzenesulfonate; Sodium stearyl sulfonate, stearyl sulfonate salts such as potassium stearyl benzenesulfonic acid.
Nonionic surfactants include linear alkylbenzene sulfonates such as linear alkylbenzene sulfonic acid and sodium linear alkylbenzene sulfonate; sodium alpha olefin sulfonate; sodium dioctyl sulfonate; glycerin caproate, glyceryl myristate Glycerin fatty acid esters such as palmitic acid glycerin ester, stearic acid glycerin ester, oleic acid glycerin ester, lauric acid glycerin ester; stearic acid diglycerin ester, oleic acid diglycerin ester, stearic acid tetraglycerin ester N, N-dihydroxyethylene stearylamine, polyoxyethylene stearylamine, polyoxy Alkylamines such as ethylene lauryl amine and polyoxypropylene stearyl amine; alkyl amides such as polyoxyethylene stearyl allide and polyoxypropylene stearyl amide; capryl alcohol, myristyl alcohol, palmityl alcohol, steal alcohol, oleyl alcohol lauryl Alcohols such as alcohol are used.
Examples of the cationic surfactant include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, octyl dimethyl ethyl ammonium ethyl sulfate, lauryl dimethyl ethyl ammonium ethyl sulfate, palmityl dimethyl ethyl ammonium ethyl sulfate, didecyl dimethyl ammonium chloride, lauryl. Quaternary ammonium salts such as dimethylbenzylammonium chloride, stearyldimethylhydroxyethylammonium paratoluenesulfonate, tributylbenzylammonium chloride; alkylbetaines such as lauryldimethylaminoacetic acid betaine; lauric acid amidopropyl betaine, coconut oil fatty acid amidopropyl betaine, Octanoic acid amide pro Fatty acid amide betaines, such as Rubetain; alkylamine oxides such as lauryl dimethyl amine oxide are used.
In addition, as the surfactant, not only one type but also a plurality may be used.

Further, the surfactant is preferably contained in an amount of 0.03% by mass or more and 1.0% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or more based on the total amount of the composition constituting the polyurethane layer 3B. It is not more than mass%, particularly preferably not less than 0.1 mass% and not more than 0.3 mass%.
When the surfactant is less than 0.03% by mass, the surfactant that bleeds on the surface of the polyurethane layer 3B decreases, and it becomes difficult to obtain a sufficient antistatic effect. On the other hand, if it exceeds 1.0% by mass, the amount of the surfactant that bleeds on the surface of the polyurethane layer 3B becomes excessive, which may cause inconveniences that inhibit the whitening of the surface and the ink adhesion.

Furthermore, the polyurethane layer 3B preferably includes a polymer having a sulfonate.
Examples of the polymer having a sulfonate include polystyrene sulfonate, sodium polystyrene sulfonate, lithium polystyrene sulfonate, ammonium polystyrene sulfonate, polyvinyl sulfonic acid, sodium polyvinyl sulfonate, lithium polyvinyl sulfonate, ammonium polyvinyl sulfonate, polyacrylamide sulfone. One or more of acid, sodium polyacrylamide sulfonate, lithium polyacrylamide sulfonate, ammonium polyacrylamide sulfonate, sodium naphthalene sulfonate formalin condensate and the like can be used.
And it is preferable to contain the polymer which has a sulfonate at 5 mass% or more and 35 mass% or less with respect to the composition whole quantity which comprises the polyurethane layer 3B, More preferably, it is 6 mass% or more and 25 mass% or less, Especially Preferably they are 7 mass% or more and 20 mass% or less.
When the amount of the polymer having a sulfonate is less than 5% by mass, the polyurethane layer 3B is imparted with conductivity, and the property that the surface of the polyurethane layer (B) is not easily charged with static electricity cannot be obtained. The ink may be repelled and printing defects may occur. On the other hand, when it exceeds 35% by mass, the polymer having a sulfonate may interfere with the adhesion between the polyurethane layer 3B and the polypropylene layer 3A and may be peeled off.
The combined use of a surfactant and a polymer having a sulfonate is possible by preventing the polarities from being opposite to each other like a cation and an anion.

The polyurethane layer 3B has a surface resistivity of 1.0 × 10 ⁸ Ω to 5.0 × 10 ¹³ Ω, more preferably 1.0 × 10 ⁹ Ω to 5.0 × 10 ¹² Ω.
If the surface specific resistance is smaller than 1.0 × 10 ⁸ Ω, the amount of the polymer having a sulfonate increases, so that the adhesion between the polyurethane layer 3B and the polypropylene layer 3A may be hindered and peeled off. On the other hand, if the surface specific resistance is larger than 5.0 × 10 ¹³ Ω, ink may be repelled on the surface of the polyurethane layer 3B, which may cause printing failure.
For this reason, it is preferable that the polyurethane layer 3B contains a polymer having a surfactant or a sulfonate so that the surface resistivity is 1.0 × 10 ⁸ Ω or more and 5.0 × 10 ¹³ Ω.
The surface resistivity can be measured by a method based on JIS K6911.

As a method for forming the polyurethane layer 3B, for example, a polyurethane resin containing an inorganic particle and a polymer having a surfactant or a sulfonate as appropriate is applied in advance using a gravure coater, a kiss coater, a bar coater, or the like. The polyurethane layer 3B is laminated and formed on one surface of a transparent polypropylene sheet by drying at 1 for 1 minute.
The thickness of the polyurethane layer 3B after drying is preferably 0.01 μm or more and 3 μm or less, and more preferably 0.08 μm or more and 0.5 μm or less. If the thickness is less than 0.01 μm, sufficient ink adhesion may not be obtained. On the other hand, if the polyurethane layer 3B is thicker than 3 μm, stickiness may occur and cause blocking, which is not preferable.

And the polyurethane layer 3B laminated | stacked on the said conditions is 150 to 900% of tensile breaking elongation, Preferably it is 200 to 850%, Especially preferably, it is 300 to 750%.
When the tensile elongation at break of the polyurethane layer 3B is lower than 150%, the polyurethane layer 3B cannot follow the elongation of the polypropylene layer 3A at the time of thermoforming, cracks occur, and the printed layer 3C cracks or peels off. This is not preferable because it may cause In addition, when the tensile elongation at break exceeds 900%, the water resistance deteriorates, which is not preferable.
The tensile breaking elongation can be measured with a sample having a thickness of 150 μm by a method based on JIS K7311.

The softening temperature of the polyurethane layer 3B is 50 ° C. or higher and 180 ° C. or lower, preferably 90 ° C. or higher and 170 ° C. or lower, and particularly preferably 100 ° C. or higher and 165 ° C. or lower.
If the softening temperature of the polyurethane layer 3B is lower than 50 ° C., the strength of the polyurethane layer 3B is insufficient at room temperature, and the printed layer 3C may be cracked or peeled off, which is not preferable. If the softening temperature is higher than 180 ° C., it cannot be sufficiently softened during thermoforming, and the polyurethane layer 3B is cracked, and the printed layer 3C is cracked or peeled off.
In addition, the softening temperature measured the flow start temperature with a Koka flow tester.

The printing layer 3C is provided adjacent to the polyurethane layer 3B.
As a printing method, a general printing method such as a screen printing method, an offset printing method, a gravure printing method, a roll coating method, or a spray coating method can be used. In addition, a metal vapor deposition made of a vapor deposition film, a laminate of a metal thin film, or the like can be used. In particular, the screen printing method is preferable because the ink film thickness can be increased, and therefore, ink cracking hardly occurs when the ink is formed into a complicated shape.
For example, in the case of screen printing, ink excellent in elongation at the time of molding is preferable, and FM3107 high density white and SIM3207 high density white manufactured by Jujo Chemical Co., Ltd. can be exemplified, but not limited thereto.

And the molded object 1 shape | molded by the predetermined shape is shape | molded by extending | stretching at least one part.
Specifically, the greatly deformed portion is formed in a complicated shape having an elongation of 150% or more, preferably 180% or more and 500% or less, particularly 200% or more and 400% or less. That is, it can be expected that the transparent polypropylene layer 3A is not whitened even if at least a part is formed into a complicated shape with an elongation of 150% or more, and that the printed layer 3C is prevented from cracking or peeling.
Here, when the elongation rate is 150% or less, the deformation amount is small and whitening is not caused even with other materials, and it is not possible to cope with a desired complex shape. In addition, when elongation rate becomes larger than 800%, since there exists a possibility that whitening may arise in 3 A of transparent polypropylene layers, or a crack, peeling, etc. may arise in 3 C of printing layers, it is preferable to set it as 800% or less.
And whitening can be visually evaluated from the outer side of a transparent molded object, for example, coloring the inside of a transparent molded object black with a coating material. When the transparent molded body is whitened, black appears to be whitish, but when it is not whitened, black appears to be clear. Further, the elongation rate can be controlled by conditions at the time of thermoforming such as the heating temperature at the time of thermoforming, the temperature of the mold, and the mold design.

Further, in the greatly elongated portion, the film thickness ratio (B / A) of the thickness dimension B after molding to the thickness dimension A before molding of the polypropylene sheet is 0.8 or less, preferably 0.01 or more. It becomes 0.75 or less, especially 0.05 or more and 0.7 or less. That is, the transparent polypropylene layer 3A may be whitened even if it is molded into a complicated shape with a film thickness ratio (B / A) in which the elongation due to deformation of the non-planar portion is increased to 0.8 or less. In addition, it can be expected to avoid cracks and peeling in the printed layer 3C.
Here, when the film thickness ratio (B / A) is larger than 0.8, the amount of partial deformation is small, and whitening does not occur even with other materials, and the desired complex shape cannot be accommodated. If the film thickness ratio (B / A) is smaller than 0.01, the transparent polypropylene layer 3A may be whitened or the printed layer 3C may be cracked or peeled. It is preferable that
The film thickness ratio can be controlled by, for example, conditions during thermoforming or mold design.

And the molded object 1 shape | molded by the non-planar shape has a surface area ratio (Y / X) which is a ratio of the size of the surface area Y after molding to the surface area X before molding of the polypropylene sheet, being 1.5 or more and 10 or less, Preferably they are 1.7 or more and 5 or less, especially 2 or more and 4 or less. That is, the transparent polypropylene layer 3A may be whitened even if it is molded into a complicated shape having a surface area ratio (Y / X) of 1.5 to 10 in which the deformation amount of the part that is formed into a non-planar shape increases. In addition, it can be expected to avoid cracks and peeling in the printed layer 3C.
Here, in molding with a surface area ratio smaller than 1.5, the amount of partial deformation is small, and whitening does not occur even with other materials, and the desired complex shape cannot be accommodated. On the other hand, when the surface area ratio is greater than 5, the transparent polypropylene layer 3A may be whitened, or the printed layer 3C may be cracked or peeled off.
For example, in the case of a cube or a rectangular parallelepiped, the surface area can be calculated from the depth of the molded product and the measured value of each side with a caliper. In the case of a molded product that is difficult to calculate from a measured value such as a curve, it can be measured by a 3D scanner such as a non-contact 3D digitizer. Further, the surface area ratio can be controlled by, for example, conditions during thermoforming or mold design.

[Manufacture of molded products]
Below, the operation | movement which shape | molds the said molded object is demonstrated.
The forming apparatus shown in FIG. 3 can be used for forming a transparent polypropylene sheet forming the formed body 1.
The manufacturing apparatus includes an extruder T die 12, a first cooling roll 13, a second cooling roll 14, a third cooling roll 15 and a fourth cooling roll 16, a metal endless belt 17, and a cooling water spray nozzle 18. The water tank 19, the water absorption roll 20, and the peeling roll 21 are provided.

The 1st cooling roll 13, the 2nd cooling roll 14, and the 3rd cooling roll 15 are metal rolls, and cooling means (illustration omitted), such as a water cooling type, is incorporated in the inside in order to enable surface temperature adjustment. Has been.
Here, the surfaces of the first and second cooling rolls 13 and 14 are covered with an elastic material 22 made of nitrile-butadiene rubber (NBR). The elastic material 22 has a hardness (measured by a method according to JIS K6301A) of 60 degrees or less and a thickness of 10 mm.
Note that at least one of the first, second, and third cooling rolls 13, 14, and 15 has a rotation shaft connected to a rotation driving unit (not shown).

The fourth cooling roll 16 is a metal roll having a mirror surface with a surface roughness of 1.0 S or less, and a cooling means (not shown) such as a water cooling type for enabling temperature adjustment of the surface is provided in the fourth cooling roll 16. Built in. Here, when the surface roughness is larger than 1.0 S, the glossiness of the obtained polypropylene sheet 11 becomes low and the sheet becomes low in transparency.
The fourth cooling roll 16 is disposed so that the extruded polypropylene sheet is sandwiched between the first cooling roll 13 via a metal endless belt 17.
The metal endless belt 17 is made of stainless steel or the like, and has a mirror surface with a surface roughness of 1.0 S or less. This metal endless belt 17 is rotatably wound around the first to third cooling rolls 13 to 15 described above.

The cooling water spray nozzle 18 is provided on the lower surface side of the fourth cooling roll 16, and the cooling water spray nozzle 18 sprays cooling water on the back surface of the metal endless belt 17. As a result, the metal endless belt 17 is rapidly cooled, and the polypropylene sheet immediately after being pressed by the first and fourth cooling rolls 13 and 16 is also rapidly cooled.
Further, the water tank 19 is formed in a box shape having an upper surface opened, and is provided so as to cover the entire lower surface of the fourth cooling roll 16. The water tank 19 collects the sprayed cooling water and discharges the collected water from a drain port 19A formed on the lower surface of the water tank 19.

The water absorption roll 20 is installed on the side surface of the fourth cooling roll 16 on the second cooling roll 14 side so as to be in contact with the metal endless belt 17, and excess cooling water attached to the back surface of the metal endless belt 17. It acts to remove.
The peeling roll 21 is disposed so that the polypropylene sheet 11 is guided and pressed against the metal endless belt 17 and the second cooling roll 14, and the polypropylene sheet 11 after cooling is peeled from the metal endless belt 17. .

The manufacturing method of the transparent polypropylene sheet 11 by rapid cooling using the manufacturing apparatus comprised as mentioned above is demonstrated.
First, the surface temperature of the metal endless belt 17 and the fourth cooling roll 16 that directly contacts and cools the extruded molten resin is maintained at a dew point of 50 ° C. or less, preferably 30 ° C. or less. Temperature control of each cooling roll 13, 14, 15, 16 is performed in advance.

  Here, if the surface temperature of the fourth cooling roll 16 and the metal endless belt 17 is equal to or lower than the dew point, condensation may occur on the surface, and uniform film formation may be difficult. On the other hand, when the surface temperature is higher than 50 ° C., the resulting polypropylene sheet 11 becomes less transparent and has more α crystals, which may be difficult to thermoform. Therefore, in this embodiment, the surface temperature is set to 14 ° C.

Next, the molten resin (excluding the nucleating agent) extruded from the T die 12 of the extruder is sandwiched between the metal endless belt 17 and the fourth cooling roll 16 on the first cooling roll 13. In this state, the molten resin is pressed by the first and fourth cooling rolls 13 and 16 and rapidly cooled at 14 ° C.
At this time, the elastic material 22 is compressed and elastically deformed by the pressing force between the first cooling roll 13 and the fourth cooling roll 16.
In the portion where the elastic material 22 is elastically deformed, that is, in the arc portion corresponding to the center angle θ1 of the first cooling roll 13, the rapidly cooled polypropylene sheet 11 is pressed in a planar manner by the cooling rolls 13 and 16. . The surface pressure at this time is 0.1 MPa or more and 20 MPa or less.

The polypropylene sheet 11 that is press-contacted as described above and is sandwiched between the fourth cooling roll 16 and the metal endless belt 17 is then connected to the metal endless belt at an arc portion corresponding to the substantially lower half circumference of the fourth cooling roll 16. The sheet 17 is sandwiched between the first cooling roller 17 and the fourth cooling roll 16, and is further rapidly cooled by spraying cooling water onto the back side of the metal endless belt 17 by the cooling water spray nozzle 18. The surface pressure at this time is 0.01 MPa or more and 0.5 MPa or less, and the temperature of the cooling water is 8 ° C.
The sprayed cooling water is collected in the water tank 19 and the collected water is discharged from the drain outlet 19A.

After the sheet pressure contact and cooling by the fourth cooling roll 16 as described above, the polypropylene sheet 11 that is in close contact with the metal endless belt 17 is moved onto the second cooling roll 14 as the metal endless belt 17 rotates. . Here, the polypropylene sheet 11 guided by the peeling roll 21 and pressed to the second cooling roll 14 side is faced by the metal endless belt 17 at the arc portion corresponding to the substantially upper half circumference of the second cooling roll 14 as described above. It is pressure-welded and cooled again at a temperature of 30 ° C. or lower.
The surface pressure at this time is 0.01 MPa or more and 0.5 MPa or less.
In addition, the water adhering to the back surface of the metal endless belt 17 is removed by the water absorption roll 20 provided during the movement from the fourth cooling roll 16 to the second cooling roll 14.

The polypropylene sheet 11 cooled on the second cooling roll 14 is peeled off from the metal endless belt 17 by a peeling roll 21 and wound up at a predetermined speed by a winding roll (not shown). The transparent polypropylene sheet 11 thus produced has an average spherulite radius of 4 μm or less, an average spherulite number of the sheet cross section of 600 / mm ² or less, a solid density of 0.896 g / cm ³ or less, and differential scanning. The maximum endothermic peak melting enthalpy ΔH of the thermal analysis (DSC) curve is less than 90 J / g, the gloss on at least one side is 90% or more, and the exothermic peak is 1 J / g or more on the low temperature side of the maximum endothermic peak, and the thickness The thickness is 50 μm or more.

The produced transparent polypropylene sheet 11 is made of, for example, a polyurethane resin containing inorganic particles in advance and further containing a surfactant or a polymer having a sulfonate as appropriate, using a gravure coater, kiss coater, bar coater or the like. The polyurethane layer 3B is laminated on one surface of the polypropylene sheet 11 by applying and drying at 80 ° C. for 1 minute.
The thickness of the polyurethane layer 3B after drying is preferably 0.01 μm or more and 3 μm or less, and more preferably 0.08 μm or more and 0.5 μm or less. If the thickness is less than 0.01 μm, sufficient ink adhesion may not be obtained. On the other hand, if the polyurethane layer 3B is thicker than 3 μm, stickiness may occur and cause blocking, which is not preferable.

  Further, in the case of screen printing, FM3107 high density white is printed with a T-250 mesh (polyester mesh) plate at a predetermined position on the surface opposite to the polypropylene sheet 11 in the polyurethane layer 3B. By drying for a minute, the printing layer 3C is laminated and a resin sheet is formed.

  Thereafter, the resin sheet is thermoformed into a predetermined shape by, for example, heating the sheet to a surface temperature of 145 ° C. with an infrared heater, pressing the mold against vacuum and compressed air, and cooling the molded sheet 1. Is manufactured.

  And the manufactured molded object 1 is installed in a predetermined metal mold | die, the molten resin of a base material is injection-molded, and the molded object in which the molded object 1 was provided in a part of surface is insert-molded. Conditions such as the resin temperature, injection pressure, and cooling at the time of injection molding can be appropriately selected according to the size of the molded body 1 and the like, but are usually 180 ° C. or higher and 250 ° C. or lower, and the pressure is 5 MPa or higher and 120 MPa or lower. And cooling at a mold temperature of about 20 ° C. or more and 90 ° C. or less.

[Effect of the embodiment]
According to the embodiment, the polyurethane resin 3A obtained by quenching the molten resin has a tensile elongation at break of 150% or more and 900% or less, a softening temperature of 50 ° C. or more and 180 ° C. or less and containing inorganic particles. The non-planar molded body 1 is molded using a sheet-like laminated body having a laminated structure having the polyurethane layer 3B. That is, by rapid cooling, for example, the average spherulite radius is 4 μm or less, the average number of spherulites in the sheet cross section is 600 / mm ² or less, the solid density is 0.896 g / cm ³ or less, and differential scanning calorimetry (DSC ) The melting end enthalpy ΔH of the maximum endothermic peak of the curve is less than 90 J / g, the gloss of at least one side is 90% or more, and the polypropylene sheet 11 has an exothermic peak of 1 J / g or more on the low temperature side of the maximum endothermic peak. The non-planar molded body 1 is molded using a resin sheet having a laminated structure having a polyurethane layer 3B made of a polyurethane resin having an elongation of 150% to 900% and a softening temperature of 50 ° C to 180 ° C.
For this reason, when winding up and unwinding the obtained sheet-like laminate, it is possible to prevent damage such as wrinkles due to blocking, and it is not necessary to use a release sheet or the like for preventing blocking. Therefore, the cost for using the release sheet can be reduced. Even if the resin sheet is molded into a complicated shape, the elongation at the time of molding is absorbed by the polyurethane layer 3B, and the elongation at the time of molding is hardly transmitted to the printing layer 3C, and the printing layer 3C is cracked or peeled off. Or inconvenience does not occur. Furthermore, even if molded into a complex shape, the polypropylene layer 3A is not whitened, and a molded body 1 having excellent design properties can be obtained, and a design excellent in a molded product having the molded body 1 in part. Sex can be imparted.

In the above embodiment, inorganic particles having a ratio (D / d) of 0.55 or more and 15.0 or less are used.
For this reason, the damage by blocking can be prevented, without impairing the adhesiveness of the printing layer 3C provided in the polyurethane layer 3B.

  Further, in the above embodiment, by adding a surfactant to the polyurethane layer 3B, the surfactant improves the wettability between the surface of the polyurethane layer 3B and the ink, and the ink is repelled, resulting in poor printing. Inconvenience can be prevented, and various inks can be used to improve versatility.

  Further, in the above-described embodiment, the polyurethane layer 3B contains a polymer having a sulfonate, whereby the polyurethane layer 3B is made conductive by the polymer having the sulfonate, and static electricity is charged on the surface of the polyurethane layer 3B. Inconvenience that the ink is repelled and printing failure occurs can be prevented, and various inks can be used to improve versatility.

In the above embodiment, the polyurethane layer 3B is formed from a resin obtained by reacting at least a diisocyanate, a high molecular weight polyol and a chain extender, and the high molecular weight polyol is selected from polyether polyol or polycarbonate polyol.
For this reason, even if the resin sheet is molded into a complicated non-planar shape, it is possible to form a good layer structure following the expansion of the polypropylene layer 3A, and the printing layer 3C is cracked or peeled off. It can prevent and can give the outstanding design property.
In particular, by forming the polyurethane layer 3B with a polyurethane resin, it is possible to prevent inconvenience that the printed layer 3C is cracked or peeled off, and the polyurethane layer 3B can be formed by using an easy method such as coating, The polyurethane layer 3B can be easily formed.

Moreover, in the said embodiment, it is set as the structure which provided the printing layer 3C in the molded object 1. FIG.
For this reason, even if the resin sheet after forming the printing layer 3C by printing on the polyurethane layer 3B is formed in a complicated shape, the printing layer 3C does not peel or crack and is made of the polypropylene sheet 11. The whitening of the polypropylene layer 3A does not occur, and an excellent design can be provided even with a complicated shape.

Moreover, in the said embodiment, the design which was excellent in the exterior goods and interior goods of the wide field | area by making it into the molded object which provided the molded object 1 formed in the complicated shape in which the polypropylene layer 3A was not whitened. Can be provided, and versatility can be improved. In particular, since it has the chemical-resistant polypropylene layer 3A, it can be stably used for a long period of time as an exterior product whose use conditions are severe.
And in the said embodiment, since the molded object which partially provided the molded object 1 by shaping | molding is shape | molded by insert shaping | molding, even if it is the complicated shape exterior product, the outstanding design property can be provided and it can manufacture easily.

[Modification]
Although the best configuration for carrying out the present invention has been disclosed in the above description, the present invention is not limited to this. That is, the present invention has been described primarily with reference to specific embodiments, but with respect to the above-described embodiments without departing from the scope of the technical idea and object of the present invention, the material, quantity, and other details. In this configuration, those skilled in the art can make various modifications.
Accordingly, the description of the materials, layer structures, and the like disclosed above is exemplary for easy understanding of the present invention, and does not limit the present invention. Descriptions with names excluding some or all of the limitations are included in the present invention.

For example, it is not limited to the structure in which the molded body is insert-molded. For example, an in-mold molding method in which a resin sheet is shaped by pressure of an injection molding resin, or a molded product having a complicated shape prepared in advance is covered. Various methods capable of providing the molded body 1 on a part of the substrate, such as a method and a transfer molding method in which the sheet is peeled off after coating to leave only ink, can be used.
Moreover, the molded object 1 is not restricted to the structure provided only in one part of the surface of the molded object, You may provide the some molded object 1. FIG.
And, as a base material, it has been described using insert-moldable thermoplastic resin, for example, by using a photo-curing resin that is cured by light, ultraviolet light, heat, etc., such as UV-curable acrylic resin, or a polymerization initiator, such as epoxy resin. Various materials such as a resin that is cured by polymerization can be used.

In addition, the molded body 1 is obtained by forming a resin sheet by laminating a polyurethane layer 3B and further a printing layer 3C on a transparent polypropylene sheet 11 constituting the polypropylene layer 3A, and molding the resin sheet into a predetermined shape. The molded body obtained by molding the polyurethane sheet 3B and the printing layer 3C on the molded body obtained by molding the polypropylene sheet 11 or molding the resin sheet provided with the polyurethane layer 3B on the polypropylene sheet 11 is not limited thereto. A print layer 3C may be provided.
And, as a method of forming the molded body 1 from the resin sheet, vacuum molding in which the space between the mold and the sheet is evacuated by heating with an infrared heater and along the mold at atmospheric pressure, or a vacuum molding mold is used. You may utilize the vacuum pressure forming method etc. which press with compressed air when aligning. In particular, vacuum / pressure forming is preferable because it can be easily formed into a complicated shape.

And in the said embodiment, although the 4 layer structure in which the three-layer molded object 1 was provided was illustrated as a molded object, the molded object 1 of the two-layer structure in which printing was not performed, or the multilayered structure of four or more layers. It can be set as the molded object 1. That is, for example, the following layer configuration may be used.
(A) Polypropylene layer (polypropylene sheet 11) 3A / polyurethane layer 3B / substrate (B) polypropylene layer 3A / polyurethane layer 3B / print layer 3C / substrate (C) print layer 3C / polyurethane layer 3B / polypropylene layer 3A / Substrate (D) Print layer 3C / Polyurethane layer 3B / Polypropylene layer 3A / Polyurethane layer 3B / Print layer 3C / Substrate (E) Polypropylene layer 3A / Polyurethane layer 3B / Print layer 3C / Polypropylene layer 3A / Substrate (F ) Polypropylene layer 3A / polyurethane layer 3B / printing layer 3C / metal thin film layer / base material and the like.
Here, in the layer configuration of (B), the printed layer 3C is protected by the polypropylene layer 3A located on the surface side, and good design properties by the printed layer 3C can be stably provided for a long period of time. In the configuration of (C), even when the printing layer 3C is weak against heat at the time of insert molding, for example, the printing layer 3C can be formed without being modified by the heat at the time of insert molding. In the layer configuration (D), high design properties can be provided by providing a plurality of printing layers 3C. In the layer configuration of (F), high designability can be provided by providing a metal thin film layer having a reflection characteristic such as an aluminum layer. Furthermore, you may provide another layer in the said layer structure.

Next, the present invention will be described more specifically based on examples.
The present invention is not limited by the following examples and comparative examples.

[Example 1]
As shown below, the polypropylene sheet 11 was manufactured under the following conditions using the manufacturing apparatus shown in FIG.
Extruder diameter: 90mm
T-die 12 width: 800 mm
Polypropylene (PP): Product name Prime Polypro E-103WA Prime Polymer Co., Ltd. (melt flow index 3 g / 10 min, homopolypropylene)
Take-up speed of the polypropylene sheet 11: 10 m / min
Surface temperature of fourth cooling roll 16 and metal endless belt 17: 14 ° C.
Cooling water temperature: 8 ° C
Cooling water spray rate: 200 liters / min

After subjecting one surface of the obtained polypropylene sheet 11 to corona treatment, the following polyurethane resin material is applied with a bar coater so that the ratio (D / d) is 0.55 (0.55 g / m ² ). And it dried at 80 degreeC for 1 minute, the polyurethane layer 3B was laminated | stacked, and the sheet-like laminated body was obtained. The dry layer thickness of the polyurethane layer 3B was 550 nm.
Polyurethane resin material: polyurethane resin (polyether polyol, trade name: Hydran WLS-202, manufactured by DIC Corporation) 97% by mass + colloidal silica (trade name: Spherica Slurry 300J, JGC Catalysts & Chemicals Co., Ltd., average particle diameter: 300 nm) 3% by mass

[Example 2]
A sheet-like laminate was obtained in the same manner as in Example 1 except that the polyurethane resin material in Example 1 was applied under the condition that the ratio (D / d) was 15.00. The dry layer thickness of the polyurethane layer 3B was 20 nm.

[Example 3]
The polyurethane resin material in Example 1 was the same as in Example 1 except that the polyurethane resin was 90% by mass + colloidal silica 10% by mass, and the ratio (D / d) was 3.00. Thus, a sheet-like laminate was obtained. The dry layer thickness of the polyurethane layer 3B was 100 nm.

[Example 4]
As the colloidal silica of the polyurethane resin material in Example 1, an average particle diameter of 140 nm (trade name Spherica Slurry 140J, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was used, except that the ratio (D / d) was applied under the condition of 1.00. Obtained a sheet-like laminate in the same manner as in Example 1. The dry layer thickness of the polyurethane layer 3B was 140 nm.

[Example 5]
As the polyurethane resin material in Example 1, 96.8% by mass of polyurethane resin + 3% by mass of colloidal silica + 0.2% by mass of surfactant (sodium styrene sulfonate, trade name: Spinomer NaSS Tosoh Organic Chemical Co., Ltd.) A sheet-like laminate was obtained in the same manner as in Example 1 except that the coating was performed under the condition that the ratio (D / d) was 1.07. The dry layer thickness of the polyurethane layer 3B was 280 nm.

[Example 6]
A sheet-like laminate was obtained in the same manner as in Example 5 except that glycerin fatty acid ester (trade name: Poem OL-200, manufactured by Riken Vitamin Co., Ltd.) was used as the surfactant in Example 5. The dry layer thickness of the polyurethane layer 3B was 280 nm.

[Example 7]
As a polyurethane resin material in Example 5, 87% by mass of polyurethane resin + 3% by mass of colloidal silica + 10% by mass of a polymer (polystyrene sulfonate amine trade name Fujistat YE908 manufactured by Fuji Chemical Co., Ltd.) having a sulfonate salt was used. Obtained a sheet-like laminate in the same manner as in Example 5. The dry layer thickness of the polyurethane layer 3B was 280 nm.

[Example 8]
A sheet-like laminate was obtained in the same manner as in Example 7 except that polycarbonate polyol (trade name Hydran WLS-213 manufactured by DIC Corporation) was used as the polyurethane resin in Example 7. The dry layer thickness of the polyurethane layer 3B was 280 nm.

[Example 9]
A sheet-like laminate was obtained in the same manner as in Example 1 except that the application of the polyurethane resin material in Example 1 was performed under the condition that the ratio (D / d) was 0.10. The dry layer thickness of the polyurethane layer 3B was 3000 nm.

[Example 10]
A sheet-like laminate was obtained in the same manner as in Example 1 except that the application of the polyurethane resin material in Example 1 was performed under the condition that the ratio (D / d) was 30.00. The dry layer thickness of the polyurethane layer 3B was 10 nm.

[Example 11]
A sheet-like laminate was obtained in the same manner as in Example 4 except that the application of the polyurethane resin material in Example 4 was performed under the condition that the ratio (D / d) was 0.10. The dry layer thickness of the polyurethane layer 3B was 1400 nm.

[Example 12]
A sheet-like laminate was obtained in the same manner as in Example 7, except that the application of the polyurethane resin material in Example 7 was performed under the condition that the ratio (D / d) was 0.31. The dry layer thickness of the polyurethane layer 3B was 980 nm.

[Comparative Example 1]
As a polyurethane resin material of Example 1, a sheet-like laminate was obtained in the same manner as in Example 1 except that only the polyurethane resin was used without using colloidal silica. The dry layer thickness of the polyurethane layer 3B was 280 nm.

[test]
Thickness, average spherulite radius, number of spherulites per unit cross-sectional area (spherulite density), presence or absence of DSC exothermic peak, melting enthalpy, polypropylene sheet 11 obtained in Examples 1-12 and Comparative Example 1 above , Internal haze, surface gloss, tensile modulus, density (solid density). Moreover, about the obtained sheet-like laminated body, it measured about blocking resistance, antistatic property, and transparency.
In addition, the tensile elasticity modulus of a polypropylene sheet can be measured by the method based on JISK7161.
Moreover, blocking resistance added the load 500g / 12cm < ² > in 50 degreeC, evaluated the blocking property 24 hours later with the following evaluation criteria, and evaluated the blocking resistance with the following evaluation criteria.
Rank 1: 0% blocked area
Rank 2: Blocked area exceeds 0% to 10% or less Rank 3: Blocked area exceeds 10% to 20% or less Rank 4: Blocked area exceeds 20% Further, regarding antistatic properties, surface The specific resistance was measured.
Also, FM3107 high density white made by Jujo Chemical Co., Ltd. is printed on a T-250 mesh (polyester mesh) plate by screen printing, and dried at 60 ° C. for 60 minutes to provide a printing layer 3C. The presence or absence of cracks was visually determined.
○: No peeling or cracking ×: There is peeling or cracking Furthermore, if there is no cracking in the printed layer 3C, a 100 mm square grid peeling test using a cellophane tape is performed, and there is no peeling between the printed layer 3C and the polyurethane layer 3B. Evaluation was performed.
These results are shown in Table 1.

  As shown in Table 1, it was recognized that blocking can be prevented by containing colloidal silica. Moreover, it was recognized that the addition of a surfactant can improve the antistatic property, and the adhesion of the ink is improved.

  The molded article of the present invention can be excellently molded even in a complicated shape, and can be widely used as, for example, an exterior product or an interior product of various articles such as mobile communication terminals, home appliances, and vehicles. It is.

DESCRIPTION OF SYMBOLS 1 ... Molded object which functions also as a laminated body 3A ... Polypropylene layer which is a polypropylene layer (A) 3B ... Polyurethane layer which is a polyurethane layer (B) 3C ... Printing layer

Claims (9)

A polypropylene layer (A) containing a polypropylene resin;
Having a laminated structure including a polyurethane layer (B) containing a polyurethane resin having a tensile elongation at breakage of 150% to 900% and a softening temperature of 50 ° C to 180 ° C,
The polyurethane layer (B) includes inorganic particles. The laminate according to claim 1,
When the average particle diameter of the inorganic particles is D, and the layer thickness dimension of the polyurethane layer is d,
A laminate having a ratio (D / d) of 0.55 or more and 15.0 or less. The laminate according to claim 2, wherein
The laminate (D / d) is 0.55 or more and 1.1 or less. The laminate according to any one of claims 1 to 3, wherein
The polyurethane layer (B) includes a surfactant. The laminate according to any one of claims 1 to 4, wherein
The polyurethane layer (B) includes a polymer having a sulfonate salt. The laminate according to any one of claims 1 to 5, wherein
A laminate, wherein the polyurethane layer (B) is printed on at least a part of a surface opposite to the side on which the polypropylene layer (A) is provided. The laminated body as described in any one of Claim 1- Claim 6 was shape | molded in the non-planar form. The molded object characterized by the above-mentioned. A molded article, wherein the molded body according to claim 7 is provided on a part of a base material by insert molding. A mirror endless belt wound around a plurality of cooling rolls, and a mirror cooling roll, wherein the mirror surface endless belt and the mirror surface cooling roll have a surface temperature maintained between a dew point and 50 ° C. A molten resin containing a polypropylene resin is introduced between and pressed into a mirror-like endless belt by a T-die extruder, pressed into a sheet shape, and the mirror-like endless belt has a temperature lower than the surface temperature of the mirror-endless belt A step of producing a polypropylene sheet by quenching by blowing cooling water at a temperature;
A step of forming a laminate by laminating a polyurethane layer containing a polyurethane resin and inorganic particles having a tensile elongation at breakage of 150% to 900% and a softening temperature of 50 ° C to 180 ° C on the polypropylene sheet;
And a step of providing the laminate on at least a part of the base material by insert molding.

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