Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C08L57/02—Copolymers of mineral oil hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
  • C08L93/04—Rosin

Definitions

• the present invention relates to a method for producing a thermoplastic elastomer foam that is lightweight and excellent in impact absorption.
• a foam made of a thermoplastic resin is excellent in molding processability, has properties such as flexibility and buffering properties, and is widely used in various applications.
• foams examples include foamed styrene / conjugated diene block copolymer hydrogenated products (Patent Document 1), and foamed crosslinked thermoplastic elastomer with thermally expandable microballoons. (Patent Document 2).
• Patent Document 1 foamed styrene / conjugated diene block copolymer hydrogenated products
• Patent Document 2 foamed crosslinked thermoplastic elastomer with thermally expandable microballoons.
• the foam obtained by the methods of Patent Document 1 and Patent Document 2 is hard and inferior in impact absorption.
• Patent Document 3 For the purpose of providing a foam excellent in impact absorption, a foam composition (Patent Document 3) using a specific conjugated diene copolymer or a hydrogenated product thereof has been developed.
• the foam composition disclosed in Patent Document 3 can finally obtain a foam by vulcanization, has a low degree of freedom in shape and low productivity, and is further derived from a vulcanizing agent. It has an odor, and the use place such as a shoe sole is limited.
• thermoplastic elastomer foam obtained by injection foaming a foamable assembly containing a thermoplastic elastomer having a specific structure and a thermally expandable microcapsule for the purpose of providing a foam that is also excellent in impact absorption and its A manufacturing method (Patent Document 4) has been developed.
• Patent Document 4 since the tackifier resin pellet used as a raw material is brittle, the properties of the tackifier resin are not stabilized as pellets and pulverized powder, and are tackified during molding. There is a possibility that the resin is unevenly distributed.
• JP-A-6-218741 Japanese Patent Laid-Open No. 11-343362 JP-A-5-345833 JP 2011-168775 A
• An object of the present invention is to stably and easily obtain a thermoplastic elastomer foam having a light weight and excellent impact absorption.
• the inventors of the present invention produced a masterbatch containing a thermoplastic elastomer excellent in handleability and a tackifier resin when molding a thermoplastic elastomer foam. It is found that the thermoplastic elastomer foam can be obtained stably and easily by eliminating the uneven distribution of the tackifying resin and the classification work step by the production method of carrying out molding with the necessary blending using The present invention has been completed.
• Thermoplastic elastomer (A) 35 to 55 comprising a block copolymer comprising a polymer block having isobutylene as a constituent monomer and a polymer block having an aromatic vinyl monomer as a constituent monomer. And a step of preparing a masterbatch of a tackifier resin containing 45% to 65% by weight of a tackifier resin (B), and thermoplastic elastomer (A) 200 to 400 with respect to 100 parts by weight of the masterbatch.
• Thermoplastic elastomer foam comprising: a step of preparing a foamable composition by mixing 2 parts by weight of 2 parts by weight of a foaming agent (C); and a step of molding the foamable composition Body manufacturing method.
• thermoplastic elastomer foam according to 1) wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene, p-methylstyrene, ⁇ -methylstyrene and indene. Body manufacturing method.
• thermoplastic elastomer foam according to 1) or 2), wherein the thermoplastic elastomer (A) is a styrene-isobutylene-styrene block copolymer.
• Tackifying resin (B) is aliphatic petroleum resin, alicyclic petroleum resin, alicyclic petroleum resin hydride, aromatic petroleum hydride, polyterpene resin, dicyclopentadiene petroleum
• the foaming agent (C) is a thermally expandable microcapsule composed of an outer shell made of a thermoplastic resin having a gas barrier property and a liquid expander encapsulated in the outer shell, and the liquid expander is the thermoplastic 5.
• thermoplastic elastomer foam obtained by the production method of any one of 1) to 5).
• a body protecting protector comprising the thermoplastic elastomer foam according to 6).
• An impact absorber comprising the thermoplastic elastomer foam according to 6).
• thermoplastic elastomer foam which is lightweight and has the outstanding impact absorption can be obtained stably and easily.
• thermoplastic elastomer (A) 35 comprising a block copolymer comprising a polymer block having isobutylene as a constituent monomer and a polymer block having an aromatic vinyl monomer as a constituent monomer.
• thermoplastic comprising: a step of producing a foamable composition by mixing ⁇ 400 parts by weight and 2 to 40 parts by weight of a foaming agent (C); and a step of molding the foamable composition
• the present invention relates to a method for producing an elastomer foam.
• thermoplastic elastomer (A) a block copolymer comprising a polymer block having isobutylene as a constituent monomer and a polymer block having an aromatic vinyl monomer as a constituent monomer is particularly preferable. It is not limited.
• the method for producing a polymer block containing isobutylene as a constituent monomer is not particularly limited.
• it can be produced by cationic polymerization of a monomer component containing isobutylene as a main component in the presence of an initiator.
• the compound represented by following General formula (1) can be used.
• the compound represented by the following general formula (1) is considered to generate a carbon cation in the presence of a Lewis acid or the like and serve as a starting point for cationic polymerization.
• (CR 1 R 2 X) n R 3 (1) [Wherein X represents a halogen atom, an alkoxy group having 1 to 6 carbon atoms or an acyloxy group having 1 to 6 carbon atoms.
• R 1 and R 2 each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R 1 and R 2 may be the same or different.
• R 3 represents a polyvalent aromatic hydrocarbon group or a polyvalent aliphatic hydrocarbon group, and n represents a natural number of 1 to 6. ].
• the compound represented by the general formula (1) is not particularly limited, but examples thereof include (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, , 3-Bis (1-chloro-1-methylethyl) benzene, 1,3,5-tris (1-chloro-1-methylethyl) benzene, 1,3-bis (1-chloro-1-methylethyl) And -5- (tert-butyl) benzene. These may be used alone or in combination of two or more. Of these, 1,4-bis (1-chloro-1-methylethyl) benzene and 1,3,5-tris (1-chloro-1-methylethyl) benzene are preferable.
• a Lewis acid catalyst may be allowed to coexist.
• the Lewis acid catalyst is not particularly limited as long as it can be used for cationic polymerization, and TiCl 4 , TiBr 4 , BCl 3 , BF 3 , BF 3 .OEt 2 , SnCl 4 , SbCl 5 , SbF 5 , WCl 6 , Examples include metal halides such as TaCl 5 , VCl 5 , FeCl 3 , ZnBr 2 , AlCl 3 , and AlBr 3 ; organometallic halides such as Et 2 AlCl and EtAlCl 2 (Et represents an ethyl group). These may be used alone or in combination of two or more. Among these, TiCl 4 , BCl 3 , and SnCl 4 are preferable from the viewpoints of catalyst capability and industrial availability.
• the amount used is not particularly limited, and can be set in view of the polymerization characteristics and polymerization concentration of the monomer used. Usually, 0.1 to 100 molar equivalents are preferable with respect to the compound represented by the general formula (1), and 1 to 50 molar equivalents are more preferable.
• an electron donor component can be present together if necessary.
• This electron donor component is considered to have an effect of stabilizing the growing carbon cation during cationic polymerization, and the addition of an electron donor can produce a polymer with a controlled molecular weight distribution. it can.
• the electron donor component is not particularly limited, and examples thereof include pyridines, amines, amides, sulfoxides, esters, and metal compounds having an oxygen atom bonded to a metal atom. These may be used alone or in combination of two or more.
• Polymerization of the monomer component containing isobutylene as a main component can be performed in an organic solvent as necessary.
• the organic solvent is not particularly limited as long as it does not substantially inhibit cationic polymerization.
• halogenated carbonization such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene and the like.
• alkylbenzenes such as benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene
• linear aliphatic hydrocarbons such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane
• Branched aliphatic hydrocarbons such as methylpropane, 2-methylbutane, 2,3,3-trimethylpentane, and 2,2,5-trimethylhexane
• Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane Oil fraction Water ⁇ made of paraffin oil and the like can be mentioned.
• organic solvents may be used alone or in combination of two or more in consideration of the balance between the polymerization characteristics of the monomers constituting the block copolymer and the solubility of the resulting polymer. Also good.
• the amount of the organic solvent used is not particularly limited, but the polymer concentration is preferably 1 to 50% by weight, more preferably 5 to 35% by weight in consideration of the viscosity of the resulting polymer solution and the ease of heat removal. % Can be determined.
• the polymerization of the monomer component containing isobutylene as a main component is preferably carried out by mixing each component under cooling, for example, at a temperature of ⁇ 100 ° C. or higher and lower than 0 ° C. From the viewpoint of balancing energy cost and polymerization stability, -80 ° C to -30 ° C is more preferable.
• the manufacturing method of the polymer block which uses an aromatic vinyl-type monomer as a constituent monomer is not specifically limited, For example, it can manufacture by superposing
• the aromatic vinyl monomer is not particularly limited.
• At least one selected from the group consisting of styrene, p-methylstyrene, ⁇ -methylstyrene and indene is preferable from the viewpoint of easy availability and physical property balance.
• the method for polymerizing the aromatic vinyl monomer is not particularly limited, and a known method can be used.
• thermoplastic elastomer (A) is not particularly limited.
• a diblock copolymer comprising a polymer block, a star block copolymer having an arm comprising a polymer block composed of an aromatic vinyl monomer and a polymer block composed of isobutylene. Examples include coalescence.
• thermoplastic elastomer (A) having these structures may be used alone or in combination of two or more.
• the production method of the block copolymer is not particularly limited, and is a known method using a polymer block having an aromatic vinyl monomer as a constituent monomer and a polymer block having isobutylene as a constituent monomer. Can be manufactured.
• thermoplastic elastomer (A) a weight ratio of a polymer block having an aromatic vinyl monomer as a constituent monomer and a polymer block having isobutylene as a constituent monomer ((isobutylene is used as a constituent monomer).
• the weight of the polymer block) / (the weight of the polymer block containing the aromatic vinyl monomer as a constituent monomer)) is not particularly limited, but the impact absorption and moldability of the foam, From the viewpoint of shape retention, 95/5 to 60/40 is preferable, and 90/10 to 65/35 is more preferable.
• thermoplastic elastomer (A) is preferably a styrene-isobutylene-styrene block copolymer from the viewpoint of efficiently absorbing energy such as impact, and a commercially available product is SIBSTAR (manufactured by Kaneka Corporation).
• the tackifier resin (B) is used from the viewpoint of improving the impact absorbability of the thermoplastic elastomer foam.
• the tackifying resin (B) is not particularly limited, and examples thereof include rosin and rosin derivatives, polyterpene resins, aromatic modified terpene resins and their hydrides, terpene phenol resins, coumarone indene resins, aliphatic petroleum resins, Alicyclic petroleum resin and its hydride, aromatic petroleum resin and its hydride, aliphatic aromatic copolymer petroleum resin and its hydride, dicyclopentadiene petroleum resin and its hydride, styrene or substituted styrene And low molecular weight polymers. These may be used alone or in combination of two or more.
• an alicyclic petroleum resin and its hydride an aliphatic petroleum resin
• It is preferably at least one selected from the group consisting of hydrides of aromatic petroleum resins, polyterpene resins, dicyclopentadiene petroleum resins, and rosin, and is particularly highly compatible with the SIBSTAR. Hydrides of alicyclic petroleum resins are preferred.
• the loss tangent (tan ⁇ ) obtained by the dynamic viscoelasticity measurement in the shear mode in the composition containing the thermoplastic elastomer (A), the tackifier resin (B), the plasticizer, and the like.
• hydrides of alicyclic petroleum resins are particularly preferable. Examples of the hydrides of alicyclic petroleum resins include Alcon manufactured by Arakawa Chemical Industries.
• the loss tangent is calculated by the ratio of the loss elastic modulus to the storage elastic modulus (loss elastic modulus / storage elastic modulus). The loss tangent represents the attenuation related to energy consumption such as impact, and the larger the value, the more the attenuation. Is expensive.
• the tackifying resin (B) preferably has a number average molecular weight of 300 to 3,000. Further, a resin having a softening point based on the ring and ball method defined in JIS K-2207 of 60 to 160 ° C., more preferably 90 to 150 ° C. is preferable.
• the content of the tackifying resin (B) is preferably 8 to 22% by weight, more preferably 9 to 20% by weight, and further preferably 10 to 18% by weight based on the total weight of the foamable composition. If the content exceeds 22% by weight, the viscosity at the time of kneading is too low, so that a sufficient kneaded state cannot be obtained, and it may be difficult to obtain a good foam, and it is less than 8% by weight. And the additive effect is difficult to appear.
• the foaming agent (C) preferably contains a thermally expandable microcapsule from the viewpoint that the closed cell ratio of the thermoplastic elastomer foam is increased.
• the heat-expandable microcapsule is obtained by encapsulating a volatile liquid expansion agent in an outer shell made of a polymer to form a microcapsule.
• it is a thermally expandable microcapsule composed of an outer shell made of a thermoplastic resin having gas barrier properties and a liquid expander encapsulated in the outer shell, and the temperature of the liquid expander is equal to or lower than the softening point of the thermoplastic resin. It is preferable that it is gaseous.
• microcapsules can be produced by suspension polymerization of a polymerizable mixture containing at least a liquid swelling agent and a polymerizable monomer in an aqueous medium. According to this method, as the polymerization reaction proceeds, a heat-expandable microcapsule having a structure in which an outer shell is formed by the produced polymer and an expansion agent is encapsulated in the outer shell is obtained. .
• thermoplastic resin having gas barrier properties is not particularly limited, and examples thereof include acrylic copolymers, vinylidene chloride polymers, polyvinyl alcohol polymers, and polycarboxylic acid polymers.
• the liquid swelling agent is not particularly limited as long as it becomes gaseous at a temperature below the softening point of the thermoplastic resin, and examples thereof include n-butane, isobutane, n-pentane, isopentane, and neopentane. .
• thermoly expandable microcapsules Since heat-expandable microcapsules are in a fine powder form, it is often difficult to mix uniformly, and there is a risk of dust explosion, etc., so there is a high concentration in a resin that can be processed at a relatively low temperature. It is preferable to mix in a state (microcapsule masterbatch) dispersed in the mixture. In this case, a value obtained by multiplying the blending amount of the microcapsule master batch by the content of the thermally expandable microcapsule in the microcapsule master batch is the blending amount of the thermally expandable microcapsule.
• the content of the foaming agent (C) is preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight, based on the total weight of the foamable composition. If the content is less than 0.5% by weight, the density of the thermoplastic elastomer foam tends to be high and the lightness tends to be inferior. On the other hand, even if it exceeds 20% by weight, it is difficult to further reduce the density of the thermoplastic elastomer foam.
• thermoplastic elastomer foam of the present invention may optionally contain components other than the components (A) to (C).
• a plasticizer can be added for the purpose of adjusting the flexibility and molding processability of the thermoplastic elastomer foam.
• a liquid or liquid material is used suitably at room temperature. Both hydrophilic and hydrophobic plasticizers can be used. Examples of such plasticizers include plasticizers for various rubbers or resins such as mineral oils, vegetable oils, and synthetics.
• the mineral oil-based plasticizer is not particularly limited, and examples thereof include naphthenic and paraffinic process oils.
• the vegetable oil-based plasticizer is not particularly limited, and examples thereof include castor oil, cottonseed oil, ramie oil, rapeseed oil, soybean oil, palm oil, palm oil, peanut oil, wax, pine oil, olive oil and the like.
• the synthetic plasticizer is not particularly limited, and examples thereof include polybutene and low molecular weight polybutadiene. Among these, paraffinic process oil or polybutene is preferable from the viewpoint of compatibility with the thermoplastic elastomer (A). These may be used alone or in combination of two or more in order to obtain desired viscosity and physical properties.
• thermoplastic elastomer foam of the present invention examples include, but are not limited to, fillers, antioxidants, flame retardants, antibacterial agents, light stabilizers, colorants, fluidity improvers, lubricants, antiblocking agents, antistatic agents, and crosslinking agents. And crosslinking aids. These may be used alone or in combination of two or more. Furthermore, as long as it does not impair the performance of the thermoplastic elastomer foam of the present invention, it may contain a resin other than the thermoplastic elastomer (A), such as various thermoplastic resins and thermosetting resins.
• a masterbatch of a tackifying resin containing a thermoplastic elastomer (A) and a tackifying resin (B) is prepared in advance.
• a thermoplastic elastomer foam can be obtained stably and easily.
• a method for producing a masterbatch of a tackifying resin is not particularly limited, and a known method can be adopted.
• a thermoplastic elastomer (A) and a tackifying resin (B) are tumbled.
• the mixture can be mixed using a ribbon blender or the like, and can be formed into a master batch using an apparatus such as a single screw extruder, a twin screw extruder, or a tandem extruder.
• the blending ratio of the thermoplastic elastomer (A) is less than 35% by weight and the blending ratio of the tackifying resin (B) is more than 65% by weight, the ratio of the tackifying resin (B) is large, so that it is melted in the extruder. In some cases, the viscosity decreases, the strands do not pull, and cannot be formed into pellets.
• the master batch pellet becomes brittle due to the high blending ratio of the tackifier resin (B), and the master batch is crushed with external pressure during storage, and the thermoplastic elastomer is molded into foam.
• the blending ratio of the thermoplastic elastomer (A) exceeds 55% by weight and the blending ratio of the tackifying resin (B) is less than 45% by weight, the ratio of the thermoplastic elastomer (A) is large. Does not melt sufficiently, the viscosity increases, and blocking may not be possible to form into a pellet.
• the masterbatch of the present tackifier resin may be subjected to surface treatment as necessary in order to prevent the pellets from sticking together during production.
• the means for performing the surface treatment is not particularly limited.
• inorganic additive powder can be used as an anti-blocking agent.
• the masterbatch of tackifier resin suppresses uneven distribution of pellets and pulverized powder generated when the tackifier resin (B) is used alone, and does not require classification work, so it does not cause labor in the manufacturing process.
• a thermoplastic elastomer foam is molded using this masterbatch, the pellets of the raw material resin are not pulverized, adhered to each other, and unevenly distributed, without causing variations in characteristics such as stable shock absorption.
• a thermoplastic elastomer foam can be obtained.
• thermoplastic elastomer (A) and a foaming agent (C) are mixed into a masterbatch of a tackifier resin to produce a foamable composition.
• the blending amount of the thermoplastic elastomer (A) is 200 to 400 parts by weight, preferably 250 to 350 parts by weight, with respect to 100 parts by weight of the master batch. If it is less than 200 parts by weight, the softening point tends to be too low and molding tends to be difficult, and if it exceeds 400 parts by weight, impact absorbability tends to be small.
• the blending amount of the foaming agent (C) is 2 to 40 parts by weight, preferably 5 to 35 parts by weight, based on 100 parts by weight of the master batch. If it is less than 2 parts by weight, foaming tends to be insufficient, and if it exceeds 40 parts by weight, shrinkage after molding tends to increase.
• thermoplastic elastomer (A), a foaming agent (C), and another additive as needed are stirred and mixed with the masterbatch of tackifying resin.
• the stirring method and the mixing order are not particularly limited, and the composition can be produced by a known method.
• thermoplastic elastomer foam ⁇ Method for producing thermoplastic elastomer foam>
• the foamable composition is molded to obtain a thermoplastic elastomer foam.
• the molding method is not particularly limited, and examples thereof include injection foam molding and extrusion foam molding. Among these, the injection foam molding method is preferable because the closed cell ratio of the thermoplastic elastomer foam is high.
• the injection foam molding method of the foamable composition will be specifically described. A known method can be applied to the injection foam molding method itself, and the molding conditions may be appropriately adjusted depending on the fluidity of the foamable composition, the type of molding machine, or the shape of the mold.
• a resin temperature of 170 to 250 ° C. a mold temperature of 10 to 100 ° C., a molding cycle of 1 to 120 minutes, an injection speed of 10 to 300 mm / second, and an injection pressure of 10 to 200 MPa.
• the closed cell ratio is preferably 80% or more, more preferably 90% or more.
• the thermoplastic elastomer foam of the present invention can be obtained by the method for producing a thermoplastic elastomer foam of the present invention.
• the thickness of the thermoplastic elastomer foam of the present invention is not particularly limited, but is preferably 0.5 to 500 mm, more preferably 1 to 250 mm, and still more preferably 3 to 150 mm. If the thickness is less than 0.5 mm, foaming may be difficult and the shock absorption may be inferior. If the thickness exceeds 500 mm, the thickness may not be stable.
• the density of the thermoplastic elastomer foam of the present invention is not particularly limited, from the viewpoint of light weight, preferably from 0.7 kg / m 3 or less, more preferably 0.6 kg / m 3 or less, 0.5 kg / m 3 or less is more preferable. Moreover, 0.3 kg / m ⁇ 3 > or more is preferable and 0.35 kg / m ⁇ 3 > or more is more preferable.
• the expansion ratio of the thermoplastic elastomer foam of the present invention is not particularly limited, but is preferably 1.1 to 50 times, more preferably 1.2 to 30 times. When the expansion ratio is less than 1.1 times, the flexibility may be inferior, and when it exceeds 50 times, the shape may be difficult to maintain because it is too soft.
• the thermoplastic elastomer foam of the present invention preferably has an impact absorbability (impact acceleration) of 250 G or less, and 200 G or less when a weight of 8 kg is dropped from a position having a height of 100 mm. More preferably, it is 150 G or less. When the impact acceleration exceeds 250G, the impact absorbability may be low.
• the lower limit of impact acceleration is preferably as small as possible, but is, for example, 10G.
• the protector for body protection of this invention consists of the thermoplastic elastomer foam of this invention.
• the protector for body protection of the present invention may be provided with the thermoplastic elastomer foam of the present invention alone, or may be an unfoamed plastic, a foam having a different expansion ratio, a film, a cloth, a nonwoven fabric, paper, etc.
• the material and the thermoplastic elastomer foam of the present invention may be integrally molded. Further, a cloth or non-woven fabric made of cotton, acrylic fiber, hair, polyester fiber or the like may be bonded to the surface of the thermoplastic elastomer foam of the present invention. It may be wrapped with foam.
• the thermoplastic elastomer foam of the present invention can have a good feel, and further, it can be sweated by a cloth or non-woven fabric during sweating during exercise, high temperature, high humidity, etc. .
• the protector for protecting the body can be directly attached to the body or applied directly to the body. In the case of using for a cloth, it is preferable that a cloth or a non-woven fabric can be attached and detached.
• the protector for body protection of this invention is used suitably by attaching to clothing.
• the clothing is not particularly limited, but clothing that covers a part or all of the lower body is preferable.
• Bottoms as outerwear to be worn on the lower body such as shorts, trunks, pants such as shorts, trunks, boxer briefs, briefs, etc.
• Inner wear for the lower body such as girdles and loincloths; socks, socks, tights, legs Clothing that is worn on the feet such as warmers and leg bonds; clothing that covers the whole body such as dresses, dresses, puffs, ties, costumes, and tights; protective clothing such as an apron, crotch, white robe, and external protector.
• bottoms and lower body inner wear are preferred, trousers and pants are more preferred, and pants are more preferred, for the purpose of absorbing impacts at sites where fractures tend to occur.
• the fabric (material, knitting method, etc.) used for clothing is not particularly limited, but from the viewpoint of improving air permeability and impact absorption, the surface of the fabric is uneven, for example, the surface has an uneven shape. It is preferable to use a knitting structure or pile knitting in which
• the method of attaching the protector for body protection of the present invention to clothing is not particularly limited.
• a method of attaching the protector to a cloth a method of attaching with an adhesive tape, a pocket, etc.
• a protector may be attached so that it may touch a body directly, and may be attached so that a body may be touched through cloth.
• the protector for body protection of this invention can be attached to arbitrary places, such as the site
• the thermoplastic elastomer foam of the present invention is preferably used by making a hole for ensuring air permeability, bonding a cloth or a nonwoven fabric, or wrapping the cloth in a cloth or a nonwoven fabric.
• thermoplastic elastomer foam when the subcutaneous fat that inherently relieves the impact received by falls etc. is relatively thin and the impact is strong against the bone, the shock absorption is emphasized and a protector with a thick thermoplastic elastomer foam is used.
• a protector with a thick thermoplastic elastomer foam There are two types, such as using a protector with a thin thermoplastic elastomer foam, with emphasis on wearability, etc. for the buttocks and the like that have a thick tissue and have some inherent shock absorption capability, but are susceptible to impact from the buttocks etc.
• a combination of the above protectors may be used.
• a protector provided with the thermoplastic elastomer foam of the present invention is used in a place where the impact is strongly received, and another protector is provided in a place where the impact is relatively mitigated. May be used.
• other protectors include urethane foams, polyethylene foams, acrylic foams, foams based on silicon-based polymers, nonwoven fabrics, and three-dimensional woven fabrics.
• the shape of the protector for body protection of the present invention is not particularly limited, and examples thereof include a rectangle, a square, a circle, an ellipse, a polygon such as a rhombus, a strip shape, a donut shape, and a surface with arbitrary irregularities. It is done. Further, in order to improve air permeability and wearing feeling, a through hole may be appropriately formed.
• the size of the protector for body protection is not particularly limited, but is preferably 1 ⁇ 1000 cm 2, more preferably 50 ⁇ 500 cm 2.
• the density of the protector for body protection according to the present invention is not particularly limited, but from the viewpoint of wearing feeling, those having the smallest possible density are preferably used. On the other hand, when the density is extremely small, the shock absorption is insufficient. There is a possibility.
• the density is preferably 300 ⁇ 700kg / m 3, more preferably 350 ⁇ 600kg / m 3, more preferably 350 ⁇ 500kg / m 3.
• the shock absorber of the present invention is composed of the thermoplastic elastomer foam of the present invention.
• the thermoplastic elastomer foam of the present invention can be used as an impact absorber as it is, but if necessary, the impact absorber can be obtained by cutting the skin layer formed during foam molding or cutting it into an appropriate shape. It can also be.
• a through hole may be provided while taking into consideration the influence on the shock absorption in order to prevent stuffiness.
• ⁇ Density> The volume was calculated from the size and thickness of a sample punched to a diameter of 30 mm, and the weight was divided by the volume.
• the density of the non-foamed resin was set to 1 kg / m 3 and calculated by dividing by the density of the obtained foam.
• ⁇ Impact acceleration> Impact when a weight of 8 kg is dropped vertically from a position of 100 mm to a sample punched to a diameter of 30 mm using a buffer material evaluation test device ACST-200 (manufactured by Shinei Test Machinery (former Yoshida Seiki))
• the acceleration (maximum acceleration) was measured using an acceleration converter AS-500A (manufactured by Kyowa Denki Co., Ltd.) and a data recording device F99-6618 (manufactured by Kyowa Denshi Co., Ltd.) attached to the weight.
• Example 1 A master batch consisting of thermoplastic elastomer (A) / tackifying resin (B) was prepared at the master batch blending ratio shown in Table 1.
• a thermoplastic elastomer (A) and a foaming agent (C) were further blended with this master batch in the number of parts shown in Table 1 to obtain a foamable composition.
• This foamable composition is melt-kneaded with an injection molding machine Si-180V H300C (46) (manufactured by Toyo Machine Metal Co., Ltd.) at a resin temperature of 200 ° C. and a back pressure of 5 MPa.
• thermoplastic elastomer foam The evaluation results of the obtained thermoplastic elastomer foam are shown in Table 1.
• Example 3 A master batch consisting of thermoplastic elastomer (A) / tackifying resin (B) was prepared at the master batch blending ratio shown in Table 1. A thermoplastic elastomer (A) and a foaming agent (C) were further blended with this master batch in the number of parts shown in Table 1 to obtain a foamable composition.
• This foamable composition is melt-kneaded with an injection molding machine Si-180V H300C (46) (manufactured by Toyo Machine Metal Co., Ltd.) at a resin temperature of 200 ° C. and a back pressure of 5 MPa. Was injected and filled at an injection speed of 85 mm / sec.
• thermoplastic elastomer foam The evaluation results of the obtained thermoplastic elastomer foam are shown in Table 1.
• Example 4 A master batch consisting of thermoplastic elastomer (A) / tackifying resin (B) was prepared at the master batch blending ratio shown in Table 1. A thermoplastic elastomer (A) and a foaming agent (C) were further blended with this master batch in the number of parts shown in Table 1 to obtain a foamable composition. This foamable composition is melt-kneaded with an injection molding machine Si-180V H300C (46) (manufactured by Toyo Machine Metal Co., Ltd.) at a resin temperature of 200 ° C. and a back pressure of 5 MPa.
• Si-180V H300C (46) manufactured by Toyo Machine Metal Co., Ltd.
• thermoplastic elastomer foam The evaluation results of the obtained thermoplastic elastomer foam are shown in Table 1.
• Example 5 A master batch consisting of thermoplastic elastomer (A) / tackifying resin (B) was prepared at the master batch blending ratio shown in Table 1. When the master batch was pelletized, partial blocking was observed, but it was collected as it was. The blocking part of this master batch was loosened, and the thermoplastic elastomer (A) and the foaming agent (C) were blended in the number of blending parts shown in Table 1 to obtain a foamable composition.
• This foamable composition is melt-kneaded with an injection molding machine Si-180V H300C (46) (manufactured by Toyo Machine Metal Co., Ltd.) at a resin temperature of 200 ° C. and a back pressure of 5 MPa.
• thermoplastic elastomer foam The evaluation results of the obtained thermoplastic elastomer foam are shown in Table 1.
• thermoplastic elastomer (A), the tackifier resin (B), and the foaming agent (C) are blended in the number of mixing parts at the time of foam molding shown in Table 1 to obtain a foamable composition. Obtained.
• This foamable composition is melt-kneaded with an injection molding machine Si-180V H300C (46) (manufactured by Toyo Machine Metal Co., Ltd.) at a resin temperature of 200 ° C. and a back pressure of 5 MPa.
• thermoplastic elastomer foam The evaluation results of the obtained thermoplastic elastomer foam are shown in Table 1.
• thermoplastic elastomer foam was obtained, but since a masterbatch of tackifying resin was not used during foam molding, thermoplastic elastomer (A), tackifying resin (B), foaming agent (C) In blending, the pellets and the pulverized powder were unevenly distributed in the tackifier resin (B). Therefore, it is necessary to perform the pellet classification work of tackifying resin (B) in advance, and the workability at the time of foam molding was poor.
• thermoplastic elastomer foam using the masterbatch of the present invention has good masterbatch processability and processability during molding, and the impact of the foam. It can be seen that the absorbency is also excellent.

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• 2016
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