JP6591921B2 - Thermoplastic elastomer composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition useful for various molded articles such as automobiles, machines, construction materials, clothing, electronic materials, food containers, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods, and the like. The present invention relates to a molded article made of a product, and a composite molded article in which the composition is fused to a member.

  Thermoplastic elastomer compositions have been proposed as useful compositions for various molded products such as automobiles, machinery, construction materials, clothing, electronic materials, food containers, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods. ing. The thermoplastic elastomer composition is required to have various physical properties depending on the use of the molded product. For example, a high coefficient of friction is required to prevent slipping in order to be used for various sporting goods, shoe soles, grips of electric tools, machine parts, and non-slip rubbers such as pallets.

  Patent Document 1 discloses that a styrene-based thermoplastic elastomer is used as a thermoplastic elastomer composition having a large friction coefficient and an anti-slip member comprising the same. Thermoplastic styrenic elastomers, especially diblock type thermoplastic styrenic elastomers, are inventions that apply a sticky appearance on the surface. Generally, styrenic elastomers have low oil resistance, and if oil adheres, There are problems that the coefficient of friction decreases, the surface softens, swells, or melts, and is unsuitable for applications where sebum or machine oil may adhere.

  On the other hand, cork is known as a material having a high friction coefficient. For example, Patent Document 2 discloses a cork friction material obtained by integrally molding cork particles of about 10 to 80 mesh through an adhesive. It is disclosed to be used for friction materials such as clutches and brake shoes.

JP 2004-238570 A JP 62-72941 A

  A thermoplastic elastomer composition having a high friction coefficient containing a styrene-based elastomer that can be used as an anti-slip rubber is known, but the styrene-based elastomer has low oil resistance. Patent Document 2 describes that cork has an excellent coefficient of friction, and that a cork friction material impregnated with oil improves wear resistance, etc., but the slip resistance is insufficient. It is.

  An object of the present invention is to provide a thermoplastic elastomer composition that is excellent in flexibility, anti-slip property, and oil resistance, and that can maintain good anti-slip property even if oil adheres to the surface, a molded article comprising the composition, and An object of the present invention is to provide a composite molded body in which the composition is fused to a member.

The present invention
[1] Block copolymer A which is at least one of polyester block copolymer A1 and urethane block copolymer A2, and 1 to 100 parts by mass of wood based on 100 parts by mass of block copolymer A A thermoplastic elastomer composition containing filler B and having an A hardness of 20 to 95,
[2] The present invention relates to a molded article comprising the thermoplastic elastomer composition according to [1], and [3] a composite molded article obtained by fusing the thermoplastic elastomer composition according to [1] and a polar resin.

  The thermoplastic elastomer composition of the present invention is excellent in flexibility, anti-slip property and oil resistance, and has an epoch-making effect that it can maintain good anti-slip property even if oil adheres to the surface. Since it is excellent in fusibility with polar resin, it is easy to apply as various industrial products and parts.

It is the schematic which shows the measuring method (normal test) of the friction coefficient implemented in the Example. It is the schematic which shows the measuring method (oil adhesion test) of the friction coefficient implemented in the Example. It is the schematic which shows the measuring method of the friction coefficient by the method prescribed | regulated to JIS-K7125.

  The thermoplastic elastomer composition of the present invention comprises a block copolymer A containing at least one of a polyester block copolymer A1 and a urethane block copolymer A2 and a wood filler B. It has excellent anti-slip properties and oil resistance, and has the effect of being excellent in fusion properties with polar resins, but it is also an epoch that it can maintain good anti-slip properties even if oil adheres to the surface This is an effective effect.

  It is the principle of lubricating oil and common technical knowledge that when an oil component is sandwiched between two contacting objects, the frictional force between the two objects is remarkably reduced. Therefore, in order to maintain the frictional force even on an object to which sebum or oil adheres, it is necessary to exclude the oil from only a part of the contact interface. Since an elastomer having a relatively high polarity is difficult to be blended with the oil component, by pressing with a partial strong force, the oil in that portion may be eliminated and the frictional force may be recovered. In the present invention, by dispersing a wood filler having an appropriate hardness as a core in a soft elastomer, a minute high-elasticity portion is formed near the surface, and a heavy load is partially applied to eliminate oil. Therefore, it is considered that a high frictional force is generated, and even if oil adheres to the surface, the decrease in slip resistance is suppressed.

  The polyester block copolymer A1 is preferably composed of a hard part (hard segment) and a soft part (soft segment) from the viewpoint of flexibility and moldability, and an aromatic polyester block as a hard segment; A polyester-polyether block copolymer having an aliphatic polyether block as a soft segment is more preferable.

  The aromatic polyester block, which is a hard segment of the polyester-polyether block copolymer, is phthalic acid, terephthalic acid, isophthalic acid, 1,4- or 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, One or more aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid and 4,4'-diphenylsulfone dicarboxylic acid or alkyl esters thereof, ethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol 1 of diols such as hexamethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4'-dihydroxydibiphenyl, 2,2-bis (4'-β-hydroxyethoxydiphenyl) propane A polycondensation product with two or more species is preferable. Examples of commercially available products include “Keyflex” (trade name, manufactured by LG Chemical), “Perprene” (trade name, manufactured by Toyobo Co., Ltd.), “Hytrel” (trade name, manufactured by Toray DuPont Co., Ltd.), “ Flexmer "(manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name) and the like.

  The aliphatic polyether block which is a soft segment of the polyester-polyether block copolymer is preferably mainly composed of polyalkylene ether glycol.

  The urethane block copolymer A2 has the formula (I): from the viewpoint of ensuring good adhesion to various base resins, molding processability, and rubbery feel.

(In the formula, A represents a hard segment composed of a diisocyanate compound and glycol, B represents a soft segment composed of a diisocyanate compound and a long chain glycol, and Y represents a residue of a urethane-bonded diisocyanate compound)
A block copolymer having a hard segment composed of a diisocyanate compound and a glycol having a molecular weight of about 50 to 500, and a soft segment composed of a diisocyanate compound and a long-chain glycol is preferable. Examples of the long-chain glycol include polyether-based ones such as polyalkylene glycol having a molecular weight of about 500 to 10,000, and polyester-based ones such as polyalkylene adipate, polycaprolactone, and polycarbonate. As the diisocyanate compound, known and commonly used compounds such as phenylene diisocyanate, trigen diisocyanate, xylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate are preferably used. These diisocyanate compounds may be the same or different in each of the soft segment and the hard segment.

  Commercially available urethane block copolymer A2 includes “Elastollan (registered trademark)” (manufactured by BASF), “Pandex (registered trademark)” (manufactured by DIC Bayer), “Rezamin (registered trademark)” ( Dainichi Seika Kogyo Co., Ltd.).

  Polyester type block copolymer A1 and urethane type block copolymer A2 may be used individually by 1 type, and may mix and use 2 or more types.

  The A hardness of the block copolymer A is preferably 50 to 98, more preferably 60 to 95, and still more preferably 70 to 90. In the present invention, the A hardness is a durometer type A hardness.

  The content of the block copolymer A in the thermoplastic elastomer composition is preferably 40 to 85% by mass, more preferably 50 to 75% by mass.

  The wood filler B means plant-derived powders such as vegetation, and examples thereof include powders such as cork, wood, bamboo, rice husk, and kenaf. When a filler having an appropriate hardness is contained, the coefficient of friction of the thermoplastic elastomer composition increases. Among the wooden fillers B, cork having both moderate hardness and flexibility and capable of maintaining the hollowness of the cell wall structure even when the composition is melted and mixed is preferable.

The particle size of the wood filler B is preferably small from the viewpoint of maintaining the smoothness of the surface of the molded body, and preferably has a certain size from the viewpoint of feeling the unique texture of the wood filler. From these viewpoints, the average particle diameter of the wood filler B is preferably 0.01 to 5 mm, more preferably 0.5 to 1 mm. The particle size of the wood filler B can be measured by a particle size measurement method such as a Coulter counter, a laser diffraction particle size distribution meter, or a length measurement analysis from an image by a microscope. In the present invention, coarse particles or irregular shapes are used. The volume-based median diameter measured by a microscopic image analysis method that enables accurate measurement including particles is taken as the average particle diameter of the wood filler B.
Further, as a method of obtaining a wood filler having a particle size suitable for the thermoplastic elastomer composition of the present invention, a wood material pulverized by a known pulverization method such as a wood chip crusher or a hammer crusher is used as a vibration sieve or an air classifier. A classification method such as the above classification method can be given. A method of removing a coarse particle by installing a screen mesh at the discharge port of the pulverization method also functions as a kind of classification method, but more preferably, two types of sieves were used and passed through a sieve having an upper limit opening. This is a classification method using a sieve having a lower limit mesh that does not pass through and remains on the sieve, and removes coarse particles and cuts fine particles that are too small to increase the melt viscosity of the composition. Is preferred.

  The content of the wood filler B is 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the block copolymer A. From the viewpoint of enhancing the properties, it is 100 parts by mass or less, preferably 70 parts by mass or less, more preferably 50 parts by mass or less.

  Further, the content of the wood filler B is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, and further preferably 5 to 20% by mass in the thermoplastic elastomer composition.

  The thermoplastic elastomer composition of the present invention preferably further includes a styrene block copolymer C from the viewpoints of flexibility and moldability, and from the viewpoint of further improving flexibility, the styrene block copolymer C. It is more preferable that softener D is included.

  When the styrenic block copolymer C or the styrenic block copolymer C and the softening agent D, which tend to be oleophilic, are blended, there is a possibility that the oil resistance and anti-slip property of the molded product may be impaired. Even if contained, there is no adverse effect on the oil and slip resistance of the entire thermoplastic elastomer composition, and flexibility and moldability are improved. This is because the styrene block copolymer C, or the styrene block copolymer C and the softening agent D, and the block copolymer A are phase-separated due to the difference in polarity. As long as the phase is the sea-island structure, the surface of the molded article composed of the thermoplastic elastomer composition remains non-lipophilic, while the styrenic block copolymer C and the softening agent D are used as the island phase. Since it exists in a thing, it is thought that the effect that the softness | flexibility and moldability of the whole composition become favorable appears.

  The styrenic block copolymer C in the present invention is preferably composed of a hard part (hard segment) and a soft part (soft segment) from the viewpoints of flexibility and moldability. A block copolymer (Z1) having a polymer block unit (s1) composed of a monomer and a polymer block unit (b1) composed of a conjugated diene compound as a soft segment is more preferable.

  Styrene monomers constituting the block unit (s1) include styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, And vinyl anthracene.

  The content of the styrenic monomer unit in the block copolymer (Z1) is preferably 10 to 70% by mass, more preferably 50 to 70% by mass, from the viewpoint of fusibility to a polar resin.

  Examples of the conjugated diene compound constituting the block unit (b1) include butadiene, isoprene, 1,3-pentadiene and the like.

The block copolymer (Z1) is preferably partially or entirely hydrogenated because unsaturated bonds are reduced by hydrogenation and heat resistance, weather resistance and mechanical properties are improved. . The hydrogenation rate is preferably 80% or more, and more preferably 90% or more. In the present invention, the hydrogenation rate is determined by measuring the content of carbon-carbon double bonds derived from the conjugated diene compound in the block copolymer by ¹ H-NMR spectrum before and after hydrogenation, Can be obtained from

  Specific examples of the hydrogenated block copolymer (Z1) include styrene-ethylene / butylene block copolymer, styrene-ethylene / butylene-styrene block copolymer (SEBS), and styrene-ethylene / propylene block copolymer. Styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-ethylene-propylene block copolymer, styrene- (ethylene-ethylene-propylene) -styrene block copolymer (SEEPS), styrene- Ethylene / Butylene (Styrene Controlled Distribution) -Styrene Block Copolymer (SEB (S) S), Styrene-Isobutylene Block Copolymer, Styrene-Isobutylene-Styrene Block Copolymer, (α-Methylstyrene) -Ethylene Butylene Block copolymer, and (α-methylstyrene) -ethylene-butylene- (α-methylstyrene) block copolymer. These may be used singly or as a mixture of two or more. From the viewpoint of raw material preparation and workability, SEBS, SEB (S) S, SEPS, and SEEPS are preferable, and SEBS, SEB (S ) S and SEEPS are more preferred.

  In the present invention, the styrenic block copolymer C is more [block unit (s1) -block unit than the [block unit (s1) -block unit (b1)] type diblock copolymer from the viewpoint of heat resistance. A (b1) -block unit (s1)] type triblock copolymer is preferred. Among the hydrogenated products, as the triblock copolymer, SEBS, SEPS, SEEPS, SEB (S) S, styrene-isobutylene-styrene block copolymer, (α-methylstyrene) -ethylene-butylene- ( α-methylstyrene) block copolymer and the like.

  The content of the triblock copolymer is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and further preferably 95% by mass or more in the styrenic block copolymer C. is there.

  The weight average molecular weight of the styrenic block copolymer C is preferably 50,000 or more, more preferably 100,000 or more from the viewpoint of oil bleed resistance, and preferably 500,000 or less, more preferably 300,000 or less from the viewpoint of moldability. It is. When the styrenic block copolymer C is composed of a plurality of block copolymers, the weighted average value of the weight average molecular weight of each block copolymer is preferably within the above range.

  The content of the styrenic block copolymer C is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 100 parts by mass of the block copolymer A from the viewpoint of flexibility and moldability. Is 20 parts by mass or more, and preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and still more preferably 40 parts by mass or less from the viewpoint of forming a sea-island structure with the block copolymer A.

  The content of the styrenic block copolymer C in the thermoplastic elastomer composition is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass.

  Examples of the softener D include rubber softeners such as paraffin oil, naphthene oil, and aromatic oil. Among these, the affinity with the styrenic block copolymer C is good, Paraffin oil is preferred from the viewpoint that bleeding does not occur easily.

The higher the kinematic viscosity of the softener D at 40 ° C., the higher the volatilization during heating and melting, and the better the bleed resistance, so it is preferably 30 mm ² / s or more, more preferably 60 mm ² / s or more, More preferably, it is 80 mm ² / s or more, from the viewpoint of improving the fusion property to the polar resin, more preferably 150 mm ² / s or more, and since the lower one is easier to handle, preferably 500 mm ² / s. s or less, more preferably 450 mm ² / s or less, and still more preferably 400 mm ² / s or less.

  The content of the softening agent D is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass with respect to 100 parts by mass of the styrenic block copolymer C from the viewpoint of flexibility and moldability. From the viewpoint of bleed resistance, it is preferably 200 parts by mass or less, more preferably 160 parts by mass or less, and still more preferably 120 parts by mass or less.

  Moreover, content of the softening agent D in a thermoplastic elastomer composition becomes like this. Preferably it is 1-40 mass%, More preferably, it is 5-35 mass%.

  The thermoplastic elastomer composition of the present invention may further contain a thickener E. By blending thickener E, the stiffness of the resin is improved when the thermoplastic elastomer composition is melt-molded and then cooled in the mold, so that the molded product can be removed from the mold even in a short cooling time. Thus, the molding cycle time can be shortened.

  As the thickener E, any one can be used as long as it has an effect of increasing the melt tension at the time of molding of the thermoplastic resin. Among them, an epoxy thickener, an acrylic thickener, etc. Is preferred.

  The epoxy thickener is preferably an epoxy compound that is a polymer having a styrene structure in the skeleton.

  Examples of commercially available epoxy thickeners include Alfon UG series manufactured by Toagosei Co., Ltd., Marproof G series manufactured by NOF Corporation, and Jonkrill ADR series manufactured by BASF.

  As acrylic thickeners, acrylic polymeric processing aids, acrylic-modified polytetrafluoroethylene, and the like are known. In the present invention, acrylic-modified polytetrafluoroethylene is preferred. Acrylic-modified polytetrafluoroethylene is thermoplastic because polytetrafluoroethylene, which has been improved in compatibility with thermoplastic resins by acrylic modification, is fibrillated by melt kneading to form a fibrous network. The moldability can be improved by increasing the melt viscosity of the resin composition.

  When it contains the thickener E, content of the thickener E in a thermoplastic elastomer composition becomes like this. Preferably it is 1-30 mass%, More preferably, it is 2-20 mass%.

  The thermoplastic elastomer composition of the present invention may contain other thermoplastic resins and thermoplastic elastomers as long as the effects of the present invention are not impaired. Among these, the polar elastomer can improve the fusion property of the composition to the polar resin. The polar elastomer is not particularly limited, and examples thereof include NBR (nitrile rubber), polyurethane rubber, epichlorohydrin rubber, polyamide thermoplastic elastomer, acrylic thermoplastic elastomer, and the like.

  The thermoplastic elastomer composition of the present invention is, as necessary, a polyolefin resin such as polypropylene and polyethylene, a reinforcing agent such as carbon black, silica, carbon fiber, and glass fiber, and inorganic filling, as long as the effects of the present invention are not impaired. Agents, insulating heat conductive fillers, pigments, hydrated metal compounds, red phosphorus, ammonium polyphosphate, antimony, silicone and other flame retardants, antistatic agents, tackifiers, crosslinking agents, crosslinking aids, thermal stabilizers, You may contain various additives, such as antioxidant, a light stabilizer, a ultraviolet absorber, a blocking inhibitor, a sealing property improving agent, a mold release agent, a coloring agent, and a fragrance | flavor.

  The thermoplastic elastomer composition of the present invention comprises, for example, a block copolymer A and a wood filler B, and, if necessary, a raw material containing a styrenic block copolymer C, a softener D, and other additives. It is obtained by solidifying by cooling.

  “Mixing” as used in the present invention is not particularly limited as long as various components are mixed well, and various components may be dissolved and mixed in a soluble organic solvent, or by melt kneading. You may mix.

  In the case of melt mixing, a kneader or a general melt extruder can be used, and it is preferable to use a single screw extruder for improving the kneading state. As for the supply to the extruder, various components may be directly supplied to the extruder, a mixture of various components using a mixing device such as a Henschel mixer in advance may be provided from one hopper, or two hoppers. Each of the components may be charged and used while being quantified with a screw or the like under the hopper.

  The thermoplastic elastomer composition can be used by directly forming a molded product obtained by melting and mixing into pellets, powders before forming a molded product to be used as a final product depending on the application. Intermediate products such as sheets can be used. For example, it is melt-mixed by an extruder, extruded into a strand, and cut into pellets such as a cylindrical shape and a rice grain by a cutter while cooling in cold water. The obtained pellets can be usually formed into a predetermined sheet-like molded product or a molded product by a molding method such as injection molding, extrusion molding, or press molding.

  The A hardness of the thermoplastic elastomer composition of the present invention is 95 or less, preferably 90 or less, more preferably 85 or less, even more preferably 80 or less from the viewpoint of flexibility, and 20 or more from the viewpoint of suppressing stickiness. Preferably it is 25 or more, more preferably 30 or more.

  From the viewpoint of moldability, the melt mass flow rate of the thermoplastic elastomer composition of the present invention at 190 ° C. and a load of 21.2 N is preferably 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more. From the viewpoint of dispersibility, the amount is preferably 10 g / 10 min or less, more preferably 5 g / 10 min or less.

  A molded body is obtained by appropriately heat-molding the thermoplastic elastomer composition of the present invention according to a conventional method. The use of the molded product obtained by thermoforming the thermoplastic elastomer composition of the present invention is not particularly limited, and general styrene elastomers, polyolefin elastomers, polyurethane elastomers, polyamide elastomers, acrylic elastomers And polyester elastomers can be used.

  The apparatus used for manufacturing a molded body using the thermoplastic elastomer composition of the present invention can be any molding machine capable of melting a molding material. Examples thereof include a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, and a mixing roll.

  The thermoplastic elastomer composition of the present invention can be used as a composite molding material, and can be suitably used for bonding members made of different materials because it is fused to various materials. Shows good fusing property.

  Examples of polar resins include polycarbonate, polyester resins, poly (meth) acrylate resins such as polymethyl methacrylate, polyethylene oxide resins, polypropylene oxide resins, polyvinyl acetate resins, polyamide resins, polyurethane resins, Polystyrene resins such as acrylonitrile-butadiene-styrene resin (ABS resin), polyvinyl ether resins, polyvinyl alcohol resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyetherimide resins, polyether ketone resins, polyethers Examples include ether ketone resins, LCP (liquid crystal polymers), ionomers, and the like, and one or more of these can be used.

  Therefore, the present invention further provides a composite molded body in which the thermoplastic elastomer composition of the present invention and a member, preferably a polar resin, are fused and integrated. Accordingly, it is possible to combine a member having a complicated joint surface and a member having joint surfaces having different shapes.

  In the present invention, the fusion is carried out by applying heat equal to or higher than the melting point of the thermoplastic elastomer composition of the present invention to form a melt, and then solidifying at a temperature equal to or lower than the melting point, thereby fixing to the interface to be fused. A phenomenon. In order to apply heat, a hot press machine, a heated roll machine, a hot air generator, heated steam, an ultrasonic welder, a high frequency welder, a laser, or the like can be used. Therefore, even if the interface of the fused part is a complicated three-dimensional shape, it can be well integrated with the complicated three-dimensional shape and integrated. The fusion between the thermoplastic elastomer composition and the member may be entirely or partially.

  When the thermoplastic elastomer composition of the present invention is fused to a polar resin, the peel strength from the polar resin is preferably 90 N / 25 mm or more from the viewpoint of adhesive properties.

  The composite molded product obtained by fusing the thermoplastic elastomer composition of the present invention to a member is injection molding, injection compression molding, insert molding, multicolor molding, vacuum molding, pressure molding, blow molding, hot press molding, foam molding, laser. The thermoplastic elastomer composition of the present invention is not self-adhesive like an adhesive and is easy to handle, although it can be obtained by molding by a method such as fusion molding or extrusion molding. Therefore, it can be applied to injection molding.

  As the composite molded body in which the thermoplastic elastomer composition of the present invention is fused to a member, an insert molded body in which a polar resin is inserted into a molded body made of a thermoplastic elastomer composition, a thermoplastic elastomer composition, and a polar resin And composite molded bodies obtained by multicolor molding.

  Since the thermoplastic elastomer composition of the present invention, a molded article using the composition, and a composite molded article are excellent in anti-slip properties, they can be used as an anti-slip material. Anti-slip materials include grip tape, grip materials, mats, shoe soles and insoles, glove contacts, floors, gratings, scaffolding boards, slopes, staircases, etc. In addition, since it is possible to maintain good anti-slip properties, it can be suitably used as a tool or a part to be gripped by the hand of a mechanical device.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Various physical properties such as raw materials used in Examples and Comparative Examples were measured by the following methods.

<Component A (Block Copolymer)>
[A hardness]
Measure with JIS K 6253 Type A.

<Component B (wood filler)>
[Average particle size]
Using a laser microscope VK-9700 manufactured by Keyence Corporation, a magnified image of a wooden filler dispersed on a glass plate was taken, and the particle size measured in a certain direction was determined by image analysis of 100 arbitrarily selected particles. Approximate the sphere, calculate the volume-based median diameter, and use it as the average particle diameter. This method is a particle size analysis method conventionally known as a ferret method.

<Component C (Styrene Block Copolymer)>
[Content of styrene monomer unit]
Proton NMR measurement is performed with a nuclear magnetic resonance apparatus (manufactured by BRUKER, Germany, DPX-400), and the content of styrene and / or styrene derivatives is determined by quantifying the characteristic groups of styrene.

(Weight average molecular weight (Mw))
Under the following measurement conditions, the molecular weight is measured in terms of polystyrene by gel permeation chromatography, and the weight average molecular weight is determined.

Measuring device and pump: JASCO (JASCO Corporation), PU-980
・ Column oven: Showa Denko KK, AO-50
・ Detector: Hitachi, RI (differential refractometer) detector L-3300
・ Column type: Showa Denko Co., Ltd. “K-805L (8.0 × 300mm)” and “K-804L (8.0 × 300mm)” each used in series ・ Column temperature: 40 ℃
・ Guard column: KG (4.6 × 10mm)
・ Eluent: Chloroform ・ Eluent flow rate: 1.0 ml / min
・ Sample concentration: about 1mg / ml
・ Sample solution filtration: 0.45μm pore size disposable filter made of polytetrafluoroethylene ・ Standard sample for calibration curve: Polystyrene made by Showa Denko KK

<Component D (softener)>
(Kinematic viscosity)
Measured at a temperature of 40 ° C. according to JIS Z 8803.

Examples 1-6 and Comparative Examples 2-5 (Example 6 is a reference example)
(1) Preparation of thermoplastic elastomer composition The materials shown in Tables 6 and 7 other than the softener were dry blended and impregnated with the softener to prepare a mixture. Thereafter, the mixture is melt-mixed with an extruder under the following conditions, extruded into strands, cooled to about 3 mm in diameter and about 3 mm in length with a cutter while cooled in cold water, and pellets of the thermoplastic elastomer composition are obtained. Manufactured.

[Melting and mixing conditions]
Extruder: B-40mm vent type single screw extruder (trade name, manufactured by Ishinaka Seisakusho)
L / D: 37
Rotation speed: 100r / min

  Details of the raw materials described in Tables 6 and 7 used in Examples and Comparative Examples are as follows.

(2) Production of molded product of thermoplastic elastomer composition The pellets were press-molded under the following conditions to produce a plate-like press-formed product having a thickness of 2 mm x width 125 mm x length 125 mm.

[Press molding conditions]
Press molding machine: 42ton heating and cooling two-stage hydraulic molding machine 100MSIII-10E (trade name, manufactured by Toho Machinery Co., Ltd.)
Heating pressure: 5MPa
Heating time: 2 minutes Cooling pressure: 5MPa
Cooling time: 2 minutes

Comparative Example 1
Adhesive mixture by mixing 100 parts by weight of urea resin (manufactured by Aika Industries, UN-830J), 27 parts by weight of flour, 16 parts by weight of water, and 1 part by weight of a curing agent (manufactured by Aika Industries, UH-10) Got.
80 parts by mass of the resulting adhesive mixture and 100 parts by mass of cork grains (volume median diameter: 0.8 mm) were mixed well, then packed in a 10 mm thick, 125 mm square mold at 90 ° C., 5 MPa 2 After press-molding for 2 minutes and then cooling for 2 minutes and taking out, it was sliced with a cutter, and a cork sheet having a thickness of 2 mm and a 125 mm square was cut out from the center.

  The following measurements were performed on the compositions obtained in Examples 1 to 6 and Comparative Examples 2 to 5 and the cork sheet of Comparative Example 1. The results are shown in Tables 6 and 7.

(1) A hardness (flexibility)
A durometer A hardness was measured in accordance with a method defined in JIS K 6253 using a press-molded product or a cork sheet that was allowed to stand at an ambient temperature of 23 ° C. for 24 hours.

(2) Melt mass flow rate (MFR)
Using a press-formed product or a cork sheet, the measurement was performed under the conditions of 190 ° C. and a load of 2.16 kg in accordance with ASTM D1238.

(3) Coefficient of friction
Using a SUS weight slide piece (200 g) having a felt surface specified in JIS K7125, the friction coefficient of the press-formed product and the cork sheet was measured.
(3-1) Normal test As shown in FIG. 1, a weight sliding piece 2 having a contact area of 40 cm ^{2 with} a metal surface other than the felt surface 1 as the contact surface, at a speed of 100 mm / min on the sheet sample 3 in the direction of the arrow The static friction coefficient and the dynamic friction coefficient between the metal surface and the surface of the sheet sample 3 were measured.
(3-2) Oil adhesion test Except that oily hand cream (Nivea Kao Co., Ltd., Nivea Cream) was applied to the entire metal surface of the weight slide piece 2 as a model material for sebum, As shown in FIG. 2, the static friction coefficient and the dynamic friction coefficient between the hand cream application surface 4 and the surface of the sheet sample 3 were measured.
According to the general rule of JIS K7125 as a method for measuring the friction coefficient, as shown in FIG. 3, a 63 mm square felt surface 1 of a weight sliding piece 2 with a contact area of 40 cm ² is a sheet sample 3 having a thickness of 0.5 mm or less. At this time, the weight slide piece 2 and the sheet sample 3 are simultaneously moved in the direction of the arrow at a speed of 100 mm / min on the mating member 5, and the friction coefficient between the sheet sample 3 and the mating material 5 is measured. Therefore, the measurement part of the friction coefficient is different between the measurement method in this embodiment and the measurement method specified in JIS K7125.
In order to clarify the difference between the two measurement methods, in FIG. 1, between the felt surface 1 and the sheet sample 3, and in FIG. 2, between the hand cream application surface 4 and the sheet sample 3, FIG. In this case, a gap is provided between the sheet sample and the counterpart material, but actually, as described above, they are in contact with each other.

(4) Fusing power to polar resin (PC fusing power / ABS fusing power)
Injection molded plate of polycarbonate (PC) resin (Mitsubishi Engineering Plastics, Iupilon H-3000) or ABS resin (Dycel Polymer, Sebian V-500SF) as a polar resin (2mm thick x 25mm wide x 125mm long) In addition, a PTFE tape wound between one end of the length and 40 mm is inserted into the mold, and the pellets obtained in Examples 1 to 6 and Comparative Examples 2 to 5 include an insert body. A fusion test piece (composite molded product) was produced by injection molding at 230 ° C. into a mold having a total size of 6 mm thick × 25 mm wide × 125 mm long.
In addition, for the cork sheet of Comparative Example 1, a strip-shaped sheet having a thickness of 2 mm, a width of 25 mm, and a length of 125 mm was cut out from a cork sheet having a thickness of 2 mm and a 125 mm square, and PTFE between one end of the length and 40 mm. Insert a tape-wrapped material in the mold, and then inject the polycarbonate resin or ABS resin into a mold that is 6mm thick x 25mm wide x 125mm long at 230 ° C. Thus, a fusion test piece was produced.
The obtained fusion test piece was subjected to the following tensile test using the easily peelable PTFE tape portion as a gripping margin.
Grab the insert member (base material layer) with a thickness of 2 mm and the skin material layer with a thickness of 4 mm formed on it with a gripper and use the method according to JIS K 6854 at an ambient temperature of 23 ° C. And the base material layer were subjected to a tensile test in the direction of 180 ° at 50 mm / min, and the peel strength (N / 25 mm) between the skin material layer and the base material layer was measured.

It turns out that the thermoplastic elastomer composition of Examples 1-6 is excellent in a softness | flexibility, slip resistance, and oil resistance, and its fusing property with polar resin is also favorable.
The cork sheet of Comparative Example 1 has a small coefficient of friction and low anti-slip properties, whereas the coefficient of friction is high by mixing with a block copolymer as in Examples 1-6.
On the other hand, by comparing Example 1 with Comparative Example 2, Example 2, 3 with Comparative Example 3, Example 4, 5 with Comparative Example 4, Example 6 with Comparative Example 5, cork is added to the thermoplastic elastomer composition. By blending, it can be seen that the friction coefficient is increased, and that the decrease in the friction coefficient is small even in the oil adhering state.
Examples 1 and 2 are compositions in which a styrenic block copolymer and paraffin oil are blended. Compared to Example 4, the friction coefficient is higher, and the dynamic friction coefficient is reduced particularly in an oil-attached state. Is small.
Examples 3 and 5 are compositions in which the amount of cork is increased. When compared with the corresponding Examples 2 and 4, the friction coefficient in the normal state is slightly reduced, but the decrease in the friction coefficient due to oil adhesion is suppressed. I understand that.
Example 6 is a composition in which a urethane block copolymer is blended. From the comparison with Comparative Example 5, the coefficient of friction is increased by blending cork in the same manner as the composition in which the polyester block copolymer is blended. It can be seen that the decrease in the coefficient of friction is small even in the oil adhesion state.

  The thermoplastic elastomer composition of the present invention is useful for various molded articles such as automobiles, machines, construction materials, clothing, electronic materials, food containers, home appliances, electrical equipment, medical equipment, packaging materials, stationery and miscellaneous goods, Furthermore, it is used for various members such as grips, tubes, packings, gaskets, cushion bodies, films, and sheets.

1 Felt surface 2 Weight slide piece 3 Sheet sample 4 Hand cream application surface 5 Counterpart

Claims (4)

It contains a block copolymer A that is a polyester block copolymer A1 and a wood filler B that is 1 to 100 parts by mass of cork with respect to 100 parts by mass of the block copolymer A, and an A hardness of 20 to 95 der is, the polyester-based block copolymer A1 is, a polyester and an aromatic polyester block and an aliphatic polyether block - Ru polyether block copolymer der thermoplastic elastomer composition.   The thermoplastic elastomer composition according to claim 1, further comprising 1 to 80 parts by mass of the styrenic block copolymer C with respect to 100 parts by mass of the block copolymer A. Claim 1 or 2 molded article comprising the thermoplastic elastomer composition. A composite molded article obtained by fusing the thermoplastic elastomer composition according to claim 1 or 2 and a polar resin.

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