CN107108947A - Thermoplastic elastomer (TPE) extrusion foaming piece - Google Patents
Thermoplastic elastomer (TPE) extrusion foaming piece Download PDFInfo
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- CN107108947A CN107108947A CN201580066347.9A CN201580066347A CN107108947A CN 107108947 A CN107108947 A CN 107108947A CN 201580066347 A CN201580066347 A CN 201580066347A CN 107108947 A CN107108947 A CN 107108947A
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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
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Abstract
It is an object of the invention to provide a kind of light weight and the excellent thermoplastic elastomer (TPE) extrusion foaming piece of impact absorbency, it can be suitably used for protector, protection pad of bodily protection for the purpose of contusion, fracture in reducing motion, medical care etc. etc..The thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is characterised by, be will obtained from the expandable composition containing (A) thermoplastic elastomer (TPE) and (B) thermal expansivity micro-capsule carries out extrusion foaming, (A) thermoplastic elastomer (TPE) be by using isobutene to be constituted the polymer blocks of monomer and using aromatic vinyl base system monomer to be constituted the block copolymer that the polymer blocks of monomer are constituted.
Description
Technical field
The present invention relates to light weight and the excellent thermoplastic elastomer (TPE) extrusion foaming piece of impact absorbency and its manufacture method.
Background technology
The foaming body being made up of thermoplastic resin has the characteristics such as light weight, resiliency, is widely used in various uses.Its
In, it is adapted to the foaming body using thermoplastic elastomer (TPE) needing resiliency, flexibility, the purposes of impact absorbency.As so
Foaming body, for example proposed in patent document 1 it is a kind of by using the hydride of styrene conjugated diene block copolymer as
The foaming body that the styrene series thermoplastic elastomer composition on basis carries out foam-injection and is molded.In addition, being carried in patent document 2
The crosslinked thermoplastic that a kind of utilization heat-expandable microsphere makes to be made up of radical crosslinking elastomer and thermoplastic resin is gone out
Property elastic composition carry out foaming thermoplastic elastomer foaming body.But, the foaming body obtained by these methods is hard
And impact absorbency is low, the material for the protector being not suitable as the purpose of protecting body.
As the protector for the purpose of protecting body, for example, a kind of installation macromolecule is proposed in patent document 3 many
Hole body is as the clothes of shock absorbing portion material, and the high-molecular porous body is by making water-soluble stomatal limiting value material be scattered in polyphenyl second
The moulding material of the polymer substances such as alkene based elastomers, polyester-based elastomer is constituted.In addition, being proposed in patent document 4
Porous silicon gel is used for sport footwear padded coaming.However, material described in these documents is used according to it
On the way, sometimes for substantially ensuring that impact absorbency and thickness becomes very thick.It can be used for protecting body it is therefore desirable to develop one kind
For the purpose of protector the excellent material of impact absorbency.
On the other hand, as thermoplastic elastomer (TPE) foaming body manufacture method, for example, being proposed in patent document 5
It is a kind of that the expandable composition being made up of thermoplastic elastomer (TPE) and thermal expansivity micro-capsule is subjected to foam-injection (using core pulling method
Foam-injection) method.However, in the method, in order to change the shape of foaming body, it is necessary to make die for injection molding,
It is therefore desirable to which the method for the shape of foaming body can easily be changed by post-processing.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 6-218741 publications
Patent document 2：11-No. 343362 publications of Japanese Unexamined Patent Publication
Patent document 3：Japanese Unexamined Patent Publication 2003-3004 publications
Patent document 4：Japanese Unexamined Patent Publication 7-3165 publications
Patent document 5：Japanese Unexamined Patent Publication 2011-168775 publications
The content of the invention
It is an object of the invention to provide a kind of light weight and the excellent thermoplastic elastomer (TPE) extrusion foaming piece of impact absorbency,
Its body that can be suitably used for for the purpose of contusion, fracture in reducing motion, medical care etc. is protected
Protector, protection pad of shield etc..
The present inventor etc. are concentrated on studies to solve above-mentioned problem, as a result find there is spy using by that will contain
The expandable composition of the thermoplastic elastomer (TPE) and thermal expansivity micro-capsule of determining structure carries out thermoplastic elastomehc obtained from extrusion foaming
Property body extrusion foaming piece, can solve the problem that above-mentioned problem, completes the present invention.
That is, the present invention relates to a kind of thermoplastic elastomer (TPE) extrusion foaming piece, it is characterised in that is by containing (A) thermoplasticity
The expandable composition of elastomer and (B) thermal expansivity micro-capsule is carried out obtained from extrusion foaming, (A) thermoplastic elastomer (TPE)
It is by using isobutene to be constituted the polymer blocks of monomer and embedding using aromatic vinyl base system monomer as the polymer for being constituted monomer
The block copolymer that section is constituted.
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, expandable composition is preferably further viscosified containing (C)
Resin.
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, expandable composition is preferably further plasticized containing (D)
Agent.
The present invention relates to a kind of manufacture method of thermoplastic elastomer (TPE) extrusion foaming piece, it is characterised in that comprising will contain
(A) process that the expandable composition of thermoplastic elastomer (TPE) and (B) thermal expansivity micro-capsule carries out extrusion foaming, (A) thermoplastic
Property elastomer be by using isobutene to be constituted the polymer blocks of monomer and using aromatic vinyl base system monomer to be constituted monomer
The block copolymer that polymer blocks are constituted.
The absorbing body of the present invention is characterised by, is made up of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention.
The protector of the bodily protection of the present invention is characterised by possessing the absorbing body of the present invention.
The thermoplastic elastomer (TPE) extrusion foaming piece light weight and softness of the present invention, therefore, with tracing ability, impact absorbency is excellent
It is different.In addition, shape can be assigned by post-processings such as punchings, it therefore, there is no need to make as injection molding mould according to shape
Complicated mould, can more easily make variously-shaped absorbing body like that.
Embodiment
＜ ＜ thermoplastic elastomer (TPE) extrusion foaming piece ＞ ＞
The thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is characterised by, is by containing (A) thermoplastic elastomer (TPE) and (B)
The expandable composition of thermal expansivity micro-capsule is carried out obtained from extrusion foaming, and (A) thermoplastic elastomer (TPE) is by with isobutyl
Alkene is to constitute the polymer blocks of monomer and embedding using aromatic vinyl base system monomer as constituted that the polymer blocks of monomer are constituted
Section copolymer.
＜ (A) thermoplastic elastomer (TPE)s ＞
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, expandable composition contains (A) thermoplastic elastomer (TPE), institute
It is by being to be constituted the polymer blocks of monomer and using aromatic vinyl base system monomer as structure using isobutene to state (A) thermoplastic elastomer (TPE)
The block copolymer constituted into the polymer blocks of monomer.
As (A) thermoplastic elastomer (TPE), as long as by using isobutene to be constituted the polymer blocks of monomer and with aromatic series
Vinyl monomer is just not particularly limited to constitute the block copolymer that the polymer blocks of monomer are constituted.
As the structure of (A) thermoplastic elastomer (TPE), it is not particularly limited, for example, can enumerates by with aromatic vinyl base system
Monomer is to constitute the polymer blocks of monomer-using isobutene to be constituted the polymer blocks of monomer-with aromatic vinyl base system
Monomer is the triblock copolymer for the polymer blocks composition for constituting monomer, by using aromatic vinyl base system monomer to be constituted monomer
Polymer blocks-constituted using isobutene as the polymer blocks for being constituted monomer diblock copolymer, with aromatic ethenyl
It is that monomer is to constitute the polymer blocks of monomer and using isobutene to be constituted that the polymer blocks of monomer are constituted with arm
Star block copolymer etc..In the present invention, in order to obtain desired physical property molding processibility, it can be used alone with this
(A) thermoplastic elastomer (TPE) of a little structures, and can also use two or more.
In (A) thermoplastic elastomer (TPE), using aromatic vinyl base system monomer as constituted the polymer blocks of monomer with different
Butylene is the weight rate ((using isobutene as the polymer blocks for being constituted monomer)/(with fragrance for the polymer blocks for constituting monomer
Race's vinyl monomer is constitutes the polymer blocks of monomer)) be not particularly limited, but from the impact absorbency of foaming body and into
From the viewpoint of shape retention under type, normal temperature, preferably 95/5~60/40, more preferably 90/10~65/35.
Using aromatic vinyl base system monomer as constituted the polymer blocks of monomer by using aromatic vinyl base system monomer as
Principal component is polymerize and formed.As aromatic vinyl base system monomer, be not particularly limited, can for example enumerate styrene,
O-, m- or p- methyl styrene, α-methylstyrene, Beta-methyl styrene, 2,6- dimethyl styrenes, 2,4- dimethyl
Styrene, Alpha-Methyl-o-methyl styrene, Alpha-Methyl-methyl styrene, Alpha-Methyl-p-methylstyrene, β-
Methyl-o-methyl styrene, Beta-methyl-methyl styrene, Beta-methyl-p-methylstyrene, 2,4,6- trimethyls
Styrene, alpha-methyl-2,6- dimethyl styrenes, alpha-methyl-2,4- dimethyl styrenes, Beta-methyl -2,6- two
Methyl styrene, Beta-methyl -2,4- dimethyl styrenes, o-, m- or p- chlorostyrene, 2,6- dichlorostyrenes, 2,4-
Dichlorostyrene, α-chloro- ortho-chlorostyrene, α-chloro- m-chlorostyrene, α-chloro- p-chlorostyrene, β-chloro- adjacent chlorine
Styrene, β-chloro- m-chlorostyrene, β-chloro- p-chlorostyrene, 2,4,6- trichlorostyrenes, α-chloro- 2,6- dichloros
Styrene, α-chloro- 2,4 dichloro benzene ethene, β-chloro- 2,6- dichlorostyrenes, β-chloro- 2,4 dichloro benzene ethene,
O-, m- or p- t-butyl styrene, o-, m- or p- methoxy styrene, o-, m- or p- 1-chloro-4-methyl-benzene, o-, m- or p- bromine
Methyl styrene, the styrene derivative replaced by silicyl, indenes, vinyl naphthalene etc..They can be used alone, can also
And use two or more.In these aromatic vinyl base system monomers, from the viewpoint of it obtains easiness and physical property balance, preferably
It is at least one kind of in styrene, p-methylstyrene, α-methylstyrene and indenes.
It is not particularly limited using the manufacture method of isobutene as the polymer blocks for being constituted monomer, for example can be by drawing
It is polymerize the monomer component using isobutene as principal component in the presence of hair agent to be manufactured.Should illustrate, using isobutene as
, can also other vinyl compounds of copolymerization as needed in the polymer blocks for constituting monomer.
As initiator, it is not particularly limited, for example, can uses the compound shown in following formulas (1).Think following
Compound shown in formula (1) generates carbocation in the presence of lewis acid etc., the starting point as cationic polymerization.
(CR1R2X)nR3 (1)
[in formula (1), X represents the acyloxy of halogen atom, the alkoxy of carbon number 1~6 or carbon number 1~6.
R1、R2Each represent the alkyl of 1 valency of hydrogen atom or carbon number 1~6, R1、R2Can be with identical, can also be different.R3For multivalence
Aromatic hydrocarbyl or multivalence aliphatic alkyl, n represent 1~6 natural number.].
As the compound shown in formula (1), it is not particularly limited, for example, can enumerates (the chloro- 1- Methylethyls of 1-)
Double (the chloro- 1- Methylethyls of the 1-) benzene of benzene, 1,4-, 1,3- double (the chloro- 1- Methylethyls of 1-) benzene, (1- of 1,3,5- tri-
Chloro- 1- Methylethyls) benzene, double (the chloro- 1- Methylethyls of the 1-) -5- tert-butyl benzenes of 1,3- etc..They can individually make
With and two or more can also be used.In these compounds, preferably Isosorbide-5-Nitrae-bis- (the chloro- 1- Methylethyls of 1-) benzene, 1,3,5- tri-
(the chloro- 1- Methylethyls of 1-) benzene.
In using isobutene as the polymerization of the monomer component of principal component, it further can also be total to lewis acid catalyst
Deposit.As lewis acid catalyst, just it is not particularly limited as long as can be used in cationic polymerization, for example, can enumerates TiCl4、
TiBr4、BCl3、BF3、BF3·OEt2、SnCl4、SbCl5、SbF5、WCl6、TaCl5、VCl5、FeCl3、ZnBr2、AlCl3、AlBr3
Deng metal halide；Et2AlCl、EtAlCl2Etc. organic metal halide etc. (Et represents ethyl).They can be used alone,
Two or more kinds may be used.In these lewis acid catalysts, from the ability as catalyst, the easiness that industrially obtains
Viewpoint consideration, preferably TiCl4、BCl3、SnCl4。
During using lewis acid catalyst, its usage amount is not particularly limited, can be with view of the polymerization of the monomer used is special
Property, polymerization concentration etc. are set.Generally, relative to the compound shown in formula (1), preferably 0.1~100 molar equivalent, more
It is preferred that 1~50 molar equivalent.
In using isobutene as the polymerization of the monomer component of principal component, further can also make as needed electron donor into
Divide and coexist.Thinking that the electron donor composition has in cationic polymerization makes the stabilized effect of growth carbocation, Neng Goutong
Cross addition electron donor and generate the polymer that the structure of narrow molecular weight distribution is controlled.As electron donor composition, do not have
It is particularly limited to, for example, can enumerates pyridines, amine, amide-type, sulfoxide type, esters, former with the oxygen that is bonded with metallic atom
Metallic compound of son etc..They can be used alone, and can also use two or more.
It can be carried out in organic solvent as needed using isobutene as the polymerization of the monomer component of principal component.As organic
Solvent, as long as being substantially not particularly limited without suppressing cationic polymerization, can for example enumerate monochloro methane, dichloromethane,
The halogenated hydrocarbons such as chloroform, ethyl chloride, dichloroethanes, chloro n-propane, chloro-normal butane, chlorobenzene；Benzene,toluene,xylene, ethylbenzene,
The alkyl benzenes such as propyl benzene, butylbenzene；The straight chain such as ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane formula fat
Race's hydro carbons；The branch chain type fat such as 2- methylpropanes, 2- methybutanes, 2,3,3- trimethylpentanes, 2,2,5- trimethyl cyclohexanes
Fat race hydro carbons；The ring type aliphatic hydrocarbon such as hexamethylene, hexahydrotoluene, ethyl cyclohexane；By the way that petroleum distillate is hydrogenated
Paraffin oil of purifying etc..The dissolubility of the polymer of polymerization property and generation in view of the monomer of composition block copolymer
Deng balance, these organic solvents can be used alone, and can also use two or more.
The usage amount of organic solvent is not particularly limited, it is contemplated that the viscosity of obtained polymer solution, except heat it is easy
Property, it can be determined in the way of the concentration of polymer is preferably 1~50 weight %, more preferably 5~35 weight %.
Polymerization using isobutene as the monomer component of principal component preferably by each composition under cooling, for example -100 DEG C with
Above and at a temperature of being less than 0 DEG C mix and carry out.From the viewpoint of equilibrium energy cost and the stability of polymerization, more preferably-
80~-30 DEG C.
As the commercially available product that can be used as (A) thermoplastic elastomer (TPE), SIBSTAR (Kaneka company systems) can be enumerated.
＜ (B) thermal expansivity micro-capsule ＞
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, expandable composition contains (B) thermal expansivity micro-capsule.Heat
Dilatancy micro-capsule be by volatile liquid swelling agent obtained from the shell that is made up of polymer carries out microencapsulation.Generally,
Suspension polymerisation can be carried out by by the polymerism mixture at least containing swelling agent and polymerizable monomer in water-medium
Method and manufacture.As polymerisation is carried out, shell is formed by the polymer generated, obtained with swollen to be wrapped into the shell
The thermal expansivity micro-capsule for the structure that swollen dose of mode is enclosed.
As the polymer for forming shell, as long as generally using the good thermoplastic resin of barrier properties for gases.Formed
Soften during the polymer heating of shell.As liquid swelling agent of the interior bag in shell resin, as long as selection is in the soft of polymer
Changing the following temperature of point turns into gasiform material.
In expandable composition, the use level of (B) thermal expansivity micro-capsule is not particularly limited, relative to except (B) composition
Total 100 parts by weight of whole compositions in addition, more preferably preferably 0.5~10 parts by weight, 1~5 parts by weight.If coordinated
Amount is less than 0.5 parts by weight, then the density that there is thermoplastic elastomer (TPE) extrusion foaming piece is uprised, the trend of light weight difference, the opposing party
Face, even if coordinating more than 10 parts by weight, it is also difficult to realize the further low-density of thermoplastic elastomer (TPE) extrusion foaming piece.
(B) thermal expansivity micro-capsule is fine powdered, therefore, is difficult to equably coordinate, and also have dust explosion more
Deng danger, therefore, it is sometimes preferred to be scattered in high concentration can in compared with the resin processed under low temperature obtained by masterbatch
State is coordinated.Now, it is worth into obtained by the content ratio of (B) thermal expansivity micro-capsule that the use level of masterbatch is multiplied by masterbatch
For the use level of (B) thermal expansivity micro-capsule.But, in the case where pre-setting the foam shaping by extrusion of compounding procedure, from mixed
Refine from the viewpoint of the dispersiveness in process, preferably directly coordinate powdered (B) thermal expansivity micro-capsule.
＜ (C) tackifying resins ＞
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, from the viewpoint of impact absorbency is improved, foaminess
Composition preferably further contains (C) tackifying resin.
As (C) tackifying resin, be not particularly limited, can for example enumerate rosin and rosin derivative, polyterpene resin,
Aromatic modified terpene resin and they hydride, terpene phenolic resin, coumarone-indene resin, fatty family Petropols,
Alicyclic ring family Petropols and its hydride, fragrant family Petropols and its hydride, aliphatic aromatic copolymerization through-stone oil
The low molecule amount of resin and its hydride, bicyclopentadiene through-stone oleoresin and its hydride, styrene or substituted phenylethylene is gathered
Compound etc..They can be used alone, and can also use two or more.
In these tackifying resins, from (A) thermoplastic elastomer (TPE) using isobutene as the polymer blocks for being constituted monomer
Compatibility it is high from the aspect of, preferably alicyclic ring family Petropols and its hydride, fatty family Petropols, fragrant family
Hydride, polyterpene resin, bicyclopentadiene through-stone oleoresin, rosin of Petropols etc..
As (C) tackifying resin, preferred number average molecular weight is 300~3000, based on the global of JIS K-2207 defineds
The softening point of method is 60~160 DEG C, the resin of more preferably 90~150 DEG C of low molecule amount.
When expandable composition contains (C) tackifying resin, its content is not particularly limited, relative to (A) thermoplastic elastic
The parts by weight of body 100, preferably 1~100 parts by weight, more preferably 10~70 parts by weight, further preferred 10~40 parts by weight.If contained
Amount is more than 100 parts by weight, then therefore excess stickiness reduction when kneading sometimes, cannot get sufficient kneaded state, it is difficult to obtain
Good foaming body, during less than 1 parts by weight, it is difficult to show additive effect.
＜ (D) plasticizer ＞
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, from the viewpoint of flexibility, expandable composition is excellent
Choosing further contains (D) plasticizer.As (D) plasticizer, be not particularly limited, generally, be adapted for use with room temperature for liquid or
The material of liquid.In addition, hydrophily and hydrophobic plasticizer can be used.As such (D) plasticizer, it can enumerate
The various rubber of mineral oil system, vegetable oil system, synthesis system etc. are used or plasticizer for resin.
As the plasticizer of mineral oil system, it is not particularly limited, oil is operated such as can enumerate naphthene series, paraffin series
Deng.As the plasticizer of vegetable oil system, it is not particularly limited, for example, can enumerates Castor oil, cottonseed oil, linseed oil, vegetable seed
Oil, soybean oil, palm oil, coconut oil, peanut oil, haze tallow, pine tar, olive oil etc..As the plasticizer of synthesis system, without special
Limit, such as can enumerate polybutene, low molecular weight polybutadiene.In these plasticizer, from (A) thermoplastic elastomer (TPE)
From the viewpoint of compatibility, preferably paraffin series operates oil or polybutene.In order to obtain desired viscosity and physical property, they can be single
Solely use, and two or more can also be used.
In the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention, expandable composition can arbitrarily contain (A)~(D)
Other compositions beyond composition.As other compositions, it is not particularly limited, for example, can enumerates filler, antioxidant, fire-retardant
Agent, antiseptic, light stabilizer, colouring agent, fluidity amendment, lubricant, anti-blocking agent, antistatic additive, crosslinking agent, crosslinking are helped
Agent etc..They can be used alone, and can also use two or more.And then, as long as the thermoplastic elastomer (TPE) of the present invention is not damaged
The scope of the performance of extrusion foaming piece, it is possible to contain various thermoplastic resins, heat-curing resin etc., (A) thermoplastic elastic
Resin beyond body.
Before extrusion foaming, compounding procedure can be set.Equipment as being used in compounding procedure, for example, can enumerate
Dual-arm kneader, compression type kneader etc..Temperature during mixing is not particularly limited, preferably 30~200 DEG C, more preferably 50~
150℃.If temperature during mixing is less than 30 DEG C, it can not be uniformly dispersed sometimes, if it exceeds 200 DEG C, then (B) is hot sometimes
Dilatancy micro-capsule starts foaming, the brokenly bubble in mixing and can not keep foaming structure.
As by the method for expandable composition extrusion foaming, it is not particularly limited, known method can be used, as
The equipment used in extrusion foaming, such as can enumerate single axle extruding machine, biaxial extruder, tandem extruder.T-shaped mould head
Temperature is not particularly limited, preferably 10~220 DEG C, more preferably 25~180 DEG C.If the temperature of T-shaped mould head is less than 10 DEG C, have
When foam to form inequality, if it exceeds 220 DEG C, then sometimes brokenly bubble and foaming structure can not be kept.Thermoplastic elastomer (TPE) extrusion hair
The hauling speed of bubble piece is not particularly limited, preferably 0.1~10.0m/min, more preferably 0.15~5.0m/min.If traction speed
Degree is less than 0.1m/min, then produces the fluctuating of piece sometimes, if it exceeds 10.0m/min, then have time slice surface thicker, piece cracking.
The thickness of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is not particularly limited, and preferably 0.1~1000mm is more excellent
Select 0.5~500mm.If thickness is less than 0.1mm, it is difficult to make it foam sometimes, if it exceeds 1000mm, then thickness is not sometimes
It is stable.
The density of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is not particularly limited, but is examined from the viewpoint of light weight
Consider, preferably 0.7kg/m3Hereinafter, more preferably 0.6kg/m3Hereinafter, further preferred 0.5kg/m3Below.The lower limit of density is without spy
Do not limit, preferably 0.3kg/m3, more preferably 0.35kg/m3。
The expansion ratio of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is not particularly limited, preferably 1.1~50 times, more
It is preferred that 1.2~30 times.If expansion ratio is 1.1 times, flexibility is poor sometimes, if it exceeds 50 times, then it is sometimes excessively soft
And be difficult to keep shape.
The ASKER E hardness of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is not particularly limited, preferably less than 80 degree,
More preferably less than 70 degree.If ASKER E hardness is more than 80 degree, flexibility is poor sometimes.
The resilience modulus of elasticity of thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is not particularly limited, preferably 50% with
Under, more preferably less than 30%.If resilience modulus of elasticity is more than 50%, sometimes impact absorbency step-down.
The counterweight from the height 100mm that make weight 8kg of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention position are fallen
When impact absorbency (impact acceleration) be preferably below 250G, more preferably below 200G, more preferably 150G with
Under.If impact acceleration is more than 250G, impact absorbency is low sometimes.The lower limit of impact acceleration is smaller more preferred, for example
For 10G.
The manufacture method ＞ ＞ of ＜ ＜ thermoplastic elastomer (TPE) extrusion foaming pieces
The manufacture method of thermoplastic elastomer (TPE) extrusion foaming piece of the present invention is characterised by, comprising will contain (A) thermoplastic
Property elastomer and (B) thermal expansivity micro-capsule expandable composition carry out extrusion foaming process, (A) thermoplastic elastomer (TPE)
It is by using isobutene to be constituted the polymer blocks of monomer and embedding using aromatic vinyl base system monomer as the polymer for being constituted monomer
The block copolymer that section is constituted.
＜ ＜ absorbing body ＞ ＞
The absorbing body of the present invention is characterised by, is made up of the thermoplastic elastomer (TPE) extrusion foaming piece of the present invention.This
The thermoplastic elastomer (TPE) extrusion foaming piece of invention will can also can also be sent out in extrusion as needed directly as absorbing body
The epidermis formed during bubble cuts off or cuts into appropriate shape and absorbing body is made.Absorbing body is being used for body
It is sultry in order to prevent during the protector of protection, through hole can be set while considering on impacting absorbefacient influence.
The protector ＞ ＞ of ＜ ＜ bodily protections
The protector of the bodily protection of the present invention is characterised by possessing the absorbing body of the present invention.The present invention's
The protector of bodily protection can individually possess the absorbing body of the present invention, and can also possess will be used as the modeling of unexpanded body
The raw material such as material, different foaming body, film, cloth, non-woven fabrics, the paper of expansion ratio and the impact absorbing body by integral forming of the present invention and
Into absorbing body.And then, it can be fitted on the surface of the absorbing body of the present invention by cotton, acrylic fiber, hair, polyester
Cloth, the non-woven fabrics of the formation such as fiber, can also be by above-mentioned cloth, the absorbing body of the non-woven wraps present invention.By so
Laminating is wrapped up, and the thoughts and feelings of the absorbing body of the present invention can be made good, and then, when in motion, high temperature and humidity etc.
It can implement sweat-absorbing function using cloth, non-woven fabrics during perspiration.In addition, from cloth, non-woven fabrics being washed or changed, can
Prevent bodily protection protector itself it is dirty so from the viewpoint of, be mounted directly by the protector of bodily protection
In the situation of body, in the way of directly contacting body in the case of use, preferably cloth, non-woven fabrics is set to wear off in advance.
The protector of the bodily protection of the present invention is compatibly used by being installed on clothes.As clothes, without spy
Do not limit, preferably cover some or all of clothes of the lower part of the body, for example, can enumerate casual pants, jeans, training pants, Saab
The trousers classes such as beautiful Na trousers, knicker bockers, five minute trousers, shorts, hot pants, skirt class, kimonos trousers skirt class etc. are worn in outside the conduct of the lower part of the body
The lower dress class of clothing；The interior clothings of the lower part of the body such as the underpants classes such as shorts, gym shorts, straight angle underpants, panties, waistband class, pocket crotch cloth；
The short cotton stockings of socks class, Japonica type, close-fitting stocking, stocking, gaiter etc. are worn in the clothes on pin；One-piece dress, female's full dress, rain
Clothing, union suit, cartoon image clothes, full body clothing etc. cover the clothes of whole body；Apron, culinary art clothes, white frock, exterior are used
Protection clothes such as protector etc..In these clothes, consider from the purpose for the impact for absorbing the position easily fractured, it is preferably lower to fill
The interior clothing of class, the lower part of the body, more preferably trousers class, underpants class, further preferred underpants class.
Dress material (raw material, weaving method etc.) used in clothes is not particularly limited, but from improve aeration, impact
From the viewpoint of absorbability, it is preferably used in the irregular dress material of surface band of dress material, for example shows the shape of bumps on surface
Braiding tissue, pile knit etc..
The method that the protector of the bodily protection of the present invention is installed on into clothes is not particularly limited, for example, can enumerate
The method of dress material, the method using installations such as adhesive tapes are sewn in, pocket is made and peace tears the method installed freely open wherein
Deng so that protector will not be offset when wearing or when washing.In addition, by the way that protector quilt shape is sewn in into dress material, Neng Gougai
Kind adaptability, the easiness of motion to body.Protector can be by with installing in the way of direct physical contact, can also be to be situated between
The mode contacted by dress material with body is installed.
The present invention bodily protection protector can be installed on clothes waistline with predecessor, flank, rear body, buttocks
Corresponding position etc. is anywhere.By the way that the position dress in the greater trochanter portion of thigh neck outside portion can protected to be provided with
The clothing of the protector of the bodily protection of the present invention, can prevent thigh from fracturing.
In addition, the protector of the bodily protection of the present invention is directly mounted at into body, energy by using adhesive tape etc.
Enough prevent the position skew of the protector of bodily protection.Now, absorbing body of the invention is preferably opened for ensuring to lead to
The hole of gas, or adhesive fabric, non-woven fabrics, or be wrapped in cloth, non-woven fabrics and use.
In addition, on relatively thin, stronger to the bone impact ground of the subcutaneous fat that script relaxes the impact being subject to by tumble etc.
Side, payes attention to impact absorbency, thick, former in hypodermis using the protector for the thermoplastic elastomer (TPE) extrusion foaming piece for possessing thickness
Originally there are some impact absorbing abilities but easily because hip are squatted etc. and by buttocks impacted etc., pay attention to dressing, using possessing heat
Protector of thermoplastic elastic extrusion foaming piece etc., can combine protector of more than two kinds and use.In addition, from dressing etc.
Viewpoint considers, by the position compared with thump, using the protector for the thermoplastic elastomer (TPE) extrusion foaming piece for possessing the present invention,
And then, such place is relatively relaxed in impact, other protectors can be used.As other protectors, for example, it can enumerate ammonia
Ester foaming body, foam polyethylene, acrylic acid foaming body, using silicon systems polymer as the foaming body of substrate resin, non-woven fabrics, solid
Fabric etc..
The shape of the protector of the bodily protection of the present invention is not particularly limited, and can enumerate rectangle, square, circle
The polygons such as shape, ellipse, rhombus, stripe shape, circular ring type, on surface with arbitrary concavo-convex shape etc..In addition, in order to improve
Aeration, wearing feeling, can be appropriately arranged with through hole.The size of the protector of bodily protection is not particularly limited, preferably 1~
1000cm2, more preferably 50~500cm2。
The density of the protector of the bodily protection of the present invention is not particularly limited, from the viewpoint of wearing feeling, is adapted to
Using density small protector as far as possible, on the other hand, when density is minimum, it is possible to which impact absorbency becomes insufficient.From this
Viewpoint consideration, density preferably 300~700kg/m3, more preferably 350~600kg/m3, further preferred 350~500kg/m3。
Embodiment
Hereinafter, enumerate embodiment the present invention will be described, but the present invention is not limited to following embodiment.Hereinafter,
" part " or " % " unless otherwise specified, just refers respectively to " parts by weight " or " weight % ".
Hereinafter, the evaluation method of the various medicines used in embodiment and comparative example, obtained material is shown in following.
Thermoplastic elastomer (TPE)：Styreneisobutylene-styrene block copolymer, Co., Ltd. Kaneka's
SIBSTAR 062T
Thermoplastic elastomer (TPE)：Styreneisobutylene-styrene block copolymer, Co., Ltd. Kaneka's
SIBSTAR 102T
Tackifying resin：The hydrogenated petroleum resin Alcon P-140 of Arakawa Chemical Industries, Ltd.
Thermal expansivity micro-capsule：The Advancell EM501 of Sekisui Chemical Co., Ltd
Thermal expansivity micro-capsule：Advancell P501E1 (masterbatch, micro-capsule containing ratio of Sekisui Chemical Co., Ltd
50 weight %)
Thermal expansivity micro-capsule：The Advancell EM403 of Sekisui Chemical Co., Ltd
Plasticizer：Paraffin series operation oil, the Diana Process Oil PW380 of Idemitsu Kosen Co., Ltd.
Thickness
Surveyed using dial thickness gauge Dial Thickness Gauge SM-114 (Teclock company systems)
It is fixed.
Density
Volume is calculated by the size for the sample for cutting into arbitrary dimension, thickness, weight divided by volume are calculated.
Expansion ratio
By the way that the density of unexpanded resin divided by the density of obtained foaming body are calculated.
ASKER E hardness
It is measured using ASKER E hardometers (macromolecule gauge company system).
Resilience modulus of elasticity
According to ISO4662, it is measured using resilience resiliometer EPH-50 types (macromolecule gauge company system).
Impact acceleration
Using padded coaming evaluation experimental device ACST-200 (Jitian's essence machine company system), to being punched into diameter 30mm's
Sample, utilizes the acceleration converter AS-500A (republicanism utility companies system) and data acquisition device F99- for being installed on counterweight
The impact acceleration when position that 6618 (republicanism utility companies systems) measure the counterweight from the height 100mm that make weight 8kg is fallen is (most
High acceleration).Impact acceleration is smaller, is evaluated as impact absorbency higher.
Aft-loaded airfoil
It is used as the protector of bodily protection, it is assumed that for each position of body, carries out using scissors, cuts stage property
Cut, using the punching of Thomson knife, whether assigned using zero × evaluation shape easy.In comparative example 1 and 2, shape is determined
For ellipse, accordingly, it is difficult to form the size bigger than its, aft-loaded airfoil is set to ×.
Embodiment 1
By (A) thermoplastic elastomer (TPE) shown in table 1, (C) tackifying resin, (B) thermal expansivity micro-capsule with the cooperation shown in table 1
Amount is mixed using Dual-arm kneader (Sen Shan manufacturing companies system, G types, capacity 50L) with 100~110 DEG C of design temperature
Refining, obtains expandable composition.The expandable composition is put into single axle extruding machine (Zhong Tian engineering companies system, screw diameter
60mm, L/D=16) hopper, heating melting is carried out in extruder with screw speed 48rpm.It is set as 160 using by temperature
DEG C T-shaped mould head extruded with die gap 6.0mm sheets, drawn with hauling speed 0.36m/min, obtain thermoplastic elastomehc
Property body extrusion foaming piece.
Embodiment 2
The thermoplastic elastomer (TPE) extrusion foaming piece obtained in embodiment 1 is heated to 170 DEG C using forcing press, added
Foam and obtain thermoplastic elastomer (TPE) extrusion foaming piece.
Embodiment 3
As (B) thermal expansivity micro-capsule, using " parts by weight of Advancell EM403 5 " replacement " Advancell EM501
3 parts by weight ", in addition, obtain thermoplastic elastomer (TPE) extrusion foaming piece similarly to Example 1.
Embodiment 4
(A) thermoplastic elastomer (TPE) shown in table 1, (D) plasticizer, (B) thermoplasticity micro-capsule are entered with the use level shown in table 1
Row blending, obtains expandable composition.The expandable composition is put into single axle extruding machine (Zhong Tian engineering companies system, screw rod
Diameter 60mm, L/D=16) hopper, heating melting is carried out in extruder with screw speed 30rpm.Set using by temperature
Extruded for 160 DEG C of T-shaped mould head with die gap 6.0mm sheets, drawn with hauling speed 0.36m/min, obtain heat
Thermoplastic elastic extrusion foaming piece.
Comparative example 1
By (A) thermoplastic elastomer (TPE) shown in table 1, (C) tackifying resin, (B) thermal expansivity micro-capsule with the cooperation shown in table 1
Amount is blended, and obtains expandable composition.The expandable composition is utilized into injection (mo(u)lding) machine " MD350S-IIIDP types "
(Yu Buxingchan Mechanology Inc. system, shut-off nozzle specification) is carried out after melting mixing with 200 DEG C of resin temperature, back pressure 15MPa,
The chamber for the elliptical shape with long side 170mm × short side 130mm being made up of stent and the But moving die that can be moved forward and backward
In the mould of room (clearance t 0=3.5mm), injection fillers are carried out in 100mm/ seconds with injection speed.After injection fillers terminate, with
The mode that gap turns into 7.0mm retreats But moving die, makes resin expanded in chamber.Foaming is cooled down 60 seconds after terminating, and obtains thermoplastic
Property elastomer foam-injection body.
Comparative example 2
(A) thermoplastic elastomer (TPE), (C) tackifying resin shown in table 1 is blended with the use level shown in table 1 and is made
Resin combination.By the resin combination using injection (mo(u)lding) machine " MD350S-IIIDP types " (Yu Buxingchan Mechanology Inc. system,
Shut-off nozzle specification) with 200 DEG C of resin temperature, back pressure 15MPa carry out melting mixing after, by stent and can advance and
The mould of the chamber (clearance t 0=3.5mm) for the elliptical shape with long side 170mm × short side 130mm that the But moving die of retrogressing is constituted
In tool, injection fillers are carried out in 100mm/ seconds with injection speed.Cooled down 60 seconds after end-of-fill, obtain thermoplastic elastomer (TPE) and be injected into
Type body.
Comparative example 3
Overlapping 3 " NP gels " (the Taica company systems, thickness 3mm) as foamable gel, obtain sample.
Using the sample obtained in embodiment 1~4, comparative example 1~3, by above-mentioned method to thickness, density, foaming
Multiplying power, ASKER E hardness, resilience modulus of elasticity, impact acceleration and aft-loaded airfoil are evaluated.Show the result in table 1.
[table 1]
According to embodiment 1~4, the result of comparative example 1~3, it is known that the thermoplastic elastomer (TPE) extrusion foaming of the present application
The impact absorbency and aft-loaded airfoil of piece are excellent.
Claims (6)
1. a kind of thermoplastic elastomer (TPE) extrusion foaming piece, it is characterised in that being will be swollen containing (A) thermoplastic elastomer (TPE) and (B) heat
The expandable composition of swollen property micro-capsule is carried out obtained from extrusion foaming, (A) thermoplastic elastomer (TPE) be by using isobutene as
The block for constituting the polymer blocks of monomer and being constituted using aromatic vinyl base system monomer as the polymer blocks for being constituted monomer is total to
Polymers.
2. thermoplastic elastomer (TPE) extrusion foaming piece according to claim 1, wherein, expandable composition further contains
(C) tackifying resin.
3. thermoplastic elastomer (TPE) extrusion foaming piece according to claim 1 or 2, wherein, expandable composition further contains
There is (D) plasticizer.
4. a kind of manufacture method of thermoplastic elastomer (TPE) extrusion foaming piece, it is characterised in that comprising (A) thermoplastic elastic will be contained
The process that the expandable composition of body and (B) thermal expansivity micro-capsule carries out extrusion foaming, (A) thermoplastic elastomer (TPE) be by with
Isobutene is to constitute the polymer blocks of monomer and constituted using aromatic vinyl base system monomer to be constituted the polymer blocks of monomer
Block copolymer.
5. a kind of absorbing body, it is characterised in that extruded by thermoplastic elastomer (TPE) according to any one of claims 1 to 3
Foamed sheet is constituted.
6. a kind of protector of bodily protection, it is characterised in that possess the absorbing body described in claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014248019 | 2014-12-08 | ||
| JP2014-248019 | 2014-12-08 | ||
| PCT/JP2015/083543 WO2016093091A1 (en) | 2014-12-08 | 2015-11-30 | Extruded thermoplastic elastomer foam sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107108947A true CN107108947A (en) | 2017-08-29 |
Family
ID=56107281
Family Applications (1)
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|---|---|---|---|
| CN201580066347.9A Pending CN107108947A (en) | 2014-12-08 | 2015-11-30 | Thermoplastic elastomer (TPE) extrusion foaming piece |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPWO2016093091A1 (en) |
| CN (1) | CN107108947A (en) |
| WO (1) | WO2016093091A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110128734A (en) * | 2019-06-11 | 2019-08-16 | 宁波邦泰汽车配件有限公司 | A kind of preparation process of compound TPE extrusion foaming piece |
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| CN107531929A (en) * | 2015-06-08 | 2018-01-02 | 株式会社钟化 | The manufacture method of thermoplastic elastomer foaming body |
| CN113861667A (en) | 2020-10-29 | 2021-12-31 | 舒莱思化学公司 | Thermoplastic elastomeric composition and its use as sole material |
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|---|---|
| WO2016093091A1 (en) | 2016-06-16 |
| JPWO2016093091A1 (en) | 2017-09-14 |
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