WO2023032842A1 - 毛状体を有する樹脂シート及びその成形品 - Google Patents
毛状体を有する樹脂シート及びその成形品 Download PDFInfo
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- WO2023032842A1 WO2023032842A1 PCT/JP2022/032194 JP2022032194W WO2023032842A1 WO 2023032842 A1 WO2023032842 A1 WO 2023032842A1 JP 2022032194 W JP2022032194 W JP 2022032194W WO 2023032842 A1 WO2023032842 A1 WO 2023032842A1
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- hair
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- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005678 polyethylene based resin Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920005673 polypropylene based resin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
Definitions
- the present invention relates to a resin sheet having hair-like bodies and a molded article thereof.
- Patent Literature 1 proposes a resin sheet having hair-like bodies regularly arranged on the surface.
- a resin sheet is used as an interior item such as a dashboard or a seat of an automobile, it needs to be secondary molded and attached to the surface of the object.
- the problem to be solved by the present invention is to provide a resin sheet and a molded article thereof that can maintain good tactile properties even after secondary molding.
- the present inventors have found that hair-like bodies are regularly arranged on at least one surface of the base layer, and a structural structure is provided between the base layer and the hair-like bodies.
- the thermoplastic resin sheet forming a continuous phase without boundaries the thermoplastic resin composition constituting the base layer and the hair-like bodies contains a urethane-based elastomer, and the urethane-based elastomer is a polyol having a number average molecular weight of 450 to 900. and a component (B) derived from an aliphatic diol having 2 to 10 carbon atoms, and the molar ratio of (A) and (B) is adjusted to 60:40 to 88:12.
- thermoplastic having regularly arranged hair-like bodies on at least one surface of the underlayer and forming a continuous phase without a structural boundary between the underlayer and the hair-like bodies
- Component (A) which is a resin sheet, wherein the thermoplastic resin composition constituting the base layer and the hair-like body contains a urethane-based elastomer, and the urethane-based elastomer is derived from a polyol having a number average molecular weight of 450 to 900; and a component (B) derived from an aliphatic diol having 2 to 10 carbon atoms, wherein the molar ratio of (A) to (B) is 60:40 to 88:12.
- FIG. 2 is a schematic plan view of the resin sheet of FIG. 1;
- FIG. 5 is a schematic vertical cross-sectional view showing a laminated structure of resin sheets according to a second embodiment of the present invention;
- the resin sheet according to the first embodiment of the present invention has hair-like bodies regularly arranged on at least one surface of the base layer, and a structural boundary exists between the base layer and the hair-like bodies.
- the base layer (1a) is a layer that serves as a base for the hair-like bodies, and refers to the portion of the reference numeral 1 other than the surface hair-like bodies 1b.
- the thickness of the underlayer refers to the thickness from the base of the hair-like body to the opposite surface of the underlayer.
- the average thickness of the underlayer is preferably 15 ⁇ m to 500 ⁇ m, more preferably 30 ⁇ m to 300 ⁇ m, even more preferably 50 ⁇ m to 150 ⁇ m. By setting the thickness to 15 ⁇ m or more, the height of the ciliary body can be sufficiently expressed. Further, by setting the thickness to 500 ⁇ m or less, the hair-like body can be efficiently formed.
- Forming a continuous phase refers to a state in which there is no seam between the base layer and the hair-like bodies and there is no discontinuity (they form a continuous phase). In this respect, it differs from the structure in which hair-like bodies are implanted in the underlying layer.
- the base layer and the hair-like bodies may have the same composition, and the bond between the base layer and the hair-like bodies may include a covalent bond.
- a covalent bond is a chemical bond formed by sharing an electron pair between two atoms.
- the underlayer and the bristles may be derived from the same solid thermoplastic resin sheet that is not separate. Deriving from the same solid thermoplastic resin sheet means, for example, that the hair-like bodies and the base layer are directly or indirectly obtained from the same resin sheet. Further, the base layer and the hair-like members may be formed from the same solid thermoplastic resin sheet. Forming from the same solid thermoplastic resin sheet means that the hair-like bodies and the base layer are directly formed by processing one resin sheet. Since there is no structural boundary between the base layer and the hairy bodies and a continuous phase is formed, separation of the hairy bodies from the base layer due to an external stimulus is suppressed, resulting in good tactile sensation. becomes a sheet. In addition, it can be manufactured in fewer steps than in the case of flocking hairy bodies.
- the base layer and the hair-like bodies are made of the same thermoplastic resin composition containing a thermoplastic resin as the main component.
- the main component means to contain 50% by mass or more.
- the content is 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
- a urethane-based elastomer (TPU) can be used as the thermoplastic resin in this embodiment.
- TPU urethane-based elastomer
- at least one or more thermoplastic resins selected from styrene resins, polyolefin resins, polyvinyl chloride resins, thermoplastic elastomers, and fluorine resins may be further included.
- the urethane-based elastomer is a resin that uses a diisocyanate and a polyol as reaction raw materials. Any combination of polyester type and polycarbonate type may be selected, and a plurality of them may be combined. In one embodiment of the present invention, a combination of an MDI-based or HDI-based diisocyanate and a carbonate-based polyol can be preferably used.
- the urethane-based elastomer contains component (A) derived from a polyol having a number average molecular weight of 450-900 and component (B) derived from an aliphatic diol having 2-10 carbon atoms.
- the urethane-based elastomer of the present embodiment is a resin containing at least two types of reaction raw materials: a polyol having a number average molecular weight of 450 to 900 and an aliphatic diol having 2 to 10 carbon atoms.
- a component derived from X means X or a reaction residue of X in a compound using X as a reaction raw material.
- component (A) derived from a polyol having a number average molecular weight of 450 to 900 means a polyol residue in a urethane component synthesized using a polyol having a number average molecular weight of 450 to 900 as a raw material, and having 2 to 10 carbon atoms.
- the component (B) derived from an aliphatic diol in (1) means a diol residue in a urethane component synthesized using an aliphatic diol having 2 to 10 carbon atoms as a raw material.
- Polyol having a number average molecular weight of 450 to 900 means a compound having a number average molecular weight of 450 to 900 and having two or more hydroxyl groups (—OH).
- the number of hydroxyl groups in the polyol is not particularly limited as long as it includes 2 and is 2 or more.
- the number average molecular weight of the polyol is preferably 475-875, more preferably 500-850.
- polycarbonate-based diols polyether-based diols, polyester-based diols, and the like can be suitably used as the polyol of the present embodiment, and polycarbonate-based diols are particularly preferable.
- Polycarbonate-based diols can be produced by subjecting an aliphatic linear diol and a carbonate compound such as dialkyl carbonate or diphenyl carbonate to polycondensation by transesterification, and the number average molecular weight of the polyol is adjusted by adjusting the blending amount thereof.
- Examples of straight-chain aliphatic diols include 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. Among them, polycarbonate-based diols using 1,6-hexanediol are preferred. .
- Polyether-based diols include, for example, polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol, etc. obtained by ring-opening polymerization of cyclic ether compounds. Among them, polytetramethylene ether glycol is preferable from the viewpoint of mechanical properties, moldability and cold resistance in TPU to be synthesized.
- polyester diols examples include polyester diols obtained from aliphatic dicarboxylic acids and aliphatic diols, polyester diols obtained from aromatic dicarboxylic acids and aliphatic diols, polycaprolactone diols obtained by ring-opening polymerization of ⁇ -caprolactone, and the like. is mentioned. Among them, a polyester diol obtained from an aliphatic dicarboxylic acid and an aliphatic diol is preferable from the viewpoint of availability and viscosity control of the resulting TPU. Incidentally, the number average molecular weight can be calculated based on the following formula.
- Number average molecular weight (56100 ⁇ number of hydroxyl groups) / hydroxyl value (The hydroxyl value of the polyol can be determined by titration in accordance with JIS K 1557. Here, the unit of the hydroxyl value is mgKOH/g. .
- the acid value of the polyol can be obtained by titration according to JIS K 1557. Here, the unit of acid value is mgKOH/g. )
- the number average molecular weight can also be determined based on GPC under the following conditions.
- GPC Gel permeation chromatography
- THF tetrahydrofuran
- the elution curve detected by the differential refractometer is plotted with the signal intensity on the vertical axis and the logarithm of the molecular weight converted to polystyrene on the horizontal axis. can be converted into a curve (hereinafter referred to as a molecular weight curve).
- a molecular weight curve As a standard polystyrene sample for preparing a calibration curve, one having a molecular weight of about 10 2 to 10 7 is used.
- the peak starting point is the time when the baseline value shows a value of 0.2 or more
- the peak end point is the time when the baseline value after the peak showing the minimum molecular weight shows a value of 0.2 or more. can do.
- Aliphatic diol having 2 to 10 carbon atoms means a hydrocarbon compound having 2 to 10 carbon atoms and having two hydroxyl groups.
- the number of carbon atoms is preferably 2-8, more preferably 2-6. Among them, 1,4-butanediol having 4 carbon atoms is preferable.
- the number average molecular weight of the aliphatic diol can be kept low, such as less than 400 or less than 200.
- aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9 - nonanediol, neopentyl glycol, diethylene glycol, triethylene glycol and the like.
- the molar ratio of the component (A) derived from a polyol having a number average molecular weight of 450 to 900 and the component (B) derived from an aliphatic diol having 2 to 10 carbon atoms is 60: 40-88:12. 63:37 to 87:13 are more preferred. Further, when the ratio is 78:22 to 88:12, a moist touch can be obtained, and when the ratio is 60:40 to 77:23, a smooth touch can be obtained.
- the component (A) derived from a polyol having a number average molecular weight of 450 to 900 is 60 mol% or more, good tactile sensation is obtained, and when it is 88 mol% or less, large deformation or disappearance of hair-like bodies due to secondary formation is prevented. can be suppressed.
- the molar ratio between the component (A) derived from a polyol having a number average molecular weight of 450 to 900 and the component (B) derived from an aliphatic diol having 2 to 10 carbon atoms is calculated from the raw materials used. - can be measured using NMR or the like;
- aromatic diisocyanate-based, aliphatic diisocyanate-based, and alicyclic diisocyanate-based ones can be used.
- aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, and the like. is mentioned.
- aliphatic diisocyanate examples include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate and the like.
- Specific examples of the alicyclic diisocyanate include hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and isophorone diisocyanate.
- the molar ratio of the diisocyanate, which is the reaction raw material of the urethane-based elastomer, to the sum of the component (A) derived from the polyol and the component (B) derived from the aliphatic diol is 70:30. ⁇ 30:70 is preferred, 60:40 to 40:60 is more preferred, and 50:50 is even more preferred.
- Styrene-based resins include homo- or copolymers of styrene-based monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene, and chlorostyrene, and those styrene-based monomers and other monomers.
- styrene-based monomers such as a styrene-acrylonitrile copolymer (AS resin), or the styrene-based monomer and further other polymers, such as diene-based rubbers such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and polychloroprene.
- AS resin styrene-acrylonitrile copolymer
- diene-based rubbers such as polybutadiene, styrene-butadiene copolymer
- a graft polymer obtained by graft polymerization in the presence of a high-strength polymer for example, polystyrene such as high impact polystyrene (HIPS resin) and styrene-acrylonitrile graft polymer (ABS resin) can be used.
- HIPS resin high impact polystyrene
- ABS resin styrene-acrylonitrile graft polymer
- a styrene-based thermoplastic elastomer can also be used.
- Polyolefin-based resin means a resin made of a polymer containing ⁇ -olefin as a monomer, and includes polyethylene-based resin and polypropylene-based resin.
- the polyethylene resin high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene, etc. can be used. and blends can also be used. Examples of the latter resin include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene-vinyl acetate-vinyl chloride copolymer. Copolymerization and blending of a resin having a polar group in the polyethylene chain, such as coalescence and further blending with a terpolymer with an acid anhydride, etc., can be mentioned.
- the polypropylene resin homopolypropylene, random polypropylene, block polypropylene, etc.
- the structure of the homopolypropylene may be isotactic, atactic, or syndiotactic.
- the ⁇ -olefin to be copolymerized with propylene preferably has 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene and 1-hexene. , 1-heptene, 1-octene, 1-nonene, and 1-decene can be used.
- block polypropylene When block polypropylene is used, a block copolymer (block polypropylene), a block copolymer containing a rubber component, a graft copolymer, or the like can be used. Besides using these olefin resins alone, other olefin resins can also be used in combination.
- polyvinyl chloride resin a vinyl chloride homopolymer or a copolymer of vinyl chloride and other comonomers can be used.
- polyvinyl chloride When polyvinyl chloride is a copolymer, it may be a random copolymer or a graft copolymer.
- graft copolymers include those obtained by using an ethylene-vinyl acetate copolymer or a thermoplastic urethane polymer as a backbone polymer and graft-polymerizing vinyl chloride onto this.
- the polyvinyl chloride of this embodiment refers to extrudable flexible polyvinyl chloride and is a composition containing additives such as polymeric plasticizers.
- polymeric plasticizer known polymeric plasticizers can be used. Examples include ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-(meth)acrylate-carbon monoxide copolymer, acetic acid Preferred examples include ethylene copolymer polymeric plasticizers such as ethylene-vinyl acetate copolymers with high vinyl content.
- Thermoplastic elastomers include those having a structure that combines soft polymer substances and hard polymer substances. Specific examples include styrene-based elastomers, olefin-based elastomers, vinyl chloride-based elastomers, polyester-based elastomers, and polyamide-based elastomers. These elastomers can be selected and used from commercially available ones.
- PVDF Polyvinylidene fluoride
- Hexafluoropropylene copolymer vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexa Fluoropropylene terpolymers, vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene terpolymers, and mixtures of two or more thereof.
- the melt mass flow rate of the thermoplastic resin composition at 190°C to 300°C is preferably 4 g/10 minutes or more. By making it 4 g/10 minutes or more, the transferability of the shape of the hair-like body can be improved.
- the melt mass flow rate is a value measured according to JIS K 7210 in a temperature range of 190°C to 300°C under a load (2.16 kg to 10.0 kg).
- the thermoplastic resin composition may be obtained by alloying the above thermoplastic resins in any ratio within the range that does not impair the effects of the present invention. Furthermore, it may contain other additives. Other additives include water and oil repellents, colorants such as pigments and dyes, lubricants and release agents such as silicon oil and alkyl esters, and fibers such as glass fibers, as long as they do not impede the effects of the present invention. Granular fine particles such as talc, clay, silica, etc., scale-like fine particles such as mica, low-molecular-weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, etc., polyether ester amide, etc. Additives such as polymeric antistatic agents, flame retardants, antibacterial agents, antiviral agents, and heat stabilizers can be added. Scrap resin generated in the resin sheet manufacturing process can also be mixed and used.
- Water and oil repellents include silicone water repellents, carnauba wax, and fluorine water and oil repellents.
- silicon include organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, etc. Among them, dimethylpolysiloxane is preferably used.
- commercially available products include "Crimbell CB50-PP", “Crimbell CB-30PE”, “Crimbell CB-1", and “Crimbell CB-50AB” (manufactured by Fuji Chemical Co., Ltd.), which are alloys of silicon with resin.
- Carnauba wax includes commercially available products such as "Carnauba No.
- fluorine-based water and oil repellents include surfactants having perfluoroalkyl groups.
- "Surflon KT-PA” manufactured by AGC Seimi Chemical Co., Ltd.
- the amount of water/oil repellent added is preferably 0.5% by mass to 25% by mass. If it is less than 0.5% by mass, sufficient water and oil repellency may not be obtained, and if it exceeds 25% by mass, moldability may deteriorate.
- antistatic agents examples include polyether ester amide-based high-molecular anti-static agents and ionomer-based high-molecular anti-static agents.
- Polyether ester amide-based high-molecular-weight antistatic agents include commercially available products such as "Perestat 230", “Perestat 6500", “Pelectron AS”, and “Pelectron HS” (manufactured by Sanyo Kasei Co., Ltd.).
- commercially available ionomer polymer type antistatic agents include "Entira SD100" and "Entira MK400” (manufactured by DuPont Mitsui Polychemicals).
- the amount of the antistatic agent added is preferably 5% by mass to 30% by mass. If the amount is less than 5% by mass, sufficient antistatic properties may not be obtained, and if the amount exceeds 30% by mass, production costs increase.
- an inorganic or organic antibacterial agent can be added.
- an inorganic system is preferable.
- metal ion (Ag, Zn, Cu) inorganic antibacterial agents, calcined shell calcium antibacterial agents, and the like are included.
- Commercially available metal ion inorganic antibacterial agents include "Bactekiller BM102VT” (manufactured by Fuji Chemical Co., Ltd.), "Novaron VZF200", “Novaron (AG300)” (manufactured by Toagosei Co., Ltd.), "KM-10D-G", “IM-10D-L” (manufactured by Sinanen Zeomic) and the like.
- calcined shell calcium-based antibacterial agent examples include "Scallow” (manufactured by FID).
- the amount of the antibacterial agent to be added is preferably 0.5% by mass to 5% by mass. If it is less than 0.5% by mass, sufficient antibacterial properties may not be obtained, and if it exceeds 5% by mass, production costs increase.
- alkyl lubricants and mold release agents such as aliphatic hydrocarbon compounds, higher fatty acid compounds, higher aliphatic alcohol compounds, fatty acid amide compounds, silicone lubricants and mold release agents, fluorine-based Lubricants, releasing agents, etc. can be used.
- the amount added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, out of 100 parts by mass in total with the resin composition, and 0.1 ⁇ 2 parts by mass is more preferred.
- the amount added is 0.01 parts by mass or more, the risk of lowering the release effect is reduced, and when the amount is 5 parts by mass or less, the risk of bleeding out onto the sheet surface is reduced.
- a masterbatch in which a lubricant/release agent is previously alloyed with a thermoplastic resin.
- "Wax Master V" manufactured by BASF
- BASF is a commercially available masterbatch based on a urethane-based thermoplastic elastomer.
- the amount of the masterbatch added is preferably 1 to 8 parts by mass, more preferably 2 to 7 parts by mass, and even more preferably 3 to 6 parts by mass out of 100 parts by mass in total with the resin composition.
- the hair-like bodies (1b) refer to portions extending like hairs from the surface of the underlayer (1a) as shown in FIG.
- the hair-like bodies are regularly arranged on the surface of the underlayer.
- regularly arranged means that the hair-like bodies are arranged in a non-random manner, that is, in a state in which they are arranged orderly (for example, at regular intervals) in one or two directions. . Whether or not the arrangement of the ciliary bodies is regular is determined based on the state of arrangement of the roots of the ciliary bodies.
- the hair-like bodies are positioned on the base layer at predetermined intervals, and the positions of the bottom surfaces of the hair-like bodies are orderly arranged in the longitudinal direction and the width direction of the base layer.
- the form of arrangement of the hair-like bodies is not particularly limited, and it is possible to select a matrix arrangement arranged vertically and horizontally, a zigzag arrangement, or the like.
- the average height (h) of the hair-like bodies is preferably 30 ⁇ m to 500 ⁇ m, more preferably 60 ⁇ m to 250 ⁇ m, even more preferably 80 ⁇ m to 200 ⁇ m, even more preferably 90 ⁇ m to 180 ⁇ m. .
- the average height is preferably 30 ⁇ m to 500 ⁇ m, more preferably 60 ⁇ m to 250 ⁇ m, even more preferably 80 ⁇ m to 200 ⁇ m, even more preferably 90 ⁇ m to 180 ⁇ m. .
- the base layer will Let h be the distance from the surface of the ciliary body.
- the total value of the intervals obtained by subdividing the distance from the tip of the hairy body to the central portion of the root by multi-point measurement is defined as the length L of the hairy body.
- the average height of the hairs and the average length of the hairs were determined by using an electron microscope and image processing software. can be measured and the arithmetic mean of the measurements can be used.
- the average diameter (d) of the hair-like bodies is preferably 1 ⁇ m to 50 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, even more preferably 5 ⁇ m to 40 ⁇ m.
- the average diameter of the ciliary bodies is obtained by measuring the diameter of the intermediate height (h/2) of the ciliary bodies from several points on the resin sheet using an electron microscope and image processing software, and calculating the arithmetic mean value of the measured values.
- the aspect ratio of the hair can be expressed as (average height of the hair/average diameter of the hair).
- the aspect ratio of the hair-like bodies is preferably 2-20, more preferably 2-10, even more preferably 2-5.
- the aspect ratio can also be based on the average base diameter of the ciliary bodies.
- the average bottom diameter of the hair-like bodies is preferably 10 ⁇ m to 150 ⁇ m, more preferably 20 ⁇ m to 120 ⁇ m, even more preferably 30 ⁇ m to 100 ⁇ m.
- the average bottom diameter of the hair-like bodies is obtained by measuring the distance between adjacent hair-like bodies at several points on the resin sheet and using the arithmetic mean value of the measured values.
- the aspect ratio based on the bottom diameter of the hair-like body is preferably 1.0 to 10, more preferably 1.0 to 5, and more preferably 1.0 to 2.5. More preferred.
- the aspect ratio By setting the aspect ratio to 1.0 or more, good tactile sensation can be secured, and by setting the aspect ratio to 10 or less, not only can good tactile sensation such as moistness, softness, and fluffyness be obtained, but also It is possible to reduce the risk that the ratio of the height to the length of the shaped body will be below a certain level.
- the average spacing (t) of the ciliary bodies is preferably 20 ⁇ m to 200 ⁇ m, more preferably 40 ⁇ m to 150 ⁇ m, even more preferably 40 ⁇ m to 100 ⁇ m.
- Ciliary spacing means the distance between the center of the root of a ciliary body and the center of the root of an adjacent hair, as shown in FIG. 2, for example.
- the shape of the hair-like body is not particularly limited, but it may have a shape in which the hair-like body extends in a direction away from the underlying layer and gradually becomes thinner as it approaches the tip, or a bulge is formed at the tip of the hair-like body.
- the shape may be such that the cross-sectional area gradually decreases with increasing distance from the underlying layer, then increases once, and then terminates.
- the shape of the tip of the hairy body may be a bud shape or a mushroom shape.
- the hair-like body has a portion located at the proximal end extending away from the underlying layer, and a portion extending from the portion located at the proximal end and bent with a constant curvature or with a curvature that gradually changes. Furthermore, it may have a spirally or spirally wound portion. In this case, the tips of the hairy bodies may be folded inward. Such a shape provides a good tactile sensation. In addition, since the bud-shaped or mushroom-shaped portion is hollow, a better tactile sensation is exhibited. When a bud-like or mushroom-like shape is formed at the hair-like tip, the ratio of the average diameter of the bud-like or mushroom-like width to the average diameter of the hair-like body is preferably 1.1 times or more.
- the height of the bud-like or mushroom-like shape is preferably 7 ⁇ m or more.
- the average diameter of the hair-like bodies, the average diameter of the bud-shaped or mushroom-shaped width, and the height are measured from electron scanning micrographs, and the arithmetic mean values are taken as values.
- the hair-like body is made of a thermoplastic resin.
- the thermoplastic resin a resin similar to the resin that can be used in the base layer can be used.
- the thermoplastic resin contained in the base layer and the hair-like bodies may at least partially form a three-dimensional crosslinked structure (for example, a three-dimensional network structure).
- a three-dimensional crosslinked structure for example, a three-dimensional network structure.
- at least a portion of the hair is crosslinked; in another embodiment, the entire surface of the hair is crosslinked;
- the entire body (from the boundary with the base layer to the tip) may be a crosslinked body.
- a method of forming a crosslinked body for example, after molding a resin sheet, a method of irradiating an electron beam on the surface having the hair-like body, or adding an organic peroxide and, during or after molding the resin sheet, A method of forming by heating and moistening can be mentioned.
- the term “tactile properties” refers to the texture and feel of the surface of the resin sheet. It is determined whether the resin sheet surface feels comfortable to the touch, and if it does, a good feel is defined as a specific texture such as moist, soft, or fluffy.
- the thickness of the resin sheet refers to the sheet thickness obtained by combining the average height of the hair-like bodies and the average thickness of the underlying layer.
- the sheet thickness is preferably 65 ⁇ m to 1600 ⁇ m, more preferably 115 ⁇ m to 1050 ⁇ m, still more preferably 165 ⁇ m to 550 ⁇ m.
- the layer structure of the resin sheet according to the second embodiment is, from top to bottom, hair-like bodies, a base layer (1), and a base layer (2).
- the hairy body is the same as that explained in the first embodiment, the explanation is omitted.
- the thickness of the hair-like bodies and the base layer represented by the sum of the average height of the hair-like bodies and the average thickness of the base layer is preferably 150 ⁇ m to 1500 ⁇ m, more preferably 150 ⁇ m to 1050 ⁇ m, and more preferably 150 ⁇ m to 500 ⁇ m. is more preferable.
- a thickness of 150 ⁇ m or more can ensure good tactile sensation, and a thickness of 1500 ⁇ m or less can reduce the production cost.
- the average thickness of the substrate layer is preferably 50 ⁇ m to 1500 ⁇ m, more preferably 100 ⁇ m to 1000 ⁇ m, even more preferably 150 ⁇ m to 500 ⁇ m.
- a thickness of 50 ⁇ m or more facilitates the film forming process, and a thickness of 1500 ⁇ m or less can reduce the production cost.
- a thermoplastic resin that has excellent adhesion to the base layer, and polycarbonate-based resins, polyester-based resins, and polymer alloy resins thereof are preferably used can be used.
- the mass ratio of the polycarbonate resin and the polyester resin is preferably 50:50 to 90:10, more preferably 60:40 to 80:20, even more preferably 65:35 to 75:25.
- the polymer alloy resin is a polymer multi-component system, and may be a polymer blend having a certain degree of compatibility by mixing, or a block copolymer or a graft copolymer by copolymerization. It may be a mixture of incompatible resins.
- Polycarbonate resins include those derived from aliphatic dihydroxy compounds and those derived from aromatic dihydroxy compounds.
- one derived from an aromatic dihydroxy compound can be preferably used, particularly one derived from an aromatic dihydroxy compound (bisphenol) in which two aromatic dihydroxy compounds are bonded via a certain linking group. preferable.
- bisphenol aromatic dihydroxy compound
- These can be prepared by a known production method by polycondensation of a dihydroxy compound and phosgene or carbonate ester, and the production method is not limited, and commercially available resins can also be used.
- polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and polymethylene terephthalate.
- Copolymer components include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and adipic acid. , sebacic acid, phthalic acid, isophthalic acid, and polyester resins obtained by copolymerizing dicarboxylic acid components such as 2,6-naphthalenedicarboxylic acid.
- the base layer may contain other additives as necessary.
- Other additives include water repellents, oil repellents, colorants such as pigments and dyes, lubricants and release agents such as silicon oil and alkyl esters, glass fibers, etc., as long as they do not impair the effects of the present invention.
- fibrous reinforcing agents and fillers granular fine particles such as talc, clay, silica, scaly fine particles such as mica, low-molecular-weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, etc., and polyether esters
- Additives such as polymeric antistatic agents such as amides, flame retardants, antibacterial agents, antiviral agents, and heat stabilizers can be added.
- Scrap resin generated in the resin sheet manufacturing process can also be mixed and used.
- the substrate layer may partially have a crosslinked structure within a range that does not impair the effects of the present invention.
- the method for producing the resin sheet according to the present invention is not limited, and any method may be used. and the step of imparting bristles.
- any resin sheet molding method can be used to produce the multilayer resin sheet.
- feedblocks and multi-manifold dies can be used.
- the layer structure of each embodiment of the resin sheet of the present invention is basically as described above. It may be added to the base material layer or may be laminated as a further layer unless deterioration such as deterioration is observed.
- the method of imparting hairy bodies is not particularly limited, and any method known to those skilled in the art can be used.
- a method of manufacturing using an extrusion molding method a method of manufacturing using a roll-to-roll method, a method of manufacturing using a photolithography method, a method of manufacturing using a heat press method, a pattern roll and UV curing a method of manufacturing using a resin, a method of manufacturing using a 3D printer, and a method of embedding hair-like bodies in a resin layer and then covalently bonding them through a polymerization reaction.
- a resin sheet is extruded by a T-die method, and casting is performed with a transfer roll having unevenness processing so as to impart a hairy body shape to the surface of the resin sheet, and a touch roll.
- a transfer roll with unevenness processing fine unevenness of several ⁇ m to several hundred ⁇ m size is regularly applied to the surface of the roll by laser engraving, electroforming, etching, mill engraving, etc. can be used.
- regularly means a state in which the unevenness is not randomly arranged, that is, a state in which the unevenness is orderly arranged in one or two directions.
- the arrangement of the projections and depressions in an embodiment it is possible to select a grid arrangement arranged vertically and horizontally, a zigzag arrangement, or the like.
- the shape of the concave-convex portion include a pyramid shape (cone, square pyramid, triangular pyramid, hexagonal pyramid, etc.), semicircle, rectangle (square prism), and the like.
- the opening diameter of the recess, the depth of the recess, and the interval between the recess shapes are several ⁇ m to several hundred ⁇ m.
- metal, ceramic, or the like can be used as the material of the transfer roll.
- the spacing of the recesses of the transfer roll By adjusting the spacing of the recesses of the transfer roll, the spacing of the hair-like bodies can be adjusted, and by adjusting the depth of the recesses of the transfer roll, the height of the hair-like bodies can be adjusted, thereby adjusting the tactile sensation.
- the surface of the transfer roll it is preferable to process the surface of the transfer roll to have a high aspect ratio.
- the aspect ratio (depth of recesses/opening diameter of recesses) in the case of processing recesses on the surface of the transfer roll is preferably 1.0 to 9.0 or 1.0 to 2.0.
- Laser engraving or electroforming is more suitable than etching, blasting, mill engraving, etc. in order to process unevenness with a high aspect ratio on the surface of the transfer roll.
- the material of the transfer roll for example, metal, ceramic, or the like can be used.
- various materials can be used. For example, rolls made of silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, and fluororubber can be used. In one embodiment, a touch roll with a rubber hardness (JIS K 6253) of 40-100 can be used. A Teflon (registered trademark) layer may be formed on the surface of the touch roll.
- Various materials can be used as the touch roll, and for example, rolls made of silicone rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, and fluororubber can be used.
- a touch roll with a rubber hardness (JIS K 6253) of 40-100 can be used.
- a Teflon (registered trademark) layer may be formed on the surface of the touch roll.
- the resin sheet of the present embodiment can be produced by using the roll set of the transfer roll and the touch roll.
- the temperature of the transfer roll is adjusted to a temperature near the crystalline melting temperature, glass transition point, or melting point of the thermoplastic resin (for example, 100 to 150 ° C. when using random polypropylene), and the transfer roll and the touch roll are adjusted.
- the resin sheet of the present embodiment can be produced by casting with a pinch pressure of 30 to 120 kg/cm 2 .
- the cast resin sheet is taken up at a line speed of 0.5 to 30 m/min using a pinch roll or the like.
- the present invention is not limited to these.
- the molded article of the present invention is a molded article using the resin sheet of the present invention.
- the resin sheet of the present invention can be used for general molding.In addition to insert molding and in-mold molding, the resin sheet of the present invention can be used for general vacuum molding, pressure molding, and other applications of these. Examples include, but are not limited to, a method of overlaying (molding) the surface of an existing molded product by heating and softening the sheet in a vacuum state and releasing it under atmospheric pressure. As a method for heating and softening the sheet before molding, a known sheet heating method such as radiation heating using an infrared heater, which is non-contact heating, can be applied.
- the resin sheet has a surface temperature of 60 ° C. to 220 ° C., and is heated for 20 seconds to 480 seconds and then molded to the surface of the existing molded product. It can be stretched by a factor of 2.50.
- the resin sheet having the surface provided with the hair-like bodies according to the present invention can be applied to the above-mentioned uses requiring good tactile sensation.
- the resin sheet of the present invention can be applied as an interior material for automobiles, an exterior material for electronic equipment, or a surface material for cosmetic containers.
- Automotive interior materials include steering wheels, dashboards, levers, switches, etc.
- an interior material obtained by molding and adhering the above resin sheet to the surface of a known instrument panel or pillar (for example, JP-A-2009-184421) can be mentioned.
- By laminating the resin sheet together it is possible to obtain an interior material imparting good tactile sensation.
- olefin-based resins, vinyl chloride-based resins, and urethane-based elastomers are preferable as the material of the resin sheet to be bonded.
- a method for bonding the resin sheet and the interior material is not particularly limited.
- Examples of electronic device exterior materials include transmitter housings for keyless entry systems, smartphone housings, smartphone cases, music player cases, game machine housings, digital camera housings, electronic notebook housings, calculator housings, tablet housings, Examples include mobile personal computer housings, keyboards, mice, and the like.
- a portable transmitter in which the resin sheet of the present invention is molded and adhered to the surface of a portable transmitter housing of a known keyless entry system for example, Japanese Unexamined Patent Application Publication No. 2005-228911
- Olefin resins and urethane elastomers are preferable as the material of the resin sheet to be bonded.
- a method for bonding the resin sheet and the housing together is not particularly limited.
- Examples of cosmetic containers include containers for face cream, face cream, foundation, and eye shadow. and laminated cosmetic containers. By laminating the resin sheet, it is possible to obtain a cosmetic container having a good tactile sensation. Olefin resins and urethane elastomers are preferable as the material of the resin sheet to be bonded. The method of bonding with the resin sheet is not particularly limited.
- a hair-like body sheet is produced by printing characters and patterns on the surface of the hair-like body by a general printing method (offset printing, gravure printing, flexographic printing, screen printing, foil stamping, etc.). , can be applied to the above applications.
- the material of the resin sheet to be printed is not particularly limited, but it is preferable to consider the printability with the ink used for printing.
- the resin sheet of the present invention is laminated with printed matter (paper, metal thin film, etc.) on which characters, patterns, etc. are printed (paper, metal thin film, etc.), non-woven fabric, etc., and laminated (dry lamination molding, extrusion lamination molding) to produce a laminate, for example, business cards.
- a business card with a tactile feel can be produced by lamination molding on the printed surface.
- the material of the resin sheet to be laminated is not particularly limited.
- Polyol A-2 Polyol B-1 was synthesized in the same manner as in the production of polyol B-1 except that 913 g of 1,6-HD and 686 g of DEC were charged so that the molar ratio of 1,6-HD and DEC was 1.33:1. A-2 was obtained. Polyol A-2 had a hydroxyl value of 172.6 (mgKOH/g) and a calculated number average molecular weight of 650. (Polyol A-3) Polyol B-1 was synthesized in the same manner as in the production of polyol B-1 except that 898 g of 1,6-HD and 700 g of DEC were charged so that the molar ratio of 1,6-HD and DEC was 1.28:1. A-3 was obtained.
- Polyol A-3 had a hydroxyl value of 149.6 (mgKOH/g) and a calculated number average molecular weight of 750.
- Polyol A-4 Polyol B-1 was synthesized in the same manner as in the production of polyol B-1 except that 878 g of 1,6-HD and 720 g of DEC were charged so that the molar ratio of 1,6-HD and DEC was 1.22:1. A-4 was obtained. Polyol A-4 had a hydroxyl value of 132.0 (mgKOH/g) and a calculated number average molecular weight of 850.
- Polyol A-5 Polyol B-1 was synthesized in the same manner as in the production of polyol B-1 except that 938 g of 1,6-HD and 660 g of DEC were charged so that the molar ratio of 1,6-HD and DEC was 1.42:1. A-5 was obtained. Polyol A-5 had a hydroxyl value of 280.5 (mgKOH/g) and a calculated number average molecular weight of 400.
- Polyol A-6) Polyol B-1 was synthesized in the same manner as in the production of polyol B-1 except that 872 g of 1,6-HD and 726 g of DEC were charged so that the molar ratio of 1,6-HD and DEC was 1.20:1. A-6 was obtained.
- Polyol A-6 had a hydroxyl value of 118.1 (mgKOH/g) and a calculated number average molecular weight of 950.
- the acid value of the polycarbonate diol was obtained by titration according to JIS K 1557. Here, the unit of acid value is mgKOH/g.
- TPU Manufacturing of TPU that will be the hair-like body and the base layer
- the polyol (A) and the aliphatic diol (B) were charged and uniformly mixed so that the composition shown in Table 1 was obtained.
- the diisocyanate (C) was added, the mixture was forcibly stirred with a hand mixer, and when the reaction temperature reached 130°C, the mixture was poured onto release paper and solidified.
- the obtained solid matter was aged in an electric furnace at 120° C. for 1 hour, cooled to room temperature, and then pulverized to obtain flaky TPU.
- the resulting flake-like TPU is compounded with (D) a release agent masterbatch in a weight ratio of 95:5 in a twin-screw extruder, and the resulting strands are granulated to form hair-like bodies and A TPU pellet (G) was obtained as a raw material for the underlayer.
- the diameters of 10 hair-like bodies at the intermediate height (h/2) were measured for each sample, and the arithmetic mean value of the 30 measured values was used.
- the average distance between the ciliary bodies the distance between the center of the base of the ciliary body and the center of the base of the adjacent ciliary body was measured at 10 points for each sample, and the arithmetic mean value of the 30 measured values was used.
- the average thickness of the underlayer the thickness from the base of the hair-like body to the interface of the other layer was measured at 10 points for each sample, and the arithmetic mean value of the 30 measured values was used.
- the average thickness of the substrate layer the thickness from the boundary with the base layer to the interface opposite to the surface having hairy bodies was measured at 10 points for each sample, and the arithmetic mean value of the 30 measured values was used.
- Table 1 shows the results of evaluation tests on various characteristics using the resin sheets obtained in each example and comparative example.
- the results shown in Table 1 revealed the following. All of the resin sheets of Examples 1 to 6 maintained good tactile sensation even after secondary molding.
- the component (A) is derived from a polyol having a number average molecular weight of 950, and the molar ratio of the component (A) and the component (B) is 90:10.
- the hair-like bodies were greatly deformed by the secondary molding, and the tactile sensation was dry and did not have good tactile sensation.
- the resin sheet of Comparative Example 2 had a molar ratio of component (A) to component (B) of 92:8. and did not have good tactile sensation.
- the component (A) is derived from a polyol having a number average molecular weight of 400, and the molar ratio of the component (A) and the component (B) is 58:42.
- the resin sheet of this embodiment can maintain good tactile properties even after secondary molding, it has industrial applicability as a resin sheet that can be secondary molded and its molded product.
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Abstract
Description
一方、そのような樹脂シートを例えば自動車のダッシュボードやシート等の内装品として用いる場合、二次成形して対象物の表面に貼り付ける必要がある。
本発明が解決しようとする課題は、二次成形後も良い触感性を維持することができる樹脂シート及びその成形品を提供することである。
(1)下地層の少なくとも一方の面に規則的に配列された毛状体を有し、下地層と毛状体との間には構造的な境界がなく連続相を形成している熱可塑性樹脂シートであって、前記下地層と毛状体を構成する熱可塑性樹脂組成物がウレタン系エラストマーを含み、前記ウレタン系エラストマーが、数平均分子量450~900のポリオールに由来する成分(A)と、炭素数2~10の脂肪族ジオールに由来する成分(B)を含み、(A)と(B)のモル比が60:40~88:12である、樹脂シート。
(2)前記毛状体の平均高さが30μm以上500μm以下、毛状体の平均径が1μm以上50μm以下、毛状体の平均間隔が20μm以上200μm以下である、(1)に記載の樹脂シート。
(3)前記ポリオールがポリカーボネート系ジオールである、(1)又は(2)に記載の樹脂シート。
(4)下地層の毛状体とは反対側の面に基材層を有する、(1)から(3)のいずれかに記載の樹脂シート。
(5)(1)から(4)のいずれかに記載の樹脂シートの成形品。
(6)インサート成形品又は真空成形品である、(5)に記載の成形品。
(7)自動車内装材、電子機器外装材、又は化粧品容器の表面に設けられている、(5)又は(6)に記載の成形品。
本発明の第一実施形態に係る樹脂シートは、下地層の少なくとも一方の面に規則的に配列された毛状体を有し、下地層と毛状体との間には構造的な境界がなく連続相を形成している熱可塑性樹脂シートであって、前記下地層と毛状体を構成する熱可塑性樹脂がウレタン系エラストマーを含み、前記ウレタン系エラストマーが、数平均分子量450~900のポリオールに由来する成分(A)と、炭素数2~10の脂肪族ジオールに由来する成分(B)を含み、(A)と(B)のモル比が60:40~88:12である、樹脂シートである。
下地層(1a)は、毛状体の下地になる層であり、符号1のうち、表面の毛状体1b以外の部分をいう。下地層の厚みは、毛状体の根元から下地層の反対側の表面までの厚みをいう。下地層の平均厚みは15μm~500μmであることが好ましく、30μm~300μmであることがより好ましく、50μm~150μmであることがより好ましい。15μm以上とすることで、毛状体の高さを十分に発現することができる。また、500μm以下とすることで、毛状体を効率よく形成することができる。下地層と毛状体との間には構造的な境界がなく、連続相を形成していてもよい。構造的に境界がないとは、下地層と毛状体とが一体型に形成され、これらの間に構造的に明確な境界部がないことを意味している。また、連続相を形成しているとは、下地層と毛状体との間に継ぎ目がなく、不連続でない(連続相となっている)状態をいう。この点で、下地層に毛状体を植毛している構造とは異なっている。下地層及び毛状体は同組成であってもよく、下地層と毛状体との結合には共有結合が含まれてもよい。共有結合とは、電子対が2つの原子に共有されることによって形成される化学結合をいうが、モノマーが連なった鎖状分子である熱可塑性樹脂において、個々のポリマーは共有結合により結合しており、ポリマー分子間で働くファンデルワールス結合や水素結合よりも強く結合している。
また、下地層及び毛状体は、別個ではない同一固体の熱可塑性樹脂シートに由来してもよい。同一固体の熱可塑性樹脂シートに由来するとは、例えば、毛状体及び下地層が同一の樹脂シートに基づいて直接的又は間接的に得られることを意味する。
また、下地層及び毛状体は、同一固体の熱可塑性樹脂シートから形成されたものであってもよい。同一固体の熱可塑性樹脂シートから形成されるとは、毛状体及び下地層が一の樹脂シートを加工することにより直接的に形成されることを意味する。
下地層と毛状体との間には構造的な境界がなく、連続相を形成していることにより、外的刺激によって毛状体が下地層から分離することが抑制され、触感性が良いシートとなる。また、毛状体を植毛する場合よりも少ない工程で製造することができる。
ポリカーボネート系ジオールは、脂肪族直鎖ジオールと、ジアルキルカーボネートやジフェニルカーボネート等のカーボネート化合物をエステル交換反応によって重縮合させることにより製造することができ、ポリオールの数平均分子量はそれらの配合量により調節することができる。脂肪族直鎖ジオールとしては、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオール等が挙げられるが、なかでも1,6-ヘキサンジオールを用いたポリカーボネート系ジオールが好ましい。
ポリエーテル系ジオールとしては、例えば、環状エーテル化合物の開環重合によって得られるポリエチレングリコール、ポリトリメチレンエーテルグリコール、ポリテトラメチレンエーテルグリコール、ポリヘキサメチレンエーテルグリコール等が挙げられる。なかでも、合成するTPU中の力学特性、成形性、耐寒性の点からポリテトラメチレンエーテルグリコールが好ましい。
ポリエステル系ジオールとしては、例えば、脂肪族ジカルボン酸と脂肪族ジオールから得られるポリエステルジオール、芳香族ジカルボン酸と脂肪族ジオールから得られるポリエステルジオール、ε-カプロラクトンの開環重合によって得られるポリカプロラクトンジオール等が挙げられる。なかでも、入手性や得られるTPUの粘度制御の観点から、脂肪族ジカルボン酸と脂肪族ジオールから得られるポリエステルジオールが好ましい。
なお、数平均分子量は下記式に基づいて算出することができる。
数平均分子量=(56100×水酸基の数)/水酸基価
(ポリオールの水酸基価は、JIS K 1557に準拠して、滴定で求めることができる。ここで、水酸基価の単位は、mgKOH/gである。
ポリオールの酸価は、JIS K 1557に準拠して、滴定で求めることができる。ここで、酸価の単位は、mgKOH/gである。)
[ゲルパーミエーションクロマトグラフィー(GPC)]
重合体の濃度が1mg/1mLのテトラヒドロフラン(THF)溶液を調製し、GPC測定装置において、40℃のヒートチャンバ中でカラムを安定化させ、この温度におけるカラムに溶媒としてTHFを毎分1mLの流速で流し、THF試料溶液を約100μL注入することで重合体の分子量分布を測定することができる。
毛状体(1b)とは、図1に示すように下地層(1a)の表面から毛状に伸びている部分をいう。毛状体は、下地層の表面に規則的に配列されている。ここで、規則的に配列されているとは、毛状体がランダムではない配列状態、即ち、一方向又は二方向に整然と(例えば一定の間隔で)配列されている状態を意味するものである。毛状体の根元の配列状態をもって毛状体の配列が規則的であるか否かを判断する。ある実施形態では、毛状体は所定の間隔で下地層上に位置し、毛状体の底面の位置が下地層の長手方向及び短手方向に整然と配列している。また、毛状体の配置形態は特に限定はされず、縦横に配置した碁盤目配置や千鳥配置などを選択することができる。毛状体が下地層の表面に規則的に配列されていることにより、均一でムラがなく、良触感性が発現しやすくなる。毛状体は、例えば指でなぞるなど荷重がかかることによって毛倒れが起こり、周囲の部分とは光沢、色調が異なって見えるフィンガーマークを形成し得る。また、毛状体により、スエード調の起毛シートのような触感となり得る。
毛状体が下地層に対してほぼ直立している場合は、毛状体の根元から先端までの長さが毛状体の高さを表すことになる。一方、毛状体が下地層に対して傾斜している場合や、毛状体が巻回する部分を有する場合は、毛状体が下地層の表面から最も離間している箇所における、下地層の表面からの距離を毛状体の高さhとする。また、毛状体の先端から根元の中央部までを多点間計測により細分化した間隔の合計値を毛状体の長さLとする。
毛状体の平均高さ、および毛状体の平均長さは、電子顕微鏡及び画像処理ソフトを用いて、樹脂シートの任意の数箇所において毛状体の高さ、および毛状体の長さを測定し、その測定値の算術平均値を用いることができる。
また、毛状体のアスペクト比は、(毛状体の平均高さ/毛状体の平均径)として表すことができる。毛状体のアスペクト比は、2~20であることが好ましく、2~10であることがより好ましく、2~5であることがさらに好ましい。アスペクト比を2以上とすることで、良触感性が確保でき、アスペクト比を20以下とすることで、しっとり感、やわらか感、ふんわり感などの良触感性が得られるだけでなく、毛状体の長さに対する高さの比が一定以下となる虞を低減することができる。
一方、アスペクト比は、毛状体の平均底面径を基準とすることもできる。毛状体の平均底面径は10μm~150μmであることが好ましく、20μm~120μmであることがより好ましく、30μm~100μmであることがさらに好ましい。毛状体の平均底面径は、樹脂シートの数箇所において、隣接する毛状体の間隔を測定し、その測定値の算術平均値を用いた値とする。毛状体の底面径を基準とした場合のアスペクト比は、1.0~10であることが好ましく、1.0~5であることがより好ましく、1.0~2.5であることがさらに好ましい。アスペクト比を1.0以上とすることで、良触感性が確保でき、アスペクト比を10以下にすることで、しっとり感、やわらか感、ふんわり感などの良触感性が得られるだけでなく、毛状体の長さに対する高さの比が一定以下となる虞を低減することができる。
本実施形態において、「触感性」とは、樹脂シートの表面の風合い、肌触りを意味する。樹脂シート表面を触った際に心地よさを感じるかを判断し、感じる場合、しっとり、やわらか、ふんわりなどの具体的な肌触り感が良いものを良触感とする。
本発明の第二実施形態に係る樹脂シートの例としては、図3に示すように、下地層の毛状体とは反対側の面に、基材層が形成された樹脂シートである。すなわち、第二実施形態に係る樹脂シートの層構成は、上から下に向かって、毛状体及び下地層(1)、基材層(2)である。
ここで、毛状体は、第一実施形態において説明したものと同じであるので、説明を省略する。但し、毛状体の平均高さ及び下地層の平均厚みの合計で表される毛状体及び下地層の厚みは、150μm~1500μmが好ましく、150μm~1050μmであることがより好ましく、150μm~500μmであることがさらに好ましい。150μm以上とすることで良触感性を確保でき、1500μm以下とすることで生産コストを抑えることができる。
基材層の平均厚みは50μm~1500μmが好ましく、100μm~1000μmであることがより好ましく、150μm~500μmであることがさらに好ましい。50μm以上とすることで、製膜工程が容易になり、1500μm以下とすることで、生産コストを抑えることができる。
第二実施形態に係る樹脂シートにおける基材層としては、下地層との接着性に優れる熱可塑性樹脂を使用することが好ましく、ポリカーボネート系樹脂やポリエステル系樹脂、またこれらのポリマーアロイ樹脂を好適に用いることができる。ポリカーボネート系樹脂とポリエステル系樹脂との質量比は、50:50~90:10が好ましく、60:40~80:20がより好ましく、65:35~75:25がさらに好ましい。
ここで、ポリマーアロイ樹脂とは、高分子多成分系のことであり、混合などにより一定の相溶性を有するポリマーブレンドであってもよいし、共重合によるブロック共重合体やグラフト共重合体であってもよく、相溶性のない樹脂同士の混合物であってもよい。
本発明に係る樹脂シートの製造方法は、限定されず、如何なる方法によってもよいが、典型的には、原料樹脂を溶融押出し、得られた押出し樹脂シートの少なくとも一方の面に規則的に配列された毛状体を付与する工程を含んでなる。
凹凸加工が成された転写ロールとして、レーザー彫刻法や電鋳法、エッチング法、ミル彫刻法などによりロールの表面に数μm~数百μmサイズの微細な凹凸が規則的に施されたものを用いることができる。ここで、規則的とは、凹凸がランダムではない配列状態、即ち、一方向又は二方向に整然と配列した状態を意味するものである。ある実施形態における凹凸の配置として、縦横に配置した碁盤目配置や千鳥配置などを選択することができる。凹凸部の形状としては、例えば、凹部の形状であれば、錐形(円錐、四角錐、三角錐、六角錐など)、半円形、矩形(四角柱)などが挙げられる。サイズとしては、凹部の開口径、凹部深さ、凹部形状の間隔が数μmから数百μmである。転写ロールの材質として、例えば金属、セラミック等を用いることができる。転写ロールの凹部の間隔を調節することで毛状体の間隔を調節することができ、転写ロールの凹部深さを調節することで毛状体高さを調節することができ、それにより触感を調節することもできる。
また、転写ロール表面に高アスペクト比の凹凸加工することが好ましい。例えば、転写ロール表面に凹部形状を加工する場合のアスペクト比(凹部深さ/凹部開口径)は1.0~9.0又は1.0~2.0であることが好ましい。転写ロール表面に高アスペクト比の凹凸加工をするには、レーザー彫刻法または、電鋳法が、エッチング法やブラスト法、ミル彫刻法等に比べて、深さ方向に精密な加工をする場合に適するため、特に好適に用いられる。
転写ロールの材質としては、例えば金属、セラミック等を用いることができる。一方、タッチロールとしては、様々な材質のものを用いることができるが、例えばシリコン系ゴム、NBR系ゴム、EPT系ゴム、ブチルゴム、クロロプレンゴム、フッ素ゴム製のロールを用いることができる。ある実施形態において、ゴム硬度(JIS K 6253)40~100のタッチロールを用いることができる。また、タッチロールの表面に、テフロン(登録商標)層が形成されていてもよい。
タッチロールとしては、様々な材質のものを用いることができるが、例えばシリコン系ゴム、NBR系ゴム、EPT系ゴム、ブチルゴム、クロロプレンゴム、フッ素ゴム製のロールを用いることができる。ある実施形態において、ゴム硬度(JIS K 6253)40~100のタッチロールを用いることができる。また、タッチロールの表面に、テフロン(登録商標)層が形成されていてもよい。
上記の転写ロール及びタッチロールのロールセットを用いることで、本実施形態の樹脂シートを製造することができる。
ある実施形態において、転写ロールの温度を熱可塑性樹脂の結晶融解温度、ガラス転移点または融点の付近の温度(例えば、ランダムポリプロピレンを用いる場合は100~150℃)に調節し、転写ロールとタッチロールとのピンチ圧を30~120Kg/cm2としてキャスティングすることで、本実施形態の樹脂シートを製造することができる。キャスティングした樹脂シートは、ピンチロール等を用いて0.5~30m/分のライン速度で引き取られる。
また、上記実施形態を具体的に示しているが、これらに限定されるものではない。
本発明の成形品は、本発明の樹脂シートを用いた成形品である。本発明の樹脂シートは、一般的な成形への対応が可能であり、成形方法としては、インサート成形、インモールド成形の他にも、一般的な真空成形、圧空成形やこれらの応用として、樹脂シートを真空状態化で加熱軟化させ、大気圧下に開放することで既存の成形品表面へオーバーレイ(成形)する方法等が挙げられるが、これらに限定されるものではない。また、成形前にシートを加熱軟化させる方法として非接触加熱である赤外線ヒーター等による輻射加熱等、公知のシート加熱方法を適応することができる。ある実施形態の真空圧空成形において、例えば樹脂シートは表面温度が60℃~220℃で、20秒~480秒間加熱してから既存の成形品表面へと成形され、表面の形状により1.05~2.50倍に延伸され得る。
本発明にかかる毛状体を表面に付与した樹脂シートは、前記に示した良触感性が必要とされる用途に適用できる。例えば、本発明の樹脂シートは、自動車内装材、電子機器外装材、又は化粧品容器の表面材として適用できる。
・(ポリオールA-1)
攪拌機、温度計、加熱装置、蒸留塔を組んだ反応装置に、1,6-ヘキサンジオール(以下、1,6HD)とジエチルカーボネート(以下、DEC)のモル比が1.38:1になるように、1,6-HDを926g、DECを671g仕込むとともに、さらに反応触媒としてテトラブチルチタネート(以下、TBT)を0.05g仕込み、窒素気流下にて徐々に190℃まで温度を上昇させた。エタノールの留出が緩慢となり蒸留塔の塔頂温度が50℃以下となった時点で、反応温度は190℃のまま、1.3kPaまで徐々に減圧を行ない、1.3kPaの圧力でさらに7時間反応させた。さらに190℃の反応温度で1.3kPa以下の減圧下、反応物の水酸基価が222~226(mgKOH/g)になるまで反応を続行し、ポリオールA-1を得た。ポリオールA-1の水酸基価は224.4(mgKOH/g)であり、数平均分子量は500と算出された。
・(ポリオールA-2)
1,6-HDとDECのモル比が1.33:1になるように、1,6-HDを913g、DECを686g仕込む以外はポリオールB-1の製造と同様の方法で合成し、ポリオールA-2を得た。ポリオールA-2の水酸基価は172.6(mgKOH/g)であり、数平均分子量は650と算出された。
・(ポリオールA-3)
1,6-HDとDECのモル比が1.28:1になるように、1,6-HDを898g、DECを700g仕込む以外はポリオールB-1の製造と同様の方法で合成し、ポリオールA-3を得た。ポリオールA-3の水酸基価は149.6(mgKOH/g)であり、数平均分子量は750と算出された。
・(ポリオールA-4)
1,6-HDとDECのモル比が1.22:1になるように、1,6-HDを878g、DECを720g仕込む以外はポリオールB-1の製造と同様の方法で合成し、ポリオールA-4を得た。ポリオールA-4の水酸基価は132.0(mgKOH/g)であり、数平均分子量は850と算出された。
・(ポリオールA-5)
1,6-HDとDECのモル比が1.42:1になるように、1,6-HDを938g、DECを660g仕込む以外はポリオールB-1の製造と同様の方法で合成し、ポリオールA-5を得た。ポリオールA-5の水酸基価は280.5(mgKOH/g)であり、数平均分子量は400と算出された。
・(ポリオールA-6)
1,6-HDとDECのモル比が1.20:1になるように、1,6-HDを872g、DECを726g仕込む以外はポリオールB-1の製造と同様の方法で合成し、ポリオールA-6を得た。ポリオールA-6の水酸基価は118.1(mgKOH/g)であり、数平均分子量は950と算出された。
なお、数平均分子量の算出は下記式に基づいて行った。
数平均分子量=(56100×2)/水酸基価
(ポリカーボネートジオールの水酸基価は、JIS K 1557に準拠して、滴定で求めた。ここで、水酸基価の単位は、mgKOH/gである。
ポリカーボネートジオールの酸価は、JIS K 1557に準拠して、滴定で求めた。ここで、酸価の単位は、mgKOH/gである。)
・(B)脂肪族ジオール:1,4-ブタンジオール
・(C-1)ジイソシアネート:ヘキサメチレンジイソシアネート(HDI)
・(C-2)ジイソシアネート:4,4’-ジフェニルメタンジイソシアネート(MDI)
・(D)離型剤マスターバッチ「ワックスマスターV」(BASF社製)
・(E)PC/ポリエステル樹脂「PCX-6694」(住化ポリカーボネート社製)
表1に記載される組成となるように、撹拌機と温度計の付いた反応容器に、ポリオール(A)、脂肪族ジオール(B)を投入し均一に混合し、得られた混合液を100℃に加熱した後、ジイソシアネート(C)を加え、ハンドミキサーで強制撹拌し、反応温度が130℃に達した時点で離型紙上に流し込み固化させた。得られた固形物を120℃の電気炉で1時間熟成させ、室温まで冷却した後、固形物を粉砕しフレーク状のTPUを得た。
得られたフレーク状のTPUは、二軸押出機で(D)離型剤マスターバッチと重量比で95:5になるようにコンパウンドし、得られたストランドを造粒することで毛状体及び下地層の原料となるTPUペレット(G)を得た。
[実施例1~6、比較例1~3]
1台の40mm単軸押出機から、毛状体及び下地層となる上記TPU(G)を流し、1台の65mm単軸押出機から、基材層となる(E)PC/ポリエステル樹脂を流し、Tダイ法により押出された樹脂シートを、酸化クロム溶射かつレーザー彫刻法で凹凸加工がなされ、60℃~150℃に調節された凹凸加工が成された転写ロールと、10℃~90℃に調節されたゴム硬度70のシリコン系ゴム製のタッチロールとを用い、キャスティングすることで、ピンチロールを用いてライン速度1m/分~15m/分で引き取った。これにより表1に示す組成、厚み及び表面形状の樹脂シートを得た。
樹脂シートの毛状体の高さ(h)、毛状体の径(d)、毛状体の間隔(t)、下地層の厚み、基材層の厚みを、レーザー顕微鏡(VK-X100、キーエンス社製)を用いて測定した。なお、測定した試料は、ミクロトームを用いて樹脂シートの任意の3箇所より断面切片を切り出し用いた。毛状体の平均高さは、それぞれの試料について毛状体10個の高さを測定し、その30測定値の算術平均値を用いた。毛状体の平均径については、それぞれの試料について10個の毛状体の中間高さ(h/2)における径を測定し、その30測定値の算術平均値を用いた。毛状体の平均間隔については、それぞれの試料について毛状体の根元の中心と隣接する毛状体の根元の中心との距離を10箇所測定し、その30測定値の算術平均値を用いた。下地層の平均厚みについては、それぞれの試料について毛状体の根元から他方の層界面までの厚みを10箇所測定し、その30測定値の算術平均値を用いた。基材層の平均厚みについては、それぞれの試料について下地層との境界から毛状体を有する面と反対の界面までの厚みを10箇所測定し、その30測定値の算術平均値を用いた。
得られた樹脂シートについて、インサート成形を実施した。幅250mm、長さ140mm、厚み3mmの樹脂プレートが得られる射出インサート成形機の金型を用意し、幅250mmと長さ140mmから形成される面に樹脂シートが隙間なく収まるよう、樹脂シートをトリミングした。トリミングした樹脂シートは、毛状体を有する面が金型表面に接触し、基材層がキャビティの樹種流動側を向くように配置した。なお、金型は幅250mmと厚み3mmから形成される面に1点ゲートを有し、樹脂シートと並行に射出樹脂が流れ込む構造とした。このような樹脂シートを配置した金型に対し、射出成形機を用いて280℃に加熱されて溶融したPC樹脂を射出し、毛状体を有する樹脂シートのインサート成形品を得た。
良触感性は、男性5人、女性5人の計10人の外部パネラーに樹脂シートを触ってもらう官能評価を実施した。樹脂シート表面を触った際の具体的な触感(滑らか、さらさら、しっとり、かさかさ、ざらざら等)のそれぞれについて10点満点で評価し、最も点数が高かった触感をその樹脂シート表面の触感とした。表1において、「〇」は、滑らか、さらさら、又はしっとりの点数が高く、二次成形後もスエード調の起毛シートのような良触感性が得られたことを示している。「×」は、かさかさ、又はざらざらの点数が高く、二次成形後の良触感性が得られなかったことを示している。
実施例1~6の全ての樹脂シートは、二次成形後も良触感性が維持された。
一方、比較例1の樹脂シートは、成分(A)が数平均分子量950のポリオールに由来するものであって、成分(A)と成分(B)のモル比が90:10の樹脂シートであるが、二次成形によって毛状体が大きく変形し、その触感性はかさかさであり、良触感性を有していなかった。
比較例2の樹脂シートは、成分(A)と成分(B)のモル比が92:8の樹脂シートであるが、二次成形によって毛状体が大きく変形し、その触感性はかさかさであって、良触感性を有していなかった。
比較例3の樹脂シートは、成分(A)が数平均分子量400のポリオールに由来するものであって、成分(A)と成分(B)のモル比が58:42の樹脂シートであるが、二次成形後も毛状体が維持されたものの、下地層と毛状体を構成する熱可塑性樹脂組成物の硬度が高く、触感性はざらざらであり、二次成形の前後いずれも良触感性を有していなかった。
1a 下地層
1b 毛状体
d 毛状体径
h 毛状体の高さ
t 毛状体の間隔
2 基材層
Claims (7)
- 下地層の少なくとも一方の面に規則的に配列された毛状体を有し、下地層と毛状体との間には構造的な境界がなく連続相を形成している熱可塑性樹脂シートであって、前記下地層と毛状体を構成する熱可塑性樹脂組成物がウレタン系エラストマーを含み、前記ウレタン系エラストマーが、数平均分子量450~900のポリオールに由来する成分(A)と、炭素数2~10の脂肪族ジオールに由来する成分(B)を含み、(A)と(B)のモル比が60:40~88:12である、樹脂シート。
- 前記毛状体の平均高さが30μm以上500μm以下、毛状体の平均径が1μm以上50μm以下、毛状体の平均間隔が20μm以上200μm以下である、請求項1に記載の樹脂シート。
- 前記ポリオールがポリカーボネート系ジオールである、請求項1又は2に記載の樹脂シート。
- 下地層の毛状体とは反対側の面に基材層を有する、請求項1又は2に記載の樹脂シート。
- 請求項1又は2に記載の樹脂シートの成形品。
- インサート成形品又は真空成形品である、請求項5に記載の成形品。
- 自動車内装材、電子機器外装材、又は化粧品容器の表面に設けられている、請求項5に記載の成形品。
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JP2017029608A (ja) | 2015-08-05 | 2017-02-09 | 株式会社エイエムジー | 化粧品容器 |
WO2018016562A1 (ja) | 2016-07-20 | 2018-01-25 | デンカ株式会社 | 毛状体を有する熱可塑性樹脂シート及びその成形品 |
WO2019049897A1 (ja) * | 2017-09-06 | 2019-03-14 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
WO2020196638A1 (ja) * | 2019-03-26 | 2020-10-01 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
JP2020189420A (ja) * | 2019-05-21 | 2020-11-26 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
WO2021145295A1 (ja) * | 2020-01-15 | 2021-07-22 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
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JP2005228911A (ja) | 2004-02-13 | 2005-08-25 | Honda Lock Mfg Co Ltd | 携帯電子機器 |
JP2009184421A (ja) | 2008-02-04 | 2009-08-20 | Honda Access Corp | カバーパネル |
JP2017029608A (ja) | 2015-08-05 | 2017-02-09 | 株式会社エイエムジー | 化粧品容器 |
WO2018016562A1 (ja) | 2016-07-20 | 2018-01-25 | デンカ株式会社 | 毛状体を有する熱可塑性樹脂シート及びその成形品 |
WO2019049897A1 (ja) * | 2017-09-06 | 2019-03-14 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
WO2020196638A1 (ja) * | 2019-03-26 | 2020-10-01 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
JP2020189420A (ja) * | 2019-05-21 | 2020-11-26 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
WO2021145295A1 (ja) * | 2020-01-15 | 2021-07-22 | デンカ株式会社 | 毛状体を有する樹脂シート及びその成形品 |
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