CN1946788A - Thermoplastic elastomer composition, formed article and sealing material having low hardness - Google Patents

Abstract

A first thermoplastic elastomer composition which comprises 100 parts by mass of the sum of 5 to 60 mass % of [A] an ethylene.alpha-olefin based copolymer having a limiting viscosity of 3.5 dl/g or more as measured in a decalin solvent at 135 DEG C, 1 to 20 mass % of [B] a polyolefin based resin and 30 to 94 mass % of [C] a mineral oil based softening agent (provided that the sum of [A], [B] and [C] is 100 mass %), and 0.1 to 50 parts by mass of a hydrogenated diene based polymer, wherein at least the above [A] an ethylene.alpha-olefin based copolymer and [B] a polyolefin based resin have been subjected to a dynamic heat treatment in the presence of a cross-linking agent; or a second thermoplastic elastomer composition obtained by substituting [A] component of the first thermoplastic elastomer composition with an oil-extended rubber consisting of 20 to 80 mass % of [A1] an ethylene.alpha-olefin based copolymer having a limiting viscosity of 3.5 dl/g or more as measured in a decalin solvent at 135 DEG C and 20 to 80 mass % of [C1] a mineral oil based softening agent (provided that the sum of [A1] and [C1] is 100 mass %). The above thermoplastic elastomer composition is excellent in processability, has a low hardness, is free from the bleeding of a softening agent such as a mineral oil, has softness, is excellent in rubbery elastic properties (rebound, compression set) and further can be recycled.

Description

Composition for thermoplastic elastomer, moulding product and sealing material having low hardness

Technical field

The present invention relates to composition for thermoplastic elastomer and use the moulding product of said composition, the sealing material of soft, more specifically, the present invention relates to forming process excellence, hardness low, have flexibility, caoutchouc elasticity (rebound resilience, compression set) are excellent, do not have mineral oil softener to ooze out composition for thermoplastic elastomer and moulding product, further relate to the sealing material having low hardness that the use composition for thermoplastic elastomer is made.

Background technology

The sealing class of using in the sealing material of usefulness such as office machine, automobile, material of construction etc. is very soft, and people attempt vulcanized rubber or sulfur foam rubber, polyurathamc or the composition for thermoplastic elastomer that can be used as the flexibility material are improved (with reference to patent documentation 1-3).It is open that composition for thermoplastic elastomer has in patent documentation 1 grade, but the composition of the document, and its flexibility is not enough, and if when adding mineral wet goods tenderizer etc., tenderizer can ooze out from the moulding product, problems such as caoutchouc elasticity reduction occur.

Vulcanized rubber or sulfur foam rubber, polyurathamc are meeting the demands aspect the characteristics such as flexibility, stopping property, but in recent years, consider that from the resource angle high recycle can not meet the demands.

Patent documentation 1: TOHKEMY 2002-201313 communique

Patent documentation 2: TOHKEMY 2002-251061 communique

Patent documentation 3: Japanese kokai publication hei 7-234579 communique

Summary of the invention

The object of the present invention is to provide forming process excellence, hardness are low, mineral wet goods tenderizer can not ooze out, have flexibility, caoutchouc elasticity (rebound resilience, compression set) the is excellent thermoplastic elastomer composition and the sealing material of moulding product and soft thereof.

The invention provides thermoplastic elastomer composition shown below and moulding product and sealing material having low hardness.

(1) composition for thermoplastic elastomer, said composition is with respect to the total of 100 mass parts [A], [B] and [C], contain [D] 0.1-50 mass parts hydrogenated diene polymer, wherein, described [A] for 5-60 quality % in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 3.5dl/g or above ethylene ' alpha '-olefin based copolymer, [B] is 1-20 quality % polyolefin-based resins, and [C] is 30-94 quality % mineral oil softener (with the 100 quality % that add up to of [A], [B] and [C]);

At least above-mentioned [A] ethylene ' alpha '-olefin based copolymer and above-mentioned [B] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent.

(2) composition for thermoplastic elastomer, said composition is with respect to the total of 100 mass parts [X], [B1] and [C2], contain [D1] 0.1-50 mass parts hydrogenated diene polymer, wherein said [X] is 5-60 quality % oil-extended rubber, it is 3.5dl/g or above ethylene ' alpha '-olefin based copolymer and [C1] 20-80 quality % mineral oil softener ([A1] and [C1] add up to 100 quality %) in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down that this oil-extended rubber contains [A1] 20-80 quality %; [B1] is 1-20 quality % polyolefin-based resins; And [C2] is 30-94 quality % mineral oil softener ([X], [B1] and [C2] add up to 100 quality %);

At least above-mentioned [A1] ethylene ' alpha '-olefin based copolymer and above-mentioned [B1] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent.

(3) composition for thermoplastic elastomer of above-mentioned (1) or (2), wherein, above-mentioned hydrogenated diene polymer [D] is following at least a for being selected from: contain the polymkeric substance of the monomeric unit that forms by conjugated diene compound hydride, contain the monomeric unit that forms by conjugated diene compound and the hydride of the polymkeric substance of the monomeric unit that forms by vinyl aromatic compounds.

(4) each composition for thermoplastic elastomer in above-mentioned (1)-(3), Shore E (Duro E) hardness that said composition is measured according to JISK6253 be 80 or below.

(5) each composition for thermoplastic elastomer in above-mentioned (1)-(4), wherein, with comprise ethylene monomer unit and by whole monomeric units of the monomeric unit of alpha-olefin compound formation add up to 100mol% the time, the content that constitutes the ethylene monomer unit of above-mentioned ethylene ' alpha '-olefin based copolymer [A] and [A1] is 35-95mol%.

(6) each composition for thermoplastic elastomer in above-mentioned (1)-(5), wherein, above-mentioned mineral oil softener [C], [C1] and [C2] are paraffin series mineral oil.

(7) each composition for thermoplastic elastomer in above-mentioned (1)-(6), wherein, above-mentioned linking agent is for being selected from 1, two (t-butyl peroxy sec.-propyl) benzene, 2 of 3-, 5-dimethyl-2,5-two (t-butyl peroxy) hexin-3,2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, α, the organo-peroxide of α-two (t-butyl peroxy) diisopropyl benzene, dicumyl peroxide and the peroxidation 2-tertiary butyl.

(8) each composition for thermoplastic elastomer in above-mentioned (1)-(7), wherein, the ethylene ' alpha '-olefin based copolymer in this composition for thermoplastic elastomer the hexanaphthene under 23 ℃ insoluble be divided into 60 quality % or more than.

(9) moulding product, these moulding product contain in above-mentioned (1)-(8) each composition for thermoplastic elastomer.

(10) sealing material having low hardness, each composition for thermoplastic elastomer is made in these material use above-mentioned (1)-(8).

(11) sealing material having low hardness of above-mentioned (10), the Xiao A hardness that this material is measured according to JIS K6253 be 40 or below.

(12) sealing material having low hardness in above-mentioned (10) or (11), this material form be selected from O type round, sheet and bar-shaped in any one shape.

(13) container, this container is a component parts with each sealing material having low hardness in above-mentioned (10)-(12).

(14) container, this container are to be formed by the complex body that sealing and chest portion constitute by the injection molding method moulding, and wherein said sealing contains in above-mentioned (10)-(12) each sealing material having low hardness.

(15) container of above-mentioned (14), wherein, above-mentioned chest portion contains thermoplastic resin and/or composition for thermoplastic elastomer, reusable edible.

(16) toner Cartridge, this toner Cartridge is a component parts with each sealing material having low hardness in above-mentioned (10)-(12).

Composition for thermoplastic elastomer of the present invention is with respect to the total of 100 mass parts following [A], [B] and [C], contain 0.1-50 mass parts [D] hydrogenated diene polymer, described [A] for 5-60 quality % in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 3.5dl/g or above ethylene ' alpha '-olefin based copolymer, [B] is 1-20 quality % polyolefin-based resins, and [C] is 30-94 quality % mineral oil softener ([A], [B] and [C] add up to 100 quality %); At least above-mentioned [A] ethylene ' alpha '-olefin based copolymer and above-mentioned [B] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent; Thus, the forming process excellence of injection moulding, extrusion molding, slush molding, compressed moulding, vacuum forming, laminated into type, calendering formation etc., hardness is low, and mineral oil softener can not ooze out, have flexibility, caoutchouc elasticity (rebound resilience, compression set) excellence.

Another composition for thermoplastic elastomer of the present invention is with respect to the total of 100 mass parts following [X], [B1] and [C2], contain 0.1-50 mass parts [D1] hydrogenated diene polymer, wherein said [X] is 5-60 quality % oil-extended rubber, this oil-extended rubber contain [A1] 20-80 quality % in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 3.5dl/g or above ethylene ' alpha '-olefin based copolymer, [C1] 20-80 quality % mineral oil softener ([A1] and [C1] add up to 100 quality %); [B1] is 1-20 quality % polyolefin-based resins; [C2] is 30-94 quality % mineral oil softener ([X], [B1] and [C2] add up to 100 quality %); At least above-mentioned [A1] ethylene ' alpha '-olefin based copolymer and above-mentioned [B1] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent, thus, the forming process excellence of injection moulding, extrusion molding, slush molding, compressed moulding, vacuum forming, laminated into type, calendering formation etc., hardness is low, mineral oil softener can not ooze out, have flexibility, caoutchouc elasticity (rebound resilience, compression set) excellence.

Above-mentioned hydrogenated diene polymer [D] is following when at least a for being selected from, its Shore E hardness by JISK6253 regulation can reach 80 or below, can obtain the softish composition: contain monomeric unit that the hydride and containing of the polymkeric substance of the monomeric unit that is formed by conjugated diene compound forms by conjugated diene compound and the hydride of the polymkeric substance of the monomeric unit that forms by vinyl aromatic compounds.

In this composition for thermoplastic elastomer, the hexanaphthene of ethylene ' alpha '-olefin based copolymer under 23 ℃ be insoluble to be divided into 60 quality % or when above, caoutchouc elasticity and physical strength excellence.

Moulding product hardness of the present invention is low, and mineral oil softener does not ooze out, has flexibility, caoutchouc elasticity (rebound resilience, compression set) excellence.And sealing material of the present invention is made of composition for thermoplastic elastomer, so reusable edible, and is very excellent aspect the saving resource.

Use this sealing material having low hardness as component parts, can provide and one-body moldedly at short notice to contain by injection moulding that the sealing of sealing material and chest portion, operation aspect are laborsaving, the container of recycle excellence.

The accompanying drawing summary

Fig. 1 is that expression is with the photo of sealing material having low hardness of the present invention as the container of the band sealing of component parts.

Fig. 2 is the photo that expression is separated into the container of the band sealing of Fig. 1 the state of sealing and chest portion.

Fig. 3 is that expression is leaked, the explanatory view of drop test.

Nomenclature

1 ... sealing, 2 ... chest portion, 10 ... container, 11 ... lid, 12 ... two tail folders, 13 ... fluting board, 14 ... sealing member, 15 ... water

The best mode that carries out an invention

Below describe the present invention in detail.

The composition for thermoplastic elastomer of the 1st scheme of the present invention is with respect to the total of 100 mass parts [A], [B] and [C], contain 0.1-50 mass parts [D] hydrogenated diene polymer, wherein said [A] for 5-60 quality % in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 3.5dl/g or above ethylene ' alpha '-olefin based copolymer, [B] is 1-20 quality % polyolefin-based resins, and [C] is 30-94 quality % mineral oil softener ([A], [B] and [C] add up to 100 quality %); At least above-mentioned [A] ethylene ' alpha '-olefin based copolymer and above-mentioned [B] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent.

The composition for thermoplastic elastomer of the 2nd scheme of the present invention is with respect to the total of 100 mass parts [X], [B1] and [C2], contain 0.1-50 mass parts [D1] hydrogenated diene polymer, wherein said [X] is 5-60 quality % oil-extended rubber, and this oil-extended rubber contains 20-80 quality %[A1] in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 3.5dl/g or above ethylene ' alpha '-olefin based copolymer and 20-80 quality %[C1] mineral oil softener ([A1] and [C1] add up to 100 quality %); [B1] is 1-20 quality % polyolefin-based resins; [C2] is 30-94 quality % mineral oil softener ([X], [B1] and [C2] add up to 100 quality %); At least above-mentioned [A1] ethylene ' alpha '-olefin based copolymer and above-mentioned [B1] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent.

Below each integrant is further specified.

1. ethylene ' alpha '-olefin based copolymer ([A] and [A1])

This ethylene ' alpha '-olefin based copolymer (being designated hereinafter simply as " EAO based copolymer ") be contain ethylene monomer unit (a1) and by except that ethene, carbonatoms is 3 or the multipolymer of the monomeric unit (a2) that forms of above alpha-olefin.

When being 100mol% with the total amount of the monomeric unit that constitutes the EAO multipolymer, the formation amount of above-mentioned ethylene monomer unit (a1) is preferably 35-95mol%, more preferably 40-90mol%, preferred especially 45-85mol%.The formation amount of ethylene monomer unit (a1) is too much, and then the flexibility of gained composition for thermoplastic elastomer has insufficient tendency, and very few, and then physical strength may be not enough.

The preferred carbonatoms of alpha-olefin that forms above-mentioned monomeric unit (a2) be 3 or more than, have: propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-methyl-1-butene alkene, 2-methyl-2-butene, 3-methyl butene, 1-hexene, 4-methyl-1-pentene, 3-Methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecylene etc.They can be used alone or with two kinds or above being used in combination.Wherein, further preferred carbonatoms is the alpha-olefin of 3-10, by using above-mentioned alpha-olefin, and when above-mentioned EAO multipolymer contains other monomeric unit, can be easily and other monomeric unit copolymerization.Particularly preferred alpha-olefin is propylene, 1-butylene, 1-hexene and 1-octene, more preferably propylene and 1-butylene.

When being 100mol% with the total amount of the monomeric unit that constitutes the EAO multipolymer, the preferred 5-65mol% of content of above-mentioned monomeric unit (a2), more preferably 10-45mol%, preferred especially 15-40mol%.The formation amount of monomeric unit (a2) is very few, and then the gained composition for thermoplastic elastomer may not show desirable caoutchouc elasticity.And too much, then the weather resistance of resulting composition may reduce.

Above-mentioned EAO multipolymer can be by above-mentioned monomeric unit (a1) and the copolymer that (a2) constitutes, and also can be by these monomeric units (a1) and (a2) and the polymkeric substance (terpolymer, tetrapolymer etc.) of other monomeric unit (a3) formation.This other monomeric unit can be enumerated the monomeric unit of non-conjugated diene compound etc.

The non-conjugated diene compound can enumerate 1, the 4-hexadiene, 1, the 5-hexadiene, 1, straight chain non-annularity diolefins such as 6-hexadiene, the 5-methyl isophthalic acid, the 4-hexadiene, 3,7-dimethyl-1, the 6-octadiene, 5,7-dimethyl-octa-1, the 6-diene, 3,7-dimethyl-1, the 7-octadiene, 7-methyl suffering-1, the 6-diene, side chain non-annularity diolefins such as dihydromyrcene, the tetrahydro-indenes, the methyltetrahydro indenes, Dicyclopentadiene (DCPD), dicyclo [2.2.1]-heptan-2, the 5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornylene, 5-isopropylidene-2-norbornylene, 5-cyclohexylidene-2-norbornylene, ester ring type diolefins such as 5-vinyl-2-norbornylene etc.They can be used alone or with two kinds or above being used in combination.Wherein, preferred 1,4-hexadiene, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene etc.

When use contains the EAO multipolymer of above-mentioned monomeric unit (a3), be 100mol% with the total amount of the monomeric unit that constitutes the EAO multipolymer, the preferred 10mol% of formation amount of then above-mentioned monomeric unit (a3) or following, more preferably 1-8mol%.Above-mentioned monomeric unit (a3) formation amount is too much, and then the weather resistance of resulting composition may descend.

The limiting viscosity of above-mentioned EAO based copolymer (in the naphthalane solvent, 135 ℃ measure down) be 3.5dl/g or more than, preferably 3.8dl/g or more than, more preferably 4.0-7.0dl/g.This limiting viscosity is lower than 3.5dl/g, and then mineral oil softener oozes out from the gained composition for thermoplastic elastomer, and caoutchouc elasticity may reduce.

Above-mentioned EAO based copolymer can use the part of the hydrogen atom in the molecule to be substituted by the halo multipolymer of halogen atoms such as chlorine atom, bromine atoms.

Can also use in the presence of these multipolymers, with the derivative (maleic anhydride, maleimide, dimethyl maleate etc.) of vinylchlorid, vinyl-acetic ester, (methyl) vinylformic acid, (methyl) acrylic acid derivative [(methyl) methyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylamide etc.], toxilic acid, toxilic acid, conjugated diene compound polymerization of unsaturated monomers such as (divinyl, isoprene, chloroprenes etc.) and the graftomer that obtains.

Above-mentioned EAO based copolymer can use separately a kind of or with two kinds or above being used in combination.

Contained EAO based copolymer [A] and polyolefin-based resins [B] and mineral oil softener [C] adds up to 100 quality % in the composition for thermoplastic elastomer with the present invention's the 1st scheme, the content of this EAO based copolymer [A] is 5-60 quality %, preferred 10-58 quality %, more preferably 15-55 quality %.Above-mentioned EAO based copolymer [A] content is too much, and then the flexibility of gained composition for thermoplastic elastomer may be not enough, and very few, then mineral oil softener [C] may ooze out.

The ethylene ' alpha '-olefin based copolymer [A1] composition for thermoplastic elastomer, that constitute oil-extended rubber [X] that is used to prepare the 2nd scheme of the present invention can directly use the multipolymer of above-mentioned explanation.The 100 quality % that add up to the EAO based copolymer [A1] that constitutes this oil-extended rubber [X] and mineral oil softener [C1], then their ratio is respectively 20-80 quality % and 20-80 quality %, preferred 25-75 quality % and 25-75 quality %, more preferably 30-70 quality % and 30-70 quality %.

In composition for thermoplastic elastomer with the 2nd scheme of the present invention contained oil-extended rubber [X] and polyolefin-based resins [B] and mineral oil softener [C2] add up to 100 quality % the time, the amount of this oil-extended rubber [X] is 5-60 quality %, preferred 10-58 quality %, more preferably 15-55 quality %.The content of above-mentioned oil-extended rubber [X] is too much, and then the flexibility of gained composition for thermoplastic elastomer may be not enough, and very few, then mineral oil softener [C1] and/or [C2] may ooze out.

Above-mentioned EAO based copolymer ([A] or [A1]) for example can be by containing Ziegler-Natta catalyst, soluble vanadium compound, organo-aluminium compound and containing in the presence of the catalyzer of solvent, with ethene, alpha-olefin and non-conjugated diene and supply with hydrogen carries out usefulness mesolow methods such as polymeric method as molecular weight regulator polymerization process as required and obtain.This polymerization can be undertaken by vapor phase process (fluidized-bed or agitated bed), liquid phase method (slurry process or solution method).

Above-mentioned soluble vanadium compound for example preferably uses VOCl ₃And VCl ₄At least a with alcohol reaction product.Alcohol can use methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, nonylcarbinol and n-dodecane alcohol etc., wherein preferably uses the alcohol of carbonatoms as 3-8.

Above-mentioned organo-aluminium compound for example has: the reaction product methylaluminoxane of triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, monochlor(in)ate diethyl aluminum, monochlor(in)ate diisobutyl aluminum, ethyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride, ethylaluminium dichloride, dichloride butyl aluminium, trimethyl aluminium and water etc.Wherein especially preferably use ethyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride, the mixture of ethyl sesquialter aluminum chloride and triisobutyl aluminium, the mixture of triisobutyl aluminium and butyl sesquialter aluminum chloride.Above-mentioned solvent preferably uses hydrocarbon, wherein especially preferably uses Skellysolve A, normal hexane, normal heptane, octane, octane-iso, hexanaphthene.They can be used alone or with two kinds or above being used in combination.

Non-oil-filled ethylene ' alpha '-olefin based copolymer [A] and can be any form of big bag, chip, particle, powder (the pulverizing product that comprise big bag) as the form of the oil-filled ethylene ' alpha '-olefin based copolymer of oil-extended rubber [X].Also non-oil-filled ethylene ' alpha '-olefin based copolymer [A] and oil-filled ethylene ' alpha '-olefin based copolymer [X] can be used in combination.

2. polyolefin-based resins ([B] and [B1])

Said polyolefins is a resin so long as contain the monomeric unit of one or more alpha-olefins and add up to and surpass 50mol% and get final product, and can be homopolymer, also can be multipolymer.During for multipolymer, can be the multipolymer between the alpha-olefin, also can be alpha-olefin with can with other monomeric multipolymer of this alpha-olefin copolymer.In addition, this polyolefin-based resins can use crystalline resin and/or amorphous resin.

For said polyolefins is resin, when using crystalline polyolefin to be resin (B-a), about its crystallinity, the degree of crystallinity that records by X-ray diffraction be 50% or more than, preferred 53% or more than, more preferably 55% or more than.This degree of crystallinity and density have confidential relation, and for example, if polypropylene, the density of alpha type crystal (monoclinic form) is 0.936g/cm ³, the density of smectic type crystallite (accurate hexagonal structure) is 0.886g/cm ³, the density of amorphous (atactic) composition is 0.850g/cm ³If poly-1-butylene, then the density of isotaxy crystalline component is 0.91g/cm ³, the density of amorphous (atactic) composition is 0.87g/cm ³

Therefore, above-mentioned crystalline polyolefin is that the density of resin (B-a) is preferably 0.89g/cm ³Or more than, more preferably 0.90-0.94g/cm ³If, in this scope, then can make degree of crystallinity be 50% or more than, if above-mentioned crystalline polyolefin is the degree of crystallinity of resin (B-a) be lower than 50% and density be lower than 0.89g/cm ³, then the thermotolerance of gained composition for thermoplastic elastomer, intensity etc. have the tendency of decline.

The preferred alpha-olefin that forms above-mentioned crystalline polyolefin and be resin (B-a) is that carbonatoms is 2 or above alpha-olefin, and more preferably carbonatoms is 2-12.Wherein preferred propylene and 1-butylene.

To constitute above-mentioned crystalline polyolefin is that the total amount of the monomeric unit of resin (B-a) is when being 100mol%, the content of monomeric unit (b1) that constitutes this crystalline polyolefin and be the alpha-olefin of resin (B-a) be preferably 80mol% or more than, more preferably 90-100mol%.

When above-mentioned crystalline polyolefin was a resin (B-a) for multipolymer, this multipolymer can be any form of segmented copolymer or random copolymers.For making the segmented copolymer of above-mentioned degree of crystallinity, be 100mol% with the monomeric unit total amount that constitutes segmented copolymer, the unitary total amount of formation of then removing outside the 'alpha '-olefin monomers unit (b1) is preferably 40mol% or following, more preferably 20mol% or following.Above-mentioned segmented copolymer can obtain by the living polymerization that uses Ziegler-Natta catalyst.

For making the random copolymers of above-mentioned degree of crystallinity, be 100mol% with the monomeric unit total amount that constitutes random copolymers, then the unitary total amount of formation except that the monomeric unit (b1) of alpha-olefin is preferably 15mol% or following, more preferably 10mol% or following.

Above-mentioned random copolymers for example can be in the presence of the catalyst component that contains Ziegler-Natta catalyst, soluble vanadium compound, organo-aluminium compound and solvent, by polymerizations such as alpha-olefin are obtained.Polymerization process has mesolow method etc., can be undertaken by vapor phase process (fluidized-bed or agitated bed), liquid phase method (slurry process or solution method) etc.During polymerization, can use hydrogen equimolecular quantity conditioning agent as required.

Above-mentioned soluble vanadium compound preferably uses VOCl ₃And/or VCl ₄Reaction product with alcohol.Alcohol has: methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, n-hexyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, nonylcarbinol and n-dodecane alcohol etc., wherein preferred carbonatoms is the alcohol of 3-8.

Above-mentioned organo-aluminium compound for example has: the reaction product methylaluminoxane of triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, monochlor(in)ate diethyl aluminum, monochlor(in)ate diisobutyl aluminum, ethyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride, ethylaluminium dichloride, dichloride butyl aluminium, trimethyl aluminium and water etc.Wherein, preferred ethyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride, the mixture of the mixture of ethyl sesquialter aluminum chloride and triisobutyl aluminium, triisobutyl aluminium and butyl sesquialter aluminum chloride.

Above-mentioned solvent preferred hydrocarbons, preferred especially Skellysolve A, normal hexane, normal heptane, octane, octane-iso, hexanaphthene.They can be used alone or with two kinds or above being used in combination.

Above-mentioned crystalline polyolefin be the fusing point of resin (B-a), promptly the maximum peak temperature by determine with dsc method be preferably 100 ℃ or more than, more preferably 120 ℃ or more than.This fusing point is lower than 100 ℃, and the tendency that is difficult to bring into play sufficient thermotolerance and intensity is then arranged.

The melt flow rate (MFR) of above-mentioned crystalline polyolefin resin (B-a) (230 ℃ of temperature, load 2.16kg) (being designated hereinafter simply as " MFR ") is preferably 0.1-1, and 000g/10 minute, more preferably 0.5-500g/10 minute, further preferred 1-100g/10 minute.This MFR is lower than 0.1g/10 minute, then the mixing processibility of feedstock composition, extrude deficiencies such as processibility.And surpass 1000g/10 minute, then the intensity of gained composition for thermoplastic elastomer has the tendency of decline.

Therefore, above-mentioned crystalline polyolefin be the preferred degree of crystallinity of resin (B-a) be 50% or more than, density is 0.89g/cm ³Or more than, the content of ethylene monomer unit is 20mol% or following, fusing point be 100 ℃ or more than, and MFR is 0.1-100g/10 minute, especially preferably uses fusing point to be 140-170 ℃ the polypropylene and/or the multipolymer of propylene and ethene.

Above-mentioned crystalline polyolefin is that resin (B-a) can be used alone or with two kinds or above being used in combination.

Using noncrystalline polyolefin is that resin (B-b) (hereinafter referred to as " amorphous polyolefin is resin (B-b) ") is when being resin as said polyolefins, the degree of crystallinity that its crystallinity is measured by X-ray diffraction is for being lower than 50%, preferred 30% or below, more preferably 20% or below.From density, above-mentioned amorphous polyolefin is that the density of resin (B2) is preferably 0.85-0.89g/cm ³, more preferably 0.85-0.88g/cm ³

The preferred alpha-olefin that forms above-mentioned amorphous polyolefin and be resin (B-b) be carbonatoms be 3 or more than, more preferably 3-12.

To constitute above-mentioned amorphous polyolefin is that the total amount of the monomeric unit of resin (B-b) is 100mol%, the content of monomeric unit (b2) that then constitutes this amorphous polyolefin and be the alpha-olefin of resin (B-b) be preferably 60mol% or more than.

Above-mentioned amorphous polyolefin is that resin (B-b) has: homopolymer such as atactic polypropylene(APP), the poly-1-butylene of atactic, surpass the propylene of 50mol% and the multipolymer of other alpha-olefin (ethene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene etc.), surpass the 1-butylene of 50mol% and the multipolymer of other alpha-olefin (ethene, propylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene etc.) etc.

The poly-1-butylene of atactic polypropylene(APP) and atactic can obtain by the polymerization of using Bis(cyclopentadienyl)zirconium compound-methylaluminoxane catalyzer.

Above-mentioned atactic polypropylene(APP) can obtain with the form of the polyacrylic by product that exemplified in the above-mentioned crystalline polyolefin based polymer (B-a).

When above-mentioned amorphous polyolefin was a resin (B-b) for multipolymer, this multipolymer can be any form of segmented copolymer and random copolymers.If be segmented copolymer, the monomeric unit (b-2) that then surpasses the alpha-olefin of 50mol% formation must be with the combination of atactic structure.This segmented copolymer can obtain by the living polymerization that uses Ziegler-Natta catalyst.Random copolymers can be by the method acquisition same with above-mentioned crystalline polyolefin based polymer (B-a).

When above-mentioned amorphous polyolefin is a resin (B-b) for the multipolymer of carbonatoms 3 or above alpha-olefin and ethene, if to constitute this amorphous polyolefin is that the total amount of the monomeric unit of resin (B-b) is 100mol%, then the content of the monomeric unit of above-mentioned alpha-olefin (b2) is preferably 60-100mol%.

Above-mentioned amorphous polyolefin is that resin (B-b) can be enumerated atactic polypropylene(APP), contain above the propylene monomer units of 50mol% and the multipolymer of ethylene monomer unit, is preferably the multipolymer of propylene and 1-butylene especially.

The above-mentioned amorphous polyolefin polystyrene conversion number-average molecular weight Mn that to be resin (B-b) measure by GPC is preferably 1,000-20,000, more preferably 1,500-15,000.

Above-mentioned amorphous polyolefin is that resin (B-b) can be used alone or with two kinds or above being used in combination.

Said polyolefins be resin can to use above-mentioned crystalline polyolefin respectively separately be that resin (B-a) and amorphous polyolefin are resin (B-b), also can they be used in combination according to purpose, purposes etc.

The 100 quality % that add up to EAO based copolymer [A], polyolefin-based resins [B], mineral oil softener [C], the amount of contained polyolefin-based resins [B] is 1-20 quality % in the composition for thermoplastic elastomer of the 1st scheme then of the present invention, preferred 3-18 quality %, more preferably 5-15 quality %.Said polyolefins is that the content of resin [B] is too much, and then the flexibility of gained composition for thermoplastic elastomer has insufficient tendency, and is very few, and then mixing processibility has the tendency of reduction.

With oil-extended rubber [X], polyolefin-based resins [B1], mineral oil softener [C2] add up to 100 quality % the time, the amount of contained polyolefin-based resins [B1] is 1-20 quality % in the composition for thermoplastic elastomer of the 2nd scheme of the present invention, preferred 3-18 quality %, more preferably 5-15 quality %.Said polyolefins is that the amount of resin [B1] is too much, and then the flexibility of gained composition for thermoplastic elastomer has not enough tendency, and is very few, and then mixing processibility has the tendency of reduction.

3. mineral oil softener ([C], [C1] and [C2])

This mineral oil softener is so long as get final product of using in the rubber item etc. is not particularly limited the mineral oil that has paraffin series, naphthene series, aromatics to be in the past.

The softener of rubber that comprises mineral oil and be hydrocarbon is the three's of aromatic ring, naphthenic ring and paraffin chain mixture normally.The carbonatoms of paraffin chain accounts for 50% in total carbon atom number or the above paraffin series mineral oil that is classified as, what the carbonatoms of naphthenic ring accounted for 30-45% in the total carbon atom number is classified as naphthene series mineral oil, and the carbonatoms of aromatic ring accounts for 30% in the total carbon atom number or the above aromatics that is classified as is mineral oil.

The mineral oil of above-mentioned paraffin series, naphthene series, aromatics system also can be used in combination them, can also be with their independent respectively uses or with two kinds or above being used in combination.Wherein, for any one of [C], [C1] and [C2], all preferred paraffin series mineral oil, preferred especially hydrowax is a mineral oil.The example of paraffin series mineral oil has: " the Diana Process OilPW90 " that the emerging product of bright dipping society makes, " Diana Process Oil PW380 " etc.

Above-mentioned mineral oil softener is preferably 300-2 by the polystyrene conversion weight-average molecular weight Mw that GPC measures, and 000, more preferably 500-1,500.Kinematic viscosity under 40 ℃ is preferably 20-800cSt, more preferably 50-600cSt.Pour point is preferably-40 to 0 ℃, more preferably-30 to 0 ℃.

Low-molecular-weight hydrocarbon such as above-mentioned mineral oil softener can be with polybutene, polyhutadiene system etc. are used in combination.

Total amount with EAO based copolymer [A], polyolefin-based resins [B], mineral oil softener [C] is 100 quality %, the amount of contained mineral oil softener [C] is 30-94 quality % in the composition for thermoplastic elastomer of the 1st scheme then of the present invention, preferred 32-87 quality %, more preferably 35-80 quality %.The content of above-mentioned mineral oil softener [C] is too much, and then the intensity of gained composition for thermoplastic elastomer has insufficient tendency, also has the situation that mineral oil softener [C] oozes out.Very few, then the flexibility of gained thermoplastic elastic composition has insufficient tendency.

Contained mineral oil softener [C2] can be and the identical tenderizer of mineral oil softener [C1] that constitutes oil-extended rubber [X] in the composition for thermoplastic elastomer of the 2nd scheme of the present invention, also can be different sorts.With the 100 quality % that add up to of oil-extended rubber [X], polyolefin-based resins [B], mineral oil softener [C2], the content of this mineral oil softener [C2] is 30-94 quality %, preferred 32-87 quality %, more preferably 35-80 quality %.The content of above-mentioned mineral oil softener [C2] is too much, and then the intensity of gained composition for thermoplastic elastomer has insufficient tendency, and mineral oil softener [C2] may ooze out.Very few, then the flexibility of gained composition for thermoplastic elastomer has insufficient tendency.

In the composition for thermoplastic elastomer of the 2nd scheme of the present invention in the composition for thermoplastic elastomer of the total amount of contained mineral oil softener than the 1st scheme the total amount of contained mineral oil softener lack.This is owing in the 2nd scheme, contained mineral oil softener [C1] in the oil-extended rubber [X].

4. hydrogenated diene polymer ([D] and [D1])

Above-mentioned hydrogenated diene polymer is so long as contain the hydride of the diene polymer of the monomeric unit that is formed by conjugated diene compound and get final product, be not particularly limited, its example has, and: hydride, (II) that (I) only contains (being total to) polymkeric substance of the monomeric unit that is formed by conjugated diene compound contains the monomeric unit that formed by conjugated diene compound and by hydride of polymkeric substance of the monomeric unit that can form with this conjugated diene compound polymeric compounds (for example vinyl aromatic compounds etc.) etc. etc.

It is a kind of separately that above-mentioned hydrogenated diene polymer can be that above-mentioned (I), above-mentioned (II) wait under each situation, also can be with two kinds or above combination.It can also be the combination of above-mentioned (I) and above-mentioned (II).This hydrogenated diene polymer can be crosslinked in composition for thermoplastic elastomer of the present invention, also can be not crosslinked.

Above-mentioned (I) has hydrogenated butadiene segmented copolymer etc.

Above-mentioned (II) has: (i) contain the polymer segment that formed by vinyl aromatic compounds and the segmented copolymer (for example hydrogenated styrene butadiene block copolymer, hydrogenated styrene isoprene block copolymer, hydrogenated styrene butadiene-isoprene segmented copolymer etc.) of the polymer segment that formed by conjugated diene compound; The random copolymers segmental segmented copolymer that (ii) contains the polymer segment that forms by vinyl aromatic compounds, forms by conjugated diolefine and vinyl aromatic compounds; The segmented copolymer of the multipolymer segment that (iii) contains the polymer segment that forms by conjugated diene compound, forms by conjugated diene compound and vinyl aromatic compounds; (iv) contain the polymer segment that forms by conjugated diene compound, form and be cumulative alternation segmental segmented copolymer by the monomeric unit that vinyl aromatic compounds forms by vinyl aromatic compounds and conjugated diene compound; (v) contain the random copolymers segment that forms by conjugated diene compound and vinyl aromatic compounds, form and be cumulative alternation segmental segmented copolymer etc. by the monomeric unit that vinyl aromatic compounds forms by vinyl aromatic compounds and conjugated diene compound.

Conjugated diene compound has: 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene etc.They can be used alone or with two kinds or above being used in combination.Wherein preferred 1,3-butadiene, isoprene, 1,3-pentadiene.

Vinyl aromatic compounds has: vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, to ethyl styrene, Vinylstyrene, 1,1-diphenyl benzene ethene, vinyl naphthalene, vinyl anthracene, N, the N-diethyl-to amino-ethyl vinylbenzene, vinyl pyridine etc.They can be used alone or with two kinds or above being used in combination.Wherein, optimization styrene.

Above-mentioned hydrogenated diene polymer can use the part of the hydrogen atom in the molecule to be substituted by the halo hydrogenated diene polymer of halogen atoms such as chlorine atom, bromine atoms.

Can also use in the presence of these polymkeric substance, with the derivative (maleic anhydride, maleimide, dimethyl maleate etc.) of vinylchlorid, vinyl-acetic ester, (methyl) vinylformic acid, (methyl) acrylic acid derivative [(methyl) methyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylamide etc.], toxilic acid, toxilic acid, conjugated diene compound polymerization of unsaturated monomers such as (divinyl, isoprene, chloroprenes etc.) and the graftomer that obtains.

The hydrogenation ratio of above-mentioned hydrogenated diene polymer be preferably 70% or more than, more preferably 90% or more than, further preferred 95% or more than.Should " hydrogenation ratio " be meant with respect to the conjugated diene unit side chain of the diene polymer before the formation hydrogenation or the number of the ethylenic unsaturated bond in the main chain, the ratio of the side chain after the hydrogenation or the number of the ethylenic unsaturated bond in the main chain.

Above-mentioned hydrogenated diene polymer can use uncrosslinked polymkeric substance, also can use crosslinked polymkeric substance.They can also be used in combination.In addition, crosslinked hydrogenated diene polymer can be by known method acquisitions in the past such as methods described later.

Above-mentioned hydrogenated diene polymer when making 5 quality % toluene solutions, the soltion viscosity under 30 ℃ be preferably 5mPas or more than, more preferably 10mPas or more than.This toluene solution viscosity is the substituted index of molecular weight, is lower than 5mPas, and then the physical strength of gained composition for thermoplastic elastomer has the tendency of decline.

Above-mentioned hydrogenated diene polymer is preferably hydrogenated styrene butadiene block copolymer, hydrogenated styrene butadiene-isoprene segmented copolymer.

Above-mentioned hydrogenated diene polymer can easily prepare by known method, for example can adopt the disclosed method of Japanese kokai publication hei 2-36244 communique, promptly, with conjugated diene compound and the vinyl aromatic compounds method by active anionic polymerization etc., polymkeric substance before the preparation hydrogenation, in the presence of catalyzer, this hydrogenation prepolymer is carried out hydrogenant method etc. then.

During active anionic polymerization, use initiators such as organolithium compound, organosiloxane compound usually.This organolithium compound has: lithium alkylides such as n-Butyl Lithium, s-butyl lithium, tert-butyl lithium, they all preferably use.In addition, employed solvent has during polymerization: hydrocarbon system solvents such as hexane, heptane, methylcyclopentane, hexanaphthene, benzene,toluene,xylene, 2-methyl butene-1,2-methyl butene-2.The mode of active anionic polymerization can be an intermittent type, also continous way, and polymerization temperature is generally 0-120 ℃ scope.

During active anionic polymerization, the alcoholate of ether, tertiary amine, basic metal (sodium, potassium etc.), phenates, sulfonate etc. can be used in combination.Its kind, usage quantity etc. can be suitably selected, the conjugated diene unit number that has ethylenic unsaturated bond in the gained hydrogenated block copolymer on the side chain and whole ratios of conjugated diene unit numbers can be easily controlled like this.

And, before active anionic polymerization is about to stop, add polyfunctional coupling agent or linking agent, make it carry out linked reaction or crosslinked, the molecular weight of polymkeric substance is increased.

Coupling agent has: Vinylstyrene, 1,2, the 4-trivinylbenzene, epoxidation 1, the 2-polyhutadiene, epoxidised soybean oil, epoxy linseed oil, benzene-1,2, the 4-triisocyanate, oxalic acid diethyl ester, diethyl malonate, diethylene adipate, Octyl adipate, dimethyl phthalate, diethyl phthalate, diethyl terephthalate, diethyl carbonate, 1,1,2, the 2-tetrachloroethane, 1, two (trichloromethyl) benzene of 4-, trichlorosilane, METHYL TRICHLORO SILANE, butyl trichlorosilane, tetrachloro silicane, (dichloromethyl) trichlorosilane, hexachloro-silane, tetraethoxysilane, tin tetrachloride, 1,3-two chloro-2-acetone etc.Wherein, preferred Vinylstyrene, epoxidation 1,2-polyhutadiene, trichlorosilane, METHYL TRICHLORO SILANE, tetrachloro silicane.

Linking agent has: Vinylstyrene, di adipate, epoxidized liquid divinyl, epoxidised soybean oil, epoxy linseed oil, Xylene Diisocyanate, diphenylmethanediisocyanate, 1,2,4-benzene triisocyanate etc.

With the polymkeric substance before the above-mentioned gained hydrogenation for example in the hydrocarbon system solvent, in the presence of hydrogenation catalyst, at hydrogen-pressure 1-100kg/cm ²,-10 can be made into required hydrogenated diene polymer to 150 ℃ temperature range internal reaction.

Hydrogenation catalyst can use the compound of the metallic element that contains periodic table of elements Ib, IVb, Vb, VIb, VIIb and VIII family elements such as being selected from Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, Pt.These compounds have: the metallocenes based compound that contains elements such as Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, metals such as Pd, Ni, Pt, Rh, Ru are supported loaded heterogeneous catalyst on carriers such as carbon, silicon-dioxide, aluminum oxide, diatomite, with the homogeneous phase Ziegler-type catalyst that the organic salt or the reductive agents such as acetylacetonate and organoaluminum of elements such as Ni, Co combine, organometallic compound or complex compounds such as Ru, Rh, the soccerballene that is adsorbed with hydrogen, carbon nanotube etc.These hydrogenation catalysts can be used alone or with two kinds or above being used in combination.Wherein, preferably can be in inert organic solvents, carry out in the homogeneous system containing of hydrogenation be selected from the element of Ti, Zr, Hf, Co and Ni Metallocenic compound, contain the Metallocenic compound of the element that is selected from Ti, Zr and Hf.Also preferred cost is low, industry is practical, make two cyclopentadiene titanium compounds and lithium alkylide reaction and the hydrogenation catalyst that obtains.

After the hydrogenation, can remove the resistates of catalyzer as required, perhaps adding phenol system or amine is antiaging agent, separates the hydrogenated diene polymer that generates from reaction soln.The separation of hydrogenated diene polymer for example can be carried out by the following method: add acetone, alcohol etc. to reaction soln and make its sedimentary method; Reaction soln is under agitation joined in the hot water, and distillation removes the method desolvate etc. then.

Above-mentioned hydrogenated diene polymer also can use following commercially available product.For example can use " セ プ ト Application " (hydrogenated styrene butadiene-isoprene segmented copolymer of Network ラ レ company preparation, the preferred grade of institute is 4044,4055,4077 etc., hydrogenated styrene butadiene block copolymer 8007,8004,8006 etc.), " Ha イ Block ラ one " etc., (preferred grade is H1052 to " the Off テ Star Network " that company of Asahi Chemical Industry makes, H1031, H1041, H1051, H1062, H1943, H1913, H1043, H1075, JT-90P etc.) etc., (preference ranking of hydrogenated styrene butadiene block copolymer is 8600 to " the ダ イ Na ロ Application " that JSR company makes, 8900 etc.) etc., (preference ranking of hydrogenated styrene butadiene block copolymer is G1650 to Network レ イ ト Application Port リ マ-ズ company " the Network レ イ ト Application " made, G1651, G1652, G1657 etc.) etc.

100 mass parts that add up to EAO based copolymer [A], polyolefin-based resins [B] and mineral oil softener [C], the content of contained hydrogenated diene polymer [D] is the 0.1-50 mass parts in the composition for thermoplastic elastomer of the 1st scheme then of the present invention, preferred 0.5-45 mass parts, further preferred 1-40 mass parts.The content of above-mentioned hydrogenated diene polymer [D] is too much, then the mobile possible deviation of gained composition for thermoplastic elastomer.Very few, then mineral oil softener [C] may ooze out.

The content of ethylene ' alpha '-olefin based copolymer [A], polyolefin-based resins [B] and mineral oil softener [C] of this moment be combined in they add up to 100 quality % the time, be respectively 5-60 quality %, 1-20 quality % and 30-94 quality %, preferred 10-58 quality %, 3-18 quality % and 32-87 quality %, further preferred 15-55 quality %, 5-15 quality % and 35-80 quality %.

100 mass parts that add up to oil-extended rubber [X], polyolefin-based resins [B1] and mineral oil softener [C2], the content of contained hydrogenated diene polymer [D1] is the 0.1-50 mass parts in the composition for thermoplastic elastomer of the 2nd scheme then of the present invention, preferred 0.5-45 mass parts, further preferred 1-40 mass parts.The content of above-mentioned hydrogenated diene polymer [D1] is too much, then the mobile possible deviation of gained composition for thermoplastic elastomer.Very few, then mineral oil softener [C2] may ooze out.

The of the present invention the 1st and the composition for thermoplastic elastomer of the 2nd scheme in except that ethylene ' alpha '-olefin based copolymer, polyolefin-based resins and hydrogenated diene polymer, can also contain other component of polymer.Other component of polymer only otherwise the physical strength of overslaugh gained composition for thermoplastic elastomer, flexibility etc. get final product is not particularly limited.

Described component of polymer has: ionomer resin, the amino acryl amides polymkeric substance, the polyethylene maleic anhydride graft copolymer, polyisobutene, the ethene vinyl chloride copolymer, ethylene-vinyl alcohol copolymer, ethylene vinyl acetate copolymer, polyethylene oxide, ethylene acrylic acid co polymer, the polypropylene maleic anhydride grafted polymer, polyisobutene and maleic anhydride grafted polymer thereof, Chlorinated Polypropylene III, 4-methylpentene-1 resin, polystyrene, ABS resin, the ACS resin, the AS resin, the AES resin, the ASA resin, the MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, permalon, polyamide resin, polycarbonate, vinyl alcohol resin, the vinyl acetal resin, fluoro-resin, polyether resin, polyethylene terephthalate, nitrile rubber and hydride thereof, acrylic rubber, silicon rubber, viton, isoprene-isobutylene rubber, natural rubber, chlorinatedpolyethylene based thermoplastic elastomerics, syndiotaxy 1, the 2-polyhutadiene, simple commixed type ethylene series thermoplastic elastomer, our factory's mix type ethylene series thermoplastic elastomer, the polyvinyl chloride thermoplastic elastomer, the polyurethane series thermoplastic elastomer, polyester based thermoplastic elastomerics, polyamide-based thermoplastic elastomer, fluorine based thermoplastic elastomerics.These component of polymer can be used alone or with two kinds or above being used in combination.

5. additive

In the composition for thermoplastic elastomer of the present invention except that mentioned component, can also contain antioxidant, static inhibitor, adhesion agent, the stopping property modifying agent, lubricant, antiaging agent, thermo-stabilizer, weather resisting agent, metal passivator, UV light absorber, photostabilizer, stablizers such as copper(greening)inhibitor, antibacterial mildew inhibitor, dispersion agent, softening agent, nucleator, fire retardant, tackifier, frothing aid, dyestuff, pigment (titanium oxide etc.), tinting materials such as carbon black, metal-powders such as ferrite, glass fibre, inorganic fibres such as steel fiber, carbon fiber, organic fibres such as Kevlar, conjugated fibre, inorganic crystal whiskers such as potassium titanate crystal whisker, granulated glass sphere, glass sphere, sheet glass, asbestos, mica, lime carbonate, talcum, wet silicon dioxide, dry type silicon-dioxide, aluminum oxide, sial, Calucium Silicate powder, hydrotalcite, kaolin, diatomite, graphite, float stone, bakelite powder, flocking, dust cork, barium sulfate, fluoro-resin, weighting agent or their mixtures such as polymeric beads, polyolefin-wax, cellulose powder, rubber powder, weighting agents such as wood powder, various additives such as low-molecular weight polymer.

6. composition for thermoplastic elastomer

Composition for thermoplastic elastomer of the present invention is that ethylene ' alpha '-olefin based copolymer and polyolefin-based resins carry out dynamic thermal treatment gained in the presence of linking agent at least.That is to say, contain crosslinked ethylene ' alpha '-olefin based copolymer and crosslinked polyolefin-based resins.In addition, employed hydrogenated diene polymer during preparation is if uncrosslinked thing also can be undertaken crosslinked by dynamic thermal treatment." dynamically thermal treatment " is meant and applies shearing force and the processing of heating two aspects.

Above-mentioned linking agent is not particularly limited, being preferably can be by the dynamic thermal treatment under the fusing point of polyolefin-based resins or above temperature, make each self-crosslinking of EAO based copolymer and polyolefin-based resins, perhaps make the crosslinked compound of EAO based copolymer and polyolefin-based resins.

Above-mentioned linking agent has: organo-peroxide, phenol are derivative, bismaleimide compound, epoxy compounds, silane compound, aminoresin, polyol crosslink agent, polyamine, triaizine compounds, metallic soap of linking agent, sulphur, sulphur compound, para benzoquinone, p-benzoqui(o)none dioxime etc.They can be used alone or with two kinds or above being used in combination.Wherein preferred organo-peroxide and phenol resins linking agent.

Organo-peroxide has: 1, two (t-butyl peroxy sec.-propyl) benzene of 3-, 2,5-dimethyl-2, two (t-butyl peroxy) hexins-3 of 5-, 2,5-dimethyl-2, two (t-butyl peroxy) hexenes-3 of 5-, 2,5-dimethyl-2, two (t-butyl peroxy) hexanes of 5-, 2,2 '-two (t-butyl peroxy)-cumic aldehydes, dicumyl peroxide, di-t-butyl peroxide, tert-butyl peroxide, peroxidation is to  alkane, 1, two (t-butyl peroxy)-3 of 1-, 3, the 5-trimethyl-cyclohexane, dilauroyl peroxide, diacetyl peroxide, peroxidized t-butyl perbenzoate, 2, the 4-dichlorobenzoperoxide, p-chlorobenzoyl peroxide, benzoyl peroxide, two (t-butyl peroxy) perbenzoate, normal-butyl-4, two (t-butyl peroxy) valerates of 4-, BPIC (t butyl peroxy isopropyl carbonate) etc.They can be used alone or with two kinds or above being used in combination.Wherein, preferred: 1, two (t-butyl peroxy sec.-propyl) benzene, 2 of 3-, 5-dimethyl-2, two (t-butyl peroxy) hexins-3,2 of 5-, 5-dimethyl-2,5-two (t-butyl peroxy) hexane and α, α-two (t-butyl peroxy) diisopropyl benzene, dicumyl peroxide, di-t-butyl peroxide.

Phenol is that linking agent for example has: shown in the following general formula (I) to substituted phenol based compound, adjacent substituted phenol aldehyde condensate, a substituted phenol aldehyde condensate, bromination alkyl phenolic condenses etc.They can be used alone or with two kinds or above being used in combination.Wherein preferably to the substituted phenol based compound.

[changing 1]

In the above-mentioned general formula (I), X is hydroxyl, haloalkyl or halogen atom, and R is the saturated hydrocarbyl of carbonatoms 1-15, and n is the integer of 0-10.

The substituted phenol based compound can be obtained by the condensation reaction to substituted phenol and aldehyde (preferred formaldehyde) in the presence of alkaline catalysts.

With respect to the total amount of employed component of polymer in the preparation of 100 mass parts composition for thermoplastic elastomer of the present invention, the usage quantity of above-mentioned linking agent is preferably the 0.01-20 mass parts, more preferably 0.1-15 mass parts, further preferred 1-10 mass parts.

When using organo-peroxide as above-mentioned linking agent, preferred 0.05-10 mass parts, more preferably 0.1-5 mass parts.The usage quantity of this organo-peroxide is too much, and then degree of crosslinking is too high, the forming process variation, or mechanical properties has the tendency of reduction.Very few, degree of crosslinking deficiency then, the caoutchouc elasticity of gained composition for thermoplastic elastomer and physical strength may reduce.

Using phenol is linking agent during as above-mentioned linking agent, preferred 0.2-10 mass parts, more preferably 0.5-5 mass parts.This phenol is that the usage quantity of linking agent is too much, and then forming process has the tendency of variation.Very few, degree of crosslinking deficiency then, the caoutchouc elasticity of gained composition for thermoplastic elastomer and physical strength may descend.

Above-mentioned linking agent can stably carry out crosslinking reaction by being used in combination with crosslinking coagent or crosslinking accelerator, particularly can form crosslinked uniformly.When particularly using organo-peroxide as above-mentioned linking agent; the preferred sulphur that uses; sulphur compound (sulphur powder; colloid sulphur; precipitated sulfur; insoluble sulphur; surface treatment sulphur; dipentamethylene thiuram tetrasulfide etc.); oxime compound (para benzoquinone oxime; p; p '-dibenzoyl quinone oximes etc.); multi-functional monomer class (ethylene glycol bisthioglycolate (methyl) acrylate; glycol ether two (methyl) acrylate; triglycol two (methyl) acrylate; Tetraglycol 99 two (methyl) acrylate; polyoxyethylene glycol two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; diallyl phthalate; tetraene propoxy-ethane; triallylcyanurate; N; N '-meta-phenylene bismaleimide; N, N '-tolylene bismaleimides; maleic anhydride; Vinylstyrene; two (methyl) zinc acrylate resin etc.) crosslinking coagent such as.They can be used alone or with two kinds or above being used in combination.Wherein preferred p, p '-dibenzoyl quinone oximes, N, N '-meta-phenylene bismaleimide, Vinylstyrene.

In the above-mentioned crosslinking coagent, N, N '-meta-phenylene bismaleimide has the effect of linking agent, therefore also can be used as linking agent and uses.

With respect to the total amount of employed component of polymer in the preparation of 100 mass parts composition for thermoplastic elastomer, the usage quantity of the crosslinking coagent when using organo-peroxide as above-mentioned linking agent is preferably 10 mass parts or following, more preferably the 0.2-5 mass parts.The usage quantity of this crosslinking coagent is too much, and then degree of crosslinking is too high, the forming process reduction, and mechanical properties has the tendency of reduction.

Using phenol is that linking agent is during as above-mentioned linking agent, the crosslinking accelerator of metal halide (tin protochloride, iron(ic) chloride etc.), Organohalogen compounds (Chlorinated Polypropylene III, brominated butyl rubber, neoprene etc.) etc. is used in combination, can regulates rate of crosslinking.More preferably except that crosslinking accelerator, also be used in combination dispersion agents such as metal oxides such as zinc oxide or stearic acid.

Composition for thermoplastic elastomer of the present invention contains crosslinked ethylene ' alpha '-olefin based copolymer, and the content of crosslinked ethylene ' alpha '-olefin based copolymer can be estimated by the insoluble composition to hexanaphthene.That is, the contained ethylene ' alpha '-olefin based copolymer of composition for thermoplastic elastomer of the present invention the insoluble branch of the hexanaphthene under 23 ℃ be preferably 60 quality % or more than, more preferably 65 quality % or more than, further preferred 70 quality % or more than.The insoluble branch of above-mentioned hexanaphthene is lower than 60 quality %, and then caoutchouc elasticity and physical strength may reduce.The measuring method of the insoluble branch of above-mentioned hexanaphthene is as described below.

The measuring method of the insoluble branch of＜hexanaphthene 〉

The about 200mg composition for thermoplastic elastomer of weighing chops up.Then with gained shred in encloses container, in 23 ℃ of hexanaphthenes that are immersed in 100ml 48 hours.Then, this cyclohexane solution is filtered, the resistates on the filter paper was used Vacuumdrier (105 ℃) dry 1 hour.Deduct the amount of theoretical mineral oil softener in the quality of dried residue and the composition for thermoplastic elastomer before soak the quality of composition for thermoplastic elastomer, with this value (soluble non-crosslinked ethylene ' alpha '-olefin based copolymer among [A], [A1]) as " final quality after the correction (p) ".

On the other hand, obtain the quality of ethylene ' alpha '-olefin based copolymer (the total amount of [A], [A1]) by the quality of the composition for thermoplastic elastomer before soaking, with this as " the initial stage quality (q) after the correction ".

Hexanaphthene is insoluble to be divided into (insoluble composition in the EAO multipolymer/EAO multipolymer total amount), can obtain by following formula.

The insoluble branch of hexanaphthene [quality %]=[{ final quality after the correction (p) } ÷ { the initial stage quality (q) after the correction }] * 100.

The Shore E hardness (according to JIS K6253) of composition for thermoplastic elastomer of the present invention be preferably 80 or below, more preferably 75 or below, further preferred 70 or below.

7. the preparation method of composition for thermoplastic elastomer

The preparation method of composition for thermoplastic elastomer of the present invention is not particularly limited so long as contain the method for carrying out dynamic heat treated ethylene ' alpha '-olefin based copolymer and polyolefin-based resins in the presence of linking agent and get final product.

Conventional method is: the feedstock composition that preparation contains ethylene ' alpha '-olefin based copolymer, polyolefin-based resins, mineral oil softener, hydrogenated diene polymer and linking agent, carry out dynamic thermal treatment to this feedstock composition.

Other method has: (i) preparation contains the feedstock composition of ethylene ' alpha '-olefin based copolymer (or oil-extended rubber), polyolefin-based resins and linking agent, and this feedstock composition is carried out dynamic thermal treatment, adds the method for other material composition then; (ii) preparation contains the feedstock composition of ethylene ' alpha '-olefin based copolymer (or oil-extended rubber), polyolefin-based resins, hydrogenated diene polymer and linking agent, and this feedstock composition is carried out dynamic thermal treatment, adds the method for other material composition etc. then.

Employed ethylene ' alpha '-olefin based copolymer, polyolefin-based resins and hydrogenated diene polymer can directly use during the preparation feedstock composition, also can make the composition that contains identical or different additive respectively and use.In addition, the shape when using the ethylene ' alpha '-olefin based copolymer can be any form of big bag, particle, chip, powder (the pulverizing product that comprise big bag or chip), also variform ethylene ' alpha '-olefin based copolymer can be used in combination.

The content of ethylene ' alpha '-olefin based copolymer [A], polyolefin-based resins [B] and mineral oil softener [C] of whole material compositions (I) that is used for the composition for thermoplastic elastomer of the 1st scheme of making be combined in they add up to 100 quality % the time, be respectively 5-60 quality %, 1-20 quality % and 30-94 quality %, preferred 10-58 quality %, 3-18 quality % and 32-87 quality %, further preferred 15-55 quality %, 5-15 quality % and 35-80 quality %.

For preparing the composition for thermoplastic elastomer of the 2nd scheme, prepare in advance the oil-extended rubber [X] that contains ethylene ' alpha '-olefin based copolymer [A1] and mineral oil softener [C1], other material compositions such as this oil-extended rubber [X] and linking agent are together used.

The content of oil-extended rubber [X], polyolefin-based resins [B1] and mineral oil softener [C2] of whole material compositions (II) that is used for preparing the composition for thermoplastic elastomer of the 1st scheme be combined in they add up to 100 quality % the time, be respectively 5-60 quality %, 1-20 quality % and 30-94 quality %, preferred 10-58 quality %, 3-18 quality % and 32-87 quality %, further preferred 15-55 quality %, 5-15 quality % and 35-80 quality %.

Preparation is during composition for thermoplastic elastomer, and the device that is used to carry out " dynamically thermal treatment " has melting mixing device etc.The processing of being undertaken by this melting mixing device can be that continous way also can be an intermittent type.

This melting mixing device for example has: open mixing roller, non-open type Banbury mixer, single screw extrusion machine, twin screw extruder, continous way mixing roll, pressurization kneader etc.Wherein consider, preferably use continous way melting mixing devices such as single screw extrusion machine, twin screw extruder, continous way mixing roll from economy, processing efficiency equal angles.The melting mixing device of continous way can be used in combination two or above identical or different device.

When using above-mentioned twin screw extruder, preferred L/D (ratio of screw rod useful length L and outer diameter D) be 30 or more than, more preferably 36-60.This twin screw extruder for example can use the twin screw extruder arbitrarily of two screw engages or non-engagement etc., and more preferably the sense of rotation of two screw rods is the twin screw extruder of same direction, screw engages.

Described twin screw extruder has: " ZSK " that " TEM " that " TEX " that " KTX " that " PCM " that pond shellfish company makes, Kobe Steel, Ltd society make, society of JSW make, toshiba machine are made, ワ one Na one company make etc.

When using above-mentioned continous way mixing roll, preferred L/D (ratio of screw rod useful length L and outer diameter D) be 5 or more than, more preferably L/D is 10.

Described continous way mixing roll has: " CIMCMP " that " the ミ Network ス ト ロ Application KTXLCMNCM " that Kobe Steel, Ltd society makes, society of JSW make etc.

Dynamically the treatment temp during thermal treatment is generally 120-350 ℃, preferred 150-290 ℃.Treatment time was generally 20 seconds-320 minutes, preferred 30 seconds-25 minutes.In addition, the shearing force that applies to mixture is: shearing rate 10-20,000/ second, preferred 100-10,000/ second.

Above-mentioned gained composition for thermoplastic elastomer hardness, particularly Shore E, Xiao A hardness are low, have flexibility, the caoutchouc elasticity excellence.Therefore when making the moulding product that only contain this composition for thermoplastic elastomer, can bring into play the character of above-mentioned excellence according to purpose and purposes.The manufacture method that contains the moulding product of composition for thermoplastic elastomer of the present invention for example has: extrusion molding, rolling-molding method, solvent cast method, injection moulding, vacuum forming, powder slush moulding method, pressure sintering etc.

8. moulding product

The feature of moulding product of the present invention is: contain above-mentioned composition for thermoplastic elastomer.

Moulding product of the present invention can be made composite product by laminated, bonding etc. with parts that contain other material etc.

Other material for example has: the composition for thermoplastic elastomer beyond rubber, resin, the present invention, metal (alloy), glass, cloth, timber etc.

Rubber and resin can use as the material that can be exemplified with other component of polymer of composition for thermoplastic elastomer blended of the present invention.

Metal (alloy) has: stainless steel, aluminium, iron, copper, nickel, zinc, lead, tin or the nickel zinc alloy that uses in automobile, boats and ships, tame electrical article etc., iron-zinc alloy, terne metal etc.

9. the sealing material that contains composition for thermoplastic elastomer:

In the composition for thermoplastic elastomer of the present invention, preferably the Xiao A hardness that will measure according to JIS K6253 be 40 or below, preferred 35 or below, more preferably 30 or below, preferred especially 22 or following composition as sealing material.The compression set (condition determination: 70 ℃, 22 hours) that this composition for thermoplastic elastomer is measured according to JISK6262 be preferably 40% or below, more preferably 38% or below, more preferably 35% or following so little distortion.Use has the sealing material that the composition for thermoplastic elastomer of above-mentioned characteristic is made, its stopping property is very excellent, and mineral oil softener can not ooze out simultaneously, and owing to be to constitute by composition for thermoplastic elastomer, therefore can and recycle easily, save aspect the resource very excellent.

The manufacture method that contains the sealing material of composition for thermoplastic elastomer of the present invention for example can be used: extrusion molding, rolling-molding method, solvent cast method, injection moulding, vacuum forming, powder slush moulding method, pressure sintering etc.

The shape of gained sealing material is not particularly limited, and for example has: O type round, sheet or bar-shaped etc.Sealing material also can be used as stopper and uses.

Sealing material of the present invention can form it into sealing, and is laminated, bonding etc. with parts such as the chest portion that contains other material etc., makes composite product, for example the goods such as container such as toner Cartridge used of used in copy machines, printer.Here, other material for example has: the composition for thermoplastic elastomer beyond rubber, resin, the present invention, metal (alloy), glass, cloth, timber etc.

When making goods such as container, chest portion can be used above-mentioned various material, and preferably the material by reusable edible constitutes.Wherein, if chest portion contains thermoplastic resin and/or composition for thermoplastic elastomer, then can and easily recycle, preferred.

The chest portion of reusable edible is preferably used in the feedstock composition explanation that is used to form composition for thermoplastic elastomer with thermoplastic resin, thermoplastic elastomer, composition for thermoplastic elastomer, has thermoplastic material in the compound that exemplifies as the synthetic branch of other polymers.Ionomer resin for example, the amino acryl amides polymkeric substance, polyethylene and maleic anhydride grafted polymer thereof, polyisobutene, the ethene vinyl chloride copolymer, ethylene-vinyl alcohol copolymer, ethylene vinyl acetate copolymer, polyethylene oxide, ethylene acrylic acid co polymer, polypropylene and maleic anhydride graft copolymer thereof, polyisobutene and maleic anhydride graft copolymer thereof, Chlorinated Polypropylene III, 4-methylpentene-1 resin, polystyrene, ABS resin, the ACS resin, the AS resin, the AES resin, the ASA resin, the MBS resin, acrylic resin, methacrylic resin, vinyl chloride resin, permalon, polyamide resin, polycarbonate, vinyl alcohol resin, the vinyl acetal resin, fluoro-resin, polyether resin, polyethylene terephthalate, chlorinatedpolyethylene based thermoplastic elastomerics, syndiotactic 1, the 2-polyhutadiene, simple commixed type ethylene series thermoplastic elastomer, ooze and mix type ethylene series thermoplastic elastomer the our factory, dynamic crosslinking type ethylene series thermoplastic elastomer, the polyvinyl chloride thermoplastic elastomer, the polyurethane series thermoplastic elastomer, polyester based thermoplastic elastomerics, polyamide-based thermoplastic elastomer, fluorine based thermoplastic elastomerics.These component of polymer can be used alone or with two kinds or above being used in combination.

If the good ethylene series material of selected and sealing material consistency as the material of casing side, then can obtain the container of chest portion and sealing heat fusion.On the other hand, if the material (thermoplastic resin that for example contains functional group) of selected and sealing material consistency difference as the chest portion material, then sealing and chest portion do not fuse and can be compound.

Specifically, the casing side material good with the sealing material consistency has polypropylene or polyethylene, with the casing side material of sealing material consistency difference ABS resin, polycarbonate, polystyrene arranged.

Container of the present invention also can use the material except that thermoplastic resin or composition for thermoplastic elastomer---metal (alloy), glass, cloth, timber etc., for example, metal (alloy) has: stainless steel, aluminium, iron, copper, nickel, zinc, lead, tin or the nickel zinc alloy that uses in automobile, boats and ships, tame electrical article etc., iron-zinc alloy, terne metal etc.

Sealing material of the present invention can form container (chest portion of sealing is housed) by forming it into sealing, preferably being undertaken compoundly by injection moulding with chest portion.In this container, the sealing that contains sealing material of the present invention can be brought into play extremely excellent sealing property when containing content such as powder such as toning agent or liquid.

Carrying out composite methods by injection moulding has: core rod regression method (core backing method), mode slider method (die slide method), rotational method etc. are filled double-colored or two kinds or above resin from different injection moulding barrels respectively successively to the mould inside injection, make the method for the moulding product of same material not or different colours material.Multiple injection also can form multilayer or multicolour forming product.

Rotational method is meant the material by first kind of color of the first barrel injection molding (first kind of material), open mould, make the once shaped product be attached to core rod one side, under this state with mould rotating disk Rotate 180 degree, matched moulds by the material of the second barrel injection molding, second look (second kind of material), is opened mould once more, from mould, take out the moulding product, make the method for compound injection moulding product thus.

Core rod regression method is meant and comprises once shaped and post forming, during once shaped, a die cavity part is sealed with mobile core rod, molten resin is filled in injection in the die cavity of vacating, semifinished product of moulding during post forming, withdraws from mobile core rod, injecting molten resin in the space of withdrawing from obtains the method with the incorporate moulding product of once shaped product.

Use the manufacture method of the container of sealing material of the present invention, in injection moulding, adopt mode slider injection moulding (DSI) as the preferred method of forming.The DSI method is summarized as follows.

At first, under the state of matched moulds, by a shot, moulding once shaped product (half moulves of hollow product) are opened mould under the state of the once shaped product being stayed die cavity.Mould is for by being located at the mode slider office structure movably on the injection moulding machine.By this office, can make mould move to once shaped product position respect to one another.Matched moulds once more, biphasic injection holds the shape resin, thus the seam portion that holds butt joint once shaped product is to become one.The above-mentioned hollow product method of forming is for example in being recorded in プ ラ ス チ Star Network エ one ジ " DSI hollow injection molding Progress in technique " (in August, 2002) 74-84 page or leaf or Japanese kokai publication sho 62-87315 communique.

Embodiment

Below exemplify embodiment and specify the present invention, the present invention is not subjected to any restriction of these embodiment.If no special instructions, " % " among the embodiment and " part " are quality criteria.

Embodiment 1

1. the preparation of composition for thermoplastic elastomer

According to ratio shown in the table 1, preparation contains the oil-extended rubber (I) of following ethylene ' alpha '-olefin based copolymer, mineral oil softener (hydrowax that the emerging product of bright dipping society makes is mineral oil, trade(brand)name " ダ イ ア Na プ ロ セ ス オ イ Le PW380 ").Then, according to the blending ratio of table 2, with this oil-extended rubber (I), following polyolefin-based resins, above-mentioned mineral oil softener, hydrogenated diene polymers close, various additives except that linking agent and crosslinking coagent mix, and obtain feedstock composition.This feedstock composition is joined in the pressurization kneader that is heated to 150 ℃ in advance (capacity 10L, モ リ ヤ マ company make), with mixing 15 minutes of 40rpm (shearing rate 200/ second), to the polyolefin-based resins fusion, each composition homodisperse.Then the mixing thing of gained molten state is made particle by feeder ruder (manufacturing of モ リ ヤ マ company).

Then,, above-mentioned particle, linking agent and crosslinking coagent are joined in the Heng Xieer mixing machine, mixed 30 seconds according to ratio shown in the table 2.Use twin screw extruder (the ratio L/D=33.5 of complete in the same way engagement type screw rod, screw flight minister degree L and screw diameter D, the manufacturing of pond shellfish company, model PCM45) then, carry out dynamic thermal treatment with 200 ℃, 1 minute and the 30 seconds residence time, 300rpm, 400/ second treatment time of shearing rate, extrude simultaneously, obtain the particulate state composition for thermoplastic elastomer.

(1) ethylene ' alpha '-olefin based copolymer

(I) ethylene, propylene 5-ethylidene-2-norbornene terpolymer

The ethylene monomer unit amount is 66mol%, and 5-ethylidene-2-norbornene monomeric unit amount is 4.5mol%, in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 5.5dl/g.

(II) ethylene, propylene 5-ethylidene-2-norbornene terpolymer

The ethylene monomer unit amount is 66mol%, and 5-ethylidene-2-norbornene monomeric unit amount is 4.5mol%, in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 2.7dl/g.

(2) polyolefin-based resins

(I) crystalline polypropylene

Use that Japanese Port リ ケ system company makes, trade(brand)name " ノ バ テ Star Network FL25R " (density: 0.90g/cm ³, MFR (230 ℃ of temperature, load 2.16kg): 23g/10 minute).

(II) propylene 1-butylene amorphous multipolymer

Use the manufacturing of the space レ キ セ of portion Application company, trade(brand)name " UBETAC APAO UT 2780 " (propylene monomer units amount: 71mol%, melt viscosity 8,000cPs, density: 0.87g/cm ³, the degree of crystallinity measured of X-ray diffraction: the polystyrene conversion number-average molecular weight Mn:6 that measures of GPC 0%,, 500).

(3) hydrogenated diene polymer

(I) styrene butadiene isoprene hydrogenated diene polymer

Use the manufacturing of Network ラ レ society, trade(brand)name " セ プ ト Application 4077 " (styrene monomer quantity of units: 30mol%, proportion: 0.91, hydrogenation ratio: toluene solution viscosity (30 ℃, concentration 5 quality %) 98%: 300mPas, melt flow rate (MFR) (230 ℃, 21.2N): do not flow, can not measure).

(II) styrene butadiene hydrogenated diene polymer

Use the manufacturing of Network ラ レ society, trade(brand)name " セ プ ト Application 8006 " (styrene monomer quantity of units: 30mol%, proportion: 0.91, hydrogenation ratio: toluene solution viscosity (30 ℃, concentration 5 quality %) 98%: 42mPas, melt flow rate (MFR) (230 ℃, 21.2N): do not flow, can not measure).

(III) styrene butadiene hydrogenated diene polymer

Use the manufacturing of Network レ イ ト Application Port リ マ one ズ company, trade(brand)name " G1651 " (styrene monomer quantity of units: 33mol%, proportion: 0.91, hydrogenation ratio: toluene solution viscosity (30 ℃, concentration 5 quality %) 99%: 50mPas, melt flow rate (MFR) (230 ℃, 21.2N): do not flow, can not measure).

(4) additive

(i) linking agent

Use Nof Corp.'s manufacturing, trade(brand)name " パ one ヘ キ サ 25B-40 " (5-dimethyl-2,5-two (t-butyl peroxy) hexane).

(ii) crosslinking coagent

Vinylstyrene (the purity: 96%) of using chemical company of Nippon Steel to make.

(iii) antiaging agent

Use the manufacturing of チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ society, trade(brand)name " イ Le ガ ノ Star Network ス 1010 " (four [methylene radical 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane).

[table 1]

				Oil-extended rubber
						(I)	(II)
				Constituent (part)	The ethylene ' alpha '-olefin based copolymer			Limiting viscosity (dl/g)
	(I)	5.5	50
					(II)	2.7			60
	Mineral oil softener						50			40

2. the evaluation of composition for thermoplastic elastomer

The particle of above-mentioned gained composition for thermoplastic elastomer is processed with injection moulding machine (manufacturing of society of JSW, model " N-100 "), made the sheet (experiment slice) of length 120mm, width 120mm and thickness 2mm.Use this sheet to carry out various evaluations.Its result charges to table 2 in the lump.

(1) melt flow rate (MFR)

According to JIS K7210, under 190 ℃, load 21N condition, measure.

(2) the insoluble branch of hexanaphthene

According to the method for putting down in writing herein, 23 ℃ of mensuration.

(3) hardness (Shore E)

According to JIS K6253, measure hardness in the mensuration beginning after 5 seconds, with this index as flexibility.

(4) hardness (Shore A)

According to JIS K6253, after beginning 5 seconds, Shore A mensuration hardness measures hardness, with this index as flexibility.

(5) tensile break strength and tension fracture elongation

Measure according to JIS K6251.

(6) compression set

According to JIS K6262, under 70 ℃, 22 hours condition, measure, with this index as caoutchouc elasticity.

(7) rebound resilience

According to JIS K6255, use リ ユ プ ケ formula rebound resilience experiment instrument, 23 ℃ of mensuration, with this index as caoutchouc elasticity.

(8) molded appearance (mineral oil softener ooze out experiment)

The rectangle experiment slice of die-cut long 40mm, wide 30mm from above-mentioned experiment slice left standstill experiment slice 168 hours in 50 ℃ thermostatic bath, visual observation outward appearance then, following evaluation.

Zero: mineral oil softener does not have and oozes out

*: mineral oil softener has and oozes out

[table 2]

				Embodiment			Comparative example
										1	2	3	1	2	3
				Material composition (part)		Oil-extended rubber	(I)	47	47							35	47		47
(II)											47
							Polyolefin-based resins	(I)	4				4	3	4	4	4
(II)	4	4	3			4				4	4
								Mineral oil softener				45	45	59	45	45	45
Hydrogenated diene polymer	(I)	5								5
								(II)				5
	(III)					25
								Linking agent				0.8	0.8	0.8	0.8	0.8
Crosslinking coagent		0.6	0.6			0.6	0.6			0.6
								Antiaging agent				0.1	0.1	0.1	0.1	0.1	0.1
The total amount of the mineral oil softener in the composition		68.5	68.5			76.5	44			68	68.5
								Having or not of dynamic crosslinking				Have	Have	Have	Have	Have	Do not have
Rerum natura	MFR (190 ℃, 21N) [g/10 minute]			8	10	8	16											5	1
								The insoluble branch of hexanaphthene [%]			87	85	86	81	84	29
	Hardness (Shore E)			55	54	55	53										59	53
								Hardness (Shore A)			26	22	24	19	22	19
	Tensile break strength [MPa]			2.1	2	2.7	1.9										1.4	0.8
								Tension fracture elongation [%]			770	750	780	720	740	930
	Compression set [%]			29	33	19	37										37	90
								Rebound resilience [%]			57	57	68	57	56	55
	Molded appearance			○	○	○	×										×	×

Embodiment 2-3 and comparative example 1-2

Use each material composition with the blending ratio of table 2, in addition obtain each composition for thermoplastic elastomer similarly to Example 1, and it is estimated.The result charges to table 2 in the lump.

In the comparative example 2, same with the foregoing description 1, the oil-extended rubber (II) of preparation table 1 uses this oil-extended rubber (II) and other material composition, mixes with the blending ratio of table 2, obtains each feedstock composition.

Comparative example 3

Blending ratio according to table 2 is mixed oil-extended rubber (I) and other material composition, obtains feedstock composition.This feedstock composition is joined the pressurization kneader that is heated to 150 ℃ in advance (capacity 10L, モ リ ヤ マ company make), with mixing 15 minutes of 40rpm (shearing rate 200/ second), to the polyolefin-based resins fusion, each composition homodisperse.Then the mixing thing of gained molten state is made particle by feeder ruder (manufacturing of モ リ ヤ マ company), obtain composition for thermoplastic elastomer, it is estimated.Its result remembers in table 2 in the lump.

The result of table 2 is as can be known: comparative example 1 is the example that does not contain the hydrogenation diene polymer, and mineral oil softener oozes out from the surface of moulding product, bad order.Comparative example 2 contains hydrogenated diene polymer, but the limiting viscosity of ethylene ' alpha '-olefin based copolymer is lower than 3.5dl/g, so mineral oil softener oozes out bad order.Comparative example 3 is examples of dynamic crosslinking not, and tensile properties is poor, so physical strength is not enough, the compression set height, and mineral oil softener oozes out bad order.

On the other hand, the hardness of the composition for thermoplastic elastomer of embodiment 1-3 (Shore E) is that 54-55, hardness (Shore A) are 22-26 as can be known, and hardness is very low, the flexibility excellence.And compression set is 29-33%, and is very little, and rebound resilience is 57-68%, and is very high, the caoutchouc elasticity excellence.There is no in addition and ooze out phenomenon, aesthetic appearance is good.

Embodiment 4-5, comparative example 4-5

1. the preparation of composition for thermoplastic elastomer

According to the blending ratio of table 3, following oil-extended rubber [X], polyolefin-based resins, mineral oil softener, hydrogenated diene polymer and additive (except linking agent and the crosslinking coagent) are mixed, make particle similarly to Example 1.

Then, according to the ratio shown in the table 3, above-mentioned particle, linking agent and crosslinking coagent are joined in the Heng Xieer mixing machine, mixed 30 seconds, carry out dynamic thermal treatment limit with the twin screw extruder limit similarly to Example 1 then and extrude, obtain three kinds of (A, B, C) granular composition for thermoplastic elastomer.

(1) oil-extended rubber [X]

1: 50 quality % ethylene/propene/5-ethylidene-2-norbornene terpolymer (ethylene content is that 66mol%, 5-ethylidene-2-norbornene content are that 4.5mol%, limiting viscosity are 5.5dl/g) of oil-filled copolymer rubber, 50 quality % paraffin series tenderizers.

(2) polyolefin-based resins

(I) crystalline polypropylene

Use that Japanese Port リ ケ system company makes, trade(brand)name " ノ バ テ Star Network FL25R " (density: 0.90g/cm ³, MFR (230 ℃ of temperature, load 2.16kg): 23g/10 minute).

(II) propylene 1-butylene amorphous multipolymer

Use that the space レ キ セ of portion Application company makes, trade(brand)name " UBETAC APAO UT2780 " (propylene monomer units amount: 71mol%, melt viscosity: 8,000cPs, density: 0.87g/cm ³, the degree of crystallinity measured of X-ray diffraction: the polystyrene conversion number-average molecular weight Mn:6 that measures of GPC 0%,, 500).

(3) mineral oil softener

Use the manufacturing of the emerging product of bright dipping society, trade(brand)name " ダ イ ア Na プ ロ セ ス オ イ Le PW90 " (paraffin series mineral oil).

(4) hydrogenated diene polymer

(I) styrene butadiene isoprene hydrogenated diene polymer

The trade(brand)name " セ プ ト Application 4077 " (styrene monomer quantity of units: 30mol%, proportion: 0.91, hydrogenation ratio: toluene solution viscosity (30 ℃, concentration 5 quality %) 98%: 300mPas, melt flow rate (MFR) (230 ℃, 21.2N): do not flow, can not measure) of using Network ラ レ society to make.

(5) additive

(i) linking agent

Use that Japanese grease society makes, trade(brand)name " パ one ヘ キ サ 25B-40 " (5-dimethyl-2,5-two (t-butyl peroxy) hexane).

(ii) crosslinking coagent

Vinylstyrene (the purity: 96%) of using chemical company of Nippon Steel to make

(iii) antiaging agent

Use the manufacturing of チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ society, trade(brand)name " イ Le ガ ノ Star Network ス 1010 " (four [methylene radical 3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane).

[table 3]

			A	B	C
						Composition (part)	Oil-extended rubber	(I)	45	47	75
Polyolefin-based resins	(I)	5	4	6
					(II)		5	4	6
	Mineral oil softener		40	45						13
Hydrogenated diene polymer					(I)		5
	Linking agent		0.8	0.8						0.8
Crosslinking coagent							0.6	0.6	0.6
	Antiaging agent		0.1	0.1						0.1
Rerum natura					The insoluble branch of hexanaphthene		[％]	85	87		86
	MFR(190℃，21N)	[g/10 minute]	6	22
					MFR(230℃，49N)		[g/10 minute]			41
	Hardness (Shore A)		20	22		42
					Tensile break strength		[MPa]	2.7	2.8	4.2
	The tension fracture elongation	[％]	700	650		740
					Compression set		[％]	33	34	38
	Oil is exudative		○	○		○

2. the evaluation of composition for thermoplastic elastomer

The particle of three kinds of composition for thermoplastic elastomer of above-mentioned gained is processed by injection moulding machine (manufacturing of society of JSW, model " N-100 "), made the sheet (experiment slice) of length 120mm, width 120mm and thickness 2mm, use this sheet to carry out various evaluations.Its result is recorded in the table 3 in the lump.

(1) oil is exudative

Placed 72 hours at 80 ℃, visual valuation oil is exudative then.

Zero: mineral oil softener does not ooze out

*: mineral oil softener has and oozes out

3. the making of band sealing container

In order to make the container of band sealing, the 220EII-P2M (dual-color forming injection moulding machine) that uses society of JSW to make is by mode slider injection moulding (M-DSI method; Trade mark), (Japanese Port リ ス チ レ Application company makes with polystyrene, grade H230) shaping box body one side (210 ℃ of barrel temperatures, 50 ℃ of die temperatures), use continuously shaped sealing one side of composition for thermoplastic elastomer (210 ℃ of barrel temperatures, 50 ℃ of die temperatures) then, obtain container with sealing.Fig. 1 represents the container 10 of gained band sealing, and Fig. 2 is the photo that expression constitutes band sealing container sealing 1 10, that contain sealing material having low hardness of the present invention and chest portion 2 isolating states.

4. sealing property evaluation method

(experimental technique)

As shown in Figure 3, fill 90% water 15 in the container (dual-color forming product) 10 of the band sealing material of in above-mentioned 3, making.Then lid 11 is covered on this container 10, the end is clamped with two tail folders (コ Network ヨ society makes: Network リ-34, mouthful wide 25mm) 12 (8).14 expression sealing members.The height of this container 10 from 1 meter fallen on fluting board 13, confirm that water in the container 10 do not have to spill.For each sample, change falling direction, carry out 5 tests (n=5).The result is as shown in table 4.

[table 4]

	Embodiment 4		Embodiment 5		Comparative example 4		Comparative example 5
								Composition for thermoplastic elastomer	A		B		C		No sealing material
n
		1	2	1	2	1	2	1
1									○	○	○	○	○	○	×
	2	○	○	○	○	○	×	×
3									○	○	○	○	×	○	×
	4	○	○	○	○	○	×	×
5									○	○	○	○	×	○	×
	Toner Cartridge leakage rate (%)	0		0		80		100

Zero: do not have and reveal; *: leakage is arranged.

(evaluation result)

By the result shown in the table 4 as can be known, sealing material having low hardness of the present invention (composition for thermoplastic elastomer=A, B) does not see and leaks that stopping property is good.And it is poor to use hardness to surpass the stopping property of the sealing material that 40 composition for thermoplastic elastomer makes.

Industrial applicability

Thermoplastic elastomer (TPE) composition flexibility of the present invention; caoutchouc elasticity (resilience; compression set) excellence; therefore can be widely used in the bumper of automobile; outer filler rod; the window sealing gasket; door seal; the conduit sealing gasket; roof cant rail; sign; interior instrument board; door is decorated; the internal and external ornament surfacings such as console case; windlace etc.; the leather seat that needs damage resistant; the encapsulant that the aircraft boats and ships are used and internal and external ornament surfacing etc.; the civil construction encapsulant; internal and external ornament surfacing or waterproof sheet etc.; usually machinery and device are with encapsulant etc.; the light current parts; the seal of water pipe; encapsulant in the fuel cell group; surfacing or shell etc., railway track seal; information instrument roller; the cleaning scraper plate; the electronic component-use film; protective film in the flat-panel monitor of semiconductor and liquid crystal indicator etc. (FPD) manufacturing step; encapsulant; the protect image films such as photo; the construction material decorating film; the medical instrument parts; electric wire; the sundry goods product; the general processed goods such as sporting goods.

Sealing material having low hardness of the present invention can carry out processing and forming by injection moulding, extrusion molding, hollow molding, compression forming, vacuum forming, laminated into type, calendering formation etc., hardness is extremely low, sealing is excellent, mineral oil softener is without oozing out, little each characteristic such as grade of compression set is all excellent, therefore can be suitable as the encapsulant of general machinery or device usefulness. And the sealing material is made of the thermoplastic elastomer (TPE) composition, and reusable edible is very excellent for earth environment, saving resource aspect.

By double-shot moulding this sealing material having low hardness and casing are carried out the one-body molded container that obtains and when containing various content, absolutely not leak, can feel at ease to use during use, during carrying.

Claims (16)

1. composition for thermoplastic elastomer, total with respect to 100 mass parts [A], [B] and [C], contain [D] 0.1-50 mass parts hydrogenated diene polymer, wherein, described [A] for 5-60 quality % in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down are 3.5dl/g or above ethylene ' alpha '-olefin based copolymer, [B] is 1-20 quality % polyolefin-based resins, and [C] be 30-94 quality % mineral oil softener, with the 100 quality % that add up to of [A], [B] and [C];

At least above-mentioned [A] ethylene ' alpha '-olefin based copolymer and above-mentioned [B] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent.

2. composition for thermoplastic elastomer, total with respect to 100 mass parts [X], [B1] and [C2], contain [D1] 0.1-50 mass parts hydrogenated diene polymer, wherein said [X] is 5-60 quality % oil-extended rubber, it is 3.5dl/g or above ethylene ' alpha '-olefin based copolymer and [C1] 20-80 quality % mineral oil softener in the naphthalane solvent, 135 ℃ of limiting viscosities of measuring down that this oil-extended rubber contains [A1] 20-80 quality %, and wherein [A1's] and [C1] adds up to 100 quality %; [B1] is 1-20 quality % polyolefin-based resins; And [C2] be 30-94 quality % mineral oil softener, and wherein [X], [B1's] and [C2] adds up to 100 quality %;

At least above-mentioned [A1] ethylene ' alpha '-olefin based copolymer and above-mentioned [B1] polyolefin-based resins carry out dynamic thermal treatment and form in the presence of linking agent.

3. claim 1 or 2 composition for thermoplastic elastomer, wherein, above-mentioned hydrogenated diene polymer [D] is following at least a for being selected from: contain monomeric unit that the hydride and containing of the polymkeric substance of the monomeric unit that is formed by conjugated diene compound forms by conjugated diene compound and the hydride of the polymkeric substance of the monomeric unit that formed by vinyl aromatic compounds.

4. each composition for thermoplastic elastomer among the claim 1-3, the Shore E hardness that said composition is measured according to JIS K6253 be 80 or below.

5. each composition for thermoplastic elastomer among the claim 1-4, wherein, with comprise ethylene monomer unit and by whole monomeric units of the monomeric unit of alpha-olefin compound formation add up to 100mol% the time, the content that constitutes the ethylene monomer unit of above-mentioned ethylene ' alpha '-olefin based copolymer [A] and [A1] is 35-95mol%.

6. each composition for thermoplastic elastomer among the claim 1-5, wherein, above-mentioned mineral oil softener [C], [C1] and [C2] are paraffin series mineral oil.

7. each composition for thermoplastic elastomer among the claim 1-6, wherein, above-mentioned linking agent is for being selected from 1, two (t-butyl peroxy sec.-propyl) benzene, 2 of 3-, 5-dimethyl-2,5-two (t-butyl peroxy) hexin-3,2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, α, the organo-peroxide of α-two (t-butyl peroxy) diisopropyl benzene, dicumyl peroxide and di-t-butyl peroxide.

8. each composition for thermoplastic elastomer among the claim 1-7, wherein, the ethylene ' alpha '-olefin based copolymer in this composition for thermoplastic elastomer the hexanaphthene under 23 ℃ insoluble be divided into 60 quality % or more than.

9. moulding product, these moulding product contain among the claim 1-8 each composition for thermoplastic elastomer.

10. sealing material having low hardness, this material use among claim 1-8 each composition for thermoplastic elastomer to make.

11. the sealing material having low hardness of claim 10, the Xiao A hardness that this material is measured according to JIS K6253 be 40 or below.

12. the sealing material having low hardness of claim 10 or 11, this material form be selected from O type round, sheet and bar-shaped in any one shape.

13. container, this container is a component parts with each sealing material having low hardness among the claim 10-12.

14. container, this container are to be formed by the complex body that sealing and chest portion constitute by the injection molding method moulding, wherein said sealing contains among the claim 10-12 each sealing material having low hardness.

15. the container of claim 14, wherein, above-mentioned chest portion contains thermoplastic resin and/or composition for thermoplastic elastomer, reusable edible.

16. toner Cartridge, this toner Cartridge is a component parts with each sealing material having low hardness among the claim 10-12.

Images