WO2022014439A1 - 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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- WO2022014439A1 WO2022014439A1 PCT/JP2021/025632 JP2021025632W WO2022014439A1 WO 2022014439 A1 WO2022014439 A1 WO 2022014439A1 JP 2021025632 W JP2021025632 W JP 2021025632W WO 2022014439 A1 WO2022014439 A1 WO 2022014439A1
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- Prior art keywords
- resin
- resin sheet
- layer
- base layer
- trichome
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Definitions
- the present invention relates to a resin sheet having a trichome and a molded product thereof.
- Patent Document 1 proposes a resin sheet having hair-like bodies regularly arranged on the surface.
- the problem to be solved by the present invention is to provide a resin sheet and a molded product thereof that have good tactile sensation and can be secondarily molded even on the surface of a member having a complicated shape.
- the present inventor has a base layer having hair-like bodies regularly arranged on one surface and a base material layer on the surface of the base layer opposite to the hair-like bodies.
- the resin sheet having the above, the thickness (a) of the base material layer is 10 ⁇ m or more and 250 ⁇ m or less, the thickness (a) of the base material layer and the thickness (b) of the base layer satisfy a ⁇ b, and the base material.
- the layer contains a polycarbonate resin and / or a styrene resin, and the base layer and the hairy body contain a thermoplastic polyurethane resin, so that the surface of the member has a good tactile sensation and a complicated shape. We have found that secondary molding is possible, and have completed the present invention.
- the thickness (a) of is 10 ⁇ m or more and 250 ⁇ m or less
- the thickness (a) of the base material layer and the thickness (b) of the base layer satisfy a ⁇ b
- the base material layer is a polycarbonate resin and / or a styrene resin.
- a resin sheet containing, and the underlying layer and hairy body contains a thermoplastic polyurethane resin.
- the resin sheet according to (1) wherein the thickness (b) of the base layer is 10 ⁇ m or more and 500 ⁇ m or less.
- the average height of the trichomes is 30 ⁇ m or more and 500 ⁇ m or less, the average diameter of the trichomes is 1 ⁇ m or more and 60 ⁇ m or less, and the average spacing of the trichomes is 20 ⁇ m or more and 200 ⁇ m or less.
- the resin sheet according to the first embodiment of the present invention has a base layer having hair-like bodies regularly arranged on one surface and a base material layer on the surface of the base layer opposite to the hair-like bodies.
- the thickness (a) of the base material layer is 10 ⁇ m or more and 250 ⁇ m or less
- the thickness (a) of the base material layer and the thickness (b) of the base layer satisfy a ⁇ b
- the base material layer is A resin sheet containing a polycarbonate-based resin and / or a styrene-based resin, and having a base layer and a hairy body containing a thermoplastic polyurethane resin. As shown in FIG.
- the layer structure of the resin sheet according to the first embodiment has a structure of a trichome and a base layer / base material layer from top to bottom.
- the base material layer in the present embodiment preferably has sufficient adhesiveness with the base layer.
- the base layer (1a) is a layer that serves as a base for the hair-like body, and refers to a portion of reference numeral 1 other than the hair-like body 1b on the surface.
- the thickness of the base layer is the thickness from the root of the trichome to the surface on the opposite side of the base layer.
- the average thickness of the base layer is preferably 10 ⁇ m or more and 500 ⁇ m or less, more preferably 50 ⁇ m or more and 450 ⁇ m or less, and further preferably 100 ⁇ m or more and 400 ⁇ m or less. By setting it to 10 ⁇ m or more, the height of the trichome can be sufficiently expressed. Further, when the thickness is 500 ⁇ m or less, trichomes can be efficiently formed.
- a continuous phase there is no structural boundary between the base layer and the trichome, and a continuous phase may be formed.
- the fact that there is no structural boundary means that the underlying layer and the trichome are integrally formed, and there is no structurally clear boundary between them.
- forming a continuous phase means a state in which there is no seam between the base layer and the trichome and the phase is not discontinuous (it is a continuous phase). In this respect, it is different from the structure in which trichomes are planted in the base layer.
- the base layer and the trichome may have the same composition, and the bond between the base layer and the trichome may include a covalent bond.
- a covalent bond is a chemical bond formed by sharing an electron pair with two atoms.
- thermoplastic resin which is a chain molecule in which monomers are linked
- individual polymers are bonded by a covalent bond. It is stronger than the van der Waals and hydrogen bonds that work between polymer molecules.
- the base layer and the trichome may be derived from the same individual thermoplastic resin sheet which is not separate. Derived from the same solid thermoplastic resin sheet means, for example, that the trichome and the underlying layer are directly or indirectly obtained based on the same resin sheet. Further, the base layer and the trichome may be formed from the same individual thermoplastic resin sheet. Forming from the same individual thermoplastic resin sheet means that the trichome and the underlying layer are directly formed by processing one resin sheet.
- the base layer and the trichome are made of the same resin composition containing a thermoplastic resin as a main component.
- the main component means that it is contained in an amount of 50% by mass or more.
- the base layer and the trichome preferably contain 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more of the thermoplastic resin.
- the thermoplastic resin in one embodiment of the present invention contains 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more of the thermoplastic polyurethane resin.
- thermoplastic resin such as a styrene resin, an olefin resin, a polyvinyl chloride resin, a thermoplastic elastomer, and a fluororesin can be further contained.
- the content of the other thermoplastic resin can be 10% by mass or more and 50% by mass or less in the total resin composition.
- Thermoplastic polyurethane resin is a resin that an isocyanate and a polyol as raw materials, as a combination, isocyanate diphenylmethane diisocyanate (MDI) system, H 12 MDI system, hexamethylene diisocyanate (HDI) system, the polyol is polyether, Either a polyester-based or a polycarbonate-based combination may be selected, or a plurality of combinations may be used. In one embodiment of the present invention, a combination of an HDI-based isocyanate and a carbonate-based polyol can be preferably used.
- MDI isocyanate diphenylmethane diisocyanate
- HDI hexamethylene diisocyanate
- a combination of an HDI-based isocyanate and a carbonate-based polyol can be preferably used.
- styrene-based resin examples include styrene-based monomers alone or polymers such as styrene, ⁇ -methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene, and chlorostyrene, and styrene-based monomers and other monomers.
- Polymers such as styrene-acrylic nitrile copolymer (AS resin), or diene rubbers such as the styrene-based monomer and other polymers such as polybutadiene, styrene-butadiene copolymer, polyisoprene, and polychloroprene.
- a graft polymer graft-polymerized in the presence of a quality polymer for example, polystyrene such as high-impact polystyrene (HIPS resin) and styrene-acrylic nitrile graft polymer (ABS resin) can be used. Further, a styrene-based thermoplastic elastomer can also be used.
- HIPS resin high-impact polystyrene
- ABS resin styrene-acrylic nitrile graft polymer
- a styrene-based thermoplastic elastomer can also be used.
- the polyolefin-based resin means a resin composed of a polymer containing ⁇ -olefin as a monomer.
- the polyolefin resin include polyethylene resin and polypropylene resin.
- the polyethylene resin high-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear medium-density polyethylene and the like can be used, and not only simple substances but also copolymers and grafts having these structures can be used. And blends can also be used.
- Examples of the latter resin include ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, and ethylene-vinyl acetate-vinyl chloride copolymer.
- Examples thereof include those obtained by copolymerizing and blending a resin having a polar group in a polyethylene chain, such as those blended with a coalescence or a ternary copolymer with an acid anhydride.
- the polypropylene resin homopolypropylene, random polypropylene, block polypropylene and the like can be used.
- the structure of the homopolypropylene may be isotactic, atactic, or syndiotactic.
- the ⁇ -olefin to be copolymerized with propylene is preferably those having 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, 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. In addition to 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 another co-monomer can be used.
- polyvinyl chloride when polyvinyl chloride is a copolymer, it may be a random copolymer or a graft copolymer.
- graft copolymer for example, an ethylene-vinyl acetate copolymer or a thermoplastic urethane polymer may be used as a stem polymer, and vinyl chloride may be graft-polymerized thereto.
- the polyvinyl chloride of the present embodiment is a composition which represents a soft polyvinyl chloride which can be extruded and contains an additive such as a polymer plasticizer.
- polymer plasticizer a known polymer plasticizer can be used, and for example, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene- (meth) acrylic acid ester-carbon monoxide copolymer, acetic acid.
- ethylene copolymer polymer plasticizer such as an ethylene-vinyl acetate copolymer having a high vinyl content.
- Thermoplastic elastomers include those having a structure in which a soft polymer substance and a hard polymer substance are combined. Specific examples thereof 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 those generally available on the market.
- PVDF Polyfluorovinylidene
- Hexafluoropropylene copolymer vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexa Included are fluoropropylene ternary copolymers, vinylidene fluoride-chlorotrifluoroethylene-hexafluoropropylene ternary copolymers, and mixtures of two or more thereof.
- the melt mass flow rate of the thermoplastic resin at 190 ° C to 300 ° C is preferably 4 g / 10 minutes or more. By setting the amount to 4 g / 10 minutes or more, the transferability of the shape of the trichome can be improved.
- the melt mass flow rate is a value measured under a load (2.16 kg to 10.0 kg) in a temperature range of 190 ° C. to 300 ° C. as a test temperature according to JIS K7210.
- thermoplastic resin may be alloyed with each of the above thermoplastic resins in an arbitrary ratio as long as the effect of the present invention is not impaired.
- other additives may be contained.
- Other additives include water and oil repellents, colorants such as pigments and dyes, mold release agents such as silicon oil and alkyl esters, and fibrous reinforcement such as glass fibers, as long as the effects of the present invention are not impaired.
- Agents and fillers include granular fine particles such as talc, clay and silica, scaly fine particles such as mica, low molecular weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, and high levels of polyether ester amides. Additives such as molecular antistatic agents, flame retardants, antibacterial agents, antiviral agents, and heat stabilizers can be added. Further, scrap resin generated in the resin sheet manufacturing process can be mixed and used.
- Examples of the water / oil repellent include silicone-based water-repellent agents, carnauba wax, and fluorine-based water-repellent / oil-repellent agents.
- Examples of silicon include organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and among them, dimethylpolysiloxane is preferably used.
- Examples of commercially available products include "Klimbell CB50-PP", “Klimbell CB-30PE", “Klimbell CB-1", and "Klimbell CB-50AB” (manufactured by Fuji Chemical Co., Ltd.), which are alloyed with silicon as a resin.
- Examples of commercially available carnauba wax include “Carnauba No. 1” (manufactured by Nikko Rika Co., Ltd.), and examples of the fluorine-based water- and oil-repellent agent include surfactants having a perfluoroalkyl group. Examples thereof include “Surflon KT-PA” (manufactured by AGC Seimi Chemical Co., Ltd.).
- the amount of the water-repellent / oil-repellent agent added is preferably 0.5% by mass to 25% by mass. If it is less than 0.5% by mass, a sufficient water / oil repellency effect may not be obtained, and if it exceeds 25% by mass, the moldability may be deteriorated.
- the antistatic agent examples include a polyether ester amide-based polymer antistatic agent and an ionomer-based polymer antistatic agent.
- examples of commercially available products of the polyether ester amide-based polymer antistatic agent include "Perestat 230", “Perestat 6500”, “Perectron AS”, and “Perectron HS” (manufactured by Sanyo Chemical Industries, Ltd.).
- Examples of commercially available products of the ionomer-based polymer type antistatic agent examples include "Entila SD100" and "Entila MK400” (manufactured by Mitsui DuPont Polychemical Co., Ltd.).
- the amount of the antistatic agent added is preferably 5% by mass to 30% by mass. If it is less than 5% by mass, sufficient antistatic property may not be obtained, and if it exceeds 30% by mass, the production cost increases.
- an inorganic type is preferable in consideration of dispersibility.
- Specific examples thereof include an inorganic antibacterial agent of metal ions (Ag, Zn, Cu), a calcined shell calcium-based antibacterial agent, and the like.
- Commercially available products of metal ion inorganic antibacterial agents include "Bactekiller BM102VT” (manufactured by Fuji Chemical Co., Ltd.), “Novalon VZF200", “Novalon (AG300)” (manufactured by Toagosei Co., Ltd.), “KM-10D-G", Examples thereof include “IM-10D-L” (manufactured by Sinanen Zeomic).
- calcined shell calcium-based antibacterial agent examples include "Scullow” (manufactured by FID).
- the amount of the antibacterial agent 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, the production cost increases.
- an alkyl-based mold release agent such as an aliphatic hydrocarbon compound, a higher fatty acid-based compound, a higher aliphatic alcohol-based compound, a fatty acid amide-based compound, a silicon-based mold release agent, a fluorine-based mold release agent, etc.
- the amount added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and 0.1 to 2 parts by mass out of a total of 100 parts by mass with the resin composition. Parts by mass are more preferred. If the amount added is less than 0.01 parts by mass, the mold release effect may be low, and if it exceeds 5 parts by mass, it may bleed out to the sheet surface.
- a masterbatch in which a lubricant / mold release agent is alloyed with a thermoplastic resin in advance.
- a commercially available masterbatch based on urethane-based thermoplastic elastomer "Wax Master V" (manufactured by BASF) can be mentioned, and it is preferable to use the masterbatch in consideration of production efficiency.
- the amount of the masterbatch added is preferably 1 to 8 parts by mass, more preferably 2 to 7 parts by mass, still more preferably 3 to 6 parts by mass, out of 100 parts by mass in total with the resin composition.
- the hair-like body (1b) means a portion extending like a hair from the surface of the base layer (1a) as shown in FIG.
- the trichomes are regularly arranged on the surface of the underlying layer.
- regularly arranged means a non-random arrangement state, that is, a state in which the hairs are arranged in an orderly manner (for example, at regular intervals) in one direction or two directions. .. Whether or not the arrangement of the trichomes is regular is determined based on the arrangement state of the roots of the trichomes.
- the trichomes are located on the underlying layer at predetermined intervals, and the positions of the bottom surface of the trichomes are neatly arranged in the longitudinal direction and the lateral direction of the underlying layer.
- the arrangement form of the trichomes is not particularly limited, and a grid arrangement or a staggered arrangement arranged vertically and horizontally can be selected. Since the trichomes are regularly arranged on the surface of the base layer, they are uniform and even, and it is easy to develop a good tactile sensation. The trichome can fall down due to a load such as tracing with a finger, and can form a finger mark that looks different in luster and color from the surrounding portion. In addition, the trichome can give a tactile feel like a suede-like brushed sheet.
- the average height (h) of the trichome is preferably 30 ⁇ m to 500 ⁇ m, more preferably 30 ⁇ m to 250 ⁇ m, further preferably 30 ⁇ m to 200 ⁇ m, and particularly preferably 90 ⁇ m to 200 ⁇ m. ..
- the average height is 30 ⁇ m or more, a good tactile sensation can be sufficiently secured, and when the average height is 500 ⁇ m or less, a good tactile sensation such as a moist feeling, a soft feeling, and a fluffy feeling can be obtained.
- the length from the root to the tip of the trichome represents the height of the trichome.
- the base layer is located at a position where the hairy body is most distant from the surface of the base layer.
- the distance from the surface of the hair be the height h of the trichome.
- the total value of the intervals obtained by subdividing the hair from the tip to the center of the root by multipoint measurement is defined as the length L of the hair.
- the average height of the trichome and the average length of the trichome are the height of the trichome and the length of the trichome at any number of places on the resin sheet using an electronic microscope and image processing software. Can be measured and the arithmetic mean value of the measured value can be used.
- the average diameter (d) of the trichome is preferably 1 ⁇ m to 60 ⁇ m, more preferably 5 ⁇ m to 50 ⁇ m, and even more preferably 5 ⁇ m to 40 ⁇ m.
- a good tactile sensation can be ensured by setting the average diameter of the hairy body to 1 ⁇ m or more, and a good tactile sensation such as a moist feeling, a soft feeling, and a fluffy feeling can be obtained by setting the average diameter of the hairy body to 60 ⁇ m or less. can get.
- For the average diameter of the trichome measure the diameter of the intermediate height (h / 2) of the trichome from several places on the resin sheet using an electron microscope and image processing software, and the arithmetic mean value of the measured value. It is a value using.
- the aspect ratio of the trichome can be expressed as (average height of trichome / average diameter of trichome).
- the aspect ratio of the trichome is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 5.
- the aspect ratio can also be based on the average bottom diameter of the trichome.
- the average bottom diameter of the trichome is preferably 10 ⁇ m to 150 ⁇ m.
- the average bottom diameter of the trichomes is a value obtained by measuring the distance between adjacent trichomes 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 trichome is preferably 1.0 to 10, more preferably 1.0 to 5, and preferably 1.0 to 2.5. More preferred. By setting the aspect ratio to 1.0 or more, good touch can be ensured, and by setting the aspect ratio to 10 or less, not only good touch such as moist, soft and fluffy feeling can be obtained, but also hair. It is possible to reduce the possibility that the ratio of the height to the length of the shape is below a certain level.
- the average spacing (t) of the trichomes is preferably 20 ⁇ m to 200 ⁇ m, more preferably 40 ⁇ m to 150 ⁇ m, and even more preferably 40 ⁇ m to 100 ⁇ m.
- the distance between the trichomes means the distance between the center of the root of the trichome and the center of the root of the adjacent trichome, for example, as shown in FIG.
- the average interval is 20 ⁇ m or more, good tactile sensation is ensured, and when it is 200 ⁇ m or less, good tactile sensation such as moist feeling, soft feeling, and fluffy feeling can be obtained.
- the average spacing of trichomes is a value obtained by measuring the spacing between adjacent trichomes at several points on the resin sheet and using the arithmetic mean value of the measured values.
- the shape of the hair-like body is not particularly limited, but it may be a shape that grows like a hair in a direction away from the base layer and gradually becomes thinner as it approaches the tip, or a structure in which a bulge is formed at the tip. That is, the shape may be such that the cross-sectional area gradually decreases, then increases once, and then terminates as the distance from the base layer increases. Further, the shape of the tip of the hairy body may be a bud shape or a mushroom shape. Further, the trichome is a portion located at the proximal end extending in a direction away from the base layer and a portion extending from the portion located at the proximal end and bending with a constant curvature or by gradually changing the curvature.
- the tip of the trichome may be folded inward. With such a shape, a good tactile sensation is developed.
- the hollow bud-shaped or mushroom-shaped portion provides a better tactile sensation.
- the ratio of the average diameter of the width of the bud-shaped or mushroom-shaped body to the average diameter of the hair-like body is preferably 1.1 times or more.
- the height of the bud-shaped or mushroom-shaped shape is preferably 7 ⁇ m or more.
- the average diameter of the trichome, the average diameter of the width of the bud or mushroom shape, and the height are measured from an electron scanning micrograph and used as the arithmetic mean value.
- the trichome is made of a thermoplastic resin.
- the thermoplastic resin the same resin as the resin that can be used in the base layer can be used.
- the thermoplastic resin contained in the base layer and the trichome 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 part of the hair is a cross-linked body
- the entire surface of the hair-like body is a cross-linked body
- the hair is a cross-linked body.
- the entire shape (from the boundary with the underlying layer to the tip) may be a crosslinked body.
- a method for forming a crosslinked body for example, a method of irradiating a surface having a trichome with an electron beam after molding a resin sheet, or a method of adding an organic peroxide to form a resin sheet during or after molding.
- Examples thereof include a method of forming by heating and humidification.
- Examples of commercially available resins include "Linkron” manufactured by Mitsubishi Chemical Corporation as a resin to which an organic peroxide is added.
- a thermoplastic resin having excellent adhesiveness to the base layer it is preferable to use a thermoplastic resin having excellent adhesiveness to the base layer, and a polycarbonate resin, a styrene resin, a polymer alloy of these, or the like is used. be able to.
- a polycarbonate resin or a styrene resin is polymer-alloyed with a thermoplastic resin such as an olefin resin, a polyester resin, a nylon resin, an acrylic resin, or a thermoplastic elastomer at an arbitrary ratio. Can be used.
- the polymer alloy ratio is preferably 99: 1 to 20:80, more preferably 80:20 to 30:70, and even more preferably 60:40 to 40:60. Further, in the case of laminating, there are laminating by coextrusion molding, non-stretching film, extrusion laminating molding using biaxially stretched film, and laminating by dry laminating molding.
- polycarbonate resin examples include those derived from an aliphatic dihydroxy compound and those derived from an aromatic dihydroxy compound.
- those derived from aromatic dihydroxy compounds can be preferably used, and in particular, those derived from two aromatic dihydroxy compounds derived from an aromatic dihydroxy compound (bisphenol) bonded via a certain binding group are used.
- aromatic dihydroxy compounds can be preferably used, and in particular, those derived from two aromatic dihydroxy compounds derived from an aromatic dihydroxy compound (bisphenol) bonded via a certain binding group are used.
- aromatic dihydroxy compounds can be preferably used, and in particular, those derived from two aromatic dihydroxy compounds derived from an aromatic dihydroxy compound (bisphenol) bonded via a certain binding group are used. preferable.
- These can be those produced by a known production method by polycondensation of a dihydroxy compound and phosgene or a carbonic acid ester, and are not limited to the production method, and commercially available resins can also be used.
- styrene-based resin as in the case of the underlayer, styrene-based monomers such as styrene, ⁇ -methylstyrene, p-methylstyrene, dimethylstyrene, pt-butylstyrene, chlorostyrene and the like alone or copolymers, and styrene thereof.
- a copolymer of a system monomer and another monomer for example, a styrene-acrylic nitrile copolymer (AS resin), or a polymer of the styrene system monomer and another polymer, such as polybutadiene, a styrene-butadiene copolymer, polyisoprene, poly.
- AS resin styrene-acrylic nitrile copolymer
- polymer of the styrene system monomer and another polymer such as polybutadiene, a styrene-butadiene copolymer, polyisoprene, poly.
- diene-based rubbery polymers such as chloroprene, such as high-impact polystyrene (HIPS resin), styrene-acrylic nitrile graft polymer (ABS resin), acrylonitrile-ethylene / propylene rubber-styrene ( Styrene such as AES)
- HIPS resin high-impact polystyrene
- ABS resin styrene-acrylic nitrile graft polymer
- the base material layer may contain other additives, if necessary.
- Other additives include colorants such as water repellents, oil repellents, pigments and dyes, lubricants / mold release agents such as silicon oils and alkyl esters, glass fibers and the like, as long as the effects of the present invention are not impaired.
- granular antistatic agents such as granular fine particles such as talc, clay and silica, scaly fine particles such as mica, low molecular weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, and polyether esters.
- the base material layer may have a partially crosslinked structure as long as the effect of the present invention is not impaired. Further, in the present embodiment, the base material layer may have a partially crosslinked structure as long as the effect of the present invention is not impaired.
- the average thickness of the base material layer is preferably 10 ⁇ m to 250 ⁇ m, more preferably 30 ⁇ m to 230 ⁇ m, and even more preferably 50 ⁇ m to 220 ⁇ m. When it is 10 ⁇ m or more, the film forming process becomes easy, and when it is 250 ⁇ m or less, it is suppressed that the value of rigidity and softness becomes high.
- the resin sheet in one embodiment of the present invention has a good tactile sensation and can be secondarily molded even on a member surface having a complicated shape. If it can be secondarily molded on the surface of a member having a complicated shape, it is suitable for use on the surface of an automobile interior member, an electronic device, an electronic device exterior material, a cosmetic container, a container member, or the like.
- "tactile” means the texture and touch of the surface of the resin sheet. Judge whether you feel comfortable when you touch the surface of the resin sheet, and if you feel it, consider it as moist, soft, fluffy, or something that feels good to the touch.
- the thickness (a) of the base material layer and the thickness (b) of the base layer satisfy a ⁇ b.
- a ⁇ b it is suppressed that the rigidity and softness become a high value, and secondary molding becomes possible on the surface of a member having a complicated shape.
- the thickness of the resin sheet means the sheet thickness obtained by combining the average height of the trichome, the average thickness of the base layer, and the average thickness of the base material layer.
- the sheet thickness is preferably 80 ⁇ m to 1000 ⁇ m, more preferably 150 ⁇ m to 900 ⁇ m, and even more preferably 300 ⁇ m to 800 ⁇ m. When the thickness is 80 ⁇ m or more, a good tactile sensation can be sufficiently ensured, and when the thickness is 1000 ⁇ m or less, the manufacturing cost can be suppressed.
- the total thickness of the base layer and the base material layer is preferably 20 ⁇ m to 750 ⁇ m, more preferably 150 ⁇ m to 600 ⁇ m, and further preferably 300 ⁇ m to 500 ⁇ m.
- the resin sheet has a rigidity of 150 mm or less, more preferably 120 mm or less, still more preferably 100 mm or less, as measured according to the 45 ° cantilever method of JIS L 1096: 2010. .. However, if the rigidity is greater than 150 mm in either the front or back of the vertical direction or the horizontal direction, it is considered that the rigidity of the resin sheet is greater than 150 mm. In one embodiment of the present invention, the resin sheet has a rigidity of 30 mm or more, more preferably 40 mm or more, still more preferably 50 mm or more, as measured according to the 45 ° cantilever method of JIS L 1096: 2010. ..
- the resin sheet in another embodiment of the present invention has a rigidity of 30 mm or more and 150 mm or less, more preferably 40 mm or more and 120 mm or less, still more preferably 50 mm in both the front and back surfaces in the vertical direction and the horizontal direction. It is 100 mm or less.
- a sealant resin layer (2) is formed between the base layer (1) and the base material layer (3). It is a resin sheet. That is, the layer structure of the resin sheet according to the second embodiment is a hairy body, a base layer (1), a sealant resin layer (2), and a base material layer (3) from top to bottom.
- the trichome is the same as that described in the first embodiment, the description thereof will be omitted.
- the sealant resin layer is for exhibiting the adhesiveness between the base layer and the base material layer, and as the resin component, a modified olefin resin, a hydrogenated styrene-based thermoplastic elastomer, or the like can be used.
- Modified olefin resins include olefins having about 2 to 8 carbon atoms such as ethylene, propylene, and butene-1, and those olefins and ethylene, propylene, butene-1,3-methylbutene-1, pentene-1,4-methyl. Copolymers of other olefins having about 2 to 20 carbon atoms such as pentene-1, hexene-1, octene-1, decene-1, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid.
- Olefin resins such as copolymers with vinyl compounds such as esters and styrene, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, ethylene-butene-1 copolymers, and propylene-butene-1
- An olefin rubber such as a polymer may be an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, or an acid halide or amide thereof.
- Imid anhydrides, esters and other derivatives, specifically, those modified under graft reaction conditions with maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. Can be used.
- unsaturated dicarboxylic acid or its anhydride particularly maleic acid or its anhydride-modified "ethylene-propylene-diene copolymer” or ethylene-propylene or butene-1 copolymer rubber is preferable.
- Examples of the hydrogenated styrene-based thermoplastic elastomer include a hydrogenated additive of a styrene-based monomer and a copolymer of butadiene or isoprene, and a hydrogenated additive of a styrene-butadiene-styrene block copolymer (styrene-ethylene-butylene-styrene block co-weight).
- hydrogenated styrene-isoprene-styrene block copolymer styrene-ethylene / propylene-styrene block copolymer
- styrene-ethylene / butylene-styrene block copolymer is particularly preferable. ..
- the average thickness of the sealant resin layer is preferably 20 ⁇ m to 90 ⁇ m, more preferably 40 ⁇ m to 80 ⁇ m. When it is 20 ⁇ m or more, it is possible to suppress delamination between the base layer and the base material layer, and when it is 90 ⁇ m or less, the production cost can be suppressed.
- the sealant resin layer may be alloyed with each of the above thermoplastic resins at an arbitrary ratio as long as the effects of the present invention are not impaired.
- it may contain other additives.
- Other additives include colorants such as water repellents, oil repellents, pigments and dyes, lubricants / mold release agents such as silicon oils and alkyl esters, glass fibers and the like, as long as the effects of the present invention are not impaired.
- fibrous reinforcing agents and fillers granular antistatic agents such as granular fine particles such as talc, clay and silica, scaly fine particles such as mica, low molecular weight antistatic agents such as salt compounds of sulfonic acid and alkali metals, and polyether esters.
- Additives such as high molecular weight antistatic agents such as amides, ultraviolet absorbers, flame retardants, antibacterial agents, antiviral agents, and heat stabilizers can be added. Further, in the present embodiment, the sealant resin layer may have a partially crosslinked structure as long as the effect of the present invention is not impaired.
- the method for producing the resin sheet according to the present invention is not limited and may be any method, but typically, the raw material resin is melt-extruded and regularly arranged on at least one surface of the obtained extruded resin sheet. It includes a step of imparting a trichome.
- any resin sheet molding method can be used when producing a single-layer sheet or a multi-layer resin sheet.
- a single layer one single-screw extruder is used, and in the case of a multi-layer, a plurality of single-screw extruders are used to melt-extrude each raw material resin and obtain a resin sheet by a T-die. Be done.
- feed blocks 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, but in addition, for example, the scrap raw material generated in the manufacturing process of the resin sheet or the molded container of the present invention has physical characteristics. As long as deterioration such as is not observed, it may be added to the base material layer or laminated as a further layer.
- the method for imparting trichomes 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 hot press method, a pattern roll and UV curing.
- a method of producing using a resin a method of producing using a 3D printer, a method of embedding a hairy body in a resin layer and then covalently bonding by a polymerization reaction, and the like.
- the resin sheet is extruded by the T-die method and cast with a transfer roll and a touch roll that have been subjected to uneven processing so as to give a trichome shape to the surface of the resin sheet.
- the resin sheet according to the present invention can be manufactured.
- a transfer roll with uneven processing a roll with fine irregularities of several ⁇ m to several hundred ⁇ m in size is regularly applied to the surface of the roll by laser engraving method, electroforming method, etching method, mill engraving method, etc. Can be used.
- the term "regular" means an arrangement state in which the unevenness is not random, that is, a state in which the irregularities are arranged in an orderly manner in one direction or two directions.
- the unevenness in a certain embodiment, it is possible to select a grid arrangement arranged vertically and horizontally, a staggered arrangement, and the like.
- the shape of the uneven portion include a cone shape (cone, quadrangular pyramid, triangular pyramid, hexagonal pyramid, etc.), a semicircle, and a rectangular shape (square pillar) in the case of the shape of the concave portion.
- 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.
- the material of the transfer roll for example, metal, ceramic or the like can be used.
- the spacing of the trichomes can be adjusted by adjusting the spacing of the recesses of the transfer roll, and the height of the trichomes can be adjusted by adjusting the depth of the recesses of the transfer roll, thereby adjusting the tactile sensation. You can also do it. Further, it is preferable to process the surface of the transfer roll with unevenness having a high aspect ratio.
- the aspect ratio (recess depth / recess opening diameter) when the concave shape is processed on the surface of the transfer roll is preferably 1.0 to 9.0.
- the laser engraving method or electroforming method is more precise in the depth direction than the etching method, blast method, mill engraving method, etc.
- the transfer roll for example, metal, ceramic or the like can be used.
- the touch roll various materials can be used, and for example, a roll made of silicon-based rubber, NBR-based rubber, EPT-based rubber, butyl rubber, chloroprene rubber, or fluororubber can be used. In certain embodiments, touch rolls having a rubber hardness (JIS K 6253) of 40 to 100 can be used. Further, a Teflon (registered trademark) layer may be formed on the surface of the touch roll.
- the touch roll various materials can be used, and for example, a roll made of silicon-based rubber, NBR-based rubber, EPT-based rubber, butyl rubber, chloroprene rubber, or fluororubber can be used. In certain embodiments, touch rolls having a rubber hardness (JIS K 6253) of 40 to 100 can be used. Further, a Teflon (registered trademark) layer may be formed on the surface of the touch roll.
- the resin sheet of the present embodiment can be manufactured.
- the temperature of the transfer roll is adjusted to a temperature near the melting point of the thermoplastic resin, the glass transition point or the melting point (for example, 100 to 150 ° C.
- the resin sheet of the present embodiment can be manufactured by casting with a pinch pressure of 30 to 120 kg / cm 2.
- the cast resin sheet is picked up at a line speed of 0.5 to 30 m / min using a pinch roll or the like.
- the said embodiment is concretely shown, it is not limited to these.
- the molded product of the present invention is a molded product using the resin sheet of the present invention.
- the resin sheet of the present invention can be used not only for general molding but also for decorative molding in which the surface of a molded product is decorated with printing at the time of molding.
- a molding method in addition to insert molding and in-mold molding, general vacuum forming, pneumatic molding and applications thereof are existing by heating and softening the resin sheet in a vacuum state and opening it under atmospheric pressure. Examples thereof include, but are not limited to, a method of overlaying (molding) on the surface of a molded product.
- a known sheet heating method such as radiant heating by an infrared heater or the like which is non-contact heating can be applied.
- a resin sheet is heated at a surface temperature of 60 ° C. to 220 ° C. for 20 seconds to 480 seconds and then molded onto the surface of an existing molded product, and 1.0 to 1.0 depending on the shape of the surface. It is stretched 4.0 times.
- the resin sheet having the hair-like body attached to the surface according to the present invention can be applied to the above-mentioned applications in which good tactile sensation is required.
- the resin sheet of the present invention can be applied as an automobile interior material, an electronic device, an electronic device exterior material, a cosmetic container or container member, a stationery member, a lighting fixture member, and a daily goods member.
- an interior material obtained by molding and laminating the above-mentioned resin sheet on the surface of a known instrument panel or pillar (for example, Japanese Patent Application Laid-Open No. 2009-184421) can be mentioned.
- an olefin resin, a vinyl chloride resin, and a urethane elastomer are preferable in consideration of weather resistance and chemical resistance.
- the method of bonding the resin sheet and the interior material is not particularly limited.
- keyless entry system transmitter housing smartphone housing, smartphone case, music player case, game machine housing, digital camera housing, electronic organizer housing, calculator housing, tablet housing, etc.
- 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 bonded to the surface of a portable transmitter housing of a known keyless entry system for example, Japanese Patent Application Laid-Open No. 2005-228911
- a portable transmitter in which the resin sheet of the present invention is molded and bonded to the surface of a portable transmitter housing of a known keyless entry system (for example, Japanese Patent Application Laid-Open No. 2005-228911) can be mentioned.
- a portable transmitter in which the resin sheet of the present invention is molded and bonded to the surface of a portable transmitter housing of a known keyless entry system (for example, Japanese Patent Application Laid-Open No. 2005-228911) can be mentioned.
- a portable transmitter By laminating the resin sheets, it is possible to obtain a portable
- the cosmetic container member examples include a container for face cream, pack cream, foundation, and eye shadow.
- a resin sheet of the present invention is placed on the surface of a lid member of a known foundation container (Japanese Patent Laid-Open No. 2017-29608).
- a cosmetic container that has been molded and bonded can be mentioned.
- By laminating the resin sheets it is possible to make a cosmetic container with a good tactile sensation.
- As the material of the resin sheet to be bonded an olefin resin and a urethane elastomer are preferable.
- the method of bonding with the resin sheet is not particularly limited.
- Examples of the stationery member include a book cover, a notebook cover, a pen case cover, and the like. It can be a book cover with waterproofness.
- the book cover form is not particularly limited.
- As the material of the sheet an olefin resin and a urethane elastomer are preferable.
- the method for producing using the resin sheet is not particularly limited.
- Examples of the lighting equipment member include lighting equipment for indoor use and vehicle interior, and examples thereof include a lighting device in which a resin sheet of the present invention is formed and bonded to the surface of a cover member of a known LED lighting device. .. By laminating the resin sheets, it is possible to obtain an LED lighting device having good tactile sensation and light diffusivity.
- a resin sheet of the present invention is formed and bonded to the surface of a cover member of a known LED lighting device. ..
- By laminating the resin sheets it is possible to obtain an LED lighting device having good tactile sensation and light diffusivity.
- an olefin resin and a fluororesin are preferable.
- the method of bonding with the resin sheet is not particularly limited.
- Examples of the daily necessities include toilet products, indoor mats, table sheets, and the like.
- a toilet device in which the resin sheet of the present invention is molded and bonded to the surface of the toilet seat member of the toilet device can be mentioned. ..
- By laminating the resin sheets it is possible to make a toilet seat with a good feel.
- an olefin resin, a vinyl chloride resin, and a fluorine resin are preferable.
- the method of bonding with the resin sheet is not particularly limited.
- a hairy sheet with characters and patterns printed on the surface of the hairy body by a general printing method offset printing method, gravure printing method, flexographic printing method, screen printing method, foil stamping, etc.
- offset printing method offset printing method, gravure printing method, flexographic printing method, screen printing method, foil stamping, etc.
- the material of the resin sheet to be printed is not particularly limited, but it is preferable to consider the printability with the ink agent used for printing.
- the resin sheet of the present invention is used to prepare a laminate formed by laminating (dry laminating molding, extrusion laminating molding) with a printed matter (paper, metal thin film, etc.) on which characters, patterns, etc. are printed, a non-woven fabric, etc., for example, a business card.
- a business card with tactile sensation can be produced by laminating on the printed surface.
- the material of the resin sheet to be laminated is not particularly limited.
- the average diameter of the trichomes the diameters of 10 trichomes 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 spacing of trichomes the distance between the center of the root of the trichome and the center of the root of the adjacent trichome 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 base layer and the base layer the thickness of each layer was measured at 10 points for each sample, and the arithmetic mean value of the 30 measured values was used.
- the thickness of the underlying layer is the distance from the root of the trichome to the interface of the other layer.
- a resin sheet is heated in a vacuum atmosphere with a double-sided vacuum forming machine (NGF-0709-S type, manufactured by Fuse Vacuum Co., Ltd.), and then vacuumed to the surface of a mold made into a miscellaneous goods container mold.
- a molded product was produced by vacuum forming.
- the sheet surface temperature at the time of molding was set to 110 ° C. as a temperature at which good tactile sensation could be sufficiently maintained.
- the shapeability was evaluated by looking at the sheet followability at the corners of the bottom surface of the container. As an evaluation standard, ⁇ was given when the follow-up was possible, and x was given when the follow-up was not possible (when breakage occurred or there was a gap between the container and the sheet).
- thermoplastic resin to be the hair-like body and the base layer is flown, and from one 65 mm single-screw extruder, thermoplastic resin to be the base material layer is flown.
- the resin sheet extruded by the T-die method is subjected to unevenness processing by chrome oxide spraying and laser engraving method, and the unevenness processing is adjusted to 60 ° C to 150 ° C, and the transfer roll is adjusted to 10 ° C to 90 ° C.
- the resin sheets of Examples 1 and 2 satisfy the evaluation regarding the tactile sensation, have a specific rigidity and softness, satisfy the evaluation criteria of the moldability and the shapeability at the time of extrusion molding, and maintain the good tactile sensation. It was shown that shapeability is ensured even in the molding temperature range.
- the sheet of the comparative example satisfied the evaluation of tactile sensation, it did not have a specific rigidity and softness, and it broke in the formative evaluation test or a gap was generated between the container and the sheet (comparison). Examples 1 to 3), wrinkles were generated during extrusion molding (Comparative Example 4), and the evaluation criteria for formability and / or formativeness during extrusion molding were not satisfied.
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Abstract
Description
(1)一方の面に規則的に配列された毛状体を有する下地層と、下地層の毛状体とは反対側の面に基材層とを有する樹脂シートであって、基材層の厚み(a)が10μm以上250μm以下であり、基材層の厚み(a)及び下地層の厚み(b)がa≦bを満たし、基材層がポリカーボネート系樹脂及び/又はスチレン系樹脂を含み、下地層及び毛状体が熱可塑性ポリウレタン樹脂を含む、樹脂シート。
(2)下地層の厚み(b)が10μm以上500μm以下である、(1)に記載の樹脂シート。
(3)JIS L 1096:2010の45°カンチレバー法に従って測定される剛軟度が150mm以下である、(1)又は(2)に記載の樹脂シート。
(4)下地層と基材層との間にシーラント層を有する、(1)から(3)のいずれかに記載の樹脂シート。
(5)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60μm以下、毛状体の平均間隔が20μm以上200μm以下である、(1)から(4)のいずれかに記載の樹脂シート。
(6)インサート成形又は真空成形された、(1)から(5)のいずれかに記載の樹脂シートの成形品。
(7)自動車内装部材、電子機器、電子機器外装材、化粧品容器又は容器部材の表面に成形された、(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、一方の面に規則的に配列された毛状体を有する下地層と、下地層の毛状体とは反対側の面に基材層とを有する樹脂シートであって、基材層の厚み(a)が10μm以上250μm以下であり、基材層の厚み(a)及び下地層の厚み(b)がa≦bを満たし、基材層がポリカーボネート系樹脂及び/又はスチレン系樹脂を含み、下地層及び毛状体が熱可塑性ポリウレタン樹脂を含む、樹脂シートである。
図1に示すように、毛状体及び下地層と基材層とが直接積層されたものである。すなわち、第一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/基材層という構成を有している。本実施形態における基材層は、下地層と十分な接着性を備えたものとするのが好ましい。
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10μm以上500μm以下であることが好ましく、50μm以上450μm以下であることがより好ましく、100μm以上400μm以下であることがさらに好ましい。10μm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、別個ではない同一個体の熱可塑性樹脂シートに由来してもよい。同一個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、同一個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。同一個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。
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。
第一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、スチレン系樹脂、これらをポリマーアロイしたもの等を用いることができる。
他の実施形態においては、ポリカーボネート系樹脂又はスチレン系樹脂に、オレフィン系樹脂、ポリエステル系樹脂、ナイロン系樹脂、アクリル系樹脂、熱可塑性エラストマーなどの熱可塑性樹脂と任意の割合でポリマーアロイしたものを用いることができる。
ポリマーアロイする割合としては、99:1~20:80が好ましく、80:20~30:70がより好ましく、60:40~40:60が更に好ましい。また、積層する場合、共押出成形による積層や無延伸フィルム、二軸延伸フィルムを用いた押出ラミネート成形、ドライラミネート成形による積層がある。
また、本実施形態において、本発明の効果を阻害しない範囲で、基材層が部分的に架橋構造を有していてもよい。
本実施形態において、基材層の平均厚みは、10μm~250μmが好ましく、30μm~230μmであることがより好ましく、50μm~220μmであることがさらに好ましい。10μm以上とすることで、製膜工程が容易になり、250μm以下とすることで、剛軟度の値が高くなるのが抑制される。
本発明の一実施形態における樹脂シートは、良い触感性を有し、かつ複雑な形状を有する部材表面にも二次成形可能である。複雑な形状を有する部材表面にも二次成形可能であれば、自動車内装部材、電子機器、電子機器外装材、化粧品容器又は容器部材等の表面への使用に適している。
また、本発明の他の実施形態における樹脂シートは、縦方向及び横方向の表裏のいずれにおいても剛軟度が30mm以上150mm以下であり、より好ましくは40mm以上120mm以下であり、さらに好ましくは50mm以上100mm以下である。
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(1)と基材層(3)との間に、シーラント樹脂層(2)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)、シーラント樹脂層(2)、基材層(3)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。
シーラント樹脂層は、下地層と基材層との接着性を発現させるためのものであり、樹脂成分としては、変性オレフィン系樹脂、水添スチレン系熱可塑性エラストマー等を用いることができる。
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、一般的な成形だけでなく、成形時に成形品表面に印刷の装飾を施す加飾成形等にも対応可能である。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1.0~4.0倍に延伸される。
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、電子機器外装材、化粧品容器又は容器部材、文房具部材、照明器具部材、生活用品部材として適用できる。
(1)毛状体及び下地層
・(A)TPU(ウレタン系エラストマー)「A3086A17J」(BASF社製)
(2)基材層
・(B)PC/ポリエステル「PCX-6694」(住化ポリカーボネート社製)
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)、下地層及び基材層の厚みを、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。下地層及び基材層の平均厚みについては、それぞれの試料について各層の厚みを10箇所測定し、その30測定値の算術平均値を用いた。なお、下地層の厚みとは、毛状体の根元から他方の層界面までの距離とする。
良触感性は、男性5人、女性5人の計10人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(滑らかさやしっとり感等)で評価し、最も多くの人数が感じた触感をその樹脂シート表面の触感とした。
作製した樹脂シートについて、JIS L 1096:2010、8.21.1記載のA法(45°カンチレバー法)に従って、カンチレバー形剛軟度試験機を用い、JIS L 0105の箇条6に従って作製した20mm×150mmの試験片を縦方向及び横方向にそれぞれ5枚採取し、それぞれ5枚の表裏について測定し、平均値を本実施例における剛軟度とした。
・測定装置:カンチレバー形剛軟度試験機(大栄化学精器社製)
・測定環境:温度23℃、湿度50%
両面真空成形機(NGF-0709-S型、布施真空社製)で樹脂シートを真空雰囲気下で加熱し、その後、雑貨入れ容器型に作製した金型の表面へ真空圧空成形することにより成形品を作製した。成形時のシート表面温度は、良触感性を十分に維持できる温度として110℃に設定した。賦形性の評価は、容器底面のコーナー部分におけるシート追従性を外観により行った。評価基準として、追従できている場合に○とし、追従できない場合(破断が起こったり、容器とシートとの間に隙間がある場合)に×とした。
押出機からTダイ法により押し出された樹脂シートを、ピンチロールを用いて引き取る際に、皺が発生することなく引き取れる場合に○とし、皺が入ってうまく引き取れない場合に×とした。
1台の40mm単軸押出機から、毛状体及び下地層となる(A)熱可塑性樹脂を流し、1台の65mm単軸押出機から、基材層となる(B)熱可塑性樹脂を流し、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。
実施例1及び2の樹脂シートは、触感性に関する評価を満足し、さらに特定の剛軟度を有し、押出成形時の成形性及び賦形性の評価基準を満たし、良触感性が維持される成形温度域においても賦形性が確保されることが示された。一方、比較例のシートは、触感性に関する評価を満足したものの、特定の剛軟度を有しておらず、賦形成評価試験において破断、もしくは容器とシートとの間に隙間が生じたり(比較例1~3)、押出成形時に皺が発生し(比較例4)、押出成形時の成形性及び/又は賦形性の評価基準を満たさなかった。
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 シーラント樹脂層
3 基材層
Claims (8)
- 一方の面に規則的に配列された毛状体を有する下地層と、下地層の毛状体とは反対側の面に基材層とを有する樹脂シートであって、
基材層の厚み(a)が10μm以上250μm以下であり、
基材層の厚み(a)及び下地層の厚み(b)がa≦bを満たし、
基材層がポリカーボネート系樹脂及び/又はスチレン系樹脂を含み、
下地層及び毛状体が熱可塑性ポリウレタン樹脂を含む、樹脂シート。 - 下地層の厚み(b)が10μm以上500μm以下である、請求項1に記載の樹脂シート。
- JIS L 1096:2010の45°カンチレバー法に従って測定される剛軟度が150mm以下である、請求項1又は2に記載の樹脂シート。
- 下地層と基材層との間にシーラント層を有する、請求項1から3のいずれか一項に記載の樹脂シート。
- 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60μm以下、毛状体の平均間隔が20μm以上200μm以下である、請求項1から4のいずれか一項に記載の樹脂シート。
- インサート成形又は真空成形された、請求項1から5のいずれか一項に記載の樹脂シートの成形品。
- 自動車内装材、電子機器、電子機器外装材、化粧品容器又は容器部材の表面に成形された、請求項6に記載の成形品。
- 原料樹脂を溶融押出し、得られた押出し樹脂シートを凹凸加工が成された転写ロールと、タッチロールでキャスティングすることにより毛状体を形成する工程を含んでなる、請求項1から5のいずれか一項に記載の樹脂シートの製造方法。
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JPWO2022014439A1 (ja) | 2022-01-20 |
JP7487309B2 (ja) | 2024-05-20 |
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US20230347635A1 (en) | 2023-11-02 |
TW202216461A (zh) | 2022-05-01 |
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