CN116265238A - Synthetic resin skin material, method for producing same, and molded article - Google Patents
Synthetic resin skin material, method for producing same, and molded article Download PDFInfo
- Publication number
- CN116265238A CN116265238A CN202211592543.8A CN202211592543A CN116265238A CN 116265238 A CN116265238 A CN 116265238A CN 202211592543 A CN202211592543 A CN 202211592543A CN 116265238 A CN116265238 A CN 116265238A
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- China
- Prior art keywords
- layer
- resin
- skin
- skin material
- synthetic resin
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 9
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- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
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- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
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- 235000014692 zinc oxide Nutrition 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
Landscapes
- Laminated Bodies (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
The present invention provides a synthetic resin skin material, a method for producing the same, and a molded article, wherein the synthetic resin skin material has good processability when being heated and molded by using a mold, and can well maintain a concave-convex pattern formed on the outermost surface even when being laminated with an intermediate layer containing various thermoplastic resins, and can form a molded article with excellent appearance. The synthetic resin skin material of the present invention comprises: a substrate layer comprising a thermoplastic resin; an intermediate layer provided on one surface of the base material layer and containing a thermoplastic resin; and a skin layer provided on the side of the intermediate layer opposite to the base material layer, having a concave-convex pattern on the surface on the side opposite to the intermediate layer side, and containing a polypropylene resin.
Description
Technical Field
The present disclosure relates to a synthetic resin skin material, a method for producing the synthetic resin skin material, and a molded body.
Background
In recent years, synthetic resin skin materials excellent in durability have been used in place of natural leather and fiber sheets in automobile interior and exterior parts (instrument panels, door trim, seats, ceilings, etc.), interior parts of railway vehicles and aircraft (trim panels, seats, ceilings, etc.), furniture, shoes, footwear, bags, interior and exterior parts for building decoration, clothing exterior materials and liners, wall finishing materials, and the like. Such a synthetic resin skin material has a natural leather-like concave-convex pattern, i.e., a grain pattern (grain pattern) on the outermost surface, the grain pattern imparting features to the appearance. For example, with respect to automobile interior products, it is important to impart a high-grade feel to a skin material for interior use as the vehicle is advanced.
As a method for producing an interior part for an automobile using such a skin material, for example, the following method has been carried out: an insert molding method, namely a method of disposing a skin material on the surface of a molding resin material and heating and molding the skin material in a molding die; or a method in which the heated skin material is vacuum-molded and then molded by injection molding from the back side of the skin material into a flowable resin; etc. However, in either method, when the heat-softened skin material is molded, the uneven pattern formed on the surface disappears by heat, and the shape of the molding die is transferred to the skin material surface, that is, the surface on the side that exhibits the appearance by heat molding. Thus, the design of the skin layer is usually expressed in terms of printing or mirror surface. In the case of forming a molded article having a concave-convex pattern on the surface, there are the following problems: it is necessary to use a mold having a concave-convex pattern corresponding to the design.
As a resin film which does not deteriorate the design even when subjected to thermoforming, there is proposed a matt acrylic resin film for thermoforming comprising: an acrylic resin film substrate; and a matting layer provided as an outermost layer on one surface of the acrylic resin film substrate, the matting layer containing a matting agent, an organosilicon compound and/or a fluorine-containing compound, and a curable binder resin (for example, refer to japanese patent application laid-open No. 2007-283665).
There has also been proposed a synthetic resin skin material comprising a base layer comprising a thermoplastic resin, an intermediate layer comprising a polyvinyl chloride resin, and a skin layer comprising a fluororesin and having a rugged pattern on the surface, which has good workability even when heat molding is performed, and which can form a molded article excellent in appearance while maintaining the rugged pattern formed on the outermost surface well (for example, refer to japanese patent application laid-open No. 2019-177499).
Disclosure of Invention
Problems to be solved by the invention
However, in the technique described in japanese patent application laid-open No. 2007-283665, when a molding resin material having a surface provided with a skin material is heat-molded, the shape of a fine uneven pattern of a degree useful for extinction can be maintained, but when a complex and deep uneven pattern is provided, the uneven pattern formed on the outermost surface of the skin material may be deformed or lost due to the influence of heat, pressure, or the like.
The synthetic resin skin material described in japanese patent application laid-open publication No. 2019-177499 has a skin layer containing a fluororesin, and has a problem that the fluororesin is expensive, although the stain resistance is excellent. Further, according to the studies of the present inventors, it has been found that when an intermediate layer containing a thermoplastic resin other than polyvinyl chloride is laminated with a skin layer containing a fluororesin, the shape maintenance effect of the uneven pattern of the skin layer may be reduced, and there is room for improvement in terms of versatility in selecting a resin to be used.
An object of an embodiment of the present invention is to provide a synthetic resin skin material which has good workability when heat-molded using a mold, and which can form a molded article excellent in appearance by maintaining a concave-convex pattern formed on the outermost surface even when laminated with an intermediate layer containing various thermoplastic resins, and a method for producing the same.
Another object of another embodiment of the present invention is to provide a molded article having a good appearance, in which a concave-convex pattern on a skin layer of a synthetic resin skin material is maintained even after heat molding.
Means for solving the problems
Means for solving the problems include the following embodiments.
<1> a synthetic resin skin material comprising: a substrate layer comprising a thermoplastic resin; an intermediate layer provided on one surface of the base material layer and containing a thermoplastic resin; and a skin layer provided on the opposite side of the intermediate layer from the base material layer, having a concave-convex pattern on the surface on the opposite side of the intermediate layer, and containing a polypropylene resin.
<2> the synthetic resin skin material according to <1>, wherein the thermoplastic resin contained in the intermediate layer contains at least one selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, acrylic resin, polyurethane resin and vinyl chloride resin.
<3> the synthetic resin skin material according to <1> or <2>, wherein the base material layer comprises at least one selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polycarbonate resin and vinyl chloride resin.
<4> the synthetic resin skin material according to any one of <1> to <3>, wherein a design layer is further provided between the intermediate layer and the skin layer.
<5> the synthetic resin skin material according to <4>, wherein the design layer is a printing ink layer containing at least one selected from the group consisting of acrylic resins, polyurethane resins, polyolefin resins, polyamide resins and vinyl chloride-vinyl acetate copolymers.
<6> the synthetic resin skin material according to any one of <1> to <5>, wherein a surface treatment layer is further provided on a surface of the skin layer on the side having the uneven pattern.
<7> the synthetic resin skin material according to <6>, wherein the surface treatment layer contains at least one selected from the group consisting of acrylic resins, polyurethane resins, polyolefin resins, polyamide resins, silicone resins, and vinyl chloride-vinyl acetate copolymers.
<8> the synthetic resin skin material according to any one of <1> to <7>, which is a skin material of a heat-molded processed product.
<9> a method for producing a synthetic resin skin material, comprising the steps of: a step of preparing a skin layer containing a polypropylene resin; a step of forming an intermediate layer using a resin composition containing a thermoplastic resin; a step of forming a base material layer using a thermoplastic resin composition containing a thermoplastic resin; a step of sequentially laminating the skin layer, the intermediate layer, and the base material layer to obtain a laminate; and
and a step of forming a concave-convex pattern on a surface of the skin layer opposite to the intermediate layer side by performing a lamination embossing process on the skin layer side of the obtained laminate by using a roll.
<10> the method for producing a synthetic resin skin material according to <9>, further comprising a step of forming a design layer between the skin layer and the intermediate layer.
<11> the method for producing a synthetic resin skin material according to <9> or <10>, further comprising a step of forming a surface treatment layer on a surface of the skin layer on the side having the uneven pattern.
<12> a molded article comprising a molding substrate and the synthetic resin skin material according to any one of <1> to <8> disposed on the surface of the molding substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to one embodiment of the present invention, a synthetic resin skin material having good workability when heat molding is performed using a mold, and also capable of maintaining a concave-convex pattern formed on the outermost surface well even when laminated with an intermediate layer containing various thermoplastic resins, and a method for producing the same can be provided, and a molded article having excellent appearance can be formed.
Further, according to another embodiment of the present invention, a molded article having a good appearance and maintaining a concave-convex pattern on a skin layer of a synthetic resin skin material even after heat molding can be provided.
Drawings
Fig. 1 is a schematic cross-sectional view showing one embodiment of the synthetic resin skin material of the present disclosure.
Fig. 2 is a schematic cross-sectional view showing one embodiment of a synthetic resin skin material further having a design layer.
Detailed Description
The synthetic resin skin material, the method for producing the synthetic resin skin material, and the molded article of the present disclosure are described in detail below.
In the following description of the constituent elements, the description is made based on the representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments.
In the present disclosure, "to" indicating a numerical range is used in a meaning including numerical values described before and after the "to" as a lower limit value and an upper limit value.
In the present disclosure, in the numerical ranges described in the sections, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in the other sections. In addition, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the embodiment.
In the present disclosure, a combination of preferred modes is a more preferred mode.
In the present disclosure, when there are a plurality of substances corresponding to each component in the composition, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition unless specifically stated.
In the present disclosure, the term "process" includes not only an independent process but also a process that is not clearly distinguishable from other processes, as long as the intended purpose of the process can be achieved.
The "layer containing a resin" in the present disclosure means "a layer formed containing a resin as a main component of the layer". That is, the "resin-containing layer" in the present disclosure is used in a meaning including both: a resin layer containing only a resin, and a layer formed of a resin composition (the resin composition further contains optional components such as a plasticizer, a colorant, and an ultraviolet absorber in addition to a resin as a main component).
In the present disclosure, "resin as a main component" means that the resin is contained in an amount of 60 mass% or more relative to the total amount of the resin composition containing the component.
Hereinafter, in the present disclosure, a polypropylene resin is sometimes abbreviated as PP resin, an acrylonitrile-butadiene-styrene copolymer is sometimes abbreviated as ABS resin, and a polyvinyl chloride resin is sometimes abbreviated as PVC resin.
< synthetic resin skin Material >
The synthetic resin skin material of the present disclosure comprises: a substrate layer comprising a thermoplastic resin; an intermediate layer provided on one surface of the base material layer and containing a thermoplastic resin; and a skin layer provided on the side of the intermediate layer opposite to the base material layer, having a concave-convex pattern on the surface on the side opposite to the intermediate layer side, and comprising a polypropylene resin.
The synthetic resin skin material of the present disclosure will be described with reference to fig. 1. Fig. 1 is a schematic cross-sectional view showing one embodiment of the layer composition of the synthetic resin skin material 10 of the present disclosure.
The synthetic resin skin material (hereinafter sometimes appropriately referred to as skin material) 10 is provided with, in order: a base material layer (hereinafter, appropriately referred to as a base material layer) 12 containing a thermoplastic resin; an intermediate layer (hereinafter sometimes referred to as an intermediate layer as appropriate) 14 comprising a thermoplastic resin provided on one face of the base material layer; and a skin layer (hereinafter, appropriately referred to as a specific skin layer) 16 having a concave-convex pattern on a surface on the opposite side from the intermediate layer 14 side and containing PP resin.
That is, one embodiment of the synthetic resin skin material 10 shown in fig. 1 has a laminated structure including a base material layer 12, an intermediate layer 14, and a specific skin layer 16 in this order, and has a concave-convex pattern such as a texture pattern on a surface of the specific skin layer 16 on a side opposite to a side where the intermediate layer 14 is in contact. When the synthetic resin skin material 10 is arranged on a molding base material described later to form a molded article, the side of the specific skin layer 16 having the concave-convex pattern is located on the outermost surface of the molded article, and therefore, the side of the specific skin layer 16 having the concave-convex pattern is sometimes referred to as a "surface" hereinafter.
Fig. 2 is a schematic cross-sectional view illustrating another manner of skin material of the present disclosure.
The synthetic resin skin material 20 shown in fig. 2 further includes a design layer 18 provided as needed between the intermediate layer 14 and the specific skin layer 16 in fig. 1. The specific skin layer 16 is located on the surface of the design layer 18 opposite to the surface facing the intermediate layer 14, and has a concave-convex pattern on the surface opposite to the surface of the design layer 18.
That is, the synthetic resin skin material 10 and the synthetic resin skin material 20 shown in fig. 1 and 2 have a concave-convex pattern on the surface of the specific skin layer 16.
The shape of the concave-convex pattern is appropriately selected according to the purpose of use of the skin material. Various modifications of geometric patterns, etc. can generally be chosen. The concave-convex pattern on the surface of the specific skin layer 16 is a pattern that characterizes the appearance of the surface of the molded article based on the skin material.
As described later, the skin material of the present disclosure can be suitably used as a skin material of a molded body formed by insert molding or the like.
The synthetic resin skin material of the present disclosure has, as a skin layer, a layer having a concave-convex pattern on one surface and containing a PP resin having good heat resistance, the concave-convex pattern formed on one surface of the skin layer being less likely to be deformed by heating, and the thermoplastic resin usable for the intermediate layer (provided on the side opposite to the side having the concave-convex pattern of the skin layer) has a high degree of freedom in selection.
Further, it is considered that, when the synthetic resin skin material of the present disclosure is placed in a mold and molten resin is injected into the mold by lamination with the intermediate layer containing a thermoplastic resin, or when the synthetic resin skin material of the present disclosure is laminated on the surface of a molding substrate and molded by the mold, the intermediate layer which is easily deformed by heating at the time of heat molding can alleviate the influence of the thermal stress of the skin layer, and therefore the deformation of the concave-convex pattern formed on the surface of the skin layer can be effectively suppressed without impairing the heat moldability of the synthetic resin skin material.
Therefore, by using the synthetic resin skin material of the present disclosure, even after the insert molding or the like is performed by the heat molding, the maintenance rate of the concave-convex pattern (for example, the texture pattern) formed on the surface of the skin layer is high, and therefore, the concave-convex pattern can be imparted to the skin layer independently of the formation of the molded body by the heat molding, and there is an advantage that the molded body having various concave-convex patterns on the surface can be produced without changing the molding die.
Furthermore, a design layer may be provided between the skin layer and the intermediate layer. The design layer to be provided as needed is not particularly limited, and thus a desired design can be formed, and the uneven pattern on the surface of the skin layer can be maintained even after the heat molding, so that the obtained molded article has a high degree of freedom in design and good design.
In the synthetic resin skin material of the present disclosure, the heat moldability such as insert molding is good, and the surface of the molded body obtained after the heat molding can favorably maintain the uneven pattern in the synthetic resin skin material. Therefore, the synthetic resin skin material of the present disclosure is excellent in design and good in hot workability, and thus can be suitably used in various applications such as a vehicle interior material obtained by laminating with a molding base material and performing thermoforming.
The skin material of the present disclosure, the material constituting the same, and the method of manufacturing the same are described in order below.
(1. Epidermis layer)
The skin layer of the skin material of the present disclosure contains PP resin. By containing the PP resin in the skin layer, the skin layer is excellent in durability and chemical resistance.
Further, since the heat resistance is good, it is considered that the concave-convex pattern retention is also good when the skin material is brought into contact with the resin molded body and the resin molded body is heated and molded.
The PP resin usable for the skin layer is not particularly limited as long as it is a PP resin obtained by polymerizing a propylene monomer as a polymerization component. Any of homopolymer, random copolymer, block copolymer is included in the PP resin in the present disclosure.
For example, a general-purpose PP resin (PP resin having crystalline isotactic PP as a main component) or the like can be used for the skin layer.
The skin layer may contain a copolymer containing monomers such as ethylene and 1-butene in addition to propylene, in addition to the PP resin, which is a homopolymer synthesized from only propylene monomers.
When the skin layer contains 2 or more PP resins, a combination of the PP resins (homopolymers) and a mixture of PP resins and PP copolymer resins containing a copolymerization component other than propylene may be used.
The skin layer may contain a resin other than the PP resin, and the content of the PP resin in the entire resin component in the skin layer is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass or more. Examples of the resin other than PP resin that can be contained in the skin layer include polyethylene resin, olefin resin other than PP resin, and the like.
In the skin layer, the PP resin may be contained in 1 kind, or may be contained in 2 or more kinds. Examples of the PP resins of 2 or more types include PP resins having different crystallinity and PP resins having different polymerization degrees.
In the case where the skin layer contains 2 or more resins, as described above, a laminate structure of 2 or more resins may be adopted in addition to a mixture of 2 or more PP resins.
For example, the outermost surface (i.e., the surface contacting the outside when the synthetic resin skin material is disposed on the molded article) may be a layer containing a PP resin, and in order to further improve the adhesion between the skin layer and the intermediate layer or the design layer provided as needed, the skin layer may have a 2-layer structure of a layer containing a PP resin and a layer containing an olefin resin other than the PP resin (also referred to as another olefin resin), for example, and the layer side containing another olefin resin may be positioned on the surface contacting the intermediate layer or the design layer.
The skin layer may be formed of PP resin, or a commercially available film may be used.
The method for forming the skin layer is not particularly limited, and a known sheet molding method can be applied. As a method for forming the skin layer, for example, extrusion, calendaring, casting, or the like can be applied.
The thickness of the skin layer is preferably in the range of 5 μm to 200 μm, more preferably in the range of 30 μm to 150 μm, from the viewpoints of durability and uneven pattern retention.
Here, the thickness of the skin layer refers to the thickness of the area of the skin layer where the concave-convex pattern is not formed.
The thickness of the skin layer and the thickness of each layer to be described later in the synthetic resin skin material can be measured by cutting the synthetic resin skin material perpendicularly to the surface direction and observing the obtained cross section. Thus, the film thickness of each layer in the synthetic resin skin material in the present disclosure refers to the film thickness after drying.
The skin layer in the skin material of the present disclosure has a concave-convex pattern on one face. The concave-convex pattern in the present disclosure means that at least a part of the skin layer has regions with different thicknesses. The concave-convex pattern is not particularly limited, and the arrangement position, depth, and the like of the concave-convex can be arbitrarily selected. Examples of the concave-convex pattern include a geometrically regular pattern, a natural leather-like irregular pattern called "grain (texture), and the like, and are not particularly limited.
The depth of the concave portion of the concave-convex pattern formed on the surface of the skin layer can be appropriately selected according to the target design of the skin material. In general, the depth of the concave portion is preferably in the range of 5 μm to 150 μm from the viewpoint of design of the skin material.
In view of the retainability of the concave-convex pattern formed on the opposite side of the intermediate layer or the surface on the design layer side described later, which is provided as needed, in the skin material of the present disclosure, the thickness of the skin layer is preferably greater than the distance between the bottom of the deepest portion of the concave-convex pattern and the top of the convex portion.
For example, when forming a concave-convex pattern having a depth of the concave portion of 1 μm or less, the thickness of the skin layer may be set to about 5 μm, and when having a shallow concave portion and a deep concave portion, as in a natural leather-like pattern, the thickness of the skin layer is preferably 10 μm or more.
The method of forming the concave-convex pattern on the surface of the skin layer opposite to the surface of the intermediate layer is not particularly limited, and a known method can be applied. As a known method, there may be mentioned: a method of forming a skin layer on a release paper having a concave-convex pattern; a method in which a skin layer having a smooth surface is first formed, and then a roll having a concave-convex pattern is brought into contact with the surface side of the skin layer to perform lamination embossing, thereby forming a concave-convex pattern in the skin layer; etc.
The surface layer is formed on the surface of the intermediate layer or the design layer, which is provided as needed, on the side opposite to the surface on the substrate layer side. For example, the skin layer formed in advance may be bonded to the intermediate layer or the design layer provided as needed, and after the skin layer is formed, the intermediate layer or the design layer provided as needed may be formed on one surface of the skin layer by a method described later.
(2. Intermediate layer)
The skin material of the present disclosure has an intermediate layer on the surface of the skin layer having no concave-convex pattern. The intermediate layer contains a thermoplastic resin.
The thermoplastic resin contained in the intermediate layer may be appropriately selected from known thermoplastic resins in consideration of the purpose of use of the skin material of the present disclosure, the shape of a molded article formed by including the skin material of the present disclosure, the purpose of use, design, and the like.
Examples of the thermoplastic resin that can be contained in the intermediate layer include acrylic resins such AS ABS resins, AS resins, and PMMA, polyurethane resins, polyvinyl acetate (PVAc), PC, and PVC resins. Among them, from the viewpoint of the concave-convex pattern retention of the skin layer, at least one selected from the group consisting of an acrylic resin such as ABS resin and PMMA, a polyurethane resin, and a PVC resin is preferably included.
The intermediate layer may contain only 1 kind of thermoplastic resin, or may contain 2 or more kinds.
The content of the thermoplastic resin in the intermediate layer may be in the range of 50 to 100 mass%, preferably 60 to 95 mass%.
The intermediate layer may contain other components such as a known additive, if necessary, in addition to the thermoplastic resin.
Examples of other components that may be contained in the intermediate layer include colorants, processing aids, plasticizers, fillers, lubricants, and the like. When the intermediate layer contains other components than the thermoplastic resin, the content of the other components is preferably used in a range that does not reduce the hot workability of the intermediate layer.
-other ingredients: coloring agent-
The intermediate layer may comprise a colorant. When the intermediate layer contains a colorant, in the case of producing a molded article using the skin material of the present disclosure, the influence of the molding base material used on the appearance of the molded article can be suppressed, and the depth can be imparted to the synthetic resin skin material and further to the color tone of the molded article in which the synthetic resin skin material is disposed.
In the case where the intermediate layer contains a colorant, the colorant is not particularly limited, and a dye, a pigment, or the like may be appropriately selected and used.
Examples of the coloring agent include inorganic pigments such as titanium white (titanium dioxide), zinc white, ultramarine, cobalt blue, iron oxide red, vermilion, chrome yellow, titanium yellow, and carbon black; organic pigments or dyes such as quinacridone, permanent red 4R, isoindolinone, hansa yellow a, phthalocyanine blue, indanthrene blue RS, nigrosine; a metal pigment selected from the group consisting of foil powders of metals such as aluminum and brass; pearl luster (pearlescent) pigments selected from the group consisting of titanium dioxide coated mica and foil powders of basic lead carbonate, and the like. Among them, pigments which are colorants excellent in weather resistance and durability are preferable.
When the intermediate layer contains a colorant, it may contain only 1 colorant, or may contain 2 or more colorants for the purpose of color matching or the like.
The content of the colorant in the resin composition used for forming the intermediate layer is not particularly limited, and the type, content, and the like of the colorant used may be appropriately selected according to the target color tone in the skin material, the shielding property of the molding substrate, and the like.
The content of the colorant is preferably 50 mass% or less relative to the total solid content of the resin composition used for forming the intermediate layer, from the viewpoint of uniformity of the layer. The solid component herein refers to the total amount of components other than the solvent among the total components of the resin composition constituting each layer such as the intermediate layer.
The thickness of the intermediate layer is preferably in the range of 30 μm to 300 μm, more preferably in the range of 50 μm to 200 μm. When the thickness is in the above range, thermal stress of the skin layer can be relaxed and the concave-convex pattern can be kept more excellent when the synthetic resin skin material is heated to form a molded article.
The method for forming the intermediate layer is not particularly limited, and a known sheet molding method can be applied. As a method for forming the intermediate layer, for example, an extrusion method, a rolling method, a casting method, or the like by extrusion molding using a T die or the like can be applied.
Among them, the rolling method is preferable in terms of ease of production and easiness of maintenance of the apparatus. Particularly, when the intermediate layer contains a colorant, the softened resin and the solid colorant can be supplied to the calender roll and molded into a sheet or film, and thus the intermediate layer containing various colorants can be easily produced.
Further, by applying the rolling method, cleaning in the apparatus required for changing the type and the amount of the colorant to be added can be performed more easily than in the molding method such as the extrusion method. Therefore, by applying the rolling method when forming the colorant-containing material as the intermediate layer, various base material layers having a desired color tone can be easily produced, and the method is also suitable for small-lot production of synthetic resin skin materials.
(3. Substrate layer)
The skin material of the present disclosure has a base material layer on the opposite side of the intermediate layer from the skin layer side.
The substrate layer comprises a thermoplastic resin. The thermoplastic resin that can be used in the base layer is not particularly limited, and can be appropriately selected from known thermoplastic resins in consideration of various conditions such as affinity with the resin that is used to form the molded article and stretchability at the time of molding.
Examples of the thermoplastic resin that can be used for the base layer include Polyethylene (PE), PP resin, PVC resin, polystyrene (PS), polyvinyl acetate (PVAc), polyurethane (polyurethane resin), ABS resin, acrylonitrile-styrene copolymer (AS resin), polycarbonate (PC), polymethyl methacrylate (PMMA), and the like.
Among them, from the viewpoint of processability, the base material layer is preferably an acrylic resin such AS PMMA, PE, PP resin, PVC resin, PS, PVAc, polyurethane resin, ABS resin, AS resin, PC, or the like, and from the viewpoint of effectively suppressing breakage of the synthetic resin skin material disposed on the surface of the base material due to melting at the time of thermoforming, the thermoplastic resin contained in the base material layer is more preferably an ABS resin, AS resin, PC, PVC resin, PC/ABS, or the like.
The base material layer may contain only 1 kind of thermoplastic resin, or may contain 2 or more kinds.
The content of the thermoplastic resin in the base material layer may be in the range of 70 to 100 mass%, preferably 60 to 95 mass%.
The base material layer may contain various components other than the thermoplastic resin, in addition to the thermoplastic resin. Examples of the other component that may be contained in the base layer include a colorant, a processing aid, a plasticizer, a filler, and a lubricant.
-other ingredients: coloring agent-
Wherein the substrate layer preferably comprises a colorant. When the base material layer contains a colorant, it is possible to suppress the influence of the molding base material on the appearance of the molded article in the case of producing the molded article by disposing the synthetic resin skin material on the surface of the resin constituting the molding base material.
The colorant that can be used in the base material layer is the same as that can be used in the intermediate layer, and a desired color tone may be selected according to the purpose. In the case where a colorant is used for the base material layer, the preferable content of the colorant may be appropriately selected depending on the purpose of the skin material.
In the case where the base layer contains a colorant, the colorant is not particularly limited, and a dye, a pigment, or the like can be suitably selected and used.
The colorant that can be used in the base material layer is the same as that can be used in the intermediate layer, and the desired colorant may be selected according to the purpose.
When the base material layer contains a colorant, the base material layer may contain only 1 colorant, or may contain 2 or more types for the purpose of color matching or the like.
Among them, black pigments such as carbon black, nigrosine and perylene black are preferable as the colorant contained in the substrate layer from the viewpoint of effectively shielding the molded substrate.
The content of the colorant in the resin composition used for forming the base material layer is not particularly limited, and the type, content, and the like of the colorant used may be appropriately selected according to the target color tone in the synthetic resin skin material, the shielding property of the molding base material, and the like.
When the base material layer contains a colorant, the content of the colorant is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, relative to the total solid content of the resin composition constituting the base material layer, from the viewpoint of uniformity of the base material layer formed.
The thickness of the base material layer is preferably in the range of 50 μm to 500 μm, more preferably in the range of 100 μm to 400 μm. When the thickness is in the above range, breakage of the synthetic resin skin material due to melting can be effectively suppressed when the synthetic resin skin material is used to form a molded article by thermal processing, and the molded substrate used in the molded article has good shielding properties.
The method for forming the base material layer is not particularly limited, and a known sheet molding method can be applied. As a method for forming the base material layer, the same method as the method for forming the intermediate layer described above, for example, extrusion, calendaring, casting, or the like can be applied.
Among them, in forming the base material layer, the rolling method is preferable in terms of ease of production and ease of maintenance of the device. Particularly, when the base material layer contains a colorant, as described in the method for forming the intermediate layer, the base material layer containing various colorants can be easily produced.
By applying the rolling method to the formation of the base material layer in the same manner as the formation of the intermediate layer, various base material layers having a desired color tone can be easily produced, and the method is also suitable for small-lot production of synthetic resin skin materials.
The thickness of each layer in the synthetic resin skin material of the present disclosure is preferably in the range of 5 μm to 200 μm, the thickness of the intermediate layer is preferably in the range of 30 μm to 300 μm, and the thickness of the base material layer is preferably in the range of 50 μm to 500 μm, as described above.
The preferred thickness of the design layer as the optional layer is as described later.
(4. Other layers)
The synthetic resin skin material may further have other layers in addition to the base material layer, the intermediate layer, and the skin layer, as long as the effect is not impaired.
Examples of the other layer include a design layer, a surface treatment layer, an adhesive layer, and an undercoat layer.
(4-1. Design layer)
The synthetic resin skin material may further have a design layer on a surface of the intermediate layer opposite to the base material layer side.
The design layer is a layer for imparting an appearance design to the synthetic resin skin material, and may be a printed layer formed by printing, a colored layer containing a colorant, or a layer in which these layers are combined. Among them, a layer formed of printing ink is preferable as the design layer in terms of the degree of freedom of design.
In the skin material of the present disclosure, the design layer is not particularly limited, and thus, by forming various design layers according to the use of the skin material as needed, a desired appearance with excellent design can be imparted to the molded body.
The design layer may be formed on the surface of the intermediate layer or the skin layer by a printing method, for example. As a printing method for forming the design layer, a method of forming the design layer by a known printing method using a printing ink containing a resin can be mentioned. As the printing ink containing a resin, at least one resin selected from the group consisting of an acrylic resin, a polyurethane resin, a polyolefin resin, a polyamide resin, and a vinyl chloride-vinyl acetate copolymer is preferably contained, and at least one selected from the group consisting of an acrylic resin, a polyurethane resin, and a vinyl chloride-vinyl acetate copolymer is more preferably contained, from the viewpoint of being capable of forming a clear printed image.
The printing method of the design layer is not particularly limited, and any printing method such as Gravure printing (gravureprinting), relief printing, offset printing, inkjet printing, screen printing, etc. may be used, and Gravure printing, screen printing, inkjet printing, etc. are preferably used. The design layer formed by the printing method may be a discontinuous layer including the adhered region of the printing ink, or may be a continuous uniform layer formed of the printing ink.
As another embodiment of the colored layer, a layer formed of a resin composition containing an optional colorant is given. Examples of the colorant include a design layer obtained by molding a resin composition obtained by incorporating a colorant in an acrylic resin into a film shape by a rolling method, an extrusion method, a casting method, or the like, and the colorant is selected from the group consisting of colorants usable in the base layer.
The acrylic resin that can be used for forming the design layer includes, for example, a polymer or copolymer of methacrylic acid or methacrylate represented by PMMA, a copolymer of alkyl methacrylate and alkyl acrylate and styrene, and the like, and a mixture of a copolymer of alkyl methacrylate and alkyl acrylate and styrene, and a copolymer of methyl methacrylate and methyl acrylate is preferable from the viewpoint of moldability.
In the case where the skin material of the present disclosure has a design layer, the thickness of the design layer is preferably in the range of 1 μm to 10 μm, more preferably in the range of 2 μm to 8 μm. When the thickness is in the above range, a desired design can be given to the synthetic resin skin material, and when a molded article is formed by heat processing using the synthetic resin skin material, a good correlation between the skin layer and the intermediate layer can be maintained, and the retainability of the uneven pattern of the skin layer is improved.
The thickness ratio of the skin material layer in forming the design layer is preferably in the range of 1 to 10 when the thickness of the intermediate layer is 100. In this way, the thickness of the design layer is preferably smaller than that of the skin layer, compared with the case where the thickness of the skin layer is in the range of 15 to 55 with respect to the thickness of the intermediate layer of 100.
(4-2. Surface treatment layer)
The skin material of the present disclosure may further have a surface treatment layer. As an example of the embodiment of the surface treatment layer, a surface (surface of the skin layer) provided on one surface of the skin layer and on the opposite side to the intermediate layer side is given.
By further providing the surface treatment layer to the skin material, it is possible to impart an arbitrary good touch to the skin material, and further, to further impart functions such as further improvement in appearance and further improvement in durability.
The surface treatment layer contains at least a resin. The resin that may be contained in the surface-treated layer may be at least one selected from the group consisting of an acrylic resin, a polyurethane resin, a polyolefin resin, a polyamide resin, a silicone resin, and a vinyl chloride-vinyl acetate copolymer, and more preferably at least one selected from the group consisting of a polyurethane resin and an acrylic resin, from the viewpoint of further improving abrasion resistance and touch.
The surface treatment layer may contain only 1 kind of resin, or may contain 2 or more kinds of resins.
The surface-treated layer may contain, in addition to the resin, a crosslinking agent, an organic filler, an inorganic filler (for example, silica particles), a lubricant, a flame retardant, an antioxidant, an antistatic agent, and the like.
For example, in the case where the surface treatment layer is provided for improving the feel of the skin material, organic particles as a filler, a colorant for the purpose of improving the design, and the like may be contained as a feel improving agent, as required.
In addition, for the purpose of further improving the abrasion resistance, a surface treatment layer including a crosslinked structure may be formed. The surface-treated layer containing a crosslinked structure can be formed by imparting a composition for forming a surface-treated layer containing a resin or a resin precursor and a crosslinking agent to the surface layer, and thereafter imparting energy to crosslink the composition.
The surface treatment layer can be formed by applying a surface treatment layer-forming resin composition containing the above resin and optional components used as needed to the surface side of the skin layer by a printing method. The details of the method for producing the surface-treated layer are described later.
The thickness of the surface treatment layer is preferably 1 μm to 30 μm, more preferably 2 μm to 20 μm, from the viewpoint of further improving the strength of the surface of the skin material.
(4-3. Adhesive layer)
The skin material of the present disclosure may include an adhesive layer on a surface of the base material layer opposite to the intermediate layer side, the adhesive layer being for improving adhesion to the molding base material.
The adhesive layer may be formed by applying at least one of a known adhesive and an adhesive to a surface of the base material layer on the opposite side of the intermediate layer side.
The adhesive used for forming the adhesive layer provided on the synthetic resin skin material as needed is not particularly limited, and is appropriately selected according to the type of molding base material. As the adhesive, for example, (1) a two-component curable polyester adhesive, (2) a two-component curable urethane adhesive, and (3) a two-component curable acrylic adhesive are suitably used.
The thickness of the adhesive layer is preferably in the range of 5 μm to 50 μm.
In the case where the adhesive layer is formed on the base material layer, an undercoat layer described in detail below may be formed between the base material layer and the adhesive layer for the purpose of improving the adhesion, and at least one of an adhesive and an adhesive may be applied to the surface of the undercoat layer to be formed, thereby forming the adhesive layer.
As a method for applying the adhesive layer to the base material layer or the undercoat layer, any of known methods such as a transfer method and a coating method can be used. The transfer method is preferably used in view of the ease with which an adhesive layer having a uniform thickness can be formed.
(4-4. Bottom coating)
In the skin material of the present disclosure, when the adhesive layer is further provided adjacent to the base material layer, a resin layer may be further provided as an undercoat layer between the adhesive layer and the base material layer for the purpose of improving adhesion between the base material layer and the resin molded body.
The primer layer may be formed by a coating method. More specifically, the primer layer can be formed by dissolving a resin for forming the primer layer in an appropriate solvent, applying the solution to the surface of the base material layer on the opposite side from the skin layer side, and drying the solution.
The resin contained in the primer layer is preferably formed using a resin such as a polyester resin, in view of good affinity with the thermoplastic resin contained in the base material layer and the adhesive or the like contained in the adhesive layer provided adjacently.
The coating amount of the resin layer is not particularly limited and is appropriately selected according to the purpose. Generally, the adhesion is improvedFrom the viewpoint of effect, it is preferably 1g/m 2 ～5g/m 2 More preferably 2g/m 2 ～3g/m 2 Is not limited in terms of the range of (a).
The skin material of the present disclosure has a skin layer that is excellent in transparency and durability on the outermost surface and has good retention of the uneven pattern when heated, and has an intermediate layer and a base material layer that are excellent in hot workability. Therefore, the surface layer of the skin material of the present disclosure is also good in the retention of the uneven pattern after the thermoforming. Therefore, the molded article can be suitably used as a skin material of a molded article requiring heat molding, and the obtained molded article can reflect the design properties of a synthetic resin skin material, and is excellent in appearance and durability such as solvent resistance.
The skin material of the present disclosure is preferably suitable for a skin material of a thermoformed processed product. That is, the skin material of the present disclosure is applicable to various applications as a synthetic resin skin material imparting design to the surface of a molded body requiring heat processing, that is, as a skin material of a heat molded product.
< method for producing synthetic resin skin Material >
The method for producing the synthetic resin skin material of the present disclosure is not particularly limited, and a known production method can be suitably employed.
Among them, the synthetic resin skin material is preferably produced by the method for producing a synthetic resin skin material of the present disclosure, which is described in detail below.
The method for producing the synthetic resin skin material of the present disclosure comprises the following steps: a step (step A) of preparing a skin layer containing a polypropylene resin; a step (step B) of forming an intermediate layer using a resin composition containing a thermoplastic resin; a step (step C) of forming a base material layer using a thermoplastic resin composition containing a thermoplastic resin; a step (step D) of sequentially laminating the skin layer, the intermediate layer, and the base material layer to obtain a laminate; and a step (step E) of applying a lamination embossing process to the skin layer side of the obtained laminate by using a nip roller, and forming a concave-convex pattern on the surface of the skin layer on the opposite side to the intermediate layer side.
The method for producing a synthetic resin skin material of the present disclosure may further include an optional step such as a step of forming a design layer between the skin layer and the intermediate layer (step F).
(Process A)
In step a, a skin layer containing PP resin is prepared. Preparing the skin layer includes forming a skin layer including a PP resin using a resin composition for forming a skin layer including a PP resin, and providing a film including a PP resin that is commercially available as both the skin layer.
In the case of forming the skin layer using the resin composition for forming the skin layer containing the PP resin, the step a may be a step of forming by a rolling method, an extrusion method, a casting method, or the like.
In the case of forming the skin layer having a laminated structure, the step a may be a step of forming a laminated film as a skin layer by a coextrusion method using 2 or more resins so that at least one layer contains PP resin.
In addition, the step a includes a case of preparing a commercially available film containing PP resin as described in the description of the skin material of the present disclosure, as the skin layer.
The PP resin used for forming the skin layer may be any of the resins described in the column of the skin layer in the skin material.
The thickness of the formed skin layer is preferably 5 μm to 200 μm, more preferably 30 μm to 150 μm.
(Process B)
In step B, first, an intermediate layer containing a thermoplastic resin is formed by a known method such as a rolling method, an extrusion method, or a casting method using a resin composition for forming an intermediate layer containing a thermoplastic resin. Among them, from the viewpoint of workability, the intermediate layer is preferably formed by a rolling method. By forming the intermediate layer by the rolling method, the intermediate layer having a uniform film thickness can be formed more easily than, for example, a melt extrusion method.
The intermediate layer may contain other components such as a colorant and a processing aid, in addition to the thermoplastic resin, depending on the purpose. When the intermediate layer contains a thermoplastic resin and other components used as needed, a resin composition for forming an intermediate layer containing a thermoplastic resin and other components may be prepared and molded into a film shape. When the colorant is contained in the intermediate layer, the layer is formed by applying the rolling method, and thus cleaning in the apparatus required for changing the type and the amount of the colorant used in the intermediate layer can be easily performed.
As an example of a method for forming an intermediate layer using a thermoplastic resin and a pigment as a colorant, a method including the steps of: adding a predetermined amount of pigment to a thermoplastic resin, and mixing by heating with a hot mixing roll to obtain a colored resin composition for forming an intermediate layer; an intermediate layer is formed by a calendaring method using the resulting colored resin composition. The process may be performed in the same manner as described above, except that the pigment charging step is not performed when a colorant is not used.
The thermoplastic resin used in the formation of the intermediate layer may use a thermoplastic resin exemplified as a thermoplastic resin that can be contained in the intermediate layer in the skin material of the present disclosure described above, among which ABS resin, acrylic resin, polyurethane resin, and PVC are preferable.
The thickness of the intermediate layer formed is preferably 30 μm to 300 μm, more preferably 50 μm to 200 μm.
(Process C)
In step C, the base material layer is formed by a known method such as a rolling method, an extrusion method, or a casting method using a resin composition for forming a base material layer containing a thermoplastic resin. Among them, from the viewpoint of processability, the base material layer is preferably formed by a rolling method.
The method for forming the base material layer by the rolling method may be performed in the same manner as the method for forming the intermediate layer using the thermoplastic resin in step B.
In the case where the base material layer contains a colorant, the base material layer may be formed by a method including the following steps as in step B: a predetermined amount of pigment is added to a thermoplastic resin for forming a base material layer, and the mixture is heated and mixed by a hot mixing roll to obtain a colored resin composition for forming a base material layer; the resulting colored resin composition was used to form a base material layer by a calendaring method.
The thermoplastic resin used in the formation of the base material layer may use the thermoplastic resins that can be contained in the base material layer illustrated in the skin material of the present disclosure described above, among which ABS resin, PC resin, and PVC resin are preferable.
The thickness of the base material layer to be formed is preferably 50 μm to 500. Mu.m, more preferably 100 μm to 400. Mu.m.
The steps a, B and C are performed in any order, and each step may be performed independently.
(Process D)
In step D, the skin layer prepared in step a, the intermediate layer formed in step B, and the base material layer formed in step C are laminated in this order to obtain a laminate.
The laminate may be formed by sequentially laminating the intermediate layer and the base material layer on one surface of the skin layer. The layers to be laminated are passed between a pair of rollers, and heated and pressed to form a laminate in which the layers of the skin layer, the intermediate layer and the base material layer are in close contact with each other. The process of forming a laminate in which the layers are closely adhered by passing between a pair of rollers and applying heat and pressure is called lamination process.
(Process E)
In step E, the surface layer side of the laminate obtained in step D, which is adjacent to each other and is in close contact with each other, is subjected to lamination embossing, and a concave-convex pattern is formed on the surface of the surface layer opposite to the intermediate layer side.
The step D and the step E may be performed simultaneously. That is, the intermediate layer and the base material layer may be laminated in this order on one surface of the skin layer, and then the laminate may be subjected to lamination embossing by using a roll, and the layers may be bonded by heating and pressing, and the desired uneven pattern may be formed on the surface of the skin layer.
As described above, the lamination process in the present disclosure refers to lamination of a plurality of resin-containing layers by passing between a pair of rolls for thermal compression bonding and thereby bonding the layers to each other.
In the present disclosure, the embossing process using a roll in the step E means that one of a pair of embossing rolls for performing thermal compression bonding uses a roll, and the surface of the laminate, which is in contact with the roll, and the surface of the skin layer in the skin material of the present disclosure is pressed by the roll, thereby forming a concave-convex pattern on the surface. In the step E, the lamination embossing may be performed with a configuration in which the roll is located on the skin layer side and the smoothing roll is located on the base material layer side. According to this method, lamination of the layers and formation of the uneven pattern in the skin layer can be performed sequentially or simultaneously in one step.
By laminating and embossing the surface of the skin layer using a roll having an arbitrary concave-convex pattern formed thereon, it is possible to bond a plurality of films containing a resin and press the films to one surface of the films containing a resin (formation of concave-convex pattern) in one step, and to transfer an arbitrary designed concave-convex pattern such as a natural leather-like concave-convex pattern to the outermost surface of the skin layer in the synthetic resin skin material formed.
By selecting the shape of the concave-convex pattern formed on the roll, a concave-convex pattern having an arbitrary concave-convex shape can be formed on the surface of the synthetic resin skin material.
The heating temperature in the lamination embossing is preferably a temperature condition in which the surface temperature of the laminate reaches 130 to 200 ℃.
The method of forming the concave-convex pattern on the skin layer is not limited to the step E, and as described above, the following method may be adopted: a layer composed of a resin composition for forming a skin layer is extruded on a release paper on which a concave-convex pattern is formed in advance, and the concave-convex pattern formed on the release paper is transferred to a surface of the resin composition layer for forming a skin layer, which is in contact with the release paper.
The method for producing a skin material of the present disclosure may include optional steps in addition to the steps a, B, C, D, and E described above, as needed.
Examples of the optional step include a step of forming a design layer between the skin layer and the intermediate layer (step F), a step of further forming a surface treatment layer on the surface of the skin layer on the side having the uneven pattern (step G), and the like.
(Process F)
The method for producing a skin material of the present disclosure may include an optional step of further forming a design layer between the skin layer prepared in step a and the intermediate layer formed in step B.
The step F is a step of forming a design layer on one surface of the skin layer prepared in the step a or the intermediate layer formed in the step B.
Examples of the method for forming the design layer include the following methods: a method of adhering a preformed design layer containing a thermoplastic resin to one side of a skin layer or an intermediate layer; a method of printing on one surface of the skin layer or the intermediate layer using a printing ink containing a resin; etc.
That is, it is preferable to apply a printing method using a printing ink to the design layer including the pattern, and a method of forming a resin composition for forming a design layer containing a colorant into a film shape by a known method to form the design layer can be applied to the design layer as a colored layer.
Examples of the resin contained in the printing ink include an acrylic resin, a polyurethane resin, a polyolefin resin, a polyamide resin, and a vinyl chloride-vinyl acetate copolymer. The printing ink may contain 1 or 2 or more of the above resins.
Among them, a printing method for forming a design layer by printing is preferable because of high degree of freedom in design.
The printing method is a method of printing a known pattern with a printing ink containing a resin, and examples thereof include a method of printing a printing ink containing a resin by a known printing method, for example, gravure printing (Gravure printing), relief printing, offset printing, inkjet printing, screen printing, and the like.
Specific examples of the printing method include printing on one surface of the skin layer by gravure printing using a printing ink containing an acrylic resin. By adjusting the size of the engraving of the printing roller used for gravure printing, printing can be performed while adjusting the application amount of the printing ink, and a design layer having various designs can be formed.
The design layer as an optional layer can be formed on one surface of the skin layer or the intermediate layer independently as required, and thus a layer having a desired design can be formed in an arbitrary color tone and an arbitrary design. Therefore, by providing the design layer, various designs according to the purpose can be given to the skin material of the present disclosure.
The thickness of the design layer is preferably 1 μm to 10 μm, more preferably 2 μm to 8 μm, from the viewpoint of imparting a design excellent in appearance to the skin layer.
(Process G)
The method for producing a skin material of the present disclosure may include an optional step (step G) of further forming a surface treatment layer on the surface of the skin layer on the side having the concave-convex pattern.
The step G is a step of forming a surface treatment layer on the surface of the skin layer (the surface of the skin layer opposite to the intermediate layer side) for the purpose of improving the touch feeling, durability, and the like.
Step G is performed by applying a composition for forming a surface treatment layer, which contains a resin and, if necessary, other optional components, to the surface of the skin layer.
The composition for forming the surface treatment layer can be applied by a known method as appropriate.
The surface treatment layer may be formed by, for example, a method of applying the composition for forming a surface treatment layer by gravure printing, a method of applying the composition by a coating apparatus such as a reverse coater or a direct coater, or the like. Among them, the gravure printing method is preferably used in terms of forming a more uniform layer.
The details of the surface treatment layer are as described above.
The thickness of the surface treatment layer is preferably 1 μm to 30 μm, more preferably 2 μm to 20 μm, from the viewpoint of further improving the strength, durability, etc. of the surface of the skin material.
< molded article >
In order to impart design to the surface of a molded article when the molded article is produced by thermoforming, the synthetic resin skin material of the present disclosure is preferably used.
The molded article of the present disclosure is a molded article comprising a molding base material and the synthetic resin skin material of the present disclosure disposed on the surface of the molding base material.
The resin contained in the molding base material used in the step of producing the molded article is not particularly limited as long as it is generally a resin used for the purpose of obtaining the molded article by thermoforming.
The resin contained in the molded body base material is preferably an ABS resin, a PC resin, a Polyethylene (PE) resin, a PP resin, a mixture of a PC resin and an ABS resin (PC/ABS), or the like, and more preferably an ABS resin, a PC resin, a PE resin, a PP resin, or the like.
The molded article can be obtained by bringing the skin material of the present disclosure into contact with a molding base material and performing thermoforming.
The method of thermoforming is not particularly limited. As the heat molding method, a known molding method such as injection molding, insert molding, extrusion, calendaring, casting, and the like can be applied.
The following methods are examples of the method for producing the molded article: an insert molding method in which the skin material of the present disclosure is placed in a mold, and then heated and melted resin as a molding base material is injected into the mold to mold; a method of disposing the skin material of the present disclosure on a surface of a molding substrate that can be preformed in advance, disposing the skin material in a mold, disposing the molding substrate, and performing heat molding in the mold; etc.
In the case of insert molding, the molding is performed by heating to the melting temperature of a resin as a molding base material. When the skin material is disposed on the surface of the molding substrate and heated for molding, the heating temperature is preferably in the range of 90 to 200 ℃.
The skin material of the present disclosure is excellent in heat moldability, and also excellent in retention of the uneven pattern formed on the surface of the skin layer after heat molding using a molten resin such as insert molding.
Therefore, the molded article of the present disclosure can maintain the uneven pattern of the skin layer of the skin material, and is excellent in design.
In addition, the skin material of the present disclosure is generally applied to an insert molding method in which it is difficult to hold a design layer or a concave-convex pattern on the surface to obtain a molded body, and the effect is remarkable.
The synthetic resin skin material of the present disclosure can be produced by a simple method, has excellent appearance and durability, and is suitable for use as a skin material for thermoforming, and therefore, can be suitably used in various fields such as interior and exterior materials for automobiles, interior parts for railway vehicles and aircraft, furniture, shoes, footwear, leather bags, interior and exterior parts for building decoration, garment exterior materials, and liners.
In addition, the molded article of the present disclosure molded by disposing the skin material of the present disclosure is excellent in design.
Examples
The synthetic resin skin material, the method for producing the same, and the molded article of the present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to the following specific examples and various modifications are possible.
(production of synthetic resin skin Material)
Example 1
First, the epidermis layer is prepared. As the skin layer, a polypropylene resin film [ Pylen (registered trademark) P1111 (trade name), toyo-yo, co., ltd., film having a thickness of 100 μm ] was prepared as the skin layer (step A).
Next, 2kg of pigment (carbon black) was charged into 100kg of an ABS resin [ TM-30G6 (trade name), techno-UMG Co., ltd.) and the mixture was heated to 200℃and molded into a sheet by a rolling method so that the thickness thereof after drying was 100. Mu.m, to obtain an intermediate layer (step B).
In a step separate from the step B, 2kg of pigment (carbon black) was charged into 100kg of ABS resin [ TM-30G6 (trade name), techno-UMG Co., ltd.) and molded into a sheet by a calendaring method so that the thickness after drying was 200 μm while heating to 200℃to obtain a base layer (step C).
The skin layer prepared in step a and the intermediate layer molded in step B are sequentially laminated to obtain a laminate. The base material layer obtained in step C was laminated on the intermediate layer side of the obtained laminate, and the laminate was embossed. At this time, a pair of rolls was used, the roll side was brought into contact with the skin layer, the smooth roll was brought into contact with the substrate layer, the layers of the laminate of skin layer/intermediate layer/substrate layer were brought into close contact with each other under the condition that the surface temperature of the laminate was 140 ℃, and the surface of the skin layer opposite to the intermediate layer side was formed into a concave-convex pattern by the rolls. The depth of the concave portion of the concave-convex pattern was 100. Mu.m (step D and step E).
A polyurethane resin (YL 454UR Varnish (trade name), toyo ink Co., ltd.) was applied to the surface of the skin layer of the laminate, and after the application, the laminate was heated at 80℃for 1 minute using a dryer to form a surface-treated layer having a thickness of 10. Mu.m (step G), to obtain a skin material of example 1.
Example 2
Films of polypropylene resin films [ unstretched polypropylene films RXC-22 (trade name), mitsui Chemicals Tohcello, inc., thickness 100 μm ] were prepared as skin layers (step A).
Next, 2kg of pigment (carbon black) was charged into 100kg of PVC resin [ Kanevinyl (registered trademark) S1008 (trade name), kaneka, co., ltd.) and the mixture was heated to 200 ℃ and formed into a sheet by a calendaring method so that the thickness after drying was 100 μm, to obtain an intermediate layer (step B).
In a step separate from the step B, 2kg of pigment (carbon black) was charged into 100kg of polycarbonate resin [ Panlite (registered trademark) L-122Y (trade name), di Kagaku Kogyo Co., ltd.) and molded into a sheet by a calendaring method so that the thickness after drying was 200 μm while heating to 200℃to obtain a base layer (step C).
A laminate of a skin layer, an intermediate layer, and a base material layer was obtained in the same manner as in example 1, except that the skin layer prepared in step a, the intermediate layer formed in step B, and the base material layer formed in step C were used, and a concave-convex pattern having a recess depth of 100 μm was formed on the surface of the skin layer opposite to the intermediate layer side.
Thereafter, a surface treatment layer was formed on the surface of the skin layer in the same manner as in step G of example 1, to obtain a skin material of example 2.
Example 3
In example 1, after step C, a printing ink [ VTP-NT (trade name), DIC Graphics Co., ltd.) containing an acrylic resin was coated on the intermediate layer side of the skin layer to form a design layer having a thickness of 5 μm after drying (step F).
Thereafter, a laminate having the design layer formed in the step F and the intermediate layer formed in the step B were laminated on the surface of the skin layer and the intermediate layer side of the skin layer prepared in the same manner as in the step a of example 1, in this order, to obtain a laminate. While bonding the substrate layer obtained in step C in the same manner as in example 1 to the intermediate layer side of the obtained laminate, each layer was bonded in the same manner as in example 1, and the uneven pattern was formed on the surface of the skin layer opposite to the design layer side by a roll, to obtain a laminate of skin layer/design layer/intermediate layer/substrate layer, and the uneven pattern was formed on the surface of the skin layer opposite to the design side, with a recess depth of 100 μm. Thereafter, a surface treatment layer was formed on the surface of the skin layer in the same manner as in step G of example 1, to obtain a skin material of example 3.
Example 4
In example 2, after step C, a printing ink [ VTP-NT (trade name), DIC Graphics Co., ltd.) containing an acrylic resin was applied to the intermediate layer side surface of the skin layer to form a design layer having a thickness of 5 μm after drying (step F).
Then, the laminate having the design layer formed in the step F and the intermediate layer formed in the step B are laminated in this order on the surface of the skin layer and the intermediate layer side of the skin layer, to obtain a laminate. While bonding the substrate layer obtained in the same manner as in step C of example 2 to the intermediate layer side of the obtained laminate, the layers were bonded in the same manner as in example 2, and the uneven pattern was formed by a roll on the surface of the skin layer opposite to the design layer side, to obtain a laminate of skin layer/design layer/intermediate layer/substrate layer, in which the uneven pattern having a recess depth of 100 μm was formed on the surface of the skin layer opposite to the design side. Thereafter, a surface treatment layer was formed on the surface of the skin layer in the same manner as in step G of example 1, to obtain a skin material of example 4.
Example 5
A skin material of example 5 was obtained in the same manner as in example 3, except that step G was not performed and the surface treatment layer was not formed in the skin material of example 3, and that the skin material was a laminate of a skin layer, a design layer, an intermediate layer, and a base material layer, and had a concave-convex pattern with a recess depth of 100 μm on the surface of the skin layer opposite to the design side.
Example 6
A skin material of example 6 was obtained in the same manner as in example 4, except that step G was not performed and the surface treatment layer was not formed in the skin material of example 4, and that the skin material was a laminate of a skin layer, a design layer, an intermediate layer, and a base material layer, and had a concave-convex pattern with a recess depth of 100 μm on the surface of the skin layer opposite to the design side.
Comparative example 1
A skin material of comparative example 1 was obtained in the same manner as in example 3 except that the polypropylene resin film [ Pylen (registered trademark) P1111 (trade name), toyobo co., ltd., thickness 100 μm ] used as the skin layer in example 3 was replaced with a polymethyl methacrylate resin film [ Acryplen (registered trademark) film HBS010P (trade name), mitsubishi chemical corporation ].
Comparative example 2
A skin material of comparative example 2 was obtained in the same manner as in example 3 except that the polypropylene resin film [ Pylen (registered trademark) P1111 (trade name), toyobo co., ltd., thickness 100 μm ] used as the skin layer in example 3 was replaced with a fluororesin film [ FT-50Y (trade name), kureha Extron co., ltd.).
Comparative example 3
In example 3, a polypropylene resin [ Pylen (registered trademark) P1111 (trade name), toyobo Co., ltd.) was used instead of the ABS resin [ TM-30G6 (trade name), techno-UMG Co., ltd.) used in the formation of the intermediate layer (step B), and the intermediate layer was formed into a sheet so as to have a thickness of 100. Mu.m. The skin material of comparative example 3 having a layer structure of a surface treatment layer, a skin layer, a design layer, and an intermediate layer was obtained in the same manner as in example 3, except that the formation of the base material layer as step C of example 3 was not performed.
The skin materials of the examples and comparative examples obtained were evaluated by the following methods. The results are shown in table 1 below.
The skin material having the skin layer of the fluorine-containing resin was prepared in the following manner with reference to JP-A2007-283665 and evaluated in the same manner as the reference example. The results are shown in Table 1.
Reference example
In example 3, a skin material of a reference example was obtained in the same manner as in example 3 except that the polypropylene resin film [ Pylen (registered trademark) P1111 (trade name), toyobo Co., ltd., thickness 100 μm ] used in the formation of the skin layer (step A) was replaced with a fluororesin film [ FT-50Y (trade name), kureha Extron Co., ltd ], and the ABS resin [ TM-30G6 (trade name), techno-UMG Co., ltd.) used in the formation of the intermediate layer (step B) was replaced with the PVC resin [ Kanevinyl (registered trademark) S1008 (trade name), kaneka ] used in the formation of the intermediate layer in example 2.
(evaluation of synthetic resin skin Material)
( 1. Evaluation of synthetic resin skin material: retention of relief pattern )
The surface roughness of the skin layer on which the uneven pattern was formed was measured by a surface roughness meter (SURFCOM 130A manufactured by tokyo precision corporation) in the synthetic resin skin materials obtained in examples, comparative examples and reference examples.
Thereafter, the surface of the skin layer of the synthetic resin skin material was heated to 130℃and maintained at the temperature for 1 minute, followed by cooling to room temperature (25 ℃). The surface roughness of the surface layer after heating and cooling was measured under the same conditions as before heating, and the surface roughness before and after heating was compared, and the recess depth retention rate was calculated by the following formula.
Recess depth retention (%) = [ depth of recess after heating/depth of recess before heating ] ×100
In the evaluation of the retention of the concave-convex pattern after heating of the synthetic resin skin material, the concave-convex pattern was found to be a level that is practically usable for the use of molded articles for thermoforming when the concave-convex retention rate was 70% or more, and a level that is practically problematic when the concave-convex retention rate was less than 70%. Among them, a recess depth retention of 30% or less is a level unsuitable for a synthetic resin skin material applied to the surface of a molded article formed by thermoforming.
(2. Production of molded article)
The synthetic resin skin materials obtained in examples, comparative examples and reference examples were placed in a mold, and a resin for a molding base material (acrylonitrile-butadiene-styrene copolymer (ABS)) was heated and melted at a temperature of 200 to 300 ℃, and then fed into the mold to perform injection molding, thereby obtaining a molded article in which the synthetic resin skin material was placed on the surface of the molding base material. The above temperature conditions refer to the melting temperature of the resin before injection.
(3. Evaluation of molded article)
The obtained molded article was evaluated according to the following criteria. The evaluation results are shown in table 1 below.
The evaluation results other than the retention of the uneven pattern were denoted as "a" when no change or deterioration in appearance was observed visually, and as "B" when no change or deterioration in appearance was observed. In addition, "-" indicates that the evaluation was not performed.
3-1. Retention of relief Pattern
The surface roughness of the molded article obtained using the skin materials of examples, comparative examples and reference examples was measured by a surface roughness meter (SURFCOM 130A, manufactured by tokyo precision co., ltd.).
The result was compared with the surface roughness of the synthetic resin skin material before molding, and the recess depth retention was calculated.
In the synthetic resin skin material on the surface of the molded body after the molded body is heated and molded, if the recess depth retention rate is 50% or more, it is determined that there is no practical problem even when the synthetic resin skin material is used for forming the molded body accompanied by heating, for example, and if the recess depth retention rate is less than 50%, it is determined that there is a practical problem.
3-2 solvent resistance (gasoline and kerosene resistance)
The molded articles obtained using the skin materials of examples, comparative examples and reference examples were immersed in gasoline and kerosene (lamp oil) as solvents for 30 minutes, respectively, and then the molded articles were pulled up and left for 1 week.
The appearance of the molded article after the placement was visually evaluated for each of the gasoline-impregnated article and the kerosene-impregnated article. Evaluation was performed according to the following criteria.
In the following criteria, evaluation a was judged to be a practically problematic level, and evaluation B was judged to be a practically problematic level.
A: when the molded article was visually observed, deterioration of the molded article due to the solvent was not confirmed.
B: when the molded article was visually observed, it was confirmed that the molded article was degraded by the solvent, resulting in a decrease in appearance.
3-3. Chemical resistance (sulfuric acid, aqueous sodium hydroxide solution)
The molded articles obtained using the skin materials of examples, comparative examples and reference examples were immersed in a sulfuric acid and a sodium hydroxide 0.4 mass% aqueous solution as chemicals for 30 minutes, respectively, and then the molded articles were pulled up and left for 1 week.
The appearance of the molded article after the placement was visually evaluated for each of the sulfuric acid-impregnated article and the sodium hydroxide aqueous solution-impregnated article. Evaluation was performed according to the following criteria.
In the following criteria, evaluation a was judged to be a practically problematic level, and evaluation B was judged to be a practically problematic level.
A: when the molded article was visually observed, no deterioration of the molded article due to chemicals was observed.
B: when the molded article was visually observed, it was confirmed that the molded article was degraded by chemicals, resulting in a decrease in appearance.
3-4 moldability
The molded articles obtained using the skin materials of examples, comparative examples and reference examples were visually evaluated for appearance. Evaluation was performed according to the following criteria.
A: when visually observed, any one of wrinkles, resin leakage, gate defects, and whitening on the surface of the molded article was not confirmed.
B: when visually observed, one or more of wrinkles, resin leakage, gate defects, and whitening on the surface of the molded article were confirmed, and degradation which was a practical problem was confirmed.
In the following criteria, evaluation a was judged to be a practically problematic level, and evaluation B was judged to be a practically problematic level.
In table 1 below, "PP" represents a polypropylene resin, "ABS" represents an acrylonitrile-butadiene-styrene copolymer, "PVC" represents a polyvinyl chloride resin, "PC" represents a polycarbonate resin, and PMMA represents a polymethyl methacrylate resin.
"-" means that the skin material does not have a corresponding layer.
As is clear from the results of table 1, the synthetic resin skin material of examples was excellent in the retention of the surface roughness (texture) pattern even under heating conditions, and the molded article obtained using the same was excellent in the durability such as solvent resistance and chemical resistance, and after the heat molding, the retention of the surface roughness (texture) pattern formed on the surface of the synthetic resin skin material was also excellent, and the solvent resistance and chemical resistance were at a level free from problems, and had excellent performances equivalent to those of the skin material of the reference example (skin layer having a fluororesin containing more expensive cost).
On the other hand, in the synthetic resin skin material of comparative example 1 in which PMMA was used as the skin layer, the concave-convex pattern was almost disappeared and could not be evaluated when the molded article was obtained after the thermoforming.
It was found that, in the skin material of comparative example 2 in which the ABS resin was contained in the intermediate layer, although the skin layer contained the fluororesin similar to the reference example, the concave-convex pattern retention ratio of the skin material and the concave-convex pattern retention of the molded article obtained using the synthetic resin skin material were both practically problematic levels.
From this, it is apparent that the skin material of the example has a skin layer containing PP resin, and the thermoplastic resin in the intermediate layer has excellent selectivity, and the degree of freedom in selecting the thermoplastic resin used in the intermediate layer is higher than that of the skin material using a skin layer containing a fluororesin.
In the case of the skin material of comparative example 3 having no base material layer although the skin layer was made of PP resin, the retention of the uneven pattern was at a level practically free from problems, but the heat moldability was poor at a level practically unusable for the formation of molded articles.
In the skin materials of examples 1 to 6, the fluorine atom content in the following evaluation was not more than the detection limit. From these results, it was found that the resin composition has performance equal to or higher than that of the conventional one, even if the resin composition does not contain an expensive fluororesin.
(evaluation method)
Fluorescent X-ray analysis (XRF) was performed in accordance with JIS K0119 (2008), and the concentration of fluorine was analyzed. The analysis conditions were energy dispersion, measurement at normal temperature and normal pressure, and spot size of 100. Mu.m.
Description of symbols
10. 20 synthetic resin skin material
12 substrate layer
14 intermediate layer
16 skin layer comprising a polypropylene resin (specific skin layer)
18 design layer
Claims (12)
1. A synthetic resin skin material comprising:
a substrate layer comprising a thermoplastic resin;
an intermediate layer provided on one surface of the base material layer and containing a thermoplastic resin; and
and a skin layer provided on the side of the intermediate layer opposite to the base material layer, having a concave-convex pattern on the surface on the side opposite to the intermediate layer side, and containing a polypropylene resin.
2. The synthetic resin skin material according to claim 1, wherein the thermoplastic resin contained in the intermediate layer contains at least one selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, acrylic resin, polyurethane resin, and vinyl chloride resin.
3. The synthetic resin skin material according to claim 1 or 2, wherein the base material layer comprises at least one selected from the group consisting of acrylonitrile-butadiene-styrene copolymer, polycarbonate resin, and vinyl chloride resin.
4. The synthetic resin skin material according to claim 1 or 2, wherein a design layer is further provided between the intermediate layer and the skin layer.
5. The synthetic resin skin material according to claim 4, wherein the design layer is a printing ink layer containing at least one selected from the group consisting of an acrylic resin, a polyurethane resin, a polyolefin resin, a polyamide resin, and a vinyl chloride-vinyl acetate copolymer.
6. The synthetic resin skin material according to claim 1 or 2, wherein a surface treatment layer is further provided on a surface of the skin layer on the side having the concave-convex pattern.
7. The synthetic resin skin material according to claim 6, wherein the surface treatment layer comprises at least one selected from the group consisting of an acrylic resin, a polyurethane resin, a polyolefin resin, a polyamide resin, a silicone resin, and a vinyl chloride-vinyl acetate copolymer.
8. The synthetic resin skin material according to claim 1 or 2, which is a skin material of a heat-molded processed product.
9. A method for producing a synthetic resin skin material, comprising the steps of:
a step of preparing a skin layer containing a polypropylene resin;
a step of forming an intermediate layer using a resin composition containing a thermoplastic resin;
a step of forming a base material layer using a thermoplastic resin composition containing a thermoplastic resin;
sequentially laminating the skin layer, the intermediate layer, and the base material layer to obtain a laminate; and
and a step of forming a concave-convex pattern on a surface of the skin layer opposite to the intermediate layer side by performing a lamination embossing process on the skin layer side of the obtained laminate by using a roll.
10. The method for producing a synthetic resin skin material according to claim 9, further comprising a step of forming a design layer between the skin layer and the intermediate layer.
11. The method for producing a synthetic resin skin material according to claim 9 or 10, further comprising a step of forming a surface treatment layer on the surface of the skin layer on the side having the concave-convex pattern.
12. A molded article comprising a molding substrate and the synthetic resin skin material according to any one of claims 1 to 8 disposed on the surface of the molding substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-205499 | 2021-12-17 | ||
| JP2021205499A JP2023090516A (en) | 2021-12-17 | 2021-12-17 | Synthetic resin skin material, method for manufacturing synthetic resin skin material, and molding |
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| Publication Number | Publication Date |
|---|---|
| CN116265238A true CN116265238A (en) | 2023-06-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211592543.8A Pending CN116265238A (en) | 2021-12-17 | 2022-12-12 | Synthetic resin skin material, method for producing same, and molded article |
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| Country | Link |
|---|---|
| JP (1) | JP2023090516A (en) |
| CN (1) | CN116265238A (en) |
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2021
- 2021-12-17 JP JP2021205499A patent/JP2023090516A/en active Pending
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- 2022-12-12 CN CN202211592543.8A patent/CN116265238A/en active Pending
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| JP2023090516A (en) | 2023-06-29 |
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