WO2018016562A1 - 毛状体を有する熱可塑性樹脂シート及びその成形品 - Google Patents
毛状体を有する熱可塑性樹脂シート及びその成形品 Download PDFInfo
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- WO2018016562A1 WO2018016562A1 PCT/JP2017/026211 JP2017026211W WO2018016562A1 WO 2018016562 A1 WO2018016562 A1 WO 2018016562A1 JP 2017026211 W JP2017026211 W JP 2017026211W WO 2018016562 A1 WO2018016562 A1 WO 2018016562A1
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Definitions
- the present invention relates to a thermoplastic resin sheet having a hair and a molded product thereof.
- Patent Document 1 proposes a decorative sheet obtained by extrusion lamination of a thermoplastic polyester resin to decorative paper.
- Patent Document 2 proposes a decorative sheet containing resin beads.
- Patent Document 3 proposes a decorative resin sheet in which a polylactic acid resin is coated with a urethane resin and the surface thereof is heat embossed.
- Patent Document 4 proposes a decorative sheet in which a protective layer made of anti-wear particles and urethane-based resin is formed on the surface of an embossed ABS resin sheet in order not to impair the uneven shape of the sheet surface.
- Patent Document 5 proposes a container having a number of streaks in a certain direction and having a fuzzy decorative surface formed by raising the streaks. However, it is desired to provide a resin sheet that exhibits a better tactile sensation.
- An object of the present invention is to provide a sheet that exhibits good touch and a molded product thereof.
- the present invention for solving the above-described problems is constituted as follows. (1) It has hairs regularly arranged on at least one surface of the underlayer, there is no structural boundary between the underlayer and the hairs, and a continuous phase is formed.
- Thermoplastic resin sheet is a thermoplastic resin using at least one of a styrene resin, an olefin resin, a polyvinyl chloride resin, a thermoplastic elastomer, a fluorine resin, a polyester resin, and a nylon resin ( The resin sheet as described in 1).
- the average height of the hairs is 100 ⁇ m or more and 1200 ⁇ m or less, the average diameter of the hairs is 1 ⁇ m or more and 50 ⁇ m or less, and the average distance between the hairs is 20 ⁇ m or more and 200 ⁇ m or less.
- the resin sheet of description (4) The resin sheet according to any one of (1) to (3), wherein the ratio of the static friction coefficient to the dynamic friction coefficient of the surface having the hair-like body is 1.0 to 10.0.
- At least one base material layer selected from a styrene resin, an olefin resin, a polyester resin, a nylon resin, an acrylic resin, and a thermoplastic elastomer is laminated on the other surface of the base layer (1 ) To (9).
- the manufacturing method of the resin sheet of crab is a styrene resin, an olefin resin, a polyester resin, a nylon resin, an acrylic resin, and a thermoplastic elastomer.
- a sheet that exhibits good tactile sensation can be provided.
- the resin sheet according to the first embodiment of the present invention has hairs regularly arranged on at least one surface of the foundation layer, and there is a structural boundary between the foundation layer and the hairs. And a thermoplastic resin sheet forming a continuous phase.
- the underlayer (1a) refers to a portion other than the ciliary body on the surface.
- the thickness of the foundation layer refers to the thickness from the base of the ciliary body to the surface on the opposite side of the foundation layer.
- the average thickness of the underlayer is preferably 50 ⁇ m to 1000 ⁇ m, and more preferably 150 ⁇ m to 800 ⁇ m. By setting the thickness to 50 ⁇ m or more, the height of the ciliary body can be sufficiently expressed. Moreover, a hair-like body can be efficiently formed by setting it as 1000 micrometers or less. There is no structural boundary between the underlayer and the hair, and a continuous phase is formed.
- “There is no structural boundary” means that the base layer and the hair-like body are integrally formed, and there is no structurally clear boundary portion between them.
- the formation of a continuous phase means a state where there is no seam between the base layer and the ciliary body and the discontinuity is not present (a continuous phase).
- the structure is different from a structure in which hairs are implanted in the base layer.
- the underlayer and the hairy body have the same composition, and the bond between the underlayer and the hairy body may include a covalent bond.
- the covalent bond refers to a chemical bond formed by sharing an electron pair between two atoms. In a thermoplastic resin that is a chain molecule in which monomers are linked, individual polymers are bonded by a covalent bond.
- the underlayer and the hair may be derived from the same solid thermoplastic resin sheet that is not separate. Deriving from the same solid thermoplastic resin sheet means that, for example, the hair and the base layer are obtained directly or indirectly based on the same resin sheet. Moreover, the base layer and the hair-like body may be formed from the same solid thermoplastic resin sheet. Being formed from the same solid thermoplastic resin sheet means that the hair and the underlayer are directly formed by processing one resin sheet. Since there is no structural boundary between the foundation layer and the ciliary body and a continuous phase is formed, separation of the ciliary body from the foundation layer due to external stimulation is suppressed, and tactile sensation is good. It becomes a sheet. Moreover, it can manufacture with fewer processes than the case where a hair-like body is planted.
- the underlayer is made of a thermoplastic resin, and includes at least one kind of a styrene resin, an olefin resin, a polyvinyl chloride resin, a thermoplastic elastomer, a fluorine resin, a polyester resin, and a nylon resin as the thermoplastic resin. Resin can be used.
- Styrenic resins include styrene monomers such as styrene, ⁇ -methyl styrene, p-methyl styrene, dimethyl styrene, pt-butyl styrene, chlorostyrene, or copolymers, styrene monomers and other monomers Copolymers such as styrene-acrylonitrile copolymer (AS resin), or diene rubber such as styrene monomer and other polymers such as polybutadiene, styrene-butadiene copolymer, polyisoprene, polychloroprene, etc.
- styrene monomers such as styrene, ⁇ -methyl styrene, p-methyl styrene, dimethyl styrene, pt-butyl styrene, chlorostyrene, or copolymers,
- Graft polymers obtained by graft polymerization in the presence of a porous polymer 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
- Styrenic thermoplastic elastomers can also be used.
- the polyolefin resin means a resin made of a polymer containing ⁇ -olefin as a monomer, and includes a polyethylene resin and a 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 a simple substance but also a copolymer or graft having such a structure. 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, 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 a blend or a ternary copolymer with an acid anhydride.
- the polypropylene resin homopolypropylene, random polypropylene, block polypropylene, or the like can be used.
- the structure of the homopolypropylene may be any of isotactic, atactic, and syndiotactic.
- the ⁇ -olefin copolymerized with propylene preferably has 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, such as ethylene, 1-butene, 1-pentene, 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. 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 comonomer 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 backbone polymer and vinyl chloride may be graft polymerized thereon.
- the polyvinyl chloride of the present embodiment is an extrudable soft polyvinyl chloride, and is a composition containing additives such as a polymer plasticizer.
- polymer plasticizer known polymer plasticizers can be used.
- ethylene-vinyl acetate-carbon monoxide copolymer ethylene- (meth) acrylate ester-carbon monoxide copolymer
- acetic acid A preferred example is an 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 material and a hard polymer material are combined. Specific examples include styrene elastomers, olefin elastomers, vinyl chloride elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers, and the like.
- polyurethane-based elastomer either polyether-based or polyester-based may be selected. These elastomers can be selected from those commercially available.
- PVDF Polyvinylidene fluoride
- VDF Polyvinylidene fluoride
- a vinylidene fluoride copolymer for example, vinylidene fluoride- Hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexa Fluoropropylene terpolymers, vinylidene fluoride-chlorotrifluoroethylene-hexafluoro
- polyester resins examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and copolymer components such as diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, and adipic acid.
- Polyester resins obtained by copolymerizing dicarboxylic acid components such as sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid can be used.
- Nylon resins include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, hexamethylenediamine, decamethylenediamine, and dodeca Aliphatic diamines such as methylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane) Diamine units such as alicyclic diamines such as m- or p-xylylenediamine, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Aromatic dicarboxylic acids such as acid,
- Polycondensates of a dicarboxylic acid unit may be used copolymers thereof.
- nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6 / 6T, Nylon 6I / 6T is available, among which nylon 6 and nylon MXD6 are preferred.
- the melt mass flow rate at 190 ° C. to 300 ° C. of the thermoplastic resin is preferably 4 g / 10 min or more. By setting it to 4 g / 10 minutes or more, the transferability of the shape of the hair can be improved.
- the melt mass flow rate is a value measured in accordance with JIS K 7210 under a load temperature (2.16 Kg to 10.0 Kg) in a test temperature range of 190 ° C. to 300 ° C.
- thermoplastic resin may be alloyed with the above-mentioned thermoplastic resins at an arbitrary ratio as long as the effects of the present invention are not impaired.
- Other additives include water and oil repellents, colorants such as pigments and dyes, release agents such as silicone oils and alkyl esters, and fibrous reinforcement such as glass fibers, as long as the effects of the present invention are not impaired.
- Additives such as agents, particulate lubricants such as talc, clay and silica, salt compounds of sulfonic acid and alkali metals, antistatic agents, ultraviolet absorbers, flame retardants and antibacterial agents can be added.
- the scrap resin generated in the resin sheet manufacturing process can be mixed and used.
- Examples of the water / oil repellent include silicon-based water repellent, carnauba wax, and fluorine-based water / oil repellent.
- Examples of silicon include organopolysiloxane, dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane. Among them, dimethylpolysiloxane is preferably used.
- Examples of commercially available products include “Crimbell CB50-PP”, “Crimbell CB-30PE”, “Crimbell CB-1”, “Crimbell CB-50AB” (manufactured by Fuji Chemical Co., Ltd.), which is an alloy of silicon and resin.
- As for the carnauba wax as a commercial product, “Carnauba No.
- a surfactant having a perfluoroalkyl group can be mentioned.
- “Surflon KT-PA” manufactured by AGC Seimi Chemical Co., Ltd.
- the addition amount of the water / oil repellent is preferably 1% by mass to 25% by mass.
- antistatic agent examples include polyether ester amide polymer antistatic agent, ionomer polymer antistatic agent and the like.
- examples of commercially available polyether ester amide polymer antistatic agents include “Pelestat 230”, “Pelestat 6500”, “Peletron AS”, and “Peletron HS” (manufactured by Sanyo Kasei Co., Ltd.).
- examples of commercially available ionomer polymer antistatic agents include “ENTILA SD100” and “ENTILA MK400” (Mitsui / DuPont Polychemical Co., Ltd.).
- the addition amount of the antistatic agent is preferably 5% by mass to 30% by mass.
- the antibacterial agent either inorganic or organic may be added.
- an inorganic system is preferable.
- specific examples include inorganic antibacterial agents of metal ions (Ag, Zn, Cu), shell-calcined calcium antibacterial agents, and the like.
- Commercially available metal ion inorganic antibacterial agents include “Bactekiller BM102VT” (Fuji Chemical Co., Ltd.), “Novalon VZF200”, “Novalon (AG300)” (Toa Gosei Co., Ltd.), “KM-10D-G”, Examples thereof include “IM-10D-L” (manufactured by Sinanen Zeomic).
- Examples of the shell-calcined calcium-based antibacterial agent include “Scarlow” (manufactured by FID).
- the addition amount of the antibacterial agent is preferably 0.5% by mass to 5% by mass.
- a hair-like body (1b) is made of a thermoplastic resin and refers to a portion extending like a hair from the surface of the base layer (1a) as shown in FIG.
- the hairs are regularly arranged on the surface of the underlayer.
- the regular arrangement means an arrangement state where the ciliary bodies are not random, that is, a state where the hair bodies are arranged in one direction or two directions in an orderly manner. It is determined whether or not the arrangement of the ciliary bodies is regular based on the arrangement state of the bases of the ciliary bodies.
- the hairs are positioned on the base layer at a predetermined interval, and the positions of the bottom surfaces of the hairs are regularly arranged in the longitudinal direction and the short direction of the base layer.
- positioning form of a hair-like body is not specifically limited,
- positioning, etc. can be selected.
- the hair-like bodies are regularly arranged on the surface of the underlayer, uniform and non-uniformity is easily exhibited and good tactile sensation is easily exhibited.
- the hair-like body may fall down when a load is applied, for example, by tracing with a finger, and may form a finger mark that looks different in gloss and color from the surrounding portion.
- seat can be provided with a hair-like body.
- the average height (h) of the hair is preferably 100 ⁇ m to 1200 ⁇ m, more preferably 200 ⁇ m to 900 ⁇ m.
- the average height is 100 ⁇ m or more, sufficient tactile sensation can be ensured, and when the average height is 1200 ⁇ m or less, good feeling such as moist feeling, soft feeling and soft feeling can be obtained.
- the hair-like body is substantially upright with respect to the base layer, the length of the hair-like body represents the height of the hair-like body.
- the ciliary body is inclined with respect to the underlayer as shown in FIG. 2 or when the ciliary body has a portion wound around as shown in FIG.
- the distance from the surface of the underlayer at the position farthest from the surface is the height of the hair.
- the height of the hair can be measured at any number of locations on the resin sheet, and the arithmetic average value of the measured values can be used.
- the average diameter (d) of the hair is preferably 1 ⁇ m to 50 ⁇ m, and more preferably 5 ⁇ m to 30 ⁇ m.
- the average diameter of the ciliary body is a value obtained by measuring the diameter of the intermediate body height (h / 2) from several places on the resin sheet and using the arithmetic average value of the measured values.
- the aspect ratio of the hairy body when the hairy body is substantially upright with respect to the base layer can be expressed as (average height of hairy body / average diameter of hairy body).
- the aspect ratio of the ciliary body is (average length of ciliary body / average ciliary body Diameter).
- the length of the hair can be measured at several locations on the resin sheet, and the arithmetic average value of the measured values can be used.
- the aspect ratio of the ciliary body is preferably 2 to 1200, more preferably 10 to 600, and still more preferably 40 to 200.
- the aspect ratio can be based on the average bottom diameter of the hair.
- the average bottom diameter of the hair is preferably 10 ⁇ m to 150 ⁇ m.
- the average bottom diameter of the ciliary body is a value obtained by measuring an interval between adjacent ciliary bodies at several locations on the resin sheet and using an arithmetic average value of the measured values.
- the aspect ratio based on the bottom diameter of the hair is preferably 0.6 to 120. By setting the aspect ratio to 0.6 or more, good tactile sensation can be secured, and the aspect ratio is 120. By making it below, good touch feeling such as moist feeling, soft feeling and soft feeling can be obtained.
- the average interval (t) between the hairs is preferably 20 ⁇ m to 200 ⁇ m, and more preferably 40 ⁇ m to 150 ⁇ m.
- the interval between the hairs means the distance between the center of the base of the hair and the center of the base of the adjacent hair. When the average interval is 20 ⁇ m or more, good touch feeling is secured, and when it is 200 ⁇ m or less, good touch feeling such as moist feeling, soft feeling, and soft feeling can be obtained.
- the average interval between the hairs is a value obtained by measuring the interval between adjacent hairs at several locations on the resin sheet and using the arithmetic average value of the measured values.
- the shape of the hair-like body is not particularly limited, but it may be a shape that extends in a hair shape in a direction away from the base layer and gradually becomes thinner as it approaches the tip, or a bulge is formed at the tip. In other words, the shape may be such that the cross-sectional area gradually decreases and then terminates after increasing as the distance from the base layer increases.
- the shape of the tip of the ciliary body may be a bud shape or a mushroom shape.
- the ciliary body is a portion located at the base end extending in a direction away from the base layer, and a portion bent from the portion located at the base end and having a constant curvature or gradually changing the curvature, Furthermore, you may have the part wound spirally or spirally.
- tip part of the ciliary body was folded inward may be sufficient. Good tactile sensation is manifested by such a shape. Moreover, when the bud-shaped or mushroom-shaped part is hollow, a better tactile sensation is expressed.
- the ratio of the average diameter of the bud or mushroom width to the average diameter of the hair is preferably 1.1 times or more.
- the height of the bud or mushroom shape is preferably 7 ⁇ m or more.
- the average diameter, bud shape, or mushroom-shaped width average diameter and height of the ciliary body are measured from an electron scanning micrograph, and the arithmetic average value is used.
- the hairy body is made of a thermoplastic resin. As the thermoplastic resin, a resin similar to the resin that can be used in the base layer can be used.
- the thickness of the resin sheet refers to a sheet thickness obtained by combining the average height of the hairs and the average thickness of the foundation layer.
- the sheet thickness is preferably 150 ⁇ m to 1500 ⁇ m, more preferably 300 to 1000 ⁇ m.
- “tactile sensation” means the texture and feel of the surface of the resin sheet. It is determined whether or not the user feels comfort when touching the surface of the resin sheet. If the user feels comfortable, a material having a good feeling of touch such as moist, soft and soft is defined as a good touch. Moreover, good tactile sensation can be defined by the aspect ratio described above, the ratio of the static friction coefficient to the dynamic friction coefficient of the resin sheet, the value of the contact cold / warm feeling, and the hardness of the resin, in addition to the sensory test such as touch feeling.
- the ratio of the static friction coefficient to the dynamic friction coefficient of the resin sheet is preferably 1.0 to 10.0, and more preferably 1.8 to 5.0. Good tactile sensation can be secured by setting the ratio of the static friction coefficient to the dynamic friction coefficient of the resin sheet to 1.0 or more. Further, when the ratio of the static friction coefficient to the dynamic friction coefficient of the resin sheet is 10.0 or less, it is possible to express tactile sensation such as moist feeling, soft feeling, and soft feeling.
- the static friction coefficient is preferably 0.2 to 2.0, and the dynamic friction coefficient is preferably 0.2 to 2.0.
- the feeling of coldness of contact of the resin sheet can measure the heat transfer rate q-max (J / cm 2 ⁇ sec) at the time of contact, and indicates that the larger the q-max value, the colder and the smaller the warmer. For this reason, q-max is preferably 0.005 to 0.500, and more preferably 0.100 to 0.350.
- q-max is preferably 0.005 to 0.500, and more preferably 0.100 to 0.350.
- Resin hardness can be measured by durometer hardness. Generally, the resin hardness is classified by a Shore hardness A type for soft resins such as elastomers, and a Shore hardness D type for hard resins such as PP. The resin hardness (hardness) is preferably 45 to 95 in Shore hardness A. By using a resin having the above hardness range, it is possible to exhibit good touch feeling such as moist feeling, soft feeling and soft feeling.
- the sealant resin layer (2) was 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 the hair and underlayer (1), the sealant resin layer (2), and the base material layer (3) from top to bottom.
- the ciliary body is the same as that described in the first embodiment, description thereof is omitted.
- the thickness of the hair and the base layer represented by the sum of the average height of the hair and the average thickness of the base layer is preferably 150 to 900 ⁇ m. When the thickness is 150 ⁇ m or more, good tactile sensation can be secured, and when the thickness is 900 ⁇ m or less, the production cost can be suppressed.
- the base material layer is preferably a thermoplastic resin such as a styrene resin, an olefin resin, a polyester resin, a nylon resin, an acrylic resin, or a thermoplastic elastomer.
- a thermoplastic resin such as a styrene resin, an olefin resin, a polyester resin, a nylon resin, an acrylic resin, or a thermoplastic elastomer.
- lamination there are lamination by co-extrusion molding, extrusion lamination molding using an unstretched film, biaxially stretched film, and lamination by dry lamination molding.
- polyester resins examples include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polymethylene terephthalate, and copolymer components such as diol components such as diethylene glycol, neopentyl glycol, polyalkylene glycol, and adipic acid.
- Polyester resins obtained by copolymerizing dicarboxylic acid components such as sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid can be used.
- Nylon resins include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, hexamethylenediamine, decamethylenediamine, and dodeca Aliphatic diamines such as methylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane) Diamine units such as alicyclic diamines such as m- or p-xylylenediamine, aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid Aromatic dicarboxylic acids such as acid,
- Polycondensates of a dicarboxylic acid unit may be used copolymers thereof.
- nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6 / 6T, Nylon 6I / 6T is available, among which nylon 6 and nylon MXD6 are preferred.
- Any vinyl polymer based on a methacrylic acid ester monomer can be used as an acrylic resin, and its structure is not particularly limited.
- the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate.
- alkyl groups such as propyl group, butyl group, pentyl group and hexyl group in the methacrylic acid ester monomer may be linear or branched.
- the methacrylic ester resin may be a homopolymer of a methacrylic ester monomer or a copolymer of a plurality of methacrylic ester monomers, and is a known vinyl compound other than a methacrylic ester such as ethylene or propylene. May have monomer units derived from butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, acrylic acid, and the like.
- the base material layer may be alloyed with the above-mentioned thermoplastic resins at an arbitrary ratio within a range not impairing the effects of the present invention.
- other additives may be contained.
- Other additives include water and oil repellents, colorants such as pigments and dyes, release agents such as silicone oils and alkyl esters, and fibrous reinforcement such as glass fibers, as long as the effects of the present invention are not impaired.
- Additives such as agents, particulate lubricants such as talc, clay and silica, salt compounds of sulfonic acid and alkali metals, antistatic agents, ultraviolet absorbers, flame retardants and antibacterial agents can be added.
- the scrap resin generated in the resin sheet manufacturing process can be mixed and used.
- the sealant resin layer is for developing the adhesion between the base layer and the base material layer.
- a modified olefin resin, a hydrogenated styrene thermoplastic elastomer, or the like can be used as the resin component.
- modified olefin resins include olefins having about 2 to 8 carbon atoms such as ethylene, propylene and butene-1, and these 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 and 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, propylene-butene-1 copolymers
- Olefin-based rubbers such as polymers can be converted into acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic , Fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid and other unsaturated carboxylic acids, or their derivatives, such as acid halides, amides, imides, anhydr
- an “ethylene-propylene-diene copolymer” modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof, or an ethylene-propylene or butene-1 copolymer rubber is preferable.
- Hydrogenated styrene thermoplastic elastomers include hydrogenated products of styrene monomers and butadiene and isoprene copolymers, and hydrogenated styrene-butadiene-styrene block copolymers (styrene-ethylene / butylene-styrene block copolymer).
- Styrene-isoprene-styrene block copolymer hydrogenated product 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 to 90 ⁇ m, more preferably 40 to 80 ⁇ m. By setting it as 20 micrometers or more, it can suppress that delamination generate
- the resin sheet according to the third embodiment of the present invention does not use the sealant resin layer (2) shown in the second embodiment, but the hair, the base layer (1), and the base material.
- Layer (3) is directly laminated. That is, the layer structure of the resin sheet according to the third embodiment is the hair and the base layer (1) / base material layer (3) from top to bottom, and the thermoplastic resin according to the second embodiment. It has a layer structure in which the sealant resin layer is removed from the sheet.
- the ciliary body and the base layer are the same as the layers in the first embodiment and the second embodiment, and thus the description thereof is omitted.
- the base material layer (3) in this embodiment has sufficient adhesiveness with the base layer.
- thermoplastic resin that is excellent in adhesiveness with the base layer as the base material layer.
- the underlayer is a fluororesin
- an acrylic resin can be used
- a styrene resin composition to which a hydrogenated styrene thermoplastic elastomer is added can also be used.
- the impact-resistant polystyrene resin and hydrogenated styrene thermoplastic elastomer are used in combination, 5 to 10 parts by mass of hydrogenated styrene thermoplastic elastomer is added to 90 to 95 parts by mass of the impact-resistant polystyrene resin.
- the addition amount of the hydrogenated styrene-based thermoplastic elastomer is 5 parts by mass or more, the adhesiveness with the underlayer is sufficient, the occurrence of delamination can be suppressed, and the production cost is 10 parts by mass or less. Can be suppressed.
- the method for producing the resin sheet according to the present invention is not limited, and any method may be used.
- the raw material resin is melt-extruded and regularly arranged on at least one surface of the obtained extruded resin sheet.
- any resin sheet molding method can be used.
- a single-screw extruder is used, and in the case of a multi-layer, each raw material resin is melt-extruded using a single-screw extruder, and a resin sheet is obtained by a T-die. It is done.
- a feed block or a multi-manifold die can be used.
- the layer structure of each embodiment of the resin sheet of the present invention is basically as described above.
- the scrap raw materials generated in the manufacturing process of the resin sheet of the present invention and the molded container are treated with physical properties. As long as deterioration such as the above is not observed, it may be added to the base material layer or may be laminated as a further layer.
- a method using an extrusion method a method using a roll-to-roll method, a method using a photolithography method, a method using a hot press method, a pattern roll and UV curing
- a method using a resin a method using a 3D printer, a method in which a hair is embedded in a resin layer, and then covalently bonded by a polymerization reaction.
- a resin sheet is extruded by a T-die method, and casting is performed with a transfer roll on which unevenness is formed and a touch roll so as to impart a hair-like shape to the surface of the resin sheet.
- the resin sheet according to the present invention can be manufactured.
- a transfer roll on which the unevenness processing is performed a transfer roll in which fine unevenness is regularly formed on the surface of the roll by a laser engraving method, an electroforming method, an etching method, a mill engraving method, or the like can be used.
- “regular” means an arrangement state in which the unevenness is not random, that is, a state in which the irregularities are arranged in one direction or two directions in an orderly manner.
- a grid arrangement or a staggered arrangement arranged vertically and horizontally can be selected.
- the shape of the concavo-convex portion include a conical shape (cone, quadrangular pyramid, triangular pyramid, hexagonal pyramid, etc.), semicircular shape, rectangular shape (quadrangular prism) and the like.
- the opening diameter of the recess, the depth of the recess, the interval between the recess shapes, etc. are several ⁇ m to several hundred ⁇ m.
- the distance between the recesses of the transfer roll By adjusting the distance between the recesses of the transfer roll, the distance between the hairs can be adjusted, and by adjusting the depth of the recesses in the transfer roll, the height of the hair can be adjusted, and the tactile sensation can also be adjusted.
- the aspect ratio (recess depth / recess opening diameter) when processing the recess shape on the surface of the transfer roll is preferably 0.5 to 6.0.
- Laser engraving method or electroforming method is suitable for precise processing in the depth direction compared to etching method, blasting method, mill engraving method, etc., to process unevenness with high aspect ratio on the transfer roll surface. Therefore, it is particularly preferably used.
- the transfer roll for example, metal, ceramic or the like can be used.
- various materials can be used as the touch roll.
- a roll made of silicon rubber, NBR rubber, EPT rubber, butyl rubber, chloroprene rubber, or fluorine rubber can be used.
- a touch roll having a rubber hardness (JIS K 6253) of 40 to 100 can be used.
- a Teflon layer may be formed on the surface of the touch roll.
- the resin sheet of this embodiment can be manufactured 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 crystal melting temperature, glass transition point or melting point of the thermoplastic resin (for example, 100 to 150 ° C.
- the resin sheet of this embodiment can be manufactured by casting at 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 said embodiment is shown concretely, it is not limited to these.
- the molded product of the present invention is formed by molding the resin sheet of the present invention.
- the hair sheet of the present invention is made of a thermoplastic resin, and thus can cope with general molding.
- Molding methods include general vacuum forming, pressure forming, and applications such as overlaying (molding) the surface of an existing molded product by heat-softening the resin sheet in a vacuum and releasing it under atmospheric pressure.
- a known sheet heating method such as radiation heating with an infrared heater or the like which is non-contact heating can be applied.
- the resin sheet is heated at 60 ° C. to 140 ° C. for 20 seconds to 480 seconds, and then molded onto the surface of an existing molded product. It can be stretched twice.
- the resin sheet provided with the hair-like body according to the present invention on the surface can be applied to applications that require the good touch feeling described above.
- the resin sheet of the present invention can be applied to automobile interior materials, electronic equipment exterior materials, cosmetic container members, stationery members, and the like.
- Automobile interior materials include handles, dashboards, levers, switches, etc., as touched parts in the car.
- an interior material in which the above-described resin sheet is bonded to a known instrument panel or pillar (for example, JP 2009-184421 A) can be given.
- By bonding the resin sheet it is possible to provide an interior material with good tactile sensation.
- As a material of the resin sheet to be bonded an olefin resin, a vinyl chloride resin, and a urethane elastomer are preferable in consideration of weather resistance and chemical resistance.
- the method for bonding the resin sheet and the interior material is not particularly limited.
- Electronic equipment exterior materials include keyless entry system transmitter housing, smartphone housing, smartphone case, music player case, game machine housing, digital camera housing, electronic notebook housing, calculator housing, tablet housing, Mobile PC housing, keyboard, mouse, etc.
- a portable transmitter in which the resin sheet of the present invention is bonded to a portable transmitter housing (for example, JP-A-2005-228911) of a known keyless entry system can be given.
- a portable transmitter having good tactile sensation can be obtained.
- a material of the resin sheet to be bonded an olefin resin and a urethane elastomer are preferable.
- the method for bonding the resin sheet and the housing is not particularly limited.
- Examples of cosmetic container members include face cream, pack cream, foundation, and eye shadow containers.
- the resin sheet of the present invention is bonded to a lid member of a known foundation container (Japanese Patent Laid-Open No. 2017-29608). And cosmetic containers. By laminating the resin sheet, a cosmetic container with good tactile sensation can be obtained.
- a material of the resin sheet to be bonded an olefin resin and a urethane elastomer are preferable.
- the method for bonding to the resin sheet is not particularly limited.
- Examples of the stationery member include a book cover, a notebook cover, and a pen case cover.
- a well-known book cover (for example, Japanese Patent Application Laid-Open No. 2007-246122) is produced using the sheet of the present invention.
- the book cover can be waterproof.
- 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 the resin sheet is not particularly limited.
- a hair sheet with characters and designs printed on the surface of the hair is printed by a general printing method (offset printing, gravure printing, flexographic printing, screen printing, foil stamping, etc.). , And can be applied to the above applications. Although it does not specifically limit as a material of the resin sheet to print, It is preferable to consider printability with the ink agent used for printing.
- the resin sheet of the present invention produces a laminate obtained by laminate molding (dry lamination molding, extrusion lamination molding) with printed matter (paper, metal thin film, etc.), non-woven fabric, etc. printed with characters, pictures, etc.
- 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 evaluation methods for various properties of the resin sheets produced in Examples and Comparative Examples and molded products obtained by vacuum-pressure forming the resin sheets are as follows.
- the average diameter of the ciliary body the diameter at the middle height (h / 2) of 10 ciliary bodies was measured for each sample, and the arithmetic average value of the 30 measured values was used.
- the average interval between the ciliary bodies the distance between the center of the base of the ciliary body and the center of the root of the adjacent ciliary body was measured for each sample, and the arithmetic average value of the 30 measured values was used.
- the average thickness of the foundation layer the thickness from the base of the hair to the other layer interface was measured at 10 locations for each sample, and the arithmetic average value of the 30 measured values was used.
- Tactile evaluation was carried out by sensory evaluation in which a total of 30 men, 15 men and 15 women, touched the resin sheet. Whether or not the user feels comfort when touching the surface of the resin sheet was judged as “ ⁇ ” or “ ⁇ ”, and when judged as “ ⁇ ”, the evaluation was made based on a specific touch feeling such as moist, soft, and soft. Among these, when the same touch feeling of 80% or more was evaluated, it was set as the touch feeling. Moreover, it was evaluated whether the same touch feeling was maintained also on the surface of the molded article which carried out the vacuum pressure forming using the resin sheet.
- Resin hardness The hardness of the resin was measured in accordance with JIS K7215 by preparing a sample having a thickness of 6 mm, a width of 25 mm, and a length of 50 mm by a hot press method, and using a type A durometer.
- the contact angle of the resin sheet was measured using an automatic contact angle meter DM-501 (manufactured by Kyowa Interface Science Co., Ltd.). In addition, purified water was used as the test solution, and the dropping amount was 6 ⁇ L. When the contact angle was 120 ° or more, the liquid repellency was high, and it was determined that liquid adhesion could be prevented.
- Vacuum / Pneumatic Molding Resin sheet is heated in a vacuum atmosphere with a double-sided vacuum molding machine (NGF-0709-S type: manufactured by Fuse Vacuum Co., Ltd.), and then vacuum-pressured onto the surface of the smartphone cover prepared in an atmospheric pressure atmosphere.
- a molded product was produced by molding. The film was heated at 80 ° C. for 120 seconds, and stretched 1.5 times at the most stretched portion.
- Examples 1, 2, 7, 10 to 12 Using a single 65mm single screw extruder, the resin sheet is extruded by the T-die method, and the temperature is adjusted to 100 ° C to 150 ° C so as to give a hair-like shape to the surface of the resin sheet.
- a resin sheet having the composition and thickness shown in Table 1 having one surface having the surface shape shown in Table 2 was obtained.
- Example 3 Using three 40mm single screw extruders and a feed block, the three-layer resin sheet is extruded by the T-die method, and an uneven process is performed by electroforming so as to give a hairy body shape to the surface of this resin sheet.
- a transfer roll formed with a touch roll By casting with a transfer roll formed with a touch roll, one surface has a surface shape shown in Table 2, and each layer has a three-layer resin sheet having the composition and thickness shown in Table 1.
- Example 4 13 to 16
- Examples 5, 17, and 18 Create a 100 mm square mold with irregularities made by electroforming so as to give a hair-like shape to the surface of the resin sheet, and use an electrothermal press machine to By hot pressing, a resin sheet having the composition and thickness shown in Table 1 having one surface having the surface shape shown in Table 2 was obtained.
- Example 6 Using two 40mm single-screw extruders and a feed block, the two-layer resin sheet is extruded by the T-die method, and an uneven process is performed by electroforming so as to give a hair-like shape to the surface of this resin sheet.
- a transfer roll formed with a touch roll By casting with a transfer roll formed with a touch roll, one surface had a surface shape shown in Table 2, and each layer had a two-layer resin sheet having the composition and thickness shown in Table 1.
- Example 8 By a laminate molding method, a three-layer resin sheet is obtained, and casting is performed with a transfer roll that has been subjected to uneven processing by an electroforming method and a touch roll so as to impart a hair-like shape to the surface of the resin sheet.
- a transfer roll that has been subjected to uneven processing by an electroforming method and a touch roll so as to impart a hair-like shape to the surface of the resin sheet.
- One surface had the surface shape shown in Table 2, and each layer obtained a resin sheet having a composition and thickness shown in Table 1 with three layers.
- Example 9 Using transfer rolls having different concavo-convex sizes, based on Example 8, one surface had the surface shape shown in Table 2, and each layer obtained a three-layer resin sheet having the composition and thickness shown in Table 1. .
- Example 2 Based on Example 3, one surface has the surface shape shown in Table 2 using a transfer roll that has been subjected to uneven processing by an etching method so as to give a bell-shaped convex shape to the surface of the resin sheet. A three-layer resin sheet having the composition and thickness shown in Table 1 for each layer was obtained.
- Example 3 Based on Example 1, the surface shape shown in Table 2 is shown on the surface of the resin sheet using a transfer roll that has been subjected to concave and convex processing by an electroforming method so as to give a square pyramid concave shape to the surface of the resin sheet. And a resin sheet having the composition and thickness shown in Table 1 was obtained.
- Example 4 instead of the transfer roll, a roll having no unevenness was used, and based on Example 1, a resin sheet having both smooth surfaces and the composition and thickness shown in Table 1 was obtained.
- Example 5 One surface has the surface shape shown in Table 2 on the basis of Example 8 using a transfer roll that has been subjected to uneven processing by an electroforming method so as to give a hexagonal pyramidal convex shape to the surface of the resin sheet. And each layer obtained the resin sheet of 3 layers of the composition and thickness which are shown in Table 1.
- the shapes of the resin sheets obtained in Examples (1 to 18) were observed under the following conditions using a field emission scanning electron microscope (FE-SEM, JSM-7001F type). From the scanning electron microscope image, it was observed that the hairs were extended in a certain direction without being intertwined. Further, the hair-like body had a structure in which the hair-like body extended in a direction away from the base layer, and a bulge was formed at the tip thereof. In other words, the shape of the hair-like body was such that the cross-sectional area gradually decreased and then increased once and then terminated as the distance from the base layer was increased.
- tip part of a hair-like body is a bud shape or a mushroom shape, and the bud shape or the mushroom shape part is partially hollow. By having such a shape, it was speculated that a better tactile sensation was expressed.
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Abstract
Description
しかしながら、より良好な触感を発現する樹脂シートの提供が望まれている。
(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。
(2)前記熱可塑性樹脂がスチレン系樹脂、オレフィン系樹脂、ポリ塩化ビニル樹脂、熱可塑性エラストマー、フッ素系樹脂、ポリエステル系樹脂、ナイロン系樹脂から少なくとも1種類以上を用いた熱可塑性樹脂である(1)に記載の樹脂シート。
(3)毛状体の平均高さが100μm以上1200μm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)または(2)に記載の樹脂シート。
(4)毛状体を有する面の動摩擦係数に対する静摩擦係数の比が1.0~10.0である(1)から(3)の何れかに記載の樹脂シート。
(5)毛状体を有する面の接触時における熱移動速度が0.005~0.500である(1)から(4)の何れかに記載の樹脂シート。
(6)前記下地層の平均厚みが50μm以上である(1)から(5)の何れかに記載の樹脂シート。
(7)毛状体が下地層から離間する方向に毛状に伸び、その先端にふくらみが形成された構成とされている(1)から(6)の何れかに記載の樹脂シート。
(8)下地層及び毛状体は、一のシートから形成された(1)から(7)の何れかに記載の樹脂シート。
(9)多層樹脂シートである(1)から(8)の何れかに記載の樹脂シート。
(10)下地層の他方の面にスチレン系樹脂、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から選択される少なくとも1層以上の基材層を積層した(1)から(9)の何れかに記載の樹脂シート。
(11)撥水撥油剤、帯電防止剤及び抗菌剤から選択される1種又は2種以上の添加剤を含む(1)から(10)の何れかに記載の樹脂シート。
(12)押出成形法によって、ダイスから溶融押出した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させて毛状体を形成することを特徴とする(1)から(11)の何れかに記載の樹脂シートの製造方法。
(13)(1)から(11)の何れかに記載の樹脂シートの成形品。
(14)文房具部材である(13)に記載の成形品。
(15)既製の成形品表面に真空圧空成形された、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である(13)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る。
下地層(1a)は、図1に示されるように、表面の毛状体以外の部分をいう。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50μm~1000μmであることが好ましく、150μm~800μmであることがより好ましい。50μm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、1000μm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る。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り、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。
毛状体(1b)とは、熱可塑性樹脂からなり、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、規則的配列とは、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配列した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、毛状体の長さが毛状体の高さを表すことになる。一方、図2に示すように毛状体が下地層に対して傾斜している場合や、図3に示すように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とする。
毛状体の平均高さは、樹脂シートの任意の数箇所において毛状体の高さを測定し、その測定値の算術平均値を用いることができる。
また、毛状体が下地層に対してほぼ直立している場合の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の毛状体のアスペクト比は、(毛状体の平均長さ/毛状体の平均径)として表すことができる。毛状体の平均長さは、樹脂シートの数箇所において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。いずれの場合も、毛状体のアスペクト比は、2~1200であることが好ましく、10~600であることがより好ましく、40~200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1200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。
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、0.6~120であることが好ましく、アスペクト比を0.6以上とすることで、良触感性が確保でき、アスペクト比を120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。
本実施形態において、樹脂シートの厚みとは、毛状体の平均高さと下地層の平均厚みを合わせたシート厚みをいう。シート厚みは、好ましくは150μm~1500μm、より好ましくは300~1000μmである。厚みを150μm以上とすることで良触感性が十分に確保でき、1500μm以下とすることで製造コストを抑えることができる。
また、静摩擦係数は0.2~2.0、動摩擦係数は0.2~2.0であることが好ましい。
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。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、150~900μmが好ましい。150μm以上とすることで良触感性を確保でき、900μm以下とすることで生産コストを抑えることができる。
基材層は、スチレン系樹脂、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が好ましい。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。
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。
本発明の第三実施形態に係る樹脂シートは、図4に示すように、第二実施形態で示したシーラント樹脂層(2)を用いずに、毛状体及び下地層(1)と基材層(3)を直接積層したものである。すなわち、第三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(3)であり、第二実施形態に係る熱可塑性樹脂シートからシーラント樹脂層を除いた層構成を有している。ここで、毛状体及び下地層は、第一実施形態及び第二実施形態における層と同じであるので、説明を省略する。一方、本実施形態における基材層(3)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。
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。そのサイズとしては、凹部の開口径、凹部深さ、凹部形状の間隔等が数μmから数百μmである。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、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を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0.5~6.0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成形してなる。従来技術では3次元成形には対応できないが、本発明の毛状体シートは熱可塑性樹脂からなるため、一般的な成形への対応が可能である。成形方法としては、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60℃~140℃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1.05~1.50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、化粧品容器部材、文具部材などに適用できる。
(1)毛状体及び下地層
・(A-1)ランダムPP 「PM822V」(サンアロマー社製)
・(A-2)ブロックPP 「PM854X」(サンアロマー社製)
・(B-1)直鎖状中密度PE(C4) 「ネオゼックス 45200」(プライムポリマー社製)
・(B-2)直鎖状低密度PE(C6) 「ウルトゼックス 20200J」(プライムポリマー社製)
・(C)スチレン系熱可塑性エラストマー 「SEポリマーAC15」(デンカ社製)
・(D)PVC 「BFV7070N」(リケンテクノス社製)
・(E)PVDF 「カイナー720」(アルケマ社製)
・(F-1)TPU(ウレタン系エラストマー)「ET880:ポリエーテル系」(BASF社製)
・(F-2)TPU(ウレタン系エラストマー)「ET680:ポリエステル系」(BASF社製)
・(G)着色剤 「PE-M-SAC GW1060 ホワイト」(大日精化社製)
・(H)着色剤 「PE-M-MD1697 レッド」(大日精化社製)
・(I)着色剤 「PE-M-MC6164 エロー」(大日精化社製)
・(J)着色剤 「PEX 1AG057 PEARL」(東京インキ社製)
・(K)着色剤 「PEX 496 SILVER AL」(東京インキ社製)
・(L-1)着色剤 「エラストランマスターカラーブラック590M50」(エフ・シー・アイ社製)
・(L-2)着色剤 「エラストランマスターカラーホワイト880M50」(エフ・シー・アイ社製)
・(M)撥水剤 「クリンベルCB50―PP」(富士ケミカル社製)
・(N)帯電防止剤 「ペレスタット230」(三洋化成社製)
・(O)抗菌剤 「バクテキラーBM102VT」(富士ケミカル社製)
・(P)離型剤 「エラストランマスターV」(エフ・シー・アイ社製)
(2)シーラント樹脂層
・(Q)水添スチレン系熱可塑性エラストマー 「タフテックM1943」(旭化成ケミカルズ社製)
・(R)変性オレフィン系重合体樹脂 「モディックF502」(三菱化学社製)
・(S)変性オレフィン系重合体樹脂 「アドマー SE810」(三井化学社製)
・(T)水添スチレン系熱可塑性エラストマー「タフテックP2000」(旭化成ケミカルズ社製)
(3)基材層
・(U)HIPS 「トーヨースチロールH850N」(東洋スチレン社製、ブタジエン含量9.0質量%)
・(V)GPPS 「HRM23」(東洋スチレン社製)
・(W)PETフィルム 「ルミラー」(東レ社製)
・(W-1)PET樹脂 「TRN-8550FF」(帝人社製)
・(X)ナイロン6フィルム 「ハーデン」(東洋紡社製)
・(X-1)ナイロン6樹脂 「1022B」(宇部興産社製)
・(Y)PMMA 「HBS000」(三菱化学社製)
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。
良触感性は、男性15人、女性15人の計30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に心地よさを感じるかを「○」、「×」判断し、「○」と判断した場合、しっとり、やわらか、ふんわりなどの具体的な肌触り感で評価した。このうち、8割以上の同じ肌触り感を評価した場合、その肌触り感とした。また、樹脂シートを用いた真空圧空成形した成形品の表面においても、同じ肌触り感が維持されているかを評価した。
静・摩擦測定機「TL201Ts (トリニティーラボ社製)」を用い、そのテーブル上に樹脂シートを、毛状体形状等を付与した面を上にして貼り付けた。接触子はウレタン製(デュロメータ硬度:32±2)を用いて、100gの荷重をかけながら、10mm/秒の速度でテーブルを動かし、静摩擦係数及び動摩擦係数を測定した。
フィンガーロボットサーモラボ(カトーテック社製)を用いて、20℃設定の試料台に樹脂シートサンプルを5分置き、樹脂シートの温度調整後、30℃の接触温度センサー(1mm×1.5mm)を接触させ、0.2秒間での熱移動速度(q-max)を測定した。
樹脂の硬度は、JISK7215に準拠し、厚み6mm、幅25mm、長さ50mmの試料を熱プレス法により作製し、タイプAデュロメータを使用して硬度を測定した。
接触角は、樹脂シートについて、自動接触角計DM-501(協和界面科学社製)を用いて測定した。また、試験液は精製水を用い、滴下量は6μLとした。接触角が120°以上であると撥液性が高く、液体の付着を防止できると判定した。
JISK6911に準拠し、雰囲気温度23℃、雰囲気湿度50%R.H.、印加電圧1000Vで樹脂シート表面の表面抵抗値を測定した。
JISK2801に準拠し、フィルム密着法により実施した。5cm×5cmの厚み1mm以内のフィルム表面に各菌液を滴下し、ポリエチレンフィルムで被覆し35℃で保存後、生菌数を測定した。
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、大気圧雰囲気下で準備したスマートフォンカバー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。80℃で120秒間加熱し、最も延伸された箇所では1.5倍に延伸された。
1台の65mm単軸押出機を使用し、Tダイ法により、樹脂シートを押し出し、この樹脂シートの表面に毛状体形状を付与するように、100℃~150℃に調節され、レーザー彫刻法で凹凸加工が成された金属製の転写ロールと、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2m/分~15m/分で引き取ることにより、一方の面が表2に示す表面形状を有する、表1に示す組成及び厚みの樹脂シートを得た。
3台の40mm単軸押出機及びフィードブロックを使用し、Tダイ法により、3層の樹脂シートを押し出し、この樹脂シートの表面に毛状体形状を付与するように、電鋳法で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、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの3層の樹脂シートを得た。
凹凸形状のサイズが異なる転写ロールを用い、実施例3と同様にして、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの3層の樹脂シートを得た。
樹脂シートの表面に毛状体形状を付与するように、電鋳法で凹凸加工が成された100mm角の金型を作成し、電熱プレス機を用いて、予め作成しておいた樹脂シートを熱プレスすることにより、一方の面が表2に示す表面形状を有する、表1に示す組成及び厚みの樹脂シートを得た。
2台の40mm単軸押出機及びフィードブロックを使用し、Tダイ法により、2層の樹脂シートを押し出し、この樹脂シートの表面に毛状体形状を付与するように、電鋳法で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、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの2層の樹脂シートを得た。
ラミネート成形法により、3層の樹脂シートを得、この樹脂シートの表面に毛状体形状を付与するように、電鋳法で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、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの3層の樹脂シートを得た。
凹凸形状のサイズが異なる転写ロールを用い、実施例8に基づいて、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの3層の樹脂シートを得た。
樹脂シートの表面にシボ形状を付与するように、ブラスト法で凹凸加工が成された転写ロールを用い、実施例6に基づいて、一方の面が、Rz(十点平均粗さ)が55μmのシボ形状を有し、表1に示す組成及び厚みの樹脂シートを得た。
樹脂シートの表面に釣鐘状の凸形状を付与するように、エッチング法で凹凸加工が成された転写ロールを用い、実施例3に基づいて、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの3層の樹脂シートを得た。
樹脂シートの表面に四角錐状の凹形状を付与するように、電鋳法で凹凸加工が成された転写ロールを用い、実施例1に基づいて、一方の面が表2に示す表面形状を有し、表1に示す組成及び厚みの樹脂シートを得た。
転写ロールに代えて凹凸加工が成されていないロールを用い、実施例1に基づいて、平滑状の両表面を有し、表1に示す組成、厚みの樹脂シートを得た。
樹脂シートの表面に六角錐状の凸形状を付与するように、電鋳法で凹凸加工が成された転写ロールを用い実施例8に基づいて、一方の面が表2に示す表面形状を有し、各層が表1に示す組成及び厚みの3層の樹脂シートを得た。
実施例1~18の全ての樹脂シートにおいて、良触感性に関する評価基準を満足する結果が得られた。その他、動摩擦係数に対する静摩擦係数、接触角においても満足する結果が得られた。また、実施例11では帯電防止性を示し、実施例12では、抗菌性を示す結果が得られた。これに対して、比較例1~5の樹脂シートでは、良触感性に関する評価基準を満足する結果が得られなかった。
走査電子顕微鏡像から、毛状体同士が絡合することなく一定方向に伸びていることが観察された。また、毛状体は下地層から離間する方向に毛状に伸び、その先端にふくらみが形成された構成となっていた。つまり、毛状体の形状は、下地層から離れるにつれ、断面積が漸次小さくなった後に一旦大きくなってから終端する形状であった。また、毛状体の先端部の形状は、つぼみ状又はきのこ形状であり、つぼみ状又はきのこ形状の部分が一部中空となっていることが観察された。このような形状を有することにより、より良好な触感が発現していることが推察された。
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 (15)
- 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。
- 前記熱可塑性樹脂がスチレン系樹脂、オレフィン系樹脂、ポリ塩化ビニル樹脂、熱可塑性エラストマー、フッ素系樹脂、ポリエステル系樹脂、ナイロン系樹脂-から少なくとも1種類以上を用いた熱可塑性樹脂である、請求項1に記載の樹脂シート。
- 毛状体の平均高さが100μm以上1200μm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または2に記載の樹脂シート。
- 毛状体を有する面の動摩擦係数に対する静摩擦係数の比が1.0~10.0である、請求項1から3の何れか一項に記載の樹脂シート。
- 毛状体を有する面の接触時における熱移動速度が0.005~0.500である請求項1から4の何れか一項に記載の樹脂シート。
- 前記下地層の平均厚みが50μm以上である、請求項1から5の何れか一項に記載の樹脂シート。
- 毛状体が下地層から離間する方向に毛状に伸び、その先端にふくらみが形成された構成とされている、請求項1から6の何れか一項に記載の樹脂シート。
- 下地層及び毛状体は、一のシートから形成された、請求項1から7の何れか一項に記載の樹脂シート。
- 多層樹脂シートである、請求項1から8の何れか一項に記載の樹脂シート。
- 下地層の他方の面にスチレン系樹脂、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から選択される少なくとも1層以上の基材層を積層した請求項1から9の何れか一項に記載の樹脂シート。
- 撥水撥油剤、帯電防止剤及び抗菌剤から選択される1種又は2種以上の添加剤を含む請求項1から10の何れか一項に記載の樹脂シート。
- 押出成形法によって、ダイスから溶融押出した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させて毛状体を形成することを特徴とする請求項1から11の何れか一項に記載の樹脂シートの製造方法。
- 請求項1から11の何れか一項に記載の樹脂シートの成形品。
- 文房具部材である請求項13に記載の成形品。
- 既製の成形品表面に真空圧空成形された、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である請求項13に記載の成形品。
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Also Published As
Publication number | Publication date |
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US11904518B2 (en) | 2024-02-20 |
US20190283301A1 (en) | 2019-09-19 |
JP7049246B2 (ja) | 2022-04-06 |
TWI752061B (zh) | 2022-01-11 |
CN109476075A (zh) | 2019-03-15 |
EP3488993B1 (en) | 2021-06-16 |
TW201815542A (zh) | 2018-05-01 |
ES2882163T3 (es) | 2021-12-01 |
EP3488993A4 (en) | 2020-03-11 |
KR20190032398A (ko) | 2019-03-27 |
EP3488993A1 (en) | 2019-05-29 |
JPWO2018016562A1 (ja) | 2019-06-06 |
KR102393696B1 (ko) | 2022-05-02 |
CN109476075B (zh) | 2021-09-14 |
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