WO2016093091A1 - Extruded thermoplastic elastomer foam sheet - Google Patents

Extruded thermoplastic elastomer foam sheet Download PDF

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Publication number
WO2016093091A1
WO2016093091A1 PCT/JP2015/083543 JP2015083543W WO2016093091A1 WO 2016093091 A1 WO2016093091 A1 WO 2016093091A1 JP 2015083543 W JP2015083543 W JP 2015083543W WO 2016093091 A1 WO2016093091 A1 WO 2016093091A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic elastomer
foam sheet
polymer block
extruded foam
present
Prior art date
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PCT/JP2015/083543
Other languages
French (fr)
Japanese (ja)
Inventor
未秋 柴谷
福田　竜司
須永　功人
健一 鯉渕
Original Assignee
株式会社カネカ
龍田化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社カネカ, 龍田化学株式会社 filed Critical 株式会社カネカ
Priority to JP2016563621A priority Critical patent/JPWO2016093091A1/en
Priority to CN201580066347.9A priority patent/CN107108947A/en
Publication of WO2016093091A1 publication Critical patent/WO2016093091A1/en

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    • 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

Definitions

  • the present invention relates to a thermoplastic elastomer extruded foam sheet that is lightweight and excellent in impact absorption and a method for producing the same.
  • thermoplastic elastomer foam is suitably used for applications that require cushioning, flexibility, and shock absorption.
  • a foam for example, Patent Document 1 proposes a foam formed by injection foaming a styrene thermoplastic elastomer component based on a hydrogenated product of a styrene / conjugated diene block copolymer.
  • Patent Document 2 proposes a thermoplastic elastomer foam obtained by foaming a crosslinked thermoplastic elastomer composition comprising a radically crosslinkable elastomer and a thermoplastic resin with a thermally expandable balloon.
  • the foam obtained by these methods is not only suitable as a material for a protector for the purpose of protecting the body because it is hard and has low impact absorbability.
  • Patent Document 3 As a protector for the purpose of body protection, for example, in Patent Document 3, a polymer porous body made of a molding material in which a water-soluble pore-forming material is dispersed in a polymer substance such as a polystyrene-based elastomer or a polyester-based elastomer, Clothing worn as a member has been proposed.
  • Patent Document 4 proposes the use of a porous silicone gel as a cushioning material for sports shoes.
  • the materials described in these documents may become thicker in order to ensure sufficient shock absorption depending on the application. Therefore, development of a material excellent in shock absorption that can be used for a protector for the purpose of body protection has been demanded.
  • Patent Document 5 discloses injection foaming (injection foaming using a core back method) of a foamable composition comprising a thermoplastic elastomer and a thermally expandable microcapsule. A method has been proposed. However, in this method, since it is necessary to produce an injection mold in order to change the shape of the foam, a method capable of easily changing the shape of the foam by post-processing has been demanded.
  • the present invention is lightweight and excellent in shock absorption, and can be suitably used for, for example, a protector for body protection and a protective mat for the purpose of reducing bruises and fractures in the fields of sports, medical care, and nursing care.
  • An object is to provide a thermoplastic elastomer extruded foam sheet.
  • thermoplastic elastomer obtained by extrusion-foaming a foamable composition containing a thermoplastic elastomer having a specific structure and thermally expandable microcapsules. It has been found that the above-mentioned problems can be solved by the foam sheet, and the present invention has been completed.
  • the present invention provides a thermoplastic block copolymer comprising (A) a polymer block having isobutylene as a constituent monomer and a polymer block having an aromatic vinyl monomer as a constituent monomer.
  • the present invention relates to an extruded foam sheet of a thermoplastic elastomer obtained by extrusion foaming an elastomer and (B) a foamable composition containing thermally expandable microcapsules.
  • the foamable composition preferably further contains (C) a tackifying resin.
  • the foamable composition preferably further contains (D) a plasticizer.
  • the present invention relates to (A) a thermoplastic elastomer which is 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 (B) It is related with the manufacturing method of the thermoplastic elastomer extrusion foam sheet characterized by including the process of extrusion-foaming the foamable composition containing a thermally expansible microcapsule.
  • the shock absorber of the present invention is characterized by comprising the thermoplastic elastomer extruded foam sheet of the present invention.
  • the protector for body protection of this invention is equipped with the shock absorber of this invention, It is characterized by the above-mentioned.
  • thermoplastic elastomer extruded foam sheet of the present invention is lightweight and flexible, it has followability and is excellent in impact absorption.
  • shape can be given by post-processing such as punching, it is not necessary to create a complicated mold for each shape like an injection mold, making it easier to create shock absorbers of various shapes Can be produced.
  • thermoplastic elastomer extruded foam sheet of the present invention is (A) a thermoplastic elastomer which is 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 (B) It is obtained by extrusion foaming a foamable composition containing thermally expandable microcapsules.
  • the foamable composition comprises (A) a polymer block containing isobutylene as a constituent monomer and a polymer block containing an aromatic vinyl monomer as a constituent monomer.
  • the thermoplastic elastomer which is a block copolymer which consists of these is contained.
  • the thermoplastic elastomer is particularly 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. It is not limited.
  • thermoplastic elastomer The structure of the thermoplastic elastomer is not particularly limited.
  • a polymer etc. are mentioned.
  • the thermoplastic elastomer (A) having these structures may be used alone or in combination of two or more.
  • 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 as constituent monomer) Polymer block) / (polymer block having an aromatic vinyl monomer as a constituent monomer)) is not particularly limited, but the impact absorbability and moldability of the foam, shape retention at room temperature From the viewpoint, 95/5 to 60/40 is preferable, and 90/10 to 65/35 is more preferable.
  • a polymer block having an aromatic vinyl monomer as a constituent monomer is formed by polymerizing an aromatic vinyl monomer as a main component.
  • 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 balance of physical properties.
  • a method for producing a polymer block containing isobutylene as a constituent monomer is not particularly limited. For example, it can be produced by polymerizing a monomer component containing isobutylene as a main component in the presence of an initiator. In addition, in the polymer block which uses isobutylene as a structural monomer, you may copolymerize another vinyl type compound as needed.
  • 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) [In the general formula (1), 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.
  • 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.
  • These 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
  • 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 the energy cost and the stability of the polymerization, ⁇ 80 to ⁇ 30 ° C. is more preferable.
  • SIBSTAR manufactured by Kaneka Corporation
  • Kaneka Corporation is an example of a commercially available product that can be used as a thermoplastic elastomer.
  • the foamable composition contains (B) thermally expandable microcapsules.
  • the heat-expandable microcapsule is obtained by microcapsulating a volatile liquid expansion agent in an outer shell made of a polymer. In general, it can be produced by a method of suspension polymerization of a polymerizable mixture containing at least a swelling agent and a polymerizable monomer in an aqueous medium. 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 good gas barrier properties may be used.
  • the polymer forming the outer shell softens when heated.
  • the liquid expansion agent to be included in the outer shell resin it is only necessary to select one that becomes gaseous at a temperature below the softening point of the polymer.
  • the amount of the (B) thermally expandable microcapsule is not particularly limited, but is 0.5 to 10 parts by weight with respect to 100 parts by weight in total of all the components except the component (B). It is preferably 1 to 5 parts by weight. If the blending amount is less than 0.5 parts by weight, the density of the thermoplastic elastomer extruded foam sheet tends to be high and the lightness tends to be inferior. On the other hand, even if it exceeds 10 parts by weight, the thermoplastic elastomer extruded foam It is difficult to reduce the density of the sheet.
  • (B) Thermally expandable microcapsules are fine powders, so it is often difficult to mix uniformly, and there is a risk of dust explosions. It may be preferable to blend in the state of a master batch dispersed in a high concentration. In this case, a value obtained by multiplying the blending amount of the master batch by the content ratio of the (B) thermally expandable microcapsule in the master batch is the blending amount of (B) the thermally expandable microcapsule.
  • the powdery (B) thermally expandable microcapsules as they are.
  • the foamable composition preferably further contains (C) a tackifying resin from the viewpoint of improving impact absorbability.
  • the tackifier resin 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.
  • the tackifier resin is a low molecular weight resin having a number average molecular weight of 300 to 3000 and 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 preferred.
  • the content is not particularly limited, but (A) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer. More preferred are parts by weight, and even more preferred is 10 to 40 parts by weight. If the content exceeds 100 parts 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 is less than 1 part by weight. And the additive effect is difficult to appear.
  • the foamable composition preferably further contains (D) a plasticizer from the viewpoint of flexibility.
  • D a plasticizer from the viewpoint of flexibility.
  • a plasticizer usually, a liquid or liquid material is suitably used at room temperature. Both hydrophilic and hydrophobic plasticizers can be used.
  • the plasticizer (D) include plasticizers for various rubbers and 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.
  • (A) Paraffinic process oil or polybutene is preferable from the viewpoint of compatibility with the thermoplastic elastomer. These may be used alone or in combination of two or more in order to obtain desired viscosity and physical properties.
  • the foamable composition may optionally contain components other than the components (A) to (D).
  • components other than the components (A) to (D) 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.
  • it may contain (A) a resin other than the thermoplastic elastomer, such as various thermoplastic resins and thermosetting resins.
  • a kneading step may be provided before extrusion foaming.
  • a double arm type kneader, a pressurization type kneader, etc. are mentioned, for example.
  • the temperature at the time of kneading is not particularly limited, but is preferably 30 to 200 ° C, more preferably 50 to 150 ° C. If the temperature at the time of kneading is less than 30 ° C., it may not be uniformly dispersed. If the temperature exceeds 200 ° C., (B) the thermally expandable microcapsule starts to foam and foams by foaming by kneading. The structure may not be maintained.
  • a method for extruding and foaming the foamable composition is not particularly limited, and a known method can be adopted.
  • the equipment used for extrusion foaming include a single-screw extruder, a twin-screw extruder, and a tandem extruder. Is mentioned.
  • the temperature of the T die is not particularly limited, but is preferably 10 to 220 ° C, more preferably 25 to 180 ° C. If the temperature of the T-die is less than 10 ° C., foaming may be uneven, and if it exceeds 220 ° C., the foam structure may be broken and the foam structure may not be maintained.
  • the take-up speed of the thermoplastic elastomer extruded foam sheet is not particularly limited, but is preferably 0.1 to 10.0 m / min, more preferably 0.15 to 5.0 m / min.
  • the take-up speed is less than 0.1 m / min, sheet undulation may occur, and when it exceeds 10.0 m / min, the sheet surface may become rough and the sheet may tear.
  • the thickness of the extruded thermoplastic elastomer foam sheet of the present invention is not particularly limited, but is preferably 0.1 to 1,000 mm, and more preferably 0.5 to 500 mm. If the thickness is less than 0.1 mm, foaming may be difficult, and if it exceeds 1,000 mm, the thickness may not be stable.
  • the density of the thermoplastic elastomer extruded foam sheet of the present invention is not particularly limited, from the viewpoint of lightness, 0.7 kg / m 3 or less is preferable, 0.6 kg / m 3 or less is more preferable, and 0.5 kg / m 3 or less is more preferable.
  • the lower limit of the density is not particularly limited, preferably 0.3kg / m 3, 0.35kg / m 3 and more preferably.
  • the expansion ratio of the extruded thermoplastic elastomer foam sheet 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 ASKER E hardness of the thermoplastic elastomer extruded foam sheet of the present invention is not particularly limited, but is preferably 80 degrees or less, and more preferably 70 degrees or less. When ASKER E hardness exceeds 80 degrees, flexibility may be inferior.
  • the rebound resilience of the thermoplastic elastomer extruded foam sheet of the present invention is not particularly limited, but is preferably 50% or less, more preferably 30% or less. If the impact resilience exceeds 50%, the impact absorbability may be lowered.
  • the thermoplastic elastomer extruded foam sheet of the present invention preferably has an impact absorption (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 the impact acceleration is more preferable, but it is, for example, 10G.
  • thermoplastic elastomer extruded foam sheet of the present invention includes: (A) a thermoplastic elastomer which is 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 (B) It includes a step of extrusion-foaming a foamable composition containing thermally expandable microcapsules.
  • the shock absorber of the present invention is characterized by comprising the thermoplastic elastomer extruded foam sheet of the present invention.
  • the thermoplastic elastomer extruded foam sheet of the present invention can be used as an impact absorber as it is, but if necessary, the skin layer formed at the time of extrusion foaming is excised or cut into an appropriate shape to absorb the impact. It can also be a body.
  • a through hole may be provided in consideration of the impact on the shock absorbability in order to prevent stuffiness.
  • the protector for body protection of this invention is equipped with the shock absorber of this invention, It is characterized by the above-mentioned.
  • the protector for body protection of the present invention may be provided with the shock absorber of the present invention alone, or a material such as unfoamed plastic, foam with different expansion ratio, film, cloth, nonwoven fabric, paper, etc.
  • the shock absorber of the present invention may be integrally formed. 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 shock absorber of the present invention, and the shock absorber of the present invention is wrapped with the cloth or non-woven fabric described above. It can be left.
  • the shock absorber of the present invention can be made to feel better, and furthermore, a sweat absorbing action can be applied by a cloth or non-woven fabric during sweating during exercise, high temperature, and high humidity.
  • 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.
  • Clothing is not particularly limited, but clothing that covers part or all of the lower body is preferable.
  • pants such as slacks, jeans, training pants, Sabrina pants, Nikkapokka, half pants, shorts, hot pants, and skirts 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 shock absorber of the present invention is preferably used by making a hole for ensuring air permeability, pasting a cloth or a nonwoven fabric, or wrapping the cloth in a cloth or a nonwoven fabric.
  • thermoplastic elastomer extruded foam sheet Two or more types, such as using a protector with a thermoplastic elastomer extruded foam sheet, with emphasis on wearability for the buttocks etc. that are susceptible to impact by the buttocks etc. You may use a combination of protectors.
  • a protector provided with the thermoplastic elastomer extruded foam sheet of the present invention is used in a place where the impact is strongly received, and another protector is used 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.
  • Thermoplastic elastomer Styrene-isobutylene-styrene block copolymer, SIBSTAR 062T manufactured by Kaneka Corporation
  • Thermoplastic elastomer Styrene-isobutylene-styrene block copolymer, SIBSTAR 102T manufactured by Kaneka Corporation
  • Tackifying resin hydrogenated petroleum resin Alcon P-140 manufactured by Arakawa Chemical Industries, Ltd.
  • Thermally expandable microcapsule ADVANCEL EM501 manufactured by Sekisui Chemical Co., Ltd. Thermally expandable microcapsules: Sekisui Chemical Co., Ltd.
  • Thermally expandable microcapsule ADVANCEL EM403 manufactured by Sekisui Chemical Co., Ltd.
  • Plasticizer Paraffin-based process oil, Diana Process Oil PW380 manufactured by Idemitsu Kosan Co., Ltd.
  • the density was calculated by calculating the volume from the size and thickness of the sample cut into an arbitrary size and dividing the weight by the volume.
  • the foaming ratio was calculated by dividing the density of the resin not foamed by the density of the obtained foam.
  • Example 1 (A) Thermoplastic elastomer, (C) Tackifying resin, and (B) Thermally expandable microcapsule shown in Table 1 with the compounding amounts shown in Table 1 (double-arm kneader, G type, capacity 50 L) And kneading at a set temperature of 100 to 110 ° C. to obtain a foamable composition.
  • thermoplastic elastomer extruded foam sheet Extruded into a sheet with a lip opening of 6.0 mm with a T-die set at a temperature of 160 ° C., and taken up at a take-off speed of 0.36 m / min, to obtain a thermoplastic elastomer extruded foam sheet.
  • Example 2 The thermoplastic elastomer extruded foam sheet obtained in Example 1 was heated to 170 ° C. with a press machine and further foamed to obtain a thermoplastic elastomer extruded foam sheet.
  • Example 3 As a thermally expandable microcapsule, a thermoplastic elastomer extruded foam sheet was prepared in the same manner as in Example 1 except that “Advancel EM501 was replaced by 3 parts by weight” and “Advancel EM403 was replaced by 5 parts by weight”. Obtained.
  • Example 4 (A) thermoplastic elastomer, (D) plasticizer, and (B) thermoplastic microcapsule shown in Table 1 were blended in the amounts shown in Table 1 to obtain a foamable composition.
  • thermoplastic elastomer extruded foam sheet Extruded into a sheet with a lip opening of 6.0 mm with a T-die set at a temperature of 160 ° C., and taken up at a take-off speed of 0.36 m / min, to obtain a thermoplastic elastomer extruded foam sheet.
  • Comparative Example 1 (A) thermoplastic elastomer, (C) tackifying resin, and (B) thermally expandable microcapsule shown in Table 1 were blended in the blending amounts shown in Table 1 to obtain a foamable composition.
  • This foamable composition was melt-kneaded with an injection molding machine “MD350S-IIIDP type” (manufactured by Ube Industries, Ltd., shutoff nozzle specification) at a resin temperature of 200 ° C.
  • Comparative Example 2 (A) thermoplastic elastomer shown in Table 1 and (C) tackifying resin were blended in the blending amounts shown in Table 1 to obtain a resin composition.
  • This resin composition was melt-kneaded with an injection molding machine “MD350S-IIIDP type” (Ube Industries, Ltd., shutoff nozzle specification) at a resin temperature of 200 ° C. and a back pressure of 15 MPa, and then moved forward and backward with the stationary mold.
  • a mold having an elliptical cavity (clearance t0 3.5 mm) having a long side of 170 mm and a short side of 130 mm, which is composed of a movable mold capable of performing injection, was injected and filled at an injection speed of 100 mm / second. After completion of filling, the mixture was cooled for 60 seconds to obtain a thermoplastic elastomer injection-molded body.
  • Comparative Example 3 Three samples of “NP gel” (manufactured by Taika Co., Ltd., thickness 3 mm), which is a foamed gel, were stacked to obtain a sample.
  • thermoplastic elastomer foam sheet of the present invention is excellent in impact absorption and post-processability.

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Abstract

The purpose of the present invention is to provide an extruded thermoplastic elastomer foam sheet which has lightweight and excellent impact absorbing properties and can be used suitably as, for example, a protector or protective mat for body protection purposes or the like which is used for reducing bruise, bone fracture or the like in the fields of sports, medicine, nursing care and the like. The extruded thermoplastic elastomer foam sheet according to the present invention is characterized by being produced by the extrusion expansion of a foamable composition comprising (A) a thermoplastic elastomer that is a block copolymer composed of a polymer block containing isobutyrene as a constituent monomer and a polymer block containing an aromatic vinyl monomer as a constituent monomer and (B) thermally expansive microcapsules.

Description

熱可塑性エラストマー押出発泡シートThermoplastic elastomer extruded foam sheet
本発明は、軽量で衝撃吸収性に優れる熱可塑性エラストマー押出発泡シート及びその製造方法に関する。 The present invention relates to a thermoplastic elastomer extruded foam sheet that is lightweight and excellent in impact absorption and a method for producing the same.
熱可塑性樹脂からなる発泡体は、軽量、緩衝性等の特性を有しており、種々の用途で広く使用されている。中でも、クッション性や柔軟性、衝撃吸収性が必要な用途には熱可塑性エラストマーの発泡体が好適に用いられている。このような発泡体として、例えば特許文献１には、スチレン・共役ジエンブロック共重合体の水素添加物をベースとしたスチレン系熱可塑性エラストマー成分を射出発泡して成形した発泡体が提案されている。また、特許文献２には、ラジカル架橋性エラストマーと熱可塑性樹脂からなる架橋された熱可塑性エラストマー組成物を、熱膨張性バルーンで発泡させてなる熱可塑性エラストマー発泡体が提案されている。しかし、これらの方法で得られる発泡体は、硬い上に衝撃吸収性が低く、身体保護を目的としたプロテクターの材料として適したものではなかった。 Foams made of thermoplastic resins have characteristics such as light weight and buffering properties, and are widely used in various applications. Among them, a thermoplastic elastomer foam is suitably used for applications that require cushioning, flexibility, and shock absorption. As such a foam, for example, Patent Document 1 proposes a foam formed by injection foaming a styrene thermoplastic elastomer component based on a hydrogenated product of a styrene / conjugated diene block copolymer. . Patent Document 2 proposes a thermoplastic elastomer foam obtained by foaming a crosslinked thermoplastic elastomer composition comprising a radically crosslinkable elastomer and a thermoplastic resin with a thermally expandable balloon. However, the foam obtained by these methods is not only suitable as a material for a protector for the purpose of protecting the body because it is hard and has low impact absorbability.
身体保護を目的としたプロテクターとして、例えば特許文献３には、ポリスチレン系エラストマー、ポリエステル系エラストマー等の高分子物質に水溶性気孔形成材を分散させた成形材料からなる高分子多孔体を、衝撃吸収部材として装着した衣類が提案されている。また、特許文献４には、多孔性シリコーンゲルをスポーツシューズ用緩衝材に用いることが提案されている。しかしながら、これらの文献に記載された材料は、その用途によっては衝撃吸収性を充分確保するために厚みが分厚くなることがあった。そのため、身体保護を目的としたプロテクターに用い得る、衝撃吸収性に優れた材料の開発が求められていた。 As a protector for the purpose of body protection, for example, in Patent Document 3, a polymer porous body made of a molding material in which a water-soluble pore-forming material is dispersed in a polymer substance such as a polystyrene-based elastomer or a polyester-based elastomer, Clothing worn as a member has been proposed. Patent Document 4 proposes the use of a porous silicone gel as a cushioning material for sports shoes. However, the materials described in these documents may become thicker in order to ensure sufficient shock absorption depending on the application. Therefore, development of a material excellent in shock absorption that can be used for a protector for the purpose of body protection has been demanded.
一方、熱可塑性エラストマーの発泡体の製造方法として、例えば、特許文献５には、熱可塑性エラストマーと熱膨張性マイクロカプセルからなる発泡性組成物を射出発泡（コアバック法を用いた射出発泡）する方法が提案されている。しかしながら、この方法では発泡体の形状を変更するために射出成形用金型を作製する必要があるため、後加工により発泡体の形状を容易に変更できる方法が求められていた。 On the other hand, as a method for producing a thermoplastic elastomer foam, for example, Patent Document 5 discloses injection foaming (injection foaming using a core back method) of a foamable composition comprising a thermoplastic elastomer and a thermally expandable microcapsule. A method has been proposed. However, in this method, since it is necessary to produce an injection mold in order to change the shape of the foam, a method capable of easily changing the shape of the foam by post-processing has been demanded.
特開平６－２１８７４１号公報JP-A-6-218741 特開平１１―３４３３６２号公報JP-A-11-343362 特開２００３－３００４号公報JP 2003-3004 A 特開平７－３１６５号公報Japanese Patent Laid-Open No. 7-3165 特開２０１１－１６８７７５号公報JP 2011-168775 A
本発明は、軽量で衝撃吸収性に優れ、例えば、スポーツや医療・介護分野等での打撲や骨折等の低減を目的とした身体保護用のプロテクターや保護用マット等に好適に用いることのできる熱可塑性エラストマー押出発泡シートを提供することを目的とする。 The present invention is lightweight and excellent in shock absorption, and can be suitably used for, for example, a protector for body protection and a protective mat for the purpose of reducing bruises and fractures in the fields of sports, medical care, and nursing care. An object is to provide a thermoplastic elastomer extruded foam sheet.
本発明者らは、上記課題を解決するため鋭意検討した結果、特定の構造を有する熱可塑性エラストマーと熱膨張性マイクロカプセルとを含有する発泡性組成物を押出発泡して得られる熱可塑性エラストマー押出発泡シートにより、上述の課題を解決できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have conducted extrusion of a thermoplastic elastomer obtained by extrusion-foaming a foamable composition containing a thermoplastic elastomer having a specific structure and thermally expandable microcapsules. It has been found that the above-mentioned problems can be solved by the foam sheet, and the present invention has been completed.
すなわち、本発明は、（Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマー、及び、（Ｂ）熱膨張性マイクロカプセルを含有する発泡性組成物を押出発泡して得られることを特徴とする熱可塑性エラストマー押出発泡シートに関する。 That is, the present invention provides a thermoplastic block copolymer comprising (A) a polymer block having isobutylene as a constituent monomer and a polymer block having an aromatic vinyl monomer as a constituent monomer. The present invention relates to an extruded foam sheet of a thermoplastic elastomer obtained by extrusion foaming an elastomer and (B) a foamable composition containing thermally expandable microcapsules.
本発明の熱可塑性エラストマー押出発泡シートにおいて、発泡性組成物は、さらに（Ｃ）粘着付与樹脂を含有することが好ましい。 In the thermoplastic elastomer extruded foam sheet of the present invention, the foamable composition preferably further contains (C) a tackifying resin.
本発明の熱可塑性エラストマー押出発泡シートにおいて、発泡性組成物は、さらに（Ｄ）可塑剤を含有することが好ましい。 In the thermoplastic elastomer extruded foam sheet of the present invention, the foamable composition preferably further contains (D) a plasticizer.
本発明は、（Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマー、及び、（Ｂ）熱膨張性マイクロカプセルを含有する発泡性組成物を押出発泡する工程を含むことを特徴とする熱可塑性エラストマー押出発泡シートの製造方法に関する。 The present invention relates to (A) a thermoplastic elastomer which is 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 (B) It is related with the manufacturing method of the thermoplastic elastomer extrusion foam sheet characterized by including the process of extrusion-foaming the foamable composition containing a thermally expansible microcapsule.
本発明の衝撃吸収体は、本発明の熱可塑性エラストマー押出発泡シートからなることを特徴とする。 The shock absorber of the present invention is characterized by comprising the thermoplastic elastomer extruded foam sheet of the present invention.
本発明の身体保護用のプロテクターは、本発明の衝撃吸収体を備えることを特徴とする。 The protector for body protection of this invention is equipped with the shock absorber of this invention, It is characterized by the above-mentioned.
本発明の熱可塑性エラストマー押出発泡シートは、軽量で柔軟であるため追従性があり、衝撃吸収性に優れている。また、打ち抜きなどの後加工により形状を付与することができるため、射出成形の金型のように複雑な金型を形状ごとに作製する必要がなく、様々な形状の衝撃吸収体をより簡便に作製することができる。 Since the thermoplastic elastomer extruded foam sheet of the present invention is lightweight and flexible, it has followability and is excellent in impact absorption. In addition, since the shape can be given by post-processing such as punching, it is not necessary to create a complicated mold for each shape like an injection mold, making it easier to create shock absorbers of various shapes Can be produced.
＜＜熱可塑性エラストマー押出発泡シート＞＞
本発明の熱可塑性エラストマー押出発泡シートは、
（Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマー、及び、
（Ｂ）熱膨張性マイクロカプセル
を含有する発泡性組成物を押出発泡して得られることを特徴とする。 << Thermoplastic elastomer extruded foam sheet >>
The thermoplastic elastomer extruded foam sheet of the present invention is
(A) a thermoplastic elastomer which is 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
(B) It is obtained by extrusion foaming a foamable composition containing thermally expandable microcapsules.
＜（Ａ）熱可塑性エラストマー＞
本発明の熱可塑性エラストマー押出発泡シートにおいて、発泡性組成物は、（Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマーを含有する。
（Ａ）熱可塑性エラストマーとしては、イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体であれば特に限定されない。 <(A) Thermoplastic elastomer>
In the thermoplastic elastomer extruded foam sheet of the present invention, the foamable composition comprises (A) a polymer block containing isobutylene as a constituent monomer and a polymer block containing an aromatic vinyl monomer as a constituent monomer. The thermoplastic elastomer which is a block copolymer which consists of these is contained.
(A) The thermoplastic elastomer is particularly 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. It is not limited.
（Ａ）熱可塑性エラストマーの構造としては、特に限定されないが、例えば、芳香族ビニル系単量体を構成単量体とする重合体ブロック－イソブチレンを構成単量体とする重合体ブロック－芳香族ビニル系単量体を構成単量体とする重合体ブロックからなるトリブロック共重合体や、芳香族ビニル系単量体を構成単量体とする重合体ブロック－イソブチレンを構成単量体とする重合体ブロックからなるジブロック共重合体、芳香族ビニル系単量体を構成単量体とする重合体ブロックとイソブチレンを構成単量体とする重合体ブロックとからなるアームを有する星型ブロック共重合体等が挙げられる。本発明では、所望の物性・成形加工性を得るため、これらの構造を有する（Ａ）熱可塑性エラストマーを単独で用いても良いし、２種以上併用しても良い。 (A) The structure of the thermoplastic elastomer is not particularly limited. For example, a polymer block containing an aromatic vinyl monomer as a constituent monomer-a polymer block containing isobutylene as a constituent monomer-aromatic Triblock copolymer composed of polymer block containing vinyl monomer as constituent monomer, and polymer block-isobutylene containing aromatic vinyl monomer as constituent monomer as constituent monomer A diblock copolymer composed of a polymer block, a star block copolymer having an arm composed of a polymer block composed of an aromatic vinyl monomer and a polymer block composed of isobutylene. A polymer etc. are mentioned. In the present invention, in order to obtain desired physical properties and moldability, the thermoplastic elastomer (A) having these structures may be used alone or in combination of two or more.
（Ａ）熱可塑性エラストマーにおいて、芳香族ビニル系単量体を構成単量体とする重合体ブロックとイソブチレンを構成単量体とする重合体ブロックとの重量比率（（イソブチレンを構成単量体とする重合体ブロック）／（芳香族ビニル系単量体を構成単量体とする重合体ブロック））は、特に限定されないが、発泡体の衝撃吸収性と成形性、常温での形状保持性の観点から、９５／５～６０／４０が好ましく、９０／１０～６５／３５がより好ましい。 (A) In a thermoplastic elastomer, 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 as constituent monomer) Polymer block) / (polymer block having an aromatic vinyl monomer as a constituent monomer)) is not particularly limited, but the impact absorbability and moldability of the foam, shape retention at room temperature From the viewpoint, 95/5 to 60/40 is preferable, and 90/10 to 65/35 is more preferable.
芳香族ビニル系単量体を構成単量体とする重合体ブロックは、芳香族ビニル系単量体を主成分として重合することにより形成される。芳香族ビニル系単量体としては、特に限定されないが、例えば、スチレン、ｏ－、ｍ－又はｐ－メチルスチレン、α－メチルスチレン、β－メチルスチレン、２，６－ジメチルスチレン、２，４－ジメチルスチレン、α－メチル－ｏ－メチルスチレン、α－メチル－ｍ－メチルスチレン、α－メチル－ｐ－メチルスチレン、β－メチル－ｏ－メチルスチレン、β－メチル－ｍ－メチルスチレン、β－メチル－ｐ－メチルスチレン、２，４，６－トリメチルスチレン、α－メチル－２，６－ジメチルスチレン、α－メチル－２，４－ジメチルスチレン、β－メチル－２，６－ジメチルスチレン、β－メチル－２，４－ジメチルスチレン、ｏ－、ｍ－又はｐ－クロロスチレン、２，６－ジクロロスチレン、２，４－ジクロロスチレン、α－クロロ－ｏ－クロロスチレン、α－クロロ－ｍ－クロロスチレン、α－クロロ－ｐ－クロロスチレン、β－クロロ－ｏ－クロロスチレン、β－クロロ－ｍ－クロロスチレン、β－クロロ－ｐ－クロロスチレン、２，４，６－トリクロロスチレン、α－クロロ－２，６－ジクロロスチレン、α－クロロ－２，４－ジクロロスチレン、β－クロロ－２，６－ジクロロスチレン、β－クロロ－２，４－ジクロロスチレン、ｏ－、ｍ－又はｐ－ｔ－ブチルスチレン、ｏ－、ｍ－又はｐ－メトキシスチレン、ｏ－、ｍ－又はｐ－クロロメチルスチレン、ｏ－、ｍ－又はｐ－ブロモメチルスチレン、シリル基で置換されたスチレン誘導体、インデン、ビニルナフタレン等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。これらの中では、スチレン、ｐ－メチルスチレン、α－メチルスチレン及びインデンからなる群から選ばれる少なくとも１種が、その入手し易さ及び物性バランスの観点から好ましい。 A polymer block having an aromatic vinyl monomer as a constituent monomer is formed by polymerizing an aromatic vinyl monomer as a main component. The aromatic vinyl monomer is not particularly limited. For example, styrene, o-, m- or p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4 -Dimethylstyrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β -Methyl-p-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β-methyl-2,4-dimethylstyrene, o-, m- or p-chlorostyrene, 2,6-dichlorostyrene, 2,4-dichlorostyrene, α-chloro-o-alkyl Rostyrene, α-chloro-m-chlorostyrene, α-chloro-p-chlorostyrene, β-chloro-o-chlorostyrene, β-chloro-m-chlorostyrene, β-chloro-p-chlorostyrene, 2,4 , 6-trichlorostyrene, α-chloro-2,6-dichlorostyrene, α-chloro-2,4-dichlorostyrene, β-chloro-2,6-dichlorostyrene, β-chloro-2,4-dichlorostyrene, o-, m- or pt-butylstyrene, o-, m- or p-methoxystyrene, o-, m- or p-chloromethylstyrene, o-, m- or p-bromomethylstyrene, silyl group And styrene derivatives, indene, vinylnaphthalene and the like substituted with. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of styrene, p-methylstyrene, α-methylstyrene and indene is preferable from the viewpoint of easy availability and balance of physical properties.
イソブチレンを構成単量体とする重合体ブロックの製造方法は、特に限定されないが、例えば、開始剤の存在下、イソブチレンを主成分とする単量体成分を重合させることにより製造することができる。なお、イソブチレンを構成単量体とする重合体ブロックにおいては、必要に応じて他のビニル系化合物を共重合してもよい。 A method for producing a polymer block containing isobutylene as a constituent monomer is not particularly limited. For example, it can be produced by polymerizing a monomer component containing isobutylene as a main component in the presence of an initiator. In addition, in the polymer block which uses isobutylene as a structural monomer, you may copolymerize another vinyl type compound as needed.
開始剤としては、特に限定されないが、例えば、下記一般式（１）で表される化合物を用いることができる。下記一般式（１）で表される化合物は、ルイス酸等の存在下、炭素陽イオンを生成し、カチオン重合の開始点になると考えられる。
（ＣＲ１Ｒ２Ｘ）ｎＲ３ （１）
［一般式（１）中、Ｘはハロゲン原子、炭素数１～６のアルコキシ基又は炭素数１～６のアシロキシ基を示す。Ｒ１、Ｒ２はそれぞれ水素原子又は炭素数１～６の１価の炭化水素基を示し、Ｒ１、Ｒ２は同一であっても異なっていても良い。Ｒ３は多価芳香族炭化水素基又は多価脂肪族炭化水素基であり、ｎは１～６の自然数を示す。］。 Although it does not specifically limit as an initiator, For example, 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)
[In the general formula (1), 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. ].
一般式（１）で表される化合物としては、特に限定されないが、例えば、（１－クロル－１－メチルエチル）ベンゼン、１，４－ビス（１－クロル－１－メチルエチル）ベンゼン、１，３－ビス（１－クロル－１－メチルエチル）ベンゼン、１，３，５－トリス（１－クロル－１－メチルエチル）ベンゼン、１，３－ビス（１－クロル－１－メチルエチル）－５－（ｔｅｒｔ－ブチル）ベンゼン等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。これらの中では、１，４－ビス（１－クロル－１－メチルエチル）ベンゼン、１，３，５－トリス（１－クロル－１－メチルエチル）ベンゼンが好ましい。 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.
イソブチレンを主成分とする単量体成分の重合においては、さらにルイス酸触媒を共存させることもできる。ルイス酸触媒としては、カチオン重合に使用できるものであれば特に限定されず、例えば、ＴｉＣｌ４、ＴｉＢｒ４、ＢＣｌ３、ＢＦ３、ＢＦ３・ＯＥｔ２、ＳｎＣｌ４、ＳｂＣｌ５、ＳｂＦ５、ＷＣｌ６、ＴａＣｌ５、ＶＣｌ５、ＦｅＣｌ３、ＺｎＢｒ２、ＡｌＣｌ３、ＡｌＢｒ３等の金属ハロゲン化物；Ｅｔ２ＡｌＣｌ、ＥｔＡｌＣｌ２等の有機金属ハロゲン化物等が挙げられる（Ｅｔはエチル基を表す）。これらは単独で用いても良いし、２種以上を併用しても良い。これらの中で、触媒としての能力、工業的な入手の容易さの観点からは、ＴｉＣｌ４、ＢＣｌ３、ＳｎＣｌ４が好ましい。 In the polymerization of the monomer component containing isobutylene as a main component, 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. For example, TiCl 4 , TiBr 4 , BCl 3 , BF 3 , BF 3 .OEt 2 , SnCl 4 , SbCl 5 , SbF 5 , WCl 6 , metal halides such as TaCl 5 , VCl 5 , FeCl 3 , ZnBr 2 , AlCl 3 , and AlBr 3 ; and 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.
ルイス酸触媒を使用する場合、その使用量は特に限定されず、使用する単量体の重合特性や重合濃度等を鑑みて設定することができる。通常、一般式（１）で表される化合物に対して０．１～１００モル当量が好ましく、１～５０モル当量がより好ましい。 When a Lewis acid catalyst is used, 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.
イソブチレンを主成分とする単量体成分の重合においては、さらに必要に応じて電子供与体成分を共存させることもできる。この電子供与体成分は、カチオン重合に際して、成長炭素カチオンを安定化させる効果があるものと考えられており、電子供与体の添加によって分子量分布の狭い構造が制御された重合体を生成することができる。電子供与体成分としては、特に限定されないが、例えば、ピリジン類、アミン類、アミド類、スルホキシド類、エステル類、金属原子に結合した酸素原子を有する金属化合物等を挙げることができる。これらは単独で用いても良いし、２種以上を併用しても良い。 In the polymerization of the monomer component containing isobutylene as a main component, 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.
イソブチレンを主成分とする単量体成分の重合は、必要に応じて有機溶媒中で行うことができる。有機溶媒としては、カチオン重合を本質的に阻害しなければ特に限定されないが、例えば、塩化メチル、ジクロロメタン、クロロホルム、塩化エチル、ジクロロエタン、ｎ－プロピルクロライド、ｎ－ブチルクロライド、クロロベンゼン等のハロゲン化炭化水素；ベンゼン、トルエン、キシレン、エチルベンゼン、プロピルベンゼン、ブチルベンゼン等のアルキルベンゼン類；エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン等の直鎖式脂肪族炭化水素類；２－メチルプロパン、２－メチルブタン、２，３，３－トリメチルペンタン、２，２，５－トリメチルヘキサン等の分岐式脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等の環式脂肪族炭化水素類；石油留分を水添精製したパラフィン油等を挙げることができる。これらの有機溶媒は、ブロック共重合体を構成する単量体の重合特性及び生成する重合体の溶解性等のバランスを考慮して、単独で用いても良いし、２種以上を併用しても良い。 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. For example, halogenated carbonization such as methyl chloride, dichloromethane, chloroform, ethyl chloride, dichloroethane, n-propyl chloride, n-butyl chloride, chlorobenzene and the like. Hydrogen; 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 添精 made of paraffin oil and the like can be mentioned. These 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 polymer produced. Also good.
有機溶媒の使用量は、特に限定されないが、得られる重合体溶液の粘度や除熱の容易さを考慮して、重合体の濃度が好ましくは１～５０重量％、より好ましくは５～３５重量％となるように決定することができる。 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.
イソブチレンを主成分とする単量体成分の重合は、各成分を冷却下、例えば－１００℃以上０℃未満の温度で混合して行うことが好ましい。エネルギーコストと重合の安定性を釣り合わせる観点からは、－８０～－３０℃がより好ましい。 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 the energy cost and the stability of the polymerization, −80 to −30 ° C. is more preferable.
（Ａ）熱可塑性エラストマーとして用い得る市販品としては、ＳＩＢＳＴＡＲ（カネカ社製）が挙げられる。 (A) SIBSTAR (manufactured by Kaneka Corporation) is an example of a commercially available product that can be used as a thermoplastic elastomer.
＜（Ｂ）熱膨張性マイクロカプセル＞
本発明の熱可塑性エラストマー押出発泡シートにおいて、発泡性組成物は、（Ｂ）熱膨張性マイクロカプセルを含有する。熱膨張性マイクロカプセルとは、揮発性の液体膨張剤を重合体からなる外殻にマイクロカプセル化したものである。一般に、水系媒体中で、少なくとも膨張剤と重合性単量体とを含有する重合性混合物を懸濁重合する方法により製造することができる。重合反応が進むにつれて、生成する重合体により外殻が形成され、その外殻内に膨張剤が包み込まれるようにして封入された構造をもつ熱膨張性マイクロカプセルが得られる。 <(B) Thermally expandable microcapsule>
In the thermoplastic elastomer extruded foam sheet of the present invention, the foamable composition contains (B) thermally expandable microcapsules. The heat-expandable microcapsule is obtained by microcapsulating a volatile liquid expansion agent in an outer shell made of a polymer. In general, it can be produced by a method of suspension polymerization of a polymerizable mixture containing at least a swelling agent and a polymerizable monomer in an aqueous medium. 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.
外殻を形成する重合体としては、一般に、ガスバリア性が良好な熱可塑性樹脂が用いられていればよい。外殻を形成する重合体は、加熱すると軟化する。外殻樹脂に内包される液体膨張剤としては、重合体の軟化点以下の温度でガス状になるものが選択されていればよい。 As the polymer forming the outer shell, generally, a thermoplastic resin having good gas barrier properties may be used. The polymer forming the outer shell softens when heated. As the liquid expansion agent to be included in the outer shell resin, it is only necessary to select one that becomes gaseous at a temperature below the softening point of the polymer.
発泡性組成物において、（Ｂ）熱膨張性マイクロカプセルの配合量は、特に限定されないが、（Ｂ）成分を除くすべての成分の合計１００重量部に対して、０．５～１０重量部であることが好ましく、１～５重量部であることがより好ましい。配合量が０．５重量部未満であると、熱可塑性エラストマー押出発泡シートの密度が高くなり軽量性に劣る傾向があり、一方、１０重量部を超えて配合しても、熱可塑性エラストマー押出発泡シートの更なる低密度化には繋がりにくい。 In the foamable composition, the amount of the (B) thermally expandable microcapsule is not particularly limited, but is 0.5 to 10 parts by weight with respect to 100 parts by weight in total of all the components except the component (B). It is preferably 1 to 5 parts by weight. If the blending amount is less than 0.5 parts by weight, the density of the thermoplastic elastomer extruded foam sheet tends to be high and the lightness tends to be inferior. On the other hand, even if it exceeds 10 parts by weight, the thermoplastic elastomer extruded foam It is difficult to reduce the density of the sheet.
（Ｂ）熱膨張性マイクロカプセルは微細な粉末状であるため、均一に配合することが困難な場合が多く、かつ粉塵爆発等の危険性もあることから、比較的低温で加工し得る樹脂中に高濃度に分散せしめたマスターバッチの状態で配合することが好ましい場合がある。この場合、マスターバッチの配合量に、マスターバッチ中の（Ｂ）熱膨張性マイクロカプセルの含有割合を乗じた値が、（Ｂ）熱膨張性マイクロカプセルの配合量となる。ただし、事前に混練工程を設ける押出発泡成形の場合には、混練工程での分散性の観点から、粉末状の（Ｂ）熱膨張性マイクロカプセルをそのまま配合することが好ましい。 (B) Thermally expandable microcapsules are fine powders, so it is often difficult to mix uniformly, and there is a risk of dust explosions. It may be preferable to blend in the state of a master batch dispersed in a high concentration. In this case, a value obtained by multiplying the blending amount of the master batch by the content ratio of the (B) thermally expandable microcapsule in the master batch is the blending amount of (B) the thermally expandable microcapsule. However, in the case of extrusion foaming in which a kneading step is provided in advance, from the viewpoint of dispersibility in the kneading step, it is preferable to blend the powdery (B) thermally expandable microcapsules as they are.
＜（Ｃ）粘着付与樹脂＞
本発明の熱可塑性エラストマー押出発泡シートにおいて、衝撃吸収性を向上させる観点から、発泡性組成物は、さらに（Ｃ）粘着付与樹脂を含有することが好ましい。 <(C) Tackifying resin>
In the thermoplastic elastomer extruded foam sheet of the present invention, the foamable composition preferably further contains (C) a tackifying resin from the viewpoint of improving impact absorbability.
（Ｃ）粘着付与樹脂としては、特に限定されないが、例えば、ロジン及びロジン誘導体、ポリテルペン樹脂、芳香族変性テルペン樹脂及びそれらの水素化物、テルペンフェノール樹脂、クマロン・インデン樹脂、脂肪族系石油樹脂、脂環族系石油樹脂及びその水素化物、芳香族系石油樹脂及びその水素化物、脂肪族芳香族共重合系石油樹脂及びその水素化物、ジシクロペンタジエン系石油樹脂及びその水素化物、スチレン又は置換スチレンの低分子量重合体等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。 (C) The tackifier resin 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.
これらの中では、（Ａ）熱可塑性エラストマー中のイソブチレンを構成単量体とする重合体ブロックとの相溶性が高いことから、脂環族系石油樹脂及びその水素化物、脂肪族系石油樹脂、芳香族系石油樹脂の水素化物、ポリテルペン樹脂、ジシクロペンタジエン系石油樹脂、ロジン等が好ましい。 Among these, (A) since the compatibility with the polymer block having isobutylene as a constituent monomer in the thermoplastic elastomer is high, an alicyclic petroleum resin and its hydride, an aliphatic petroleum resin, Preferred are hydrides of aromatic petroleum resins, polyterpene resins, dicyclopentadiene petroleum resins, rosin and the like.
（Ｃ）粘着付与樹脂としては、数平均分子量が３００～３０００、ＪＩＳ　Ｋ－２２０７に定められた環球法に基づく軟化点が６０～１６０℃、より好ましくは９０～１５０℃である低分子量の樹脂が好ましい。 (C) The tackifier resin is a low molecular weight resin having a number average molecular weight of 300 to 3000 and 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 preferred.
発泡性組成物が（Ｃ）粘着付与樹脂を含有する場合、その含有量は、特に限定されないが、（Ａ）熱可塑性エラストマー１００重量部に対して、１～１００重量部が好ましく、１０～７０重量部がより好ましく、１０～４０重量部がさらに好ましい。含有量が１００重量部を超えると、混練時の粘度が低下しすぎるため、十分な混練状態が得られず、良好な発泡体を得ることが困難となる場合があり、１重量部未満であると添加効果が現れがたい。 When the foamable composition contains (C) a tackifying resin, the content is not particularly limited, but (A) is preferably 1 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer. More preferred are parts by weight, and even more preferred is 10 to 40 parts by weight. If the content exceeds 100 parts 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 is less than 1 part by weight. And the additive effect is difficult to appear.
＜（Ｄ）可塑剤＞
本発明の熱可塑性エラストマー押出発泡シートにおいて、柔軟性の観点から、発泡性組成物は、さらに（Ｄ）可塑剤を含有することが好ましい。（Ｄ）可塑剤としては、特に限定されないが、通常、室温で液体又は液状の材料が好適に用いられる。また親水性及び疎水性のいずれの可塑剤も使用できる。このような（Ｄ）可塑剤としては、鉱物油系、植物油系、合成系等の各種ゴム用又は樹脂用可塑剤が挙げられる。 <(D) Plasticizer>
In the extruded foam sheet of the thermoplastic elastomer of the present invention, the foamable composition preferably further contains (D) a plasticizer from the viewpoint of flexibility. (D) Although it does not specifically limit as a plasticizer, Usually, a liquid or liquid material is suitably used at room temperature. Both hydrophilic and hydrophobic plasticizers can be used. Examples of the plasticizer (D) include plasticizers for various rubbers and resins such as mineral oils, vegetable oils, and synthetics.
鉱物油系の可塑剤としては、特に限定されないが、例えば、ナフテン系、パラフィン系等のプロセスオイル等が挙げられる。植物油系の可塑剤としては、特に限定されないが、例えば、ひまし油、綿実油、あまみ油、なたね油、大豆油、パーム油、やし油、落花生油、木ろう、パインオイル、オリーブ油等が挙げられる。合成系の可塑剤としては、特に限定されないが、例えば、ポリブテン、低分子量ポリブタジエン等が挙げられる。これらの中でも、（Ａ）熱可塑性エラストマーとの相溶性の観点から、パラフィン系プロセスオイル又はポリブテンが好ましい。これらは所望の粘度及び物性を得るために、単独で用いても良いし、２種以上を併用しても良い。 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, (A) Paraffinic process oil or polybutene is preferable from the viewpoint of compatibility with the thermoplastic elastomer. These may be used alone or in combination of two or more in order to obtain desired viscosity and physical properties.
本発明の熱可塑性エラストマー押出発泡シートにおいて、発泡性組成物は、任意に（Ａ）～（Ｄ）成分以外の他の成分を含有していても良い。他の成分としては、特に限定されないが、例えば、充填剤、酸化防止剤、難燃剤、抗菌剤、光安定剤、着色剤、流動性改良剤、滑剤、ブロッキング防止剤、帯電防止剤、架橋剤、架橋助剤等が挙げられる。これらは単独で用いても良いし、２種以上を併用しても良い。さらに、本発明の熱可塑性エラストマー押出発泡シートの性能を損なわない範囲であれば、各種熱可塑性樹脂、熱硬化性樹脂等、（Ａ）熱可塑性エラストマー以外の樹脂を含有していても良い。 In the thermoplastic elastomer extruded foam sheet of the present invention, the foamable composition may optionally contain components other than the components (A) to (D). Examples of other components 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 extruded thermoplastic elastomer foam sheet of the present invention, it may contain (A) a resin other than the thermoplastic elastomer, such as various thermoplastic resins and thermosetting resins.
押出発泡の前に、混練工程を設けても良い。混練工程に用いる機器としては、例えば、双腕型ニーダー、加圧型ニーダー等が挙げられる。混練時の温度は、特に限定されないが、３０～２００℃が好ましく、５０～１５０℃がより好ましい。混練時の温度が３０℃未満であると、均一に分散できないことがあり、２００℃を超えると、（Ｂ）熱膨張性マイクロカプセルが発泡を開始してしまい、混練にて破泡して発泡構造を保てないことがある。
発泡性組成物を押出発泡する方法としては、特に限定されず公知の方法を採用することができ、押出発泡に用いる機器としては、例えば、単軸押出機、二軸押出機、タンデム押出機等が挙げられる。Ｔダイの温度は、特に限定されないが、１０～２２０℃が好ましく、２５～１８０℃がより好ましい。Ｔダイの温度が１０℃未満であると、発泡にムラができることがあり、２２０℃を超えると、破泡して発泡構造を保てないことがある。熱可塑性エラストマー押出発泡シートの引き取り速度は、特に限定されないが、０．１～１０．０ｍ／ｍｉｎが好ましく、０．１５～５．０ｍ／ｍｉｎがより好ましい。引き取り速度が０．１ｍ／ｍｉｎ未満であると、シートの波打ちが発生することがあり、１０．０ｍ／ｍｉｎを超えると、シート表面が粗くなり、シートが裂けることがある。 A kneading step may be provided before extrusion foaming. As an apparatus used for a kneading | mixing process, a double arm type kneader, a pressurization type kneader, etc. are mentioned, for example. The temperature at the time of kneading is not particularly limited, but is preferably 30 to 200 ° C, more preferably 50 to 150 ° C. If the temperature at the time of kneading is less than 30 ° C., it may not be uniformly dispersed. If the temperature exceeds 200 ° C., (B) the thermally expandable microcapsule starts to foam and foams by foaming by kneading. The structure may not be maintained.
A method for extruding and foaming the foamable composition is not particularly limited, and a known method can be adopted. Examples of the equipment used for extrusion foaming include a single-screw extruder, a twin-screw extruder, and a tandem extruder. Is mentioned. The temperature of the T die is not particularly limited, but is preferably 10 to 220 ° C, more preferably 25 to 180 ° C. If the temperature of the T-die is less than 10 ° C., foaming may be uneven, and if it exceeds 220 ° C., the foam structure may be broken and the foam structure may not be maintained. The take-up speed of the thermoplastic elastomer extruded foam sheet is not particularly limited, but is preferably 0.1 to 10.0 m / min, more preferably 0.15 to 5.0 m / min. When the take-up speed is less than 0.1 m / min, sheet undulation may occur, and when it exceeds 10.0 m / min, the sheet surface may become rough and the sheet may tear.
本発明の熱可塑性エラストマー押出発泡シートの厚みは、特に限定されないが、０．１～１，０００ｍｍが好ましく、０．５～５００ｍｍがより好ましい。厚みが０．１ｍｍ未満であると、発泡させることが困難となることがあり、１，０００ｍｍを超えると、厚みが安定しないことがある。 The thickness of the extruded thermoplastic elastomer foam sheet of the present invention is not particularly limited, but is preferably 0.1 to 1,000 mm, and more preferably 0.5 to 500 mm. If the thickness is less than 0.1 mm, foaming may be difficult, and if it exceeds 1,000 mm, the thickness may not be stable.
本発明の熱可塑性エラストマー押出発泡シートの密度は、特に限定されないが、軽量性の観点からは、０．７ｋｇ／ｍ３以下が好ましく、０．６ｋｇ／ｍ３以下がより好ましく、０．５ｋｇ／ｍ３以下がさらに好ましい。密度の下限は、特に限定されないが、０．３ｋｇ／ｍ３が好ましく、０．３５ｋｇ／ｍ３がより好ましい。 Although the density of the thermoplastic elastomer extruded foam sheet of the present invention is not particularly limited, from the viewpoint of lightness, 0.7 kg / m 3 or less is preferable, 0.6 kg / m 3 or less is more preferable, and 0.5 kg / m 3 or less is more preferable. The lower limit of the density is not particularly limited, preferably 0.3kg / m 3, 0.35kg / m 3 and more preferably.
本発明の熱可塑性エラストマー押出発泡シートの発泡倍率は、特に限定されないが、１．１～５０倍が好ましく、１．２～３０倍がより好ましい。発泡倍率が１．１倍未満であると、柔軟性が劣る場合があり、５０倍を超えると、柔らかすぎて形状保持が困難となることがある。 The expansion ratio of the extruded thermoplastic elastomer foam sheet 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.
本発明の熱可塑性エラストマー押出発泡シートのＡＳＫＥＲ　Ｅ硬度は、特に限定されないが、８０度以下が好ましく、７０度以下がより好ましい。ＡＳＫＥＲ　Ｅ硬度が８０度を超えると、柔軟性が劣る場合がある。 The ASKER E hardness of the thermoplastic elastomer extruded foam sheet of the present invention is not particularly limited, but is preferably 80 degrees or less, and more preferably 70 degrees or less. When ASKER E hardness exceeds 80 degrees, flexibility may be inferior.
本発明の熱可塑性エラストマー押出発泡シートの反発弾性率は、特に限定されないが、５０％以下が好ましく、３０％以下がより好ましい。反発弾性率が５０％を超えると、衝撃吸収性が低くなることがある。 The rebound resilience of the thermoplastic elastomer extruded foam sheet of the present invention is not particularly limited, but is preferably 50% or less, more preferably 30% or less. If the impact resilience exceeds 50%, the impact absorbability may be lowered.
本発明の熱可塑性エラストマー押出発泡シートは、重量８ｋｇの錘を高さ１００ｍｍの位置から落下させた際の衝撃吸収性（衝撃加速度）が、２５０Ｇ以下であることが好ましく、２００Ｇ以下であることがより好ましく、１５０Ｇ以下であることがさらに好ましい。衝撃加速度が２５０Ｇを超えると、衝撃吸収性が低いことがある。衝撃加速度の下限は小さいほど好ましいが、例えば、１０Ｇである。 The thermoplastic elastomer extruded foam sheet of the present invention preferably has an impact absorption (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 the impact acceleration is more preferable, but it is, for example, 10G.
＜＜熱可塑性エラストマー押出発泡シートの製造方法＞＞
本発明の熱可塑性エラストマー押出発泡シートの製造方法は、
（Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマー、及び、
（Ｂ）熱膨張性マイクロカプセル
を含有する発泡性組成物を押出発泡する工程を含むことを特徴とする。 << Method for Producing Thermoplastic Elastomer Foamed Sheet >>
The method for producing a thermoplastic elastomer extruded foam sheet of the present invention includes:
(A) a thermoplastic elastomer which is 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
(B) It includes a step of extrusion-foaming a foamable composition containing thermally expandable microcapsules.
＜＜衝撃吸収体＞＞
本発明の衝撃吸収体は、本発明の熱可塑性エラストマー押出発泡シートからなることを特徴とする。本発明の熱可塑性エラストマー押出発泡シートは、そのまま衝撃吸収体とすることもできるが、必要に応じて、押出発泡時に形成される表皮層を切除したり、適当な形状に切り出したりして衝撃吸収体とすることもできる。衝撃吸収体を身体保護用のプロテクターに用いる場合、蒸れを防止するために、衝撃吸収性に対する影響を考慮しつつ貫通孔を設けても構わない。 << Shock absorber >>
The shock absorber of the present invention is characterized by comprising the thermoplastic elastomer extruded foam sheet of the present invention. The thermoplastic elastomer extruded foam sheet of the present invention can be used as an impact absorber as it is, but if necessary, the skin layer formed at the time of extrusion foaming is excised or cut into an appropriate shape to absorb the impact. It can also be a body. When the shock absorber is used as a protector for body protection, a through hole may be provided in consideration of the impact on the shock absorbability in order to prevent stuffiness.
＜＜身体保護用のプロテクター＞＞
本発明の身体保護用のプロテクターは、本発明の衝撃吸収体を備えることを特徴とする。本発明の身体保護用のプロテクターは、本発明の衝撃吸収体を単独で備えていても良いし、未発泡体であるプラスチック、発泡倍率の異なる発泡体、フィルム、布、不織布、紙等の素材と本発明の衝撃吸収体とを一体成形したものを備えていても良い。さらに、本発明の衝撃吸収体の表面に綿、アクリル繊維、毛、ポリエステル繊維等でできた布や不織布を貼り合わせていても良いし、上述の布や不織布で本発明の衝撃吸収体を包んでいても良い。このように貼り合わせたり包んだりすることで、本発明の衝撃吸収体の感触を良好にし、さらに、運動時や高温・多湿時等の発汗時に布や不織布によって吸汗作用を施すことができる。また、布や不織布を洗濯したり取り替えたりすることができ、身体保護用のプロテクター自体の汚れを防止することができるという観点から、身体保護用のプロテクターを直接身体に取り付ける場合や直接身体にあたるように用いる場合には、布や不織布を着脱できるようにしておくことが好ましい。 << Protector for body protection >>
The protector for body protection of this invention is equipped with the shock absorber of this invention, It is characterized by the above-mentioned. The protector for body protection of the present invention may be provided with the shock absorber of the present invention alone, or a material such as unfoamed plastic, foam with different expansion ratio, film, cloth, nonwoven fabric, paper, etc. And the shock absorber of the present invention may be integrally formed. 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 shock absorber of the present invention, and the shock absorber of the present invention is wrapped with the cloth or non-woven fabric described above. It can be left. By sticking or wrapping in this way, the shock absorber of the present invention can be made to feel better, and furthermore, a sweat absorbing action can be applied by a cloth or non-woven fabric during sweating during exercise, high temperature, and high humidity. In addition, from the viewpoint that cloth and non-woven fabric can be washed and replaced, and the protector for protecting the body itself can be prevented from being soiled, 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.
本発明の身体保護用のプロテクターは、衣類へ取り付けることで好適に用いられる。衣類としては、特に限定されないが、下半身の一部又は全部を覆う衣類が好ましく、例えば、スラックス、ジーンズ、トレーニングパンツ、サブリナパンツ、ニッカポッカ、ハーフパンツ、半ズボン、ホットパンツ等のズボン類、スカート類、袴類等の、下半身に着用するアウターウェアとしてのボトムス類；ショーツ、トランクス、ボクサーブリーフ、ブリーフ等のパンツ類、ガードル類、ふんどし等の下半身用インナーウェア類；靴下類、足袋、タイツ、レッグウォーマー、脚絆等の足につける衣類；ワンピース、ドレス、合羽、つなぎ、着ぐるみ、全身タイツ等の全身を覆う衣類；エプロン、割烹着、白衣、外装用プロテクター等の防護用衣類等が挙げられる。これらの中では、骨折しやすい部位での衝撃を吸収する目的から、ボトムス類、下半身用インナーウェア類が好ましく、ズボン類、パンツ類がより好ましく、パンツ類がさらに好ましい。 The protector for body protection of this invention is used suitably by attaching to clothing. Clothing is not particularly limited, but clothing that covers part or all of the lower body is preferable. For example, pants such as slacks, jeans, training pants, Sabrina pants, Nikkapokka, half pants, shorts, hot pants, and skirts 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. Of these, 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.
衣類に用いられる生地（素材、編繊方法等）は、特に限定されないが、通気性、衝撃吸収性を向上させる観点からは、生地の表面に凹凸を付けたもの、例えば、表面に凹凸の形状が現れる編み組織、パイル編み等を用いることが好ましい。 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
本発明の身体保護用のプロテクターを衣類へ取り付ける方法は、特に限定されないが、プロテクターが着用時あるいは洗濯時にずれないように、例えば、生地に縫い付ける方法、粘着テープ等で取り付ける方法、ポケットを作りその中で着脱自在に取り付ける方法等が挙げられる。また、キルト状にプロテクターを生地に縫い付けることにより、身体へのフィット性、運動のしやすさが改善できる。プロテクターは、身体に直接触れるように取り付けても良いし、生地を介して身体に触れるように取り付けても良い。 The method of attaching the protector for body protection of the present invention to clothing is not particularly limited. For example, a method of attaching the protector to a cloth, a method of attaching with an adhesive tape, a pocket, etc. Among them, there is a method of detachably attaching. Moreover, by fitting the protector to the fabric in a quilt shape, the fit to the body and the ease of exercise can be improved. 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.
本発明の身体保護用のプロテクターは、衣類の腰回りにおける前身頃、脇部、後身頃、臀部に対応する部位等の任意の箇所に取り付けることができる。大腿骨頚部外側部の大転子部を保護できる位置に、本発明の身体保護用のプロテクターを取り付けた衣類を着用することで、大腿骨骨折を防止することが可能となる。 The protector for body protection of this invention can be attached to arbitrary places, such as the site | part corresponding to the front body, side part, back body, and buttocks in the waist circumference of clothing. It is possible to prevent a femoral fracture by wearing a garment to which the protector for body protection of the present invention is attached at a position where the greater trochanter portion of the outer portion of the femoral neck can be protected.
また、本発明の身体保護用のプロテクターを粘着テープ等を用いて身体に直接取り付けることで、身体保護用のプロテクターの位置ずれを防止することができる。その際、本発明の衝撃吸収体は、通気性確保のための穴を開けたり、布や不織布を貼り合わせたり、布や不織布に包んで用いることが好ましい。 In addition, by directly attaching the protector for body protection of the present invention to the body using an adhesive tape or the like, it is possible to prevent displacement of the protector for body protection. At that time, the shock absorber of the present invention is preferably used by making a hole for ensuring air permeability, pasting a cloth or a nonwoven fabric, or wrapping the cloth in a cloth or a nonwoven fabric.
また、本来転倒等によって受ける衝撃を緩和する皮下脂肪が比較的薄く骨に対し衝撃が強くかかるところには、衝撃吸収性を重視し、厚手の熱可塑性エラストマー押出発泡シートを備えたプロテクターを用い、皮下組織が厚く、本来の衝撃吸収能力は多少あるが、尻もち等によって衝撃を受けやすい臀部等には、着用性を重視し、熱可塑性エラストマー押出発泡シートを備えたプロテクターを用いる等、２種類以上のプロテクターを組み合わせて使用しても良い。また、着用性等の観点から、衝撃を強く受ける場所には本発明の熱可塑性エラストマー押出発泡シートを備えたプロテクターを用い、さらに、衝撃が比較的緩和されるようなところには、他のプロテクターを用いても構わない。他のプロテクターとしては、例えば、ウレタン発泡体、ポリエチレン発泡体、アクリル発泡体、シリコン系重合体を基材樹脂とする発泡体、不織布、立体織物等が挙げられる。 In addition, in the place where the subcutaneous fat that originally relaxes the impact received by falling etc. is relatively thin and the impact is strong against the bone, the impact absorption is emphasized, and a protector equipped with a thick thermoplastic elastomer extruded foam sheet is used, Two or more types, such as using a protector with a thermoplastic elastomer extruded foam sheet, with emphasis on wearability for the buttocks etc. that are susceptible to impact by the buttocks etc. You may use a combination of protectors. In addition, from the viewpoint of wearability and the like, a protector provided with the thermoplastic elastomer extruded foam sheet of the present invention is used in a place where the impact is strongly received, and another protector is used in a place where the impact is relatively mitigated. May be used. Examples of other protectors include urethane foams, polyethylene foams, acrylic foams, foams based on silicon-based polymers, nonwoven fabrics, and three-dimensional woven fabrics.
本発明の身体保護用のプロテクターの形状は、特に限定されないが、長方形、正方形、円形、楕円形、ひし形等の多角形、短冊型、ドーナツ型、表面に任意の凹凸を付けたもの等が挙げられる。また、通気性や装着感の向上のため、適宜貫通孔をあけても良い。身体保護用のプロテクターの大きさは、特に限定されないが、１～１０００ｃｍ２が好ましく、５０～５００ｃｍ２がより好ましい。 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.
本発明の身体保護用のプロテクターの密度は、特に限定されないが、着用感の観点からはできるだけ密度が小さいものが好適に使用される一方で、極端に密度が小さい場合は衝撃吸収性が不十分となる可能性がある。この観点から、密度は３００～７００ｋｇ／ｍ３が好ましく、３５０～６００ｋｇ／ｍ３がより好ましく、３５０～５００ｋｇ／ｍ３がさらに好ましい。 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. In this respect, the density is preferably 300 ~ 700kg / m 3, more preferably 350 ~ 600kg / m 3, more preferably 350 ~ 500kg / m 3.
以下、実施例を挙げて本発明を説明するが、本発明は以下の実施例に限定されない。以下、「部」又は「％」は特記ない限り、それぞれ「重量部」又は「重量％」を意味する。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to a following example. Hereinafter, “part” or “%” means “part by weight” or “% by weight”, respectively, unless otherwise specified.
以下に、実施例及び比較例で用いた各種薬品、得られた材料の評価方法を以下に示す。
熱可塑性エラストマー：スチレン－イソブチレン－スチレンブロック共重合体、株式会社カネカ製のＳＩＢＳＴＡＲ　０６２Ｔ
熱可塑性エラストマー：スチレン－イソブチレン－スチレンブロック共重合体、株式会社カネカ製のＳＩＢＳＴＡＲ　１０２Ｔ
粘着付与樹脂：荒川化学工業株式会社製の水添石油樹脂アルコンＰ－１４０
熱膨張性マイクロカプセル：積水化学工業株式会社製のアドバンセルＥＭ５０１
熱膨張性マイクロカプセル：積水化学工業株式会社製のアドバンセルＰ５０１Ｅ１（マスターバッチ、マイクロカプセル含有率５０重量％）
熱膨張性マイクロカプセル：積水化学工業株式会社製のアドバンセルＥＭ４０３
可塑剤：パラフィン系プロセス油、出光興産株式会社製のダイアナプロセスオイルＰＷ３８０ Below, the evaluation method of the various chemical | medical agents used by the Example and the comparative example and the obtained material is shown below.
Thermoplastic elastomer: Styrene-isobutylene-styrene block copolymer, SIBSTAR 062T manufactured by Kaneka Corporation
Thermoplastic elastomer: Styrene-isobutylene-styrene block copolymer, SIBSTAR 102T manufactured by Kaneka Corporation
Tackifying resin: hydrogenated petroleum resin Alcon P-140 manufactured by Arakawa Chemical Industries, Ltd.
Thermally expandable microcapsule: ADVANCEL EM501 manufactured by Sekisui Chemical Co., Ltd.
Thermally expandable microcapsules: Sekisui Chemical Co., Ltd. Advancel P501E1 (masterbatch, microcapsule content 50% by weight)
Thermally expandable microcapsule: ADVANCEL EM403 manufactured by Sekisui Chemical Co., Ltd.
Plasticizer: Paraffin-based process oil, Diana Process Oil PW380 manufactured by Idemitsu Kosan Co., Ltd.
・厚み
ダイアルシックネスゲージＳＭ－１１４（テクロック社製）にて測定した。 -Measured with a thickness dial thickness gauge SM-114 (manufactured by Teclock).
・密度
任意のサイズに切り出したサンプルのサイズ、厚みから体積を算出し、重量を体積で除することで算出した。 The density was calculated by calculating the volume from the size and thickness of the sample cut into an arbitrary size and dividing the weight by the volume.
・発泡倍率
発泡していない樹脂の密度を、得られた発泡体の密度で除することで算出した。 The foaming ratio was calculated by dividing the density of the resin not foamed by the density of the obtained foam.
・ＡＳＫＥＲ　Ｅ硬度
ＡＳＫＥＲ　Ｅ硬度計（高分子計器社製）にて測定した。 -ASKER E hardness Measured with an ASKER E hardness meter (manufactured by Kobunshi Keiki Co., Ltd.).
・反発弾性率
ＩＳＯ４６６２に準拠し、反発弾性試験機ＥＰＨ－５０型（高分子計器社製）にて測定した。 -Rebound resilience was measured with a rebound resilience tester EPH-50 (manufactured by Kobunshi Keiki Co., Ltd.) in accordance with ISO4662.
・衝撃加速度
緩衝材料評価試験装置ＡＣＳＴ－２００（吉田精機社製）を用い、直径３０ｍｍに打ち抜いたサンプルに対し、重量８ｋｇの錘を高さ１００ｍｍの位置から落下させた際の衝撃加速度（最大加速度）を錘に取り付けた加速度変換機ＡＳ－５００Ａ（共和電業社製）とデータ収録装置Ｆ９９－６６１８（共和電業社製）を用いて計測した。衝撃加速度が小さいほど、衝撃吸収性が高いと評価した。 -Impact acceleration (maximum acceleration) when a weight of 8 kg is dropped from a position of 100 mm height on a sample punched to a diameter of 30 mm using an impact acceleration buffer material evaluation test device ACST-200 (manufactured by Yoshida Seiki Co., Ltd.) ) Was attached to the weight 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.) The smaller the impact acceleration, the higher the impact absorption.
・後加工性
身体保護用のプロテクターとして、身体の種々の部位に使用することを想定して、はさみやカッターでの切り抜き、トムソン刃などでの打ち抜きを行い、形状付与が容易かどうかを○×にて評価した。比較例１及び２では形状が楕円形と決まっているため、それより大きなサイズとすることは困難として、後加工性を×とした。 ・ As a protector for post-processing body protection, use scissors, cutting with a cutter, punching with a Thomson blade, etc. Evaluated. In Comparative Examples 1 and 2, since the shape is determined to be an ellipse, it is difficult to obtain a larger size, and the post-workability is set to x.
実施例１
表１に示す（Ａ）熱可塑性エラストマー、（Ｃ）粘着付与樹脂、（Ｂ）熱膨張性マイクロカプセルを表１に示す配合量で双腕型ニーダー（森山製作所社製、Ｇ型、容量５０Ｌ）にて１００～１１０℃の設定温度にて混練し、発泡性組成物を得た。この発泡性組成物を、単軸押出機（中田エンジニアリング社製、スクリュー径６０ｍｍ、Ｌ／Ｄ＝１６）のホッパーに投入し、スクリュー回転数４８ｒｐｍにて押出機内で加熱溶融した。温度を１６０℃に設定したＴダイにてリップ開度６．０ｍｍにてシート状に押し出し、引き取り速度０．３６ｍ／ｍｉｎにて引き取り、熱可塑性エラストマー押出発泡シートを得た。 Example 1
(A) Thermoplastic elastomer, (C) Tackifying resin, and (B) Thermally expandable microcapsule shown in Table 1 with the compounding amounts shown in Table 1 (double-arm kneader, G type, capacity 50 L) And kneading at a set temperature of 100 to 110 ° C. to obtain a foamable composition. This foamable composition was put into a hopper of a single screw extruder (manufactured by Nakata Engineering Co., Ltd., screw diameter 60 mm, L / D = 16), and heated and melted in the extruder at a screw rotation speed of 48 rpm. Extruded into a sheet with a lip opening of 6.0 mm with a T-die set at a temperature of 160 ° C., and taken up at a take-off speed of 0.36 m / min, to obtain a thermoplastic elastomer extruded foam sheet.
実施例２
実施例１で得られた熱可塑性エラストマー押出発泡シートを、プレス機にて１７０℃に加熱し、追加発泡させて熱可塑性エラストマー押出発泡シートを得た。 Example 2
The thermoplastic elastomer extruded foam sheet obtained in Example 1 was heated to 170 ° C. with a press machine and further foamed to obtain a thermoplastic elastomer extruded foam sheet.
実施例３
（Ｂ）熱膨張性マイクロカプセルとして、「アドバンセルＥＭ５０１を３重量部」に代えて「アドバンセルＥＭ４０３を５重量部」にしたこと以外、実施例１と同様にして熱可塑性エラストマー押出発泡シートを得た。 Example 3
(B) As a thermally expandable microcapsule, a thermoplastic elastomer extruded foam sheet was prepared in the same manner as in Example 1 except that “Advancel EM501 was replaced by 3 parts by weight” and “Advancel EM403 was replaced by 5 parts by weight”. Obtained.
実施例４
表１に示す（Ａ）熱可塑性エラストマー、（Ｄ）可塑剤、（Ｂ）熱可塑性マイクロカプセルを表１に示す配合量でブレンドし、発泡性組成物を得た。この発泡性組成物を、単軸押出機（中田エンジニアリング社製、スクリュー径６０ｍｍ、Ｌ／Ｄ＝１６）のホッパーに投入し、スクリュー回転数３０ｒｐｍにて押出機内で加熱溶融した。温度を１６０℃に設定したＴダイにてリップ開度６．０ｍｍにてシート状に押し出し、引き取り速度０．３６ｍ／ｍｉｎにて引き取り、熱可塑性エラストマー押出発泡シートを得た。 Example 4
(A) thermoplastic elastomer, (D) plasticizer, and (B) thermoplastic microcapsule shown in Table 1 were blended in the amounts shown in Table 1 to obtain a foamable composition. This foamable composition was put into a hopper of a single screw extruder (manufactured by Nakata Engineering Co., Ltd., screw diameter 60 mm, L / D = 16), and heated and melted in the extruder at a screw rotation speed of 30 rpm. Extruded into a sheet with a lip opening of 6.0 mm with a T-die set at a temperature of 160 ° C., and taken up at a take-off speed of 0.36 m / min, to obtain a thermoplastic elastomer extruded foam sheet.
比較例１
表１に示す（Ａ）熱可塑性エラストマー、（Ｃ）粘着付与樹脂、（Ｂ）熱膨張性マイクロカプセルを表１に示す配合量でブレンドし、発泡性組成物を得た。この発泡性組成物を、射出成形機「ＭＤ３５０Ｓ－ＩＩＩＤＰ型」（宇部興産機械社製、シャットオフノズル仕様）にて、樹脂温度２００℃、背圧１５ＭＰａで溶融混練した後、固定型と前進及び後退が可能な可動型とから構成される、長辺１７０ｍｍ×短辺１３０ｍｍの楕円形状のキャビティ（クリアランスｔ０＝３．５ｍｍ）を有する金型中に、射出速度１００ｍｍ／秒で射出充填した。射出充填完了後に、クリアランスが７．０ｍｍになるように可動型を後退させて、キャビティ内の樹脂を発泡させた。発泡完了後６０秒冷却し、熱可塑性エラストマー射出発泡体を得た。 Comparative Example 1
(A) thermoplastic elastomer, (C) tackifying resin, and (B) thermally expandable microcapsule shown in Table 1 were blended in the blending amounts shown in Table 1 to obtain a foamable composition. This foamable composition was melt-kneaded with an injection molding machine “MD350S-IIIDP type” (manufactured by Ube Industries, Ltd., shutoff nozzle specification) at a resin temperature of 200 ° C. and a back pressure of 15 MPa, A mold having an elliptical cavity (clearance t0 = 3.5 mm) having a long side of 170 mm and a short side of 130 mm composed of a movable mold capable of retreating was injected and filled at an injection speed of 100 mm / second. After the injection filling was completed, the movable mold was retracted so that the clearance was 7.0 mm, and the resin in the cavity was foamed. After completion of foaming, the product was cooled for 60 seconds to obtain a thermoplastic elastomer injection foam.
比較例２
表１に示す（Ａ）熱可塑性エラストマー、（Ｃ）粘着付与樹脂を表１に示す配合量でブレンドして樹脂組成物とした。この樹脂組成物を、射出成形機「ＭＤ３５０Ｓ－ＩＩＩＤＰ型」（宇部興産機械社製、シャットオフノズル仕様）にて、樹脂温度２００℃、背圧１５ＭＰａで溶融混練した後、固定型と前進及び後退が可能な可動型とから構成される、長辺１７０ｍｍ×短辺１３０ｍｍの楕円形状のキャビティ（クリアランスｔ０＝３．５ｍｍ）を有する金型中に、射出速度１００ｍｍ／秒で射出充填した。充填完了後６０秒冷却し、熱可塑性エラストマー射出成形体を得た。 Comparative Example 2
(A) thermoplastic elastomer shown in Table 1 and (C) tackifying resin were blended in the blending amounts shown in Table 1 to obtain a resin composition. This resin composition was melt-kneaded with an injection molding machine “MD350S-IIIDP type” (Ube Industries, Ltd., shutoff nozzle specification) at a resin temperature of 200 ° C. and a back pressure of 15 MPa, and then moved forward and backward with the stationary mold. A mold having an elliptical cavity (clearance t0 = 3.5 mm) having a long side of 170 mm and a short side of 130 mm, which is composed of a movable mold capable of performing injection, was injected and filled at an injection speed of 100 mm / second. After completion of filling, the mixture was cooled for 60 seconds to obtain a thermoplastic elastomer injection-molded body.
比較例３
発泡ゲルである「ＮＰゲル」（タイカ社製、厚み３ｍｍ）を３枚重ね、サンプルを得た。 Comparative Example 3
Three samples of “NP gel” (manufactured by Taika Co., Ltd., thickness 3 mm), which is a foamed gel, were stacked to obtain a sample.
実施例１～４、比較例１～３で得られたサンプルを用いて、上述した方法により、厚み、密度、発泡倍率、ＡＳＫＥＲ　Ｅ硬度、反発弾性率、衝撃加速度及び後加工性を評価した。結果を表１に示す。 Using the samples obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the thickness, density, expansion ratio, ASKER E hardness, impact resilience, impact acceleration, and post-workability were evaluated by the methods described above. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
実施例１～４、比較例１～３の結果から、本願発明の熱可塑性エラストマー押出発泡シートは衝撃吸収性及び後加工性に優れていることが分かる。 From the results of Examples 1 to 4 and Comparative Examples 1 to 3, it can be seen that the extruded thermoplastic elastomer foam sheet of the present invention is excellent in impact absorption and post-processability.

Claims (6)

  1. （Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマー、及び、
    （Ｂ）熱膨張性マイクロカプセル
    を含有する発泡性組成物を押出発泡して得られることを特徴とする熱可塑性エラストマー押出発泡シート。     (A) a thermoplastic elastomer which is 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
    (B) A thermoplastic elastomer extruded foam sheet obtained by extrusion foaming a foamable composition containing thermally expandable microcapsules.
  2. 発泡性組成物は、さらに（Ｃ）粘着付与樹脂を含有する請求項１記載の熱可塑性エラストマー押出発泡シート。 The thermoplastic elastomer extruded foam sheet according to claim 1, wherein the foamable composition further comprises (C) a tackifying resin.
  3. 発泡性組成物は、さらに（Ｄ）可塑剤を含有する請求項１又は２記載の熱可塑性エラストマー押出発泡シート。 The thermoplastic elastomer extruded foam sheet according to claim 1 or 2, wherein the foamable composition further contains (D) a plasticizer.
  4. （Ａ）イソブチレンを構成単量体とする重合体ブロックと、芳香族ビニル系単量体を構成単量体とする重合体ブロックとからなるブロック共重合体である熱可塑性エラストマー、及び、
    （Ｂ）熱膨張性マイクロカプセル
    を含有する発泡性組成物を押出発泡する工程を含むことを特徴とする、熱可塑性エラストマー押出発泡シートの製造方法。     (A) a thermoplastic elastomer which is 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
    (B) A method for producing a thermoplastic elastomer extruded foam sheet, comprising a step of extrusion foaming a foamable composition containing thermally expandable microcapsules.
  5. 請求項１～３のいずれか１項に記載の熱可塑性エラストマー押出発泡シートからなることを特徴とする衝撃吸収体。 An impact absorber comprising the thermoplastic elastomer extruded foam sheet according to any one of claims 1 to 3.
  6. 請求項５記載の衝撃吸収体を備えることを特徴とする身体保護用のプロテクター。 A protector for body protection, comprising the shock absorber according to claim 5.
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