CN1693354A - Thermoplastic elastomer composition and process for producing the same - Google Patents

Thermoplastic elastomer composition and process for producing the same Download PDF

Info

Publication number
CN1693354A
CN1693354A CN 200510077957 CN200510077957A CN1693354A CN 1693354 A CN1693354 A CN 1693354A CN 200510077957 CN200510077957 CN 200510077957 CN 200510077957 A CN200510077957 A CN 200510077957A CN 1693354 A CN1693354 A CN 1693354A
Authority
CN
China
Prior art keywords
rubber
composition
ethylene series
mass parts
thermoplastic elastomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200510077957
Other languages
Chinese (zh)
Other versions
CN100500755C (en
Inventor
森川明彦
鼎健太郎
中西英雄
前田稔
冈本隆浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
JSR Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JSR Corp filed Critical JSR Corp
Publication of CN1693354A publication Critical patent/CN1693354A/en
Application granted granted Critical
Publication of CN100500755C publication Critical patent/CN100500755C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention relates to a thermoplastic elastomer composition and the production method, formed by dynamically cross binding the polymer composition containing a rubber and an olefin resin and the average grain diameter of the rubber grain is in the specific range, thereby ensuring preferable mechanical properties such as flexibility, elasticity and recovery property and the proportionality of the moldability. The thermoplastic elastomer composition of the invention is characterized in that: under the existence of a cross linker, the invention is formed by dynamic heat treatment of the polymer composition with a rubber, an olefin resin, a softener, a (methyl) acrylic ester resin and a maleimide compound. Wherein, when the rubber, the olefin resin and the softener have a quality of total 100percent, the maleimide compound has a quality portion of 0.3-10 and the (methyl) acrylic ester resin has a quality portion of 1-30.

Description

Composition for thermoplastic elastomer and manufacture method thereof
The application is dividing an application of application number 02818331.2, June 27 2002 applying date, denomination of invention " composition for thermoplastic elastomer and manufacture method thereof ".
Technical field
The present invention relates to composition for thermoplastic elastomer and manufacture method thereof.More particularly, harmonious excellent composition for thermoplastic elastomer and the manufacture method thereof that relate to mechanical characteristics such as flexibility and rebound resilience and forming process.In addition, relate to excellent composition for thermoplastic elastomer and manufacture method thereof such as flexibility, scratch resistance, mechanical characteristics and caoutchouc elasticity.In addition, the composition for thermoplastic elastomer and the manufacture method thereof that relate to injection weldability excellence.In addition, relate to initial stage sliding, durable sliding, wear resistant, thermal welding and forming process excellence, the molded appearance of moulding product and feel good thermoplastic elastic composition and manufacture method thereof.
Background technology
The composition for thermoplastic elastomer that in the presence of linking agent rubber and ethylene series resin is carried out dynamic thermal treatment and constitute does not need vulcanization process, can be with the forming method of common thermoplastic resin, for example injection molding, special-shaped extrusion moulding, rolling processing, blow molding etc. easily make it become the moulding product.
But it is poor that these ethylene series dynamic crosslinking type thermoplastic elastomers and vulcanized rubber are compared rebound resilience.Up to the present, in order to improve its rebound resilience, studied the high Mooneyization of raising cross-linking density and rubber etc.Be improved by these method rebound resiliences, but the mobile of composition for thermoplastic elastomer significantly reduces.In addition,, there is the method that cooperates peroxide breakdown type ethylene series rubber in order to improve forming process, but the problem of using this method to exist rebound resilience to reduce.Like this, use method in the past, be difficult to obtain the harmonious good thermoplastic elastic composition of rebound resilience and forming process.
In addition, in recent years, as the soft material of rubber like, do not need vulcanization process, have thermoplastic elastomer with the equal forming process of thermoplastic resin and receive publicity in fields such as trolley part, household electrical appliances parts, medical treatment, food machinery parts, electric wire and groceries and use.Now, as such thermoplastic elastomer, having developed with commercially available has various elastomericss such as polyolefin, polystyrene, polyurethane series, polyester system, polyvinyl chloride.In these elastomericss, be that random copolymer rubber is the blend of main raw material or is that random copolymer rubber is a main raw material and to carry out partial cross-linked ethylene series dynamic crosslinking type thermoplastic elastomer with linking agent particularly useful with ethylene series resin and ethene-alpha-olefin with ethylene series resin and ethene-alpha-olefin.They have excellent thermotolerance, weathering resistance, winter hardiness and forming process, and more inexpensive.Therefore, particularly in fields such as trolley part, as the equivalent material that turns to the metal parts of argument with light weight, with improve component life and reduce cost be argument the RIM polyurethane part equivalent material, with the course of processing oversimplify, recovery property and reduce cost be argument vulcanized rubber equivalent material and with improve component life and improve contaminative be argument the equivalent material etc. of soft PVC receive publicity, its demand is increasing year by year.
But the anti-surface tear (scratch resistance) of ethylene series dynamic crosslinking type thermoplastic elastomer is poor, is being used for the moulding product that requirement has scratch resistance, for example existing problems during the skin material of inner panel, support case etc.
In addition, excellences such as the thermotolerance of ethylene series dynamic crosslinking type thermoplastic elastomer, ozone resistance, weathering resistance, have the caoutchouc elasticity identical simultaneously, on the other hand, have the roughly the same formabilities of ethylene series thermoplastic resin such as polyethylene, polypropylene with vulcanized rubber.Utilize this point, can be used as the moulding product that require caoutchouc elasticity, for example the collision bumper of automobile, the outer dress with lace, window sealing seal with sealed strip, top curb rafter (roofsiderail), badge, interior dress skin material etc. with sealed strip, luggage with sealed strip, door sealing.In addition, the various sealed strips that also can use as building materials etc.In these purposes, the sealed strip of using etc. with, vehicle body sealing with, door sealing especially for the sealing of the window of the automobile that requires caoutchouc elasticity, and building materials compare with the ethylene series dynamic crosslinking type thermoplastic elastomer that is used for other purposes with the ethylene series dynamic crosslinking type thermoplastic elastomer of sealed strip etc., can make by the amount that increases ethene-alpha-olefin based copolymer rubber constituent.
But mobile low during the ethylene series dynamic crosslinking type thermoplastic elastomer forming process that makes like this directly made the weather strip for automobile of complicated shape and building materials with difficulties such as sealed strips with injection molding.On the other hand, the operation in the past of these sealed strip classes of moulding, very complicated and the activity duration is long as following, from laborsaving, improve viewpoint such as productivity, wish to improve strongly.
The molding procedure of sealed strip class, the occasion of for example common vulcanized rubber, its method is by with the special-shaped extrusion moulding of unvulcanized rubber, make the straight line portion of sealed strip, should the abnormal shape extrusion molding article after the sulfuration, in split cavity, fill the curve junction surface between the end of moulding product, vulcanize, engage.But, need vulcanization process in this method 2 times.Thereby, this operation shortens the activity duration for being simplified, also considered the bonding part between the end of the special-shaped extrusion molding article of sulfurized is replaced to the method that does not need sulfurized ethylene series dynamic crosslinking type thermoplastic elastomer, further the special-shaped extrusion molding article of straight line portion is also replaced to the method for ethylene series dynamic crosslinking type thermoplastic elastomer, wish to use the former method aspect practical.When the junction surface between the end of this abnormal shape extrusion molding article is replaced with the method for ethylene series dynamic crosslinking type thermoplastic elastomer, the method of taking is that special-shaped extrusion molding article is put into split cavity, ethylene series dynamic crosslinking type thermoplastic elastomer is expelled to the junction surface, thereby with melt bonded between the end.But, as a rule, be difficult carrying out melt bonded for practical then intensity.For example, when in the public clear 61-53933 communique of spy, having proposed between extrusion molding article, to engage, made the then method of intensity raising by following the body preheating with ethylene series dynamic crosslinking type thermoplastic elastomer.In addition, the spy opens and has proposed in the clear 59-221347 communique when same joint, has cooperated the ethylene series dynamic crosslinking type thermoplastic elastomer of crystallinity poly-1-butylene by use, also can not make the then method of intensity raising even do not carry out preheating.But, in these methods, especially, can't obtain effect of sufficient when when then body is the ethylene series vulcanized rubber.Therefore, when being any of ethylene series vulcanized rubber and ethylene series dynamic crosslinking type thermoplastic elastomer by then body, wish to develop the also excellent ethylene series composition for thermoplastic elastomer of injection weldability strongly.
In addition, ethylene series dynamic crosslinking type thermoplastic elastomer has flexibility, character with excellent rubber, in addition owing to do not need vulcanization process, therefore can make the moulding product as injection molding, special-shaped extrusion moulding, rolling processing, blow molding etc. with the forming method of common thermoplastic resin.Therefore, in recent years, energy-conservation from what is called, as to save resource, recovery viewpoint, as the equivalent material purposes of vulcanized rubber or vinyl chloride resin, it need be in continuous expansion in trolley part, industrial goods, electrical and electronic parts, building materials etc.
But with in the parts, it is poor with respect to the sliding of window glass to exist at automobiles such as glass slide (glass run channel), window lace, the low problem that waits of weather resistance.
In order to improve this sliding, the spy opens and discloses the ethylene series composition for thermoplastic elastomer that has cooperated organopolysiloxane (organopolysiloxane) and aliphatic amide in ethylene series dynamic crosslinking type thermoplastic elastomer in the 2000-26668 communique.In addition, the spy opens the 2000-143884 communique and discloses in ethylene series dynamic crosslinking type thermoplastic elastomer and cooperated acrylic acid modified organopolysiloxane and higher fatty acid or higher fatty acid amides, and with the ethylene series composition for thermoplastic elastomer of they and usefulness.
But sliding is all undesirable, because fatty acid amide is separated out, therefore also has the problem of bad order.
In addition, the spy opens to disclose in the 2000-959000 communique in ethylene series dynamic crosslinking type thermoplastic elastomer and also uses, cooperates viscosity 10～less than 10 6The organopolysiloxane of cSt, viscosity 10 6～10 8The ethylene series composition for thermoplastic elastomer of the organopolysiloxane of cSt and fluoropolymer.
But, because a large amount of organopolysiloxanes that cooperate, though sliding is good, but and the low organopolysiloxane of intermiscibility of ethylene series dynamic crosslinking type thermoplastic elastomer is separated out, feel to be clamminess and worthless problem when existing, wish that strongly exploitation is not separated out and the ethylene series dynamic crosslinking type thermoplastic elastomer of excellent in sliding property with surperficial the contact.
Summary of the invention
In view of above-mentioned practical situation, the object of the present invention is to provide the harmonious excellent composition for thermoplastic elastomer and the manufacture method thereof of mechanical characteristics such as flexibility and rebound resilience and forming process.
Another object of the present invention also is to provide and has in the past the feature of ethylene series dynamic crosslinking type thermoplastic elastomer and the thermoplastic elastomer composition and the manufacture method thereof of scratch resistance excellence concurrently.
In addition, another object of the present invention also is to provide injection weldability excellence, follow body and all have high then intensity even follow quilt that body and ethylene series dynamic crosslinking type thermoplastic elastomer constitute for the quilt that constitutes by the ethylene series vulcanized rubber, and surface tear improves, especially for the composition for thermoplastic elastomer and the manufacture method thereof of the purposes that needs the heat fusing adhesion.
In addition, the present invention also aims to provide excellence, the molded appearance of moulding product and feel good thermoplastic elastic composition and manufacture method thereof such as initial stage sliding, durable sliding, wear resistant, heat fusing tackiness and forming process.
The present invention is as follows.
1, composition for thermoplastic elastomer, it constitutes by the polymer composition that contains rubber and ethylene series resin is carried out dynamic thermal treatment in the presence of linking agent, it is characterized in that: the gel fraction of contained rubber is more than 80% in this composition for thermoplastic elastomer, the number average particle diameter of contained rubber particles (dn) is below the 3 μ m in this composition for thermoplastic elastomer, and the ratio (dv/dn) of volume average particle size (dv) and this number average particle diameter (dn) is below 1.5.
2, according to the composition for thermoplastic elastomer of above-mentioned 1 record, wherein, above-mentioned gel fraction is more than 95%, and above-mentioned dn is below the 2 μ m.
3, according to above-mentioned 1 composition for thermoplastic elastomer of putting down in writing, wherein, when above-mentioned rubber and above-mentioned ethylene series resin were added up to 100 mass parts, this rubber was 20～95 mass parts, this ethylene series resin is 5～80 mass parts, and above-mentioned linking agent is 0.05～10 mass parts.
4, according to above-mentioned 1 composition for thermoplastic elastomer of putting down in writing, wherein, above-mentioned rubber is that ethene-alpha-olefin is a copolymer rubber, and this ethene-alpha-olefin is that copolymer rubber is being 2.0～6.8dl/g with naphthane as solvent, 135 ℃ of limiting viscosities [η] of measuring down.
5, composition for thermoplastic elastomer is characterized in that: in the presence of linking agent, the polymer composition that contains rubber, ethylene series resin, (methyl) acrylic ester resin and hydrogenated diene polymer is carried out dynamic thermal treatment and constitutes.
6, according to above-mentioned 5 composition for thermoplastic elastomer of putting down in writing, wherein, above-mentioned hydrogenated diene polymer constitutes by having based on the polymer blocks of vinyl aromatic unit with based on the multipolymer hydrogenation of the polymer blocks of conjugated diene unit.
7, according to above-mentioned 5 composition for thermoplastic elastomer of putting down in writing, wherein, when above-mentioned rubber, above-mentioned ethylene series resin, above-mentioned (methyl) acrylic resin and above-mentioned hydrogenated diene polymer are added up to 100 weight parts, this rubber is 20～95 quality %, this ethylene series resin is 3～70 quality %, should (methyl) acrylic resin be 1～20 quality %, this hydrogenated diene polymer be 1～10 quality %.
8, according to above-mentioned 5 composition for thermoplastic elastomer of putting down in writing, wherein, above-mentioned rubber is that ethene-alpha-olefin is a copolymer rubber, and this ethene-alpha-olefin is that copolymer rubber is being 2.0～6.8dl/g with naphthane as solvent, 135 ℃ of limiting viscosities [η] of measuring down.
9, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, the polymer composition that will contain rubber, ethylene series resin, tenderizer and maleimide compound carries out dynamic thermal treatment and constitutes, wherein, when described rubber, described ethylene series resin and described tenderizer are added up to 100 quality %, this ethylene series resin is 5～36 weight %, and when this rubber, this ethylene series resin and this tenderizer were added up to 100 mass parts, this maleimide compound was 0.3～10 mass parts.
10, according to the composition for thermoplastic elastomer of above-mentioned 9 records, wherein, when described rubber, described ethylene series resin and described tenderizer were added up to 100 quality %, this rubber was 20～85 quality %, and this tenderizer is 10～75 quality %.
11, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, the polymer composition that contains rubber, ethylene series resin, tenderizer, (methyl) acrylic ester resin and maleimide compound is carried out dynamichandling and form, wherein, when this rubber, this ethylene series resin and this tenderizer are added up to 100 mass parts, this maleimide compound is 0.3～10 mass parts, should (methyl) acrylic resin be 1～30 mass parts.
12, according to the composition for thermoplastic elastomer of above-mentioned 11 records, wherein, above-mentioned polymer composition also contains hydrogenated diene polymer, and this hydrogenated diene polymer is 0.1～1 with respect to the mass ratio of above-mentioned (methyl) acrylic resin.
13, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, be that the polymer composition of copolymer rubber, ethylene series resin, tenderizer and maleimide compound carries out dynamic thermal treatment and forms containing ethene-alpha-olefin, this ethene-alpha-olefin is that copolymer rubber is being 2.0～6.8dl/g with naphthane as solvent, 135 ℃ of limiting viscosities [η] of measuring down, wherein, when this rubber, this ethylene series resin and this tenderizer added up to 100 mass parts, this maleimide compound was 0.3～10 mass parts.
14, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, containing rubber, ethylene series resin, tenderizer, being that the polymer composition of unmodified organopolysiloxane of high viscosity more than the 10000cSt and modification organopolysiloxane carries out dynamic thermal treatment and constitutes at the unmodified organopolysiloxane of low viscosity of 25 ℃ of not enough 10000cSt of the viscosity of measuring down, according to JIS K2283 25 ℃ of viscosity of measuring down according to JIS K2283.
15, according to above-mentioned 14 composition for thermoplastic elastomer of putting down in writing, wherein, when above-mentioned rubber, above-mentioned ethylene series resin and above-mentioned tenderizer were added up to 100 mass parts, this rubber was 20～69 mass parts, this ethylene series resin is 1～50 mass parts, and this tenderizer is 20～79 mass parts.
16, according to above-mentioned 14 composition for thermoplastic elastomer of putting down in writing, wherein, when above-mentioned rubber, above-mentioned ethylene series resin and above-mentioned tenderizer are added up to 100 mass parts, the unmodified organopolysiloxane of above-mentioned low viscosity is 1～10 mass parts, the unmodified organopolysiloxane of above-mentioned high viscosity is 1～10 mass parts, and above-mentioned modification organopolysiloxane is 0.2～20 mass parts.
17, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, to containing oil-extended rubber, the ethylene series resin, the back interpolation tenderizer of Pei Heing as required, according to the unmodified organopolysiloxane of JISK2283 at 25 ℃ of not enough 10000cSt of the viscosity of measuring down, is that the polymer composition of unmodified organopolysiloxane more than the 10000cSt and modification organopolysiloxane carries out dynamic thermal treatment and constitutes according to JIS K2283 25 ℃ of viscosity of measuring down, wherein, oil-extended rubber contains rubber and tenderizer, when this rubber and this tenderizer are added up to 100 quality %, this rubber is 30～70 quality %, and this tenderizer is 30～70 quality %.
18, according to above-mentioned 17 composition for thermoplastic elastomer of putting down in writing, wherein, when above-mentioned oil-extended rubber, above-mentioned ethylene series resin and above-mentioned back interpolation tenderizer are added up to 100 mass parts, this oil-extended rubber is 30～99 mass parts, this ethylene series resin is 1～50 mass parts, it is 50 mass parts following (wherein, comprising 0 mass parts) that tenderizer is added in this back.
19, according to above-mentioned 17 composition for thermoplastic elastomer of putting down in writing, wherein, when above-mentioned oil-extended rubber, above-mentioned ethylene series resin and above-mentioned back interpolation tenderizer are added up to 100 mass parts, the unmodified organopolysiloxane of above-mentioned low viscosity is 1～10 mass parts, the unmodified organopolysiloxane of above-mentioned high viscosity is 1～10 mass parts, and above-mentioned modification organopolysiloxane is 0.2～20 quality %.
20, according to above-mentioned 14 or 17 composition for thermoplastic elastomer of putting down in writing, wherein, above-mentioned rubber is that ethene-alpha-olefin is a copolymer rubber, and this ethene-alpha-olefin is that copolymer rubber is being 2.0～6.8dl/g with naphthane as solvent, 135 ℃ of limiting viscosities [η] of measuring down.
21, the manufacture method of composition for thermoplastic elastomer, it is characterized in that: the polymer composition that will contain rubber and ethylene series resin with closed mixing machine reaches other additives that do not comprise linking agent, or contain rubber and ethylene series resin polymer composition, linking agent at least a portion and do not comprise other additive melting mixings of linking agent, become the melting mixing thing, this melting mixing thing or this melting mixing thing and the additive that at least contain linking agent supplied in continous way forcing machine, carry out dynamic thermal treatment thereafter.
22, the manufacture method of composition for thermoplastic elastomer is characterized in that: cooperate linking agent in the polymer composition that contains rubber and ethylene series resin, thereafter, supply in interconnective a plurality of continous way mixing roll, carry out dynamic thermal treatment.
23, the manufacture method of composition for thermoplastic elastomer, it is characterized in that: the polymer composition that will contain rubber and ethylene series resin is supplied with from the raw material introduction part of this continous way opposite spin twin shaft extruder of the extrusion device of the continous way opposite spin twin shaft mixing roll at upper reaches and dirty equidirectional rotation twin shaft mixing roll configured in series, by this continous way opposite spin twin shaft mixing roll that this polymer composition is mixing, the limit remains on below 250 ℃ the mixing thing temperature of this continous way opposite spin twin shaft mixing roll outlet, the limit should supply to this equidirectional rotation twin shaft extruder by mixing thing, carried out dynamic crosslinking.
24, the manufacture method of composition for thermoplastic elastomer, it is characterized in that: the polymer composition that will contain rubber, ethylene series resin and organo-peroxide is supplied with from the raw material introduction part of this continous way opposite spin twin shaft extruder of the extrusion device of the continous way opposite spin twin shaft mixing roll at upper reaches and dirty equidirectional rotation twin shaft mixing roll configured in series, by this continous way opposite spin twin shaft mixing roll that this polymer composition is mixing, the limit is with the mixing thing temperature (t of this continous way opposite spin twin shaft mixing roll outlet a) be controlled at T h-30≤t a≤ T h+ 30 (℃) scope, the limit should supply to this equidirectional rotation twin shaft extruder by mixing thing, carried out dynamic crosslinking, wherein, and when the fusing point of this ethylene series resin is T mThe time, 1 minute half life temperature T of organo-peroxide h(℃) at T m≤ T h≤ T m+ 50 (℃) scope.
According to the present invention, can obtain following effect.
According to the present invention,, can become the harmonious excellent composition for thermoplastic elastomer of mechanical characteristics such as flexibility and rebound resilience and forming process by the polymer composition dynamic crosslinking that will constitute by rubber and ethylene series resin etc.In addition, if use this constituent, use injection molding, extrusion moulding, slush molding, compressed moulding, vacuum forming, laminated into type, calendering formation etc. to carry out handling ease.
In addition, particularly can become the ethylene series composition for thermoplastic elastomer of scratch resistance excellence, particularly for beyond use exterior member, electrical equipment in the automobile weather strip, sponge, lace etc. of ethylene series thermoplastic elastomer moulded products such as shell, require the belt slab products etc. of scratch resistance useful.
In addition, also can become the composition for thermoplastic elastomer of injection weldability excellence, particularly except various Compound Machining product, can be widely used in general processed goods with injection weld portion.For example, can be used for the collision bumper of automobile, outer dress with lace, window sealing with sealed strip, door sealing with sealed strip, vehicle body sealing with sealed strip, the curb rafter at top, badge, inside and outside dress skin material, can also be used for aircraft and boats and ships with sealing material or inside and outside dress skin material etc., building-sealing material for building, inside and outside dress skin material or waterproof and sealing material etc., common mechanical, device be with sealing material etc., the liner of light current part or clamshell etc., sundry goods product, sports goods etc.
In addition, can become excellences such as initial stage sliding, durable sliding, wear resistant, the molded appearance of moulding product and feel good thermoplastic elastic composition can be used as automobiles such as glass slide, window lace with parts etc.
[1] contains the composition for thermoplastic elastomer of the rubber particles of specified particle diameter
Composition for thermoplastic elastomer of the present invention is characterised in that: in the presence of linking agent, the polymer composition that contains rubber and ethylene series resin is carried out dynamic thermal treatment and forms.Especially, its for the composition for thermoplastic elastomer that carries out dynamic thermal treatment at the polymer composition that will contain rubber and ethylene series resin in the presence of the linking agent and form (below, be called " the specified particle diameter rubber particles contains composition [A] "), the gel fraction that this specified particle diameter rubber particles contains the rubber that contains in the composition [A] is more than 80%, the number average particle diameter (dn) that this specified particle diameter rubber particles contains the rubber particles that contains in the composition [A] is below the 3 μ m, and the ratio (dv/dn) of volume average particle size (dv) and this number average particle diameter (dn) is below 1.5.
(1) rubber
1. the kind of rubber
Rubber is not particularly limited, for example can exemplify synthetic polyisoprene, divinyl rubber, styrene butadiene rubbers, natural rubber, chloroprene rubber, isoprene-isobutylene rubber, nitrile and be rubber, hydrogenated nitrile and be rubber, norbornene rubbers, ethene-alpha-olefin is copolymer rubber, acrylic rubber, ethylene-acrylate rubber, viton, chlorosulfonated polyethylene rubber, epichloro hydrin rubber, silicon rubber, urethanes, polysulfide rubber, phosphonitrile rubber, 1,2-polyhutadiene etc.Wherein, optimal ethylene-alpha-olefin is a copolymer rubber.Can only use these rubber a kind, also can more than 2 kinds and use.
2. ethene-alpha-olefin is a copolymer rubber
Ethene-alpha-olefin be copolymer rubber (below, abbreviate " copolymer rubber " sometimes as) be with ethylene unit, the alpha-olefin unit that do not comprise ethene is the unitary rubber of main composition.When all being designated as 100 moles of % with this copolymer rubber, optimal ethylene unit and alpha-olefin unit add up to 90 moles more than the %.
As the alpha-olefin that is used to make this copolymer rubber, can exemplify the alpha-olefin of carbon numbers 3～12 such as propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-amylene, 1-octene, 1-decene, 1-hendecene.Wherein, preferred propylene and 1-butylene.Can only use these alpha-olefins a kind, also can more than 2 kinds and use.
In addition, as other monomers, can use non-conjugated diene.As this non-conjugated diene, can exemplify 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene, 5-methyl isophthalic acid, 8-nonadiene, Dicyclopentadiene (DCPD), 5-ethylidene-2-norbornene, 5-vinyl-2-norbornylene, 2,5-norbornadiene etc.Wherein, preferred especially Dicyclopentadiene (DCPD) and 5-ethylidene-2-norbornene.Can only use these non-conjugated dienes a kind, also can more than 2 kinds and use.
As copolymer rubber, optimal ethylene-alpha-olefin binary copolymerization rubber, ethylene-alpha-olefin-nonconjugated propylene-diene terpolymer rubber etc.As this ethene-alpha-olefin binary copolymerization rubber, use ethylene-propylene copolymer rubber and ethene-1-butylene copolymer rubber more.During all as 100 moles of %, ethylene content is preferably 50～95 moles of % in these copolymer rubbers, preferred especially 60～90 moles of % with copolymer rubber.
In addition, as ethylene-alpha-olefin-nonconjugated propylene-diene terpolymer rubber, use ethene-third hydrocarbon-Dicyclopentadiene (DCPD) terpolymer rubber, ethylene-propylene-5-vinyl-2-norbornylene terpolymer rubber, ethene-1-butylene-Dicyclopentadiene (DCPD) terpolymer rubber more, reach ethene-1-butylene-5-vinyl-2-norbornylene terpolymer rubber.When ethylene unit and propylene units or 1-butylene unit are added up to 100 moles of %, preferred 50～95 moles of % of ethylene content in these copolymer rubbers, preferred especially 60～90 moles of %.In addition, when ethylene unit and propylene units or 1-butylene unit were added up to 100 moles of %, Dicyclopentadiene (DCPD) or 5-vinyl-2-norbornylene content was preferably 3～10 moles of %, is preferably 3～8 moles of % especially.
If 50 moles of % of ethylene content less than in the copolymer rubber, the tendency (when particularly having used organo-peroxide as linking agent) that then exists cross-linking efficiency to reduce can't become the copolymer rubber with desirable rerum natura sometimes.On the other hand, if ethylene content surpasses 95 moles of %, then the flexibility of copolymer rubber reduces, and is therefore inadvisable.
In addition, with naphthane at the ethene-alpha-olefin of 135 ℃ of mensuration be the limiting viscosity [η] of copolymer rubber for more than the 1.0dl/g, preferred 2.0～6.8dl/g, more preferably 3.5～6.8dl/g, most preferably 4.5～6.0dl/g.If the not enough 2.0dl/g of this limiting viscosity, rebound resilience reduces sometimes.On the other hand, if surpass 6.8dl/g, then the tendency that exists processibility to descend during moulding is therefore inadvisable.
As copolymer rubber, except above-mentioned binary copolymerization rubber and terpolymer rubber, the halogenation copolymer rubber that can also use the part of the hydrogen atom that these copolymer rubbers contain to be replaced by halogen atoms such as chlorine atom, bromine atoms.In addition, can also use with respect to binary copolymerization rubber, terpolymer rubber and halogenation copolymer rubber, make (methyl) acrylic acid derivatives such as vinylchlorid, vinyl acetate between to for plastic, (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) glycidyl acrylate, (methyl) acrylamide, toxilic acid, maleic anhydride, the maleic anhydride maleic acid derivatives such as imines, dimethyl maleate that contract, the graft copolymerization rubber of monomer-grafted copolymerization such as divinyl, isoprene, chloroprene equiconjugate diene etc.Can distinguish a kind that only uses these halogenation copolymer rubbers and graft copolymerization rubber, also can be more than 2 kinds and usefulness, also can use halogenation copolymer rubber and graft copolymerization rubber.
Copolymer rubber for example can use, be matched with in the presence of the catalyzer that constitutes by Ziegler-Natta catalyst, soluble vanadium compound and organo-aluminium compound of solvent, in the usefulness such as non-conjugated diene polymeric method when constantly supplying with hydrogen as required and making ethene, alpha-olefin and terpolymer rubber as molecular weight regulator-the low-pressure process polymerization process makes.This polymerization can be carried out with liquid phase methods such as vapor phase processs such as thermopnore, agitated bed, slurry process, solution methods.
As soluble vanadium compound, preferably use VOCl 3And/or VCl 4Resultant of reaction with alcohol.As this 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, n-dodecane alcohol etc.Wherein, the alcohol of preferred carbon number 3～8.
In addition, as organo-aluminium compound, for example can use aluminium trimethide alkane as the resultant of reaction of triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminium sesqui chloride, butyl aluminium sesquichloride, ethyl aluminum dichloride, two chlorobutyl aluminium, trimethyl aluminium and water.Wherein, the mixture of mixture, triisobutyl aluminium and the butyl aluminium sesquichloride of preferred especially ethyl aluminium sesqui chloride, butyl aluminium sesquichloride, ethyl aluminium sesqui chloride and butyl aluminium sesquichloride.
In addition, as solvent, preferred hydrocarbons solvent, preferred especially Skellysolve A, normal hexane, normal heptane, octane, octane-iso, hexanaphthene.Can only use these materials a kind, also can more than 2 kinds and use.
When rubber and ethylene series resin are added up to 100 mass parts, preferred 20～95 mass parts of the amount of the rubber that polymer composition contained, more preferably 40～94 mass parts, most preferably 60～93 mass parts.If amount less than 20 mass parts of rubber then exist the specified particle diameter rubber particles to contain the flexibility of composition [A] and the tendency that elasticity reduces.On the other hand, if its amount surpasses 95 mass parts, then the specified particle diameter rubber particles contains the flowability reduction of composition [A], and forming process significantly worsens, and is worthless.
3. the gel fraction of rubber
The gel fraction that the specified particle diameter rubber particles contains the rubber that composition [A] contained is more than 80%, and is preferred more than 90%, preferred especially more than 95%, further preferred more than 96%, more preferably more than 97%.Being conceived to the specified particle diameter rubber particles, to contain the physical strength of composition [A] good, and this gel fraction is preferably more than 95%, if less than 95%, then physical strength descends, and caoutchouc elasticity is also undesirable simultaneously.The measuring method of this gel fraction is as described below.
The about 200mg specified particle diameter of weighing rubber particles contains composition [A], it is cut out thin., use encloses container thereafter, 23 ℃ down with the hexanaphthene of this shred at 100ml in dipping 48 hours.Then, this shred is fetched on the filter paper, under 105 ℃, carries out 1 hour drying under reduced pressure with Vacuumdrier.From the quality of this drying residue, deduct quality, and the 2. quality of the ethylene series resin that test portion contained before the hexanaphthene dipping of the insoluble composition of hexanaphthene (weighting agent, pigment etc.) beyond the 1. rubber and ethylene series resin, with resulting value as " final quality of correction (p) ".
On the other hand, from the quality of test portion, deduct the quality of the solvable composition of hexanaphthene (for example tenderizer) beyond the 3. rubber and ethylene series resin, 1. quality, and the 4. quality of ethylene series resin of the insoluble composition of hexanaphthene (weighting agent, pigment etc.) beyond rubber and the ethylene series resin, with resulting value as " the initial stage quality (q) of correction ".
Gel fraction (the insoluble composition of hexanaphthene) is tried to achieve by following formula.
Gel fraction (quality %)=[{ final quality of correction (p) } ÷ { the initial stage quality (q) of correction }] * 100
4. the amount of rubber
When rubber and ethylene series resin are added up to 100 mass parts, preferred 20～95 mass parts of the amount of rubber, more preferably 40～94 mass parts, most preferably 60～93 mass parts.If amount less than 20 mass parts of this rubber then exist the flexibility of thermoplastic elastomer and the tendency that elasticity reduces.On the other hand, if its amount surpasses 95 mass parts, then the flowability of composition for thermoplastic elastomer reduces, and forming process is also undesirable, and is therefore inadvisable.
5. cross-linked rubber particle
The specified particle diameter rubber particles contains in the composition [A] the cross-linked rubber particle can use infiltration type electron microscope (below, be called " TEM ") to observe.The TEM photo that obtains by this cross-linked rubber particle is taken a picture is drawn a portrait analysis, the area calculating that the use portrait is analyzed the cross-linked rubber particle that obtains is below the 3 μ m at the number average particle diameter dn that the specified particle diameter rubber particles contains rubber particles in the composition [A], below the preferred 2 μ m, more preferably below the 1.4 μ m, most preferably below the 1.0 μ m, and volume average particle size dv that tries to achieve with number average particle diameter dn and the ratio dv/dn of number average particle diameter dn are below 1.5, preferred below 1.4, more preferably below 1.3.In this scope, can become have concurrently the required good caoutchouc elasticity of purpose, mechanical characteristics, and the specified particle diameter rubber particles of forming process contain composition [A].Even the dv/dn ratio is below 1.5, if number average particle diameter dn surpasses 2 μ m, particularly surpass 3 μ m, then there is the tendency of forming process reduction.In addition, even number average particle diameter dn is below the 3 μ m, below 2 μ m, if dv/dn is than surpassing 1.5, the tendency that then exists mechanical characteristics to reduce.In addition, when the dv/dn ratio was 1, expression particle diameter state of homogeneous all along with than 1 big, then was expressed as for each heterogeneity state all of particle diameter.
With TEM this specified particle diameter rubber particles is contained composition [A] when observing, at first, making the specified particle diameter rubber particles contain composition [A] with freezing shave machine becomes thin slice, uses staining agents such as ruthenium tetroxide, perosmic anhydride, chlorsulfonic acid, acetic acid uranium, phospho-wolframic acid, iodide ion, trifluoroacetic acid to dye.When the selective staining agent, the kind that need contain the functional group that molecule had of composition [A] according to the specified particle diameter rubber particles as the object of observation is selected optimal staining agent.As this staining agent, optimal is ruthenium tetroxide, perosmic anhydride.
Then, the thin slice that painted specified particle diameter rubber particles contains composition [A] is amplified 2000 times, take a picture with TEM.
Number average particle diameter and volume average particle size are resolved by the portrait of TEM photo and are tried to achieve, for example, resolve software as portrait, can use Image-Pro Plus Ver.4.0 for Windows (MediaCybernetics company (USA) manufacturing, the プ ラ ネ ト ロ of Zhu Shi commercial firm Application are sold) etc.
Resolve the area of asking for crosslinked particle by portrait, can calculate number average particle diameter dn, reach volume average particle size dv by following formula.Specifically, can use J.MACROMOL.SCI.-PHYS., B38 (5﹠amp; 6), the method for calculation of 527 (1999) middle records.
1) by the TEM photo being drawn a portrait the area of resolving the cross-linked rubber particle the try to achieve diameter (dn when being scaled proper circle j) calculating formula
d n j = 4 π · A particle
A: the TEM photo is drawn a portrait the area of resolving the cross-linked rubber particle try to achieve
2) count the calculating formula of average cross-linked rubber particle diameter (dn)
d n = Σ i d n j n
3) calculating formula of volume averaging cross-linked rubber particle diameter (dv)
d v = Σ i d nj 3 n 3
(2) ethylene series resin
As being used for the ethylene series resin that specified particle diameter rubber particles of the present invention contains composition [A], can use crystallinity ethylene series resin and/or noncrystalline ethylene series resin.
1. crystallinity ethylene series resin
Crystallinity ethylene series resin is not particularly limited, and preferably is the crystallinity ethylene series resin of main composition unit with the alpha-olefin.That is, when the ethylene series resin all be 100 moles of % the time, the preferred unitary content of alpha-olefin is 80 moles more than the %, especially preferably contains 90 moles more than the %.
Crystallinity ethylene series resin can be the homopolymer of alpha-olefin, also can be the multipolymer of alpha-olefin more than 2 kinds.In addition, also can be alpha-olefin and the monomeric multipolymer beyond it.In addition, also can be the different crystallinity ethylene series resin more than 2 kinds and/or the mixture of copolymer resins.
As the alpha-olefin that is used to make crystallinity ethylene series resin, preferred carbon number is the alpha-olefin more than 3, more preferably uses the alpha-olefin of the carbon number of putting down in writing in aforementioned copolymer rubber 3～12.In addition, when crystallinity ethylene series resin is and during the multipolymer of ethene, when with this multipolymer during all as 100 moles of %, optimal ethylene content is 40 moles below the %, is preferably 20 moles especially below the %.
When crystallinity ethylene series resin was multipolymer, this multipolymer can be any one of random copolymers and segmented copolymer.But in order to become the random copolymers with following degree of crystallinity, when this random copolymers all was designated as 100 moles of %, the unitary total content of formation that preferably removes alpha-olefin was 15 moles below the %, preferred especially 10 moles below the %.In addition, when being segmented copolymer, when this segmented copolymer all is designated as 100 moles of %, preferably make except that the unitary total content of the formation of alpha-olefin be 40 moles below the %, be preferably especially below 20 moles.
In addition, random copolymers for example can be made with the method identical with aforementioned copolymer rubber.In addition, the living polymerization that segmented copolymer can be by using Ziegler-Natta catalyst etc. is made.
The degree of crystallinity that the crystallinity of this crystallinity ethylene series resin is measured with X-ray diffraction method is represented, is preferably more than 50%, more preferably more than 53%, most preferably more than 55%.In addition, this degree of crystallinity and density are closely related.For example, under the polyacrylic situation, the density of α type crystallization (monoclinic form) is 0.936g/cm 3About, the density of dish-like crystallite (plan hexagonal structure) is 0.886g/cm 3About, the density of noncrystalline (random) composition is 0.850g/cm 3About.In addition, under the situation of poly-1-butylene, isotactic crystalline density is 0.91g/cm 3About, the density of noncrystalline (random) composition is 0.87g/cm 3About.Therefore, when it for degree of crystallinity was crystalline polymer more than 50%, preferred density was 0.89g/cm 3More than, be preferably 0.90～0.94g/cm especially 3If this degree of crystallinity less than 50%, or the not enough 0.89g/cm of density 3, the tendency that then exists thermotolerance, intensity etc. that the specified particle diameter rubber particles contains composition [A] to reduce.
In addition, the maximum peak temperature of the crystallinity ethylene series resin of measuring with differential scanning calorimeter, promptly fusing point (below, abbreviate " T as m") because of used monomeric difference is different, but be preferably more than 100 ℃, be preferably especially more than 120 ℃.If this T m100 ℃ of less thaies then exist to obtain the enough thermotolerances and the tendency of intensity.
In addition, be preferably 0.1～100g/10 branch, be preferably 0.5～80g/10 branch especially in the melt flow index of the crystallinity ethylene series resin of measuring under the condition of the heavy 2.16kg of 230 ℃ of temperature, load (below, abbreviate " MFR " as).If then there is mixing processibility in MFR is not enough 0.1g/10 branch, extrudes unfavorable tendency such as processibility.On the other hand, if MFR surpasses 100g/10, the tendency that then exists intensity to reduce.
Therefore, as crystallinity ethylene series resin, especially preferably use degree of crystallinity more than 50%, density 0.89g/cm 3More than, following, the T of 20 moles of % of amount of ethylene unit mBe more than 100 ℃, MFR is that 0.1～100g/10 branch, fusing point are 140～170 ℃ the polypropylene and/or the multipolymer of propylene and ethene.
2. noncrystalline ethylene series resin
Noncrystalline ethylene series resin is not particularly limited, and preferably is the noncrystalline ethylene series resin of principal constituent with the alpha-olefin unit.That is, when all being 100 moles of %, preferably contain the above alpha-olefin of 50 moles of %, especially preferably contain 60 moles more than the % with noncrystalline ethylene series resin.
This noncrystalline ethylene series resin can be the homopolymer of alpha-olefin, also can be the multipolymer of the alpha-olefin more than 2 kinds.In addition, also can be alpha-olefin and the monomeric multipolymer beyond it.In addition, also can be the different polymkeric substance more than 2 kinds and/or the mixture of multipolymer.
As the alpha-olefin that is used to make noncrystalline ethylene series resin, the preferred alpha-olefin of carbon number more than 3, the alpha-olefin of identical carbon number 3～12 when more preferably using with aforementioned copolymer rubber.
As noncrystalline ethylene series resin, can exemplify homopolymer such as Atactic Polypropelene, atactic polybutene 1, and the multipolymer (preferably containing the above 1-butylene unit of 50 moles of %) of other alpha-olefins such as multipolymer (preferably containing the above propylene units of 50 moles of %), 1-butylene and the ethene of other alpha-olefins such as propylene and ethene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, propylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene etc.
When noncrystalline ethylene series resin was made of multipolymer, this multipolymer can be any one of random copolymers and segmented copolymer.But, under the situation of segmented copolymer, in this multipolymer propylene units, 1-butylene unit etc. become the alpha-olefin unit of principal constituent must be with the random structure combination.In addition, for by alpha-olefin and the multipolymer of the ethene noncrystalline ethylene series resin that constitute of carbon number more than 3, when multipolymer all was 100 moles of %, preferred alpha-olefin content was 50 moles more than the %, is preferably 60～100 moles of % especially.
As noncrystalline ethylene series resin, the multipolymer of multipolymer, propylene (containing 50 moles more than the %) and the 1-butylene of preferred especially Atactic Polypropelene (propylene content 50 moles more than the %), propylene (containing 50 moles more than the %) and ethene etc.
In addition, this Atactic Polypropelene by product of can be used as crystalline polypropylene obtains.In addition, Atactic Polypropelene and atactic polybutene 1 can obtain by the polymerization that the catalyzer of compound and aluminium trimethide alkane has been made up in use.In addition, random copolymers can use the method identical with aforesaid copolymer rubber to make, and the living polymerization that segmented copolymer can be by using Ziegler-Natta catalyst etc. is made.
In addition, the melt viscosity of noncrystalline ethylene series resin in the time of 190 ℃ is preferably below the 50Pa s, more preferably below 0.1～30Pa s, most preferably is 0.2～20Pa s.If this melt viscosity surpasses 50Pa s, when then the injection of vulcanized rubber and thermoplastic elastomer is being melted, exist and the tendency that is reduced by the then intensity of body.
In addition, with the preferred less than 50% of noncrystalline ethylene series resin crystallinity of X-ray diffraction method mensuration, more preferably below 30%, most preferably below 20%.Identical during with crystallinity ethylene series resin, this degree of crystallinity and density are closely related, and density is preferably 0.85～0.89g/cm 3, more preferably 0.85～0.88g/cm 3For degree of crystallinity surpass 50% and density surpass 0.89g/cm 3At least one side the time, when vulcanized rubber and thermoplastic elastomer injection are being melted, exist and the tendency that is reduced by the then intensity of body.
In addition, the number-average molecular weight (M of this noncrystalline ethylene series resin n) be preferably 1000～20000, more preferably 1500～15000.
As this ethylene series resin, can and use crystallinity ethylene series resin and noncrystalline ethylene series resin, also can only use either party.
3. the amount of ethylene series resin
When rubber and ethylene series resin added up to 100 mass parts, the amount of ethylene series resin was preferably 5～80 mass parts, and more preferably 6～60 mass parts most preferably are 7～40 mass parts.If amount less than 5 mass parts of this ethylene series resin, then (the ethylene series resin is sea (matrix) to the specified particle diameter rubber particles phase structure (morphology) that contains composition [A] for the good island structure as dynamic crosslinking type elastomeric characteristic, cross-linked rubber is island (domain structure)), forming process, mechanical characteristics reduce sometimes.On the other hand, if its amount surpasses 80 mass parts, then the specified particle diameter rubber particles contains the flexibility and the caoutchouc elasticity reduction of composition [A], and is therefore inadvisable.
(3) tenderizer
Contain in the composition [A] at this specified particle diameter rubber particles and to contain tenderizer usually.This tenderizer is not particularly limited, for example can exemplify, 1. carboxylic acid is a tenderizer: stearic acid, lauric acid etc., 2. vegetables oil is a tenderizer: Oleum Cocois, Oleum Gossypii semen, linseed oil, the vegetable seeds wet goods, 3. Stockholm tar, 4. ointment: white factice, dark substitute, translucent ointment etc., 5. mineral oil softener: paraffin series mineral oil, naphthalene is a mineral oil, fragrance family mineral oil etc., 6. ester is a tenderizer: dibutyl phthalate, dioctyl phthalate (DOP), Octyl adipate, hexanodioic acid two (butyl glycol) ester, hexanodioic acid two (butylcarbitol) ester, dioctyl sebacate, Uniflex DBS, phosphoric acid trimethylbenzene phenolic ester, phosphoric acid cresols phenyl ester, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, polyethers is a softening agent, hexanodioic acid is a polyester etc., 7. the hydrocarbon system tenderizer: polybutene system, polyhutadiene system etc.Wherein, preferred mineral oil softener, more preferably weight-average molecular weight is 300～2000, particularly 500～1500 mineral oil softener.By mineral oil is that softener of rubber that hydrocarbon constitutes is generally aromatic ring, naphthalene nucleus, and paraffin chain three's mixture, and the naphthalene system carbon number oily, aromatic ring that the carbon number that the carbon number that is divided into the paraffin chain accounts for the paraffin series oil of whole carbon numbers 50% or more, naphthalene nucleus accounts for whole carbon numbers 30～45% accounts for the fragrant family oil of whole carbon numbers more than 30%.In the present invention, preferred paraffin series oil, preferred especially hydrowax is an oil.In addition, preferred 40 ℃ kinetic viscosity is 20～800cSt, particularly 50～600cSt, and yield point is a hydrocarbon for-40～0 ℃, particularly-30～0 ℃ mineral oil.Can only use these materials a kind, also can more than 2 kinds and use.
Per 100 mass parts rubber, the amount of tenderizer can be for below 200 mass parts, below preferred 180 mass parts, more preferably below 150 mass parts, most preferably below 100 mass parts.If the amount of tenderizer surpasses 150 mass parts, particularly surpass 200 mass parts, then tenderizer contains the constituent [A] from the specified particle diameter rubber particles and separates out the tendency that exists mechanical characteristics and caoutchouc elasticity to reduce.When this tenderizer uses oil-extended rubber, can be the tenderizer that is contained in this oil-extended rubber, also can add again later on and cooperate.
This specified particle diameter rubber particles contains constituent [A] to be processed with injection molding, extrusion moulding, slush molding, compressed moulding, vacuum forming, laminated into type, calendering formation etc. easily, can become the body formed product of thermoplastic elastic of caoutchouc elasticity, mechanical characteristics excellence.
[2] contain the composition for thermoplastic elastomer of acrylic ester resin
Another composition for thermoplastic elastomer involved in the present invention (below, be called " acrylate contains constituent [B] ") be characterised in that: in the presence of linking agent, the polymer composition that contains rubber, ethylene series resin, (methyl) acrylic ester resin and hydrogenated diene based copolymer is carried out dynamic thermal treatment and forms.
Contain in the composition [B] at this acrylic ester resin, rubber and ethylene series resin can use aforementioned substances respectively.As rubber, special optimal ethylene-alpha-olefin is a random copolymer rubber.In addition, as the ethylene series resin, can use crystallinity ethylene series resin and/or noncrystalline ethylene series resin.As crystallinity ethylene series resin, special optimization polypropylene and propylene-ethylene copolymers.In addition, as noncrystalline ethylene series resin, preferred especially Atactic Polypropelene (propylene content 50 moles more than the %), propylene (containing 50 moles more than the %) and the multipolymer of ethene and the multipolymer of propylene (containing 50 moles more than the %) and 1-butylene.
In addition, contain in the composition [B] at this acrylic ester resin, when rubber, ethylene series resin, (methyl) acrylic ester resin and hydrogenated diene polymer added up to 100 quality %, rubber was preferably 20～95 quality %, more preferably 30～90 quality %.In addition, the ethylene series resin is preferably 3～70 quality %, more preferably 5～60 quality %.If the amount deficiency of rubber 20 quality %, then the acrylic ester resin contains the flexibility and the caoutchouc elasticity reduction of constituent [B].On the other hand, if surpass 95 quality %, then the acrylic ester resin contains the flowability reduction of composition [B], the tendency that exists forming process significantly to worsen.In addition, if the amount deficiency of ethylene series resin 3 quality %, then (the ethylene series resin is sea (matrix) to the acrylic ester resin phase structure (morphology) that contains composition [B] for the good island structure as dynamic crosslinking type elastomeric characteristic, cross-linked rubber is island (domain structure)), forming process, mechanical characteristics reduce sometimes.On the other hand, if surpass 70 quality %, then the acrylic ester resin contains the flexibility and the caoutchouc elasticity reduction of [B], and is therefore inadvisable.
This acrylic ester resin contains in the composition [B] and contains aforesaid tenderizer usually.Per 100 mass parts rubber, the amount of this tenderizer can be preferably below 180 mass parts for below 200 mass parts, more preferably below 150 mass parts, most preferably is below 100 mass parts.If the amount of tenderizer surpasses 150 mass parts, particularly surpass 200 mass parts, then tenderizer is separated out from acrylate based resin composition [B], the tendency that exists mechanical properties and caoutchouc elasticity to reduce.When this tenderizer used oil-extended rubber, the tenderizer for containing in this oil-extended rubber only also can add later on again and cooperates.
(1) (methyl) acrylic ester resin
As (methyl) acrylic ester resin, can use with monomer with acrylic or methacrylic acid group polymer of vinyl monomer as principal constituent.What is called has the monomer of acrylic or methacrylic acid group, be meant monomer with 1 above acrylic or methacrylic acid group, for example can exemplify: methyl acrylate, ethyl propenoate, the vinylformic acid n-propyl, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, sec-butyl acrylate, 2-methyl butyl acrylate, 3-methyl butyl acrylate, the just own ester of vinylformic acid, the positive heptyl ester of vinylformic acid, the vinylformic acid n-octyl, alkyl acrylates such as 2-ethylhexyl acrylate, ethylene glycol diacrylate, 1, the 2-propylene glycol diacrylate, 1, the ammediol diacrylate, 1, the 2-butylene glycol diacrylate, 1, the 3-butylene glycol diacrylate, 1, diacrylates such as 4-butylene glycol diacrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, the methacrylic tert-butyl acrylate, the secondary butyl ester of methacrylic acid, 2-methyl butyl methacrylic ester, 3-methyl butyl methacrylic ester, the just own ester of methacrylic acid, the positive heptyl ester of methacrylic acid, n octyl methacrylate, alkyl methacrylates such as 2-ethylhexyl methacrylic ester, 1,2-propylene glycol dimethacrylate, 1, the ammediol dimethacrylate, 1, the 2-butylene glycol dimethacrylate, 1, the 3-butylene glycol dimethacrylate, 1, alkyl dimethacrylates such as 4-butylene glycol dimethacrylate etc.
In (methyl) acrylic ester resin, the homopolymer of preferable methyl methyl acrylate or be other monomeric multipolymers of principal constituent and minor amounts of copolymerized with the methyl methacrylate.As other monomers, for example can exemplify: vinylformic acid, acrylate metal salt, methyl acrylate, ethyl propenoate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, esters of acrylic acids such as 2-ethylhexyl acrylate, the methacrylic acid metal salt, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, the methacrylic tert-butyl acrylate, the 2-hydroxyethyl meth acrylate, glycidyl methacrylate, methyl acrylic esters such as cyclohexyl methacrylate, acetates such as vinyl acetate, vinylbenzene, aromatic ethenyl compounds such as alpha-methyl styrene, maleic anhydride, the maleic acid mono alkyl ester class, the dialkyl maleate class, maleimides such as N-phenylmaleimide etc.
The type of multipolymer is not particularly limited, and can be random copolymers, segmented copolymers such as diblock, three blocks, many blocks, wedge shape block, multistage graft copolymer etc. any.In addition, the structure of (methyl) acrylic ester resin is not particularly limited, can be for straight chain type, branching type, multi-layered type any.
The MFR that (methyl) acrylic ester resin is measured under 230 ℃ of temperature, the heavy 3.8kg of load is not particularly limited, and is preferably 0.1～100g/10 branch, more preferably 0.5～80g/10 branch.
The acrylic ester resin contains preferred 1～20 quality % of amount of (methyl) acrylic ester resin in the composition [B], more preferably 5～15 quality %.If this amount less than 1 quality %, then the acrylic ester resin contains the scratch resistance reduction of composition [B].On the other hand, if surpass 20 quality %, then the acrylic ester resin contains the flexibility and the caoutchouc elasticity reduction of composition [B], and is therefore inadvisable.
(2) hydrogenated diene polymer
As hydrogenated diene polymer, for example can exemplify homopolymer with conjugate diene monomer, the random copolymers of conjugate diene monomer and vinyl aromatic monomers, the segmented copolymer that the polymer blocks of vinyl aromatic monomers and the polymer blocks of conjugate diene monomer constitute, the segmented copolymer that the block of random copolymer of the polymer blocks of vinyl aromatic monomers and conjugate diene monomer and vinyl aromatic monomers constitutes, the segmented copolymer that the copolymer block of the polymer blocks of conjugate diene monomer and conjugate diene monomer and vinyl aromatic monomers constitutes, the segmented copolymer that the taper block that the polymer blocks of conjugate diene monomer and vinyl aromatic monomers and conjugate diene monomer constitute and vinyl aromatic monomers is cumulative constitutes, the segmented copolymer that the taper block that the block of random copolymer of conjugate diene monomer and vinyl aromatic monomers and vinyl aromatic monomers and conjugate diene monomer constitute and vinyl aromatic monomers is cumulative constitutes, ethylenic linkage is that following polybutadiene block of 30 quality % and the ethylenic linkage diene polymers such as segmented copolymer that surpass the polymer blocks of the conjugate diene monomer of 30 quality % and constitute (below, also the polymkeric substance before these hydrogenation is called " hydrogenation prepolymer " sometimes) carry out hydrogenation and the hydrogenated diene polymer that obtains.
In these hydrogenated diene polymers, preferably have based on vinyl aromatic monomers polymer blocks (A) and based on the hydrogenation thing of the conjugated diene polymer of the polymer blocks (B) of conjugate diene monomer.
Polymer blocks (A) is for the homopolymer of vinyl aromatic monomers or have and surpass 50 quality %, preferred 70 quality % and contain the unitary vinyl aromatic monomers of vinyl aromatic monomers unit and other monomers that can copolymerization, the copolymerization structure of preferred conjugated diolefine, in addition, polymer blocks (B) is for the homopolymer of conjugate diene monomer or have the structure of other monomer copolymerizations that make the following vinyl aromatic monomers of 5 quality % etc., and block structure is (A-B) n-A type (n is 1～10 integer) or (A-B) segmented copolymer of m type (m is 2～10 integer).In addition, can have short B block in the A block of end.In addition, can be for having the segmented copolymer of [(A-B) n] m-M type (M is coupling agent residues such as Si or Sn, and m is the valence mumber of coupling agent residue, is 2～4 integer, and n is 1～10 integer, preferred 1 or 2) structure.
This segmented copolymer can have a plurality of polymer blocks (A) and/or polymer blocks (B), for example, can be A 1-B-A 2Type or A 1-B 1-A 2-B 2Type.Here, constitute block A 1And A 2Monomeric unit can be identical, also can be different.In addition, B block 1And B 2Weight-average molecular weight separately can be identical, also can be different.
As the vinyl aromatic monomers that is used to make the hydrogenation prepolymer, can exemplify vinylbenzene, alpha-methyl styrene, p-methylstyrene, t-butyl styrene, Vinylstyrene, N, the N-dimethyl-to aminoethyl vinylbenzene, 2,4-dimethyl styrene, N, the N-diethyl-to aminoethyl vinylbenzene, 2,4-dimethyl styrene, vinyl naphthalene, vinyl anthracene etc., optimization styrene and alpha-methyl styrene.Can only use these materials a kind, also can more than 2 kinds and use.
In addition, as the conjugate diene monomer that is used to make the hydrogenation prepolymer, can exemplify 1,3-divinyl, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl isophthalic acid, 3-pentadiene, 1,3-hexadiene, 4,5-dimethyl-1,3-octadiene, chloroprene etc., preferred 1,3-butadiene and isoprene.Can only use these materials a kind, also can more than 2 kinds and use.
In polymer blocks A, can mainly above-mentioned conjugate diene monomer with other monomers of vinyl aromatic monomers copolymerization, preferred especially 1,3-butadiene and isoprene.
Be used to make the conjugate diene monomer of hydrogenation prepolymer and the proportion of composing of vinyl aromatic monomers (conjugate diene monomer/vinyl aromatic monomers) preferred mass ratio is 95/5～40/60, more preferably 93/7～45/55.
In addition, there is no particular restriction for the ethylenic linkage content of the conjugated diene unit of hydrogenation prepolymer (1 of the conjugated diene unit of hydrogenation prepolymer, 2-and 3, the ratio of 4-ethylenic linkage), preferred 50～85%, and more preferably 60～85%.
In this hydrogenated diene based copolymer, more than 80% of two keys of the conjugated diolefine origin that the conjugated diene unit of preferred hydrogenation prepolymer has, preferred especially more than 90% by saturated.If saturated ratio less than 80%, then reduction such as weathering resistance.In addition, the weight-average molecular weight of hydrogenated diene polymer is 5000～1000000, is preferably 10000～500000.
The amount that the acrylic ester resin contains hydrogenated diene polymer in the constituent [B] is preferably 1～10 quality %, more preferably 2～9 quality %.If this amount less than 1 quality %, then rubber, particularly ethene-alpha-olefin are the consistency deterioration of copolymer rubber and ethylene series resin and (methyl) acrylic ester resin, the tendency that exists mechanical characteristics to reduce.On the other hand, if surpass 20 quality %, then the acrylic ester resin contains the flexibility and the caoutchouc elasticity reduction of composition [B], and is therefore inadvisable.
This acrylic ester resin contains composition [B] and has flexibility and excellent scratch resistance and forming process, can be widely used for using the collision bumper of the automobile of ethylene series thermoplastic elastomer in the past, outer dress lace, window sealing sealed strip, the door sealing sealed strip, vehicle body sealing sealed strip, the curb rafter at top, badge, inner panel, land inside and outside dress skin materials such as seat-box, can also be used for aircraft and boats and ships with sealing material or inside and outside dress skin material etc., building-sealing material for building, inside and outside dress skin material or waterproof and sealing material etc., common mechanical, device is with sealing material etc., the liner of light current part or clamshell etc., the sundry goods product, sports goods etc.
[3] contain the composition for thermoplastic elastomer of maleimide
In addition, composition for thermoplastic elastomer of the present invention in addition (below, be called " maleimide compound contains composition [C] "), it is characterized in that: in the presence of linking agent, to contain rubber, the ethylene series resin, the polymer composition of tenderizer and maleimide compound carries out dynamic thermal treatment and constitutes, wherein, when with described rubber, when described ethylene series resin and described tenderizer add up to 100 quality %, this ethylene series resin is 5～36 quality %, and work as this rubber, when this ethylene series resin and this tenderizer added up to 100 mass parts, this maleimide compound was 0.3～10 mass parts.
Contain in the composition [C] at this maleimide compound, rubber and ethylene series resin can use aforementioned substances respectively.As rubber, special optimal ethylene-alpha-olefin is a random copolymer rubber.In addition, as the ethylene series resin, can use crystallinity ethylene series resin and/or noncrystalline ethylene series resin.As crystallinity ethylene series resin, special optimization polypropylene and propylene-ethylene copolymers.In addition, as noncrystalline ethylene series resin, preferred especially Atactic Polypropelene (propylene content 50 moles more than the %), propylene (containing 50 moles more than the %) and the multipolymer of ethene and the multipolymer of propylene (containing 50 moles more than the %) and 1-butylene.
In addition, contain in the composition [C] at this maleimide compound, when rubber, ethylene series resin and tenderizer added up to 100 quality %, rubber was preferably 20～85 quality %, more preferably 30～80 quality %.In addition, the ethylene series resin is preferably 5～36 quality %, more preferably 10～36 quality %.If the amount deficiency of rubber 20 quality %, then maleimide compound contains the flexibility and the caoutchouc elasticity reduction of constituent [C].On the other hand, if surpass 85 quality %, then maleimide compound contains the flowability reduction of composition [C], the tendency that exists forming process significantly to worsen.In addition, if the amount deficiency of ethylene series resin 5 quality %, then (the ethylene series resin is sea (matrix) to the maleimide compound phase structure (morphology) that contains composition [C] for the good island structure as dynamic crosslinking type elastomeric characteristic, cross-linked rubber is island (domain structure)), forming process, mechanical characteristics reduce sometimes.On the other hand, if the amount surplus of ethylene series resin, then maleimide compound contains the flexibility and the caoutchouc elasticity reduction of composition [C], and is therefore inadvisable.
This maleimide compound contains in the composition [C] and contains aforesaid tenderizer usually.When rubber, ethylene series resin and tenderizer added up to 100 quality %, the amount of this tenderizer was 10～75 quality %, was preferably 20～60 quality %.If the amount deficiency of tenderizer 10 quality %, it is undesirable that then maleimide compound contains the forming process of composition [C].On the other hand, if surpass 75 quality %, then caoutchouc elasticity and mechanical properties reduce.When this tenderizer used oil-extended rubber, the tenderizer for containing in this oil-extended rubber only also can add later on again and cooperates.
Contain in the composition [C] at this maleimide compound, polymer composition can also contain (methyl) acrylic ester resin.As this (methyl) acrylic ester resin, can use aforesaid (methyl) acrylic ester resin.In addition, when rubber, ethylene series resin and tenderizer added up to 100 quality %, (methyl) acrylic ester resin was preferably 1～30 mass parts, more preferably 5～15 mass parts.Amount less than 1 mass parts of (if methyl) acrylic ester resin, it is undesirable that then maleimide compound contains the scratch resistance of composition [C].On the other hand, if surpass 30 mass parts, then maleimide compound contains the flexibility and the caoutchouc elasticity reduction of composition [C], is worthless therefore.
In addition, contain in the composition [C] at this maleimide compound, except (methyl) acrylic ester resin, polymer composition can also contain hydrogenated diene polymer.As this hydrogenated diene polymer, can use aforesaid hydrogenated diene polymer.In addition, the amount of this hydrogenated diene polymer is 0.1～1 with respect to the mass ratio of (methyl) acrylic ester resin preferably, more preferably 0.3～0.7.If this mass ratio less than 0.1, then rubber, particularly ethene-alpha-olefin are the consistency deterioration of random copolymer rubber and ethylene series resin and (methyl) acrylic ester resin, the tendency that exists mechanical characteristics to reduce.On the other hand, if surpass 1, then the maleinamide compound contains the flexibility and the caoutchouc elasticity reduction of composition [C], and is therefore inadvisable.
(1) maleimide compound
Maleimide compound is using linking agent, particularly organo-peroxide to carry out playing when crosslinked the effect of crosslinking coagent.As this maleimide compound, can exemplify N, N '-meta-phenylene bismaleimide etc., preferred N, N '-toluene maleimide (CAS sequence number: 3006-93-7).
When the total amount of rubber, ethylene series resin and tenderizer was 100 mass parts, the amount of maleimide compound was 0.3～10 mass parts, was preferably 0.4～8 mass parts, more preferably 0.5～5 mass parts.If amount less than 0.3 mass parts of maleimide compound then can't become injection melting property and injection sometimes and melt the maleimide compound of the rebound resilience excellence of portion and contain composition [C].On the other hand, if surpass 10 mass parts, then degree of crosslinking excessively increases, forming process deterioration sometimes, and melting property of injection suffers damage on the contrary.
Because this composition [C] that contains maleimide compound has excellent injection weldability, therefore can become and ethylene-propylene rubber, ethylene-propylene-elastoprene, ethene-butene rubber, ethene-butylene-ethylene series vulcanized rubbers such as elastoprene, ethylene-acrylate rubber, chlorinatedpolyethylene, chlorosulfonated polyethylene, styrene butadiene rubbers, paracril, chloroprene rubber, vinylformic acid (class) rubber, vulcanized rubbers such as urethanes, the ethylene series thermoplastic elastomer, polyester based thermoplastic elastomerics, the polyurethane series thermoplastic elastomer, thermoplastic elastomers such as polyamide-based thermoplastic elastomer are injected welding and are made the body formed product of its compound thermoplastic elastic.As adherend, special preferred alkenes is vulcanized rubber and ethylene series thermoplastic elastomer.
[4] contain the composition for thermoplastic elastomer of polysiloxane
In addition, other composition for thermoplastic elastomer of the present invention (below, be called " composition [D] that contains polysiloxane "), it is characterized in that: in the presence of linking agent to containing rubber, tenderizer, ethylene series resin, being that the polymer composition of unmodified organopolysiloxane of high viscosity more than the 10000cSt and modification organopolysiloxane carries out dynamic thermal treatment and forms at the unmodified organopolysiloxane of low viscosity of 25 ℃ of not enough 10000cSt of the viscosity of measuring down, according to JIS K2283 25 ℃ of viscosity of measuring down according to JIS K2283.
Contain in the composition [D] at this polysiloxane, rubber and ethylene series resin can use aforementioned substances respectively.As rubber, special optimal ethylene-alpha-olefin is a copolymer rubber.In addition, as the ethylene series resin, can use crystallinity ethylene series resin and/or noncrystalline ethylene series resin.As crystallinity ethylene series resin, special optimization polypropylene and propylene-ethylene copolymers.In addition, as noncrystalline ethylene series resin, preferred especially atactic polypropylene(APP) (propylene content 50 moles more than the %), propylene (containing 50 moles more than the %) and the multipolymer of ethene and the multipolymer of propylene (containing 50 moles more than the %) and 1-butylene.
In addition, contain in the composition [D] of polysiloxane at this, when rubber, ethylene series resin and tenderizer added up to 100 mass parts, rubber was preferably 20～69 mass parts, and more preferably 23～65 mass parts most preferably are 25～60 mass parts.In addition, the ethylene series resin is preferably 1～50 mass parts, and more preferably 2～45 mass parts most preferably are 5～40 mass parts.If amount less than 20 mass parts of rubber, the flexibility and the caoutchouc elasticity that then contain the composition [D] of polysiloxane reduce.On the other hand, if surpass 69 mass parts, the flowability that then contains the composition [D] of polysiloxane reduces, and has the tendency of the remarkable deterioration of forming process.In addition, if amount less than 1 mass parts of ethylene series resin, the phase structure (morphology) of composition [D] that then contains polysiloxane is for (the ethylene series resin is sea (matrix), and cross-linked rubber is island (domain structure) as the good island structure of dynamic crosslinking type thermoplastic elastic body characteristics.), forming process, mechanical characteristics reduce sometimes.On the other hand, if surpass 50 mass parts, the flexibility and the caoutchouc elasticity that then contain the composition [D] of polysiloxane reduce, and be therefore inadvisable.
This contains in the composition [D] of polysiloxane and contains aforesaid tenderizer usually.When rubber, ethylene series resin and tenderizer added up to 100 mass parts, the amount of this tenderizer was preferably 20～79 mass parts, and more preferably 25～75 mass parts most preferably are 25～70 mass parts.If amount less than 20 mass parts of tenderizer then contain composition [D] mobile not enough of polysiloxane.On the other hand, if surpass 79 mass parts, then sometimes when mixing the dispersion of rubber and ethylene series resin bad, the tendency that exists caoutchouc elasticity also to reduce.When using oil-extended rubber, this tenderizer is the tenderizer for containing in this oil-extended rubber only, also can add later on to cooperate again.
This composition [D] that contains polysiloxane also can be to containing oil-extended rubber in the presence of linking agent, the ethylene series resin, according to the unmodified organopolysiloxane of JIS K2283 at 25 ℃ of not enough 10000cSt of the viscosity of measuring down, is that the polymer composition of unmodified organopolysiloxane more than the 10000cSt and modification organopolysiloxane carries out dynamic thermal treatment and obtains according to JIS K2283 25 ℃ of viscosity of measuring down, wherein, oil-extended rubber contains rubber and tenderizer, when this rubber and this tenderizer add up to 100 quality %, this rubber is 30～70 quality %, and this tenderizer is 30～70 quality %.
In having used the composition that contains polysiloxane [D] of this oil-extended rubber, rubber and ethylene series resin also can use aforementioned substances respectively.As rubber, special optimal ethylene-alpha-olefin is a copolymer rubber.In addition, as the ethylene series resin, can use crystallinity ethylene series resin and/or noncrystalline ethylene series resin.As crystallinity ethylene series resin, special optimization polypropylene and propylene-ethylene copolymers.In addition, as noncrystalline ethylene series resin, preferred especially atactic polypropylene(APP) (propylene content 50 moles more than the %), propylene (containing 50 moles more than the %) and the multipolymer of ethene and the multipolymer of propylene (containing 50 moles more than the %) and 1-butylene.
In addition, when the rubber that constitutes oil-extended rubber and tenderizer added up to 100 quality %, amount separately was preferably 30～70 quality %, and more preferably 35～65 quality % most preferably are 40～60 quality %.As rubber less than 30 quality %, or tenderizer is when surpassing 70 quality %, and tenderizer is separated out from the composition [D] that contains polysiloxane, the tendency that exists mechanical characteristics and caoutchouc elasticity to reduce.On the other hand, if rubber surpasses 70 quality %, or tenderizer less than 30 quality %, then there is the tendency of the forming process reduction of the composition [D] that contains polysiloxane.In addition,, be not particularly limited, can use aforesaid various material as this tenderizer.
In addition, contain in the composition [D] of polysiloxane, also can add making it further contain tenderizer as required by the back at this.When oil-extended rubber, ethylene series resin, and the tenderizer that adds of back when adding up to 100 mass parts, the tenderizer of this back interpolation is preferably below 50 mass parts, more preferably below 45 mass parts, most preferably is below 40 mass parts.If its amount surpasses 50 mass parts, then sometimes when mixing the dispersion of rubber and ethylene series resin bad, the tendency that exists caoutchouc elasticity also to reduce.Tenderizer as add this back is not particularly limited, and can use aforesaid various material.
In addition, contain in the composition [D] of polysiloxane at this, when oil-extended rubber, ethylene series resin, and the tenderizer that adds of back when adding up to 100 mass parts, oil-extended rubber is preferably 30～99 mass parts, more preferably 35～97 mass parts most preferably are 40～95 mass parts.In addition, the ethylene series resin is preferably 1～50 mass parts, and more preferably 2～45 mass parts most preferably are 5～40 mass parts.If amount less than 30 mass parts of rubber, the flexibility that then contains the composition [D] of polysiloxane sometimes reduces.On the other hand, if surpass 99 mass parts, the flowability that then contains the composition [D] of polysiloxane reduces, and has the tendency of the remarkable deterioration of forming process.In addition, if amount less than 1 mass parts of ethylene series resin, the phase structure (morphology) of composition [D] that then contains polysiloxane is for (the ethylene series resin is sea (matrix), and cross-linked rubber is island (domain structure) as the good island structure of dynamic crosslinking type thermoplastic elastic body characteristics.), forming process, mechanical characteristics reduce sometimes.On the other hand, if surpass 50 mass parts, then polysiloxane contains the flexibility and the caoutchouc elasticity reduction of composition [D], and is therefore inadvisable.
(1) the unmodified organopolysiloxane of low viscosity or high viscosity
The unmodified organopolysiloxane of low viscosity or high viscosity is not particularly limited.As this unmodified organopolysiloxane, can exemplify dimethyl polysiloxane, methyl phenyl silicone, fluoro polysiloxane, tetramethyl tetraphenyl polysiloxane, hydrogenated methyl dialkylene polysiloxane etc., wherein, preferred dimethyl polysiloxane.In addition, the unmodified organopolysiloxane of low viscosity can be identical compound with the unmodified organopolysiloxane of high viscosity, also can be different compounds.
1. the unmodified organopolysiloxane of low viscosity
The unmodified organopolysiloxane of low viscosity, its viscosity of 25 ℃ stipulating in JIS K2283 is not enough 10000cSt, preferred not enough 7000cSt, more preferably not enough 5000cSt.
In addition, when oil-extended rubber, ethylene series resin, and the tenderizer that adds of back when adding up to 100 mass parts, the amount of the unmodified organopolysiloxane of low viscosity is preferably 1～10 mass parts, and more preferably 1～8 mass parts most preferably is 1～5 mass parts.In addition, if use 25 ℃ the viscosity of in JIS K2283, stipulating to be the unmodified organopolysiloxane of the low viscosity of not enough 10000cSt, the tendency that exists the unmodified organopolysiloxane of this low viscosity from the composition [D] that contains polysiloxane, to separate out separately.
2. the unmodified organopolysiloxane of high viscosity
The unmodified organopolysiloxane of high viscosity, its viscosity of 25 ℃ stipulating in JIS K2283 is more than the 10000cSt, to be preferably 10000～1000000cSt, more preferably 10000～100000cSt.
When oil-extended rubber, ethylene series resin, and the tenderizer that adds of back when adding up to 100 mass parts, the amount of the unmodified organopolysiloxane of low viscosity is preferably 1～10 mass parts, and more preferably 1～8 mass parts most preferably is 1～5 mass parts.In addition, if use 25 ℃ the viscosity of stipulating in JIS K2283 to be the unmodified organopolysiloxane of the high viscosity more than the 10000cSt separately, the sliding deficiency is therefore inadvisable sometimes.
If with 25 ℃ the viscosity of stipulating among the JIS K2283 is that 25 ℃ viscosity stipulating among the unmodified organopolysiloxane of low viscosity of not enough 10000cSt and the JIS K2283 is unmodified organopolysiloxane of high viscosity and the usefulness more than the 10000cSt, sliding significantly improves.Their amounts separately, the preferred unmodified organopolysiloxane of low viscosity is 1～10 mass parts, and the unmodified organopolysiloxane of high viscosity is 1～10 mass parts, more preferably the unmodified organopolysiloxane of low viscosity is 1～5 mass parts, and the unmodified organopolysiloxane of high viscosity is 1～5 mass parts.
(2) modification organopolysiloxane
As the modification organopolysiloxane, so long as organopolysiloxane has been carried out chemically modified with functional group, be not particularly limited, for example can the exemplified by acrylic modification, epoxide modified, alkyl-modified, amino modified, carboxy-modified, pure modification, fluorine modification, the modification of alkyl allyl polyether, epoxidized polyether modification etc.Wherein, preferred acrylic acid modified organopolysiloxane, preferably make can copolymerization with acrylate or vinylformic acid monomeric mixture and organopolysiloxane graft copolymerization.
As can graft polymerization to the acrylate of organopolysiloxane, can the exemplified by acrylic methyl esters, alkyl acrylate such as ethyl propenoate, propyl acrylate, butyl acrylate, Ethyl acrylate, vinylformic acid pentyl ester, Octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, octadecyl acrylate, alkoxyalkyl acrylate such as methoxyethyl acrylate, fourth oxygen ethyl propylene acid esters, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate etc., can only use them a kind, also can more than 2 kinds and use.
In addition, as can with the monomer of acrylic ester copolymer, for example can exemplify hydroxyls such as 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate and contain unsaturated monomer etc.Can only use them a kind, also can more than 2 kinds and use.
During graft polymerization, organopolysiloxane and acrylate or can with the monomeric ratio of acrylic ester copolymer, the mass ratio of preferred [organopolysiloxane/acrylate or can with the monomer of acrylic ester copolymer] is 9/1～1/9, more preferably 8/2～2/8.As acrylic acid modified organopolysiloxane, can exemplify chemical industry society of SHIN-ETSU HANTOTAI (Shin-Etsu Chemical Co., Ltd.) trade(brand)name of Zhi Zaoing " X-22-8171 " and " Chaline R-2 " that day letter chemical industry society (Nissin Chemical IndustryCo.) makes etc.
When oil-extended rubber, ethylene series resin, and the tenderizer that adds of back when adding up to 100 mass parts, the amount of modification organopolysiloxane is preferably 0.2～20 mass parts, and more preferably 0.5～15 mass parts most preferably is 1～10 mass parts.Because give the effect of sliding, this modification organopolysiloxane plays the effect of the compatilizer of polymer composition and unmodified organopolysiloxane in containing the composition of polysiloxane [D].Therefore, if amount less than 0.2 mass parts of modification organopolysiloxane, then compatibilized is undesirable, and the dispersion that produces unmodified organopolysiloxane and polymer composition in mixing roll is bad, has the tendency of the forming process deterioration of extrusion moulding and injection molding etc.On the other hand, if surpass 20 mass parts, the tendency that then exists flexibility, mechanical characteristics to reduce.
Because this composition [D] that contains polysiloxane has excellent caoutchouc elasticity and thermoplasticity, therefore easily with the common forming method of thermoplastic resin, for example injection molding, extrusion moulding, slush molding, compressed moulding, vacuum forming, laminated into type, calendering formation etc. are processed.In addition, can easily foam as required, stretch, follow, secondary processing such as printing, application, plating.Therefore, except the various Compound Machining product with injection weld portion, this composition [D] that contains polysiloxane also can be used in general processed goods widely.For example, can be used for the collision bumper of automobile, outer dress with lace, window sealing with sealed strip, door sealing with sealed strip, vehicle body sealing with sealed strip, the curb rafter at top, badge, inside and outside dress skin material, can also be used for aircraft and boats and ships with sealing material or inside and outside dress skin material etc., building-sealing material for building, inside and outside dress skin material or waterproof and sealing material etc., common mechanical, device be with sealing material etc., the liner of light current part or clamshell etc., sundry goods product, sports goods etc.
[5] linking agent
As being used for crosslinked linking agent, can using and contain composition [A], acrylic ester resin at the specified particle diameter rubber particles and contain composition [B], maleimide compound and contain composition [C] and polysiloxane and contain identical material in any of composition [D].As this linking agent, for example can exemplify derivative, bismaleimide compound, epoxy compounds, silane compound, aminoresin, polyol crosslink agent, polyamine, triaizine compounds and the metallic soap etc. of organo-peroxide, phenolic resin crosslinking agent, sulphur, sulfur compound, para benzoquinone, p-benzoqui(o)none dioxime, preferred especially organo-peroxide and phenolic resin crosslinking agent.
Organo-peroxide is preferred, and the fusing point of used polyolefin-based resins is designated as T mThe time, 1 minute half life temperature T of organo-peroxide hAt T m≤ T h≤ T m+ 50 (℃) scope in.
If T hLess than T m, then under the situation that the melting mixing of rubber and ethylene series resin does not also fully carry out, crosslinking reaction just begins, and the caoutchouc elasticity of composition for thermoplastic elastomer and physical strength reduce sometimes.On the other hand, if T hSurpass T m+ 50 (℃), thereby then crosslinking temperature is crossed the low crosslinked deficiency that produces, and has the caoutchouc elasticity of composition for thermoplastic elastomer and the tendency that physical strength reduces.
As organo-peroxide, can exemplify 1,3-two (t-butyl peroxy sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3,25-dimethyl-25-two (t-butylperoxy) hexene-3,2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,2-two (t-butylperoxy)-cumic aldehyde, dicumyl peroxide, di-t-butyl peroxide, tert-butyl peroxide, to oxidation to menthane, 1,1-two (t-butylperoxy)-3,3, the 5-trimethyl-cyclohexane, dilauroyl peroxide, diacetyl peroxide, t-butyl per(oxy)benzoate, 2,4-dichloro-benzoyl superoxide, to the chlorobenzoyl superoxide, benzoyl peroxide, two (t-butylperoxy) peroxy benzoate, normal-butyl-4,4-two (t-butylperoxy) valerate, BPIC (t butyl peroxy isopropyl carbonate) etc.Wherein, preferred 1,3-two (t-butyl peroxy sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3,2,5-2 etc. decompose the higher material of temperature.Can only use them a kind, also can more than 2 kinds and use.
In addition, when using organo-peroxide as linking agent, can by and make crosslinking reaction stable with crosslinking coagent, particularly can form the crosslinking structure of homogeneous.As this crosslinking coagent, can exemplify sulphur or powder sulphur, colloid sulphur, precipitation sulphur, insoluble sulfur, surface treatment sulphur, sulfur compounds such as dipentamethylene thiuram tetrasulfide, the para benzoquinone oxime, p, p '-oxime compounds such as dibenzoyl quinone oximes, ethylene glycol bisthioglycolate (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, TEG two (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Phthalic acid, diallyl ester, tetraene propoxy-ethane, triallyl cyanurate, N, a N '-benzene bismaleimides, N, N '-toluene bismaleimides, maleic anhydride, Vinylstyrene, multi-functional monomer classes such as two (methyl) zinc acrylate resin etc.Wherein, preferred p, p '-dibenzoyl quinone oximes, N, a N '-benzene bismaleimides, Vinylstyrene.Can only use them a kind, also can more than 2 kinds and use.In addition, in these crosslinking coagents, N, a N '-benzene bismaleimides has the effect of linking agent, therefore can be used as linking agent and uses.
When using organo-peroxide as linking agent, when polymer composition was 100 mass parts, its usage quantity was preferably 0.05～10 mass parts, more preferably 0.1～5 mass parts.If amount less than 0.05 mass parts of organo-peroxide, degree of crosslinking deficiency then, the caoutchouc elasticity of composition for thermoplastic elastomer and physical strength reduce sometimes.On the other hand, if surpass 10 mass parts, then degree of crosslinking excessively increases, the tendency that exists forming process deterioration or mechanical properties to reduce.
When polymer composition is 100 mass parts, when using organo-peroxide below preferred 10 mass parts of usage quantity of crosslinking coagent as linking agent, 0.2～5 mass parts more preferably.If the amount of crosslinking coagent surpasses 10 weight parts, then degree of crosslinking excessively increases, the tendency that exists forming process deterioration or mechanical properties to reduce.
In addition, as phenol is linking agent, for example can exemplify the para-orientation phenol based compound shown in the following general formula (I), ortho position fortified phenol-aldehyde condensate, position fortified phenol-aldehyde condensate, bromo alkylphenol-aldehyde condensate etc., preferred especially para-orientation phenol based compound.
Figure A20051007795700361
Wherein, n is 0～10 integer, and X is hydroxyl, haloalkyl or halogen atom, and R is the saturated hydrocarbyl of carbon number 1～15.
In addition, para-orientation phenol based compound is in the presence of basic catalyst, and the condensation reaction by para-orientation phenol and aldehyde (preferred formaldehyde) obtains.
As linking agent, when using phenol to be linking agent, when polymer composition is 100 mass parts, be preferably 0.2～10 mass parts, more preferably it is 0.5～5 mass parts.If phenol is linking agent less than 0.2 mass parts, degree of crosslinking deficiency then, the caoutchouc elasticity of composition for thermoplastic elastomer and physical strength reduce sometimes.On the other hand, if surpass 10 mass parts, then there is the tendency of the forming process deterioration of thermoplastic elastomer.
These phenol are that linking agent can use separately, but in order to adjust rate of crosslinking, also can and use crosslinking accelerator.As this crosslinking accelerator, can exemplify metal halides such as tindichloride, iron trichloride, reach Organohalogen compounds such as Chlorinated Polypropylene III, brominated butyl rubber, neoprene etc.
In addition, except crosslinking accelerator, more preferably further and with dispersion agents such as metal oxide such as zinc oxide or stearic acid.
[6] other various additives
Can make specified particle diameter rubber particles composition [A] as required, the acrylic ester resin contains composition [B], maleimide compound contains composition [C] and polysiloxane and contains and contain other various additives in the composition [D], for example, lubricant, anti-aging agent, thermo-stabilizer, weather resisting agent, nonactive dose of metal, UV light absorber, photostabilizer, the copper evil prevents stablizers such as agent, processing aid, releasing agent, fire retardant, static inhibitor, fungi-proofing-mould inhibitor, dispersion agent, softening agent, crystallization nucleating agent, tackifier, frothing aid, titanium oxide, 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 aramid fiber, conjugated fibre, inorganic crystal whiskers such as calcium titanate whisker, granulated glass sphere, glass sphere, sheet glass, asbestos, mica, lime carbonate, magnesiumcarbonate, clay, kaolin, talcum, wet silicon dioxide, dry type silicon-dioxide, Calucium Silicate powder, hydrotalcite, diatomite, graphite, pumice, bakelite powder, velveteen, dust cork, barium sulfate, fluoro-resin, polymkeric substance pearl thing, natural silicic acid, weighting agent or their mixtures such as synthetic silicic acid, polyolefin-wax, cellulose powder, the fluorine powder, silica flour, rubber powder, weighting agents such as wood powder, silicone oil and low-molecular weight polymer etc.
[7] manufacture method of composition for thermoplastic elastomer
The specified particle diameter rubber particles contain composition [A], acrylic ester resin contain composition [B], maleimide compound contain composition [C] and polysiloxane contain composition [D] (below, during with these compositions [A]～[D] general name, be called " composition for thermoplastic elastomer ") all can be by identical method manufacturing.
(1) manufacture method of use batch-type closed mixing machine and continous way forcing machine
Composition for thermoplastic elastomer can be made by the following method: use the batch-type closed mixing machine to contain polymer composition and at least a portion of linking agent and other composition blending dispersion of adding as required of rubber, polyolefin-based resins, after modulating mixing thing, this mixing thing is carried out dynamic crosslinking by continous way forcing machines such as twin screw extruders.In addition, also can make by the following method: use the batch-type closed mixing machine other composition blending dispersion that do not comprise linking agent that contain the polymer composition of rubber, polyolefin-based resins and add as required, after modulating mixing thing, this mixing thing and linking agent and other compositions of adding are as required carried out dynamic crosslinking by continous way forcing machines such as twin screw extruders.So-called should " dynamic crosslinking ", be meant apply shearing force and heat carry out under the situation aspect two crosslinked.In addition, the mixed processes that carries out blending dispersion can carry out continuously with the crosslinked operation of carrying out dynamic crosslinking.
1. batch-type closed mixing machine
As above-mentioned closed mixing machine, can exemplify compression type kneader, Banbury kneader, Bradley Bender kneader etc.
When using closed mixing machine that polymer composition is carried out blending dispersion, the method for supplying with tenderizer is not particularly limited, and can be coupled in advance in the polymer composition, perhaps, also can supply in the closed mixing machine respectively with polymer composition.In addition, can after with the polymer composition blending dispersion, supply with tenderizer, also can use oil-extended rubber.
In addition, particularly contain in the manufacturing of composition [D] at polysiloxane, remove linking agent, when using closed mixing machine that polymer composition is carried out melting mixing, poly-organic osmanthus oxygen alkane of unmodified and modification and tenderizer can mix with polymer composition in advance, also can supply to respectively under situation about not being pre-mixed in the closed mixing machine, order is not particularly limited.In addition, can drop into unmodified poly-organic osmanthus oxygen alkane, the poly-organic osmanthus oxygen alkane of modification and tenderizer after with the polymer composition melting mixing, also can just drop into closed mixing machine simultaneously from beginning with polymer composition, carry out melting mixing, it is not particularly limited in proper order.
In addition, in order to put in the continous way forcing machine, preferably in advance mixing thing is chopped up with the synthetic mixing thing of closed mixing machine.As the method for making shred, can use and be processed into particle shape, also can will once be processed into particle shape with dull and stereotyped tablets press with mill material in blocks, the method that mixing thing is chopped up is not particularly limited.
2. continous way forcing machine
The continous way forcing machine is not particularly limited, can use single screw extrusion machine, twin screw extruder, double rotor type forcing machine etc., but preferred twin screw extruder especially preferably uses preferred more than 30, more preferably 36～60 the twin screw extruder of L/D (ratio of effectively long L of screw rod and outer diameter D).As this twin screw extruder, for example can use 2 screw engages, twin screw extruder arbitrarily such as not mesh.More preferably the sense of rotation of 2 screw rods is the twin screw extruder of same direction, screw engages.As such twin screw extruder, can exemplify Chi Beishe and make GT, the manufacturing KTX of Kobe Steel, Ltd society, the manufacturing TEX of society of JSW, manufacturing TEM, the Warner Inc. manufacturing ZSK of toshiba machine society (being trade mark) etc.
Use the continous way forcing machine, when making composition for thermoplastic elastomer by dynamic crosslinking, supply method as linking agent, can adopt and use the blending and stirring machine to mix with the mixing thing of supplying with crosslinking reaction in advance, the methods of supplying with the method for continous way forcing machine or supplying with from the machine barrel peristome that is arranged between hopper and the die head etc. are not particularly limited.
The method of supply weighting agent etc. also is not particularly limited, and can add in closed mixing machine, also can add in the continous way forcing machine, in addition, also can supply with in both.
The condition of dynamic crosslinking is different because of the difference of the fusing point of employed ethylene series resin, the kind of linking agent etc., but treatment temp is preferably at the fusing point (T of ethylene series resin m) the above and scope below 250 ℃.If less than the melting temperature (Tm) of ethylene series resin, then can not produce mixing deficiency fully with rubber and ethylene series resin melting mixing, the mechanical properties of composition for thermoplastic elastomer reduces sometimes.On the other hand,, then produce the deterioration of rubber, have the tendency of the mechanical properties reduction of composition for thermoplastic elastomer if surpass 250 ℃.
(2) manufacture method of use continous way opposite spin twin shaft mixing roll and equidirectional rotation twin screw extruder
Composition for thermoplastic elastomer can be by following method manufacturing: from being positioned at the continous way opposite spin twin shaft mixing roll of upstream, and configured in series be positioned at the equidirectional rotation twin screw extruder in downstream the raw material introduction part of continous way opposite spin twin shaft mixing roll of extrusion device supply with and to contain rubber, the polymer composition of ethylene series resin, with continous way opposite spin twin shaft mixing roll with the feedstock composition blending dispersion, the limit remains on below 250 ℃ the temperature of mixing thing of the outlet of continous way opposite spin twin shaft mixing roll, and dynamic crosslinking is carried out with equidirectional rotation twin screw extruder in the limit.
In this manufacture method, the melting mixing of the polymer composition of in continous way opposite spin twin shaft mixing roll, supplying with, and the blending dispersion of linking agent, the mixing thing that is controlled in below the certain temperature is supplied with in the equidirectional rotation twin screw extruder, thereby the dynamic crosslinking reaction is finished.The temperature of the mixing thing of the outlet of continous way opposite spin twin shaft mixing roll is because of the difference difference of the ethylene series resin and the linking agent of use, but must be controlled in certain temperature, under the state that the crosslinking reaction that this temperature can be carried out in continous way opposite spin twin shaft mixing roll is inhibited, carry out the melting mixing of polymer composition, in addition, the deterioration of rubber that contains in order to prevent in the polymer composition and ethylene series resin, this temperature remains on below 250 ℃.
In addition, composition for thermoplastic elastomer can be made with the following method: from the continous way opposite spin twin shaft mixing roll that is positioned at the upstream, and configured in series be positioned at the equidirectional rotation twin screw extruder in downstream the raw material introduction part of continous way opposite spin twin shaft mixing roll of extrusion device supply with the polymer composition that contains rubber, ethylene series resin and organo-peroxide, with the feedstock composition blending dispersion, the limit makes the temperature t of mixing thing of the outlet of continous way opposite spin twin shaft mixing roll with continous way opposite spin twin shaft mixing roll aBe controlled at T h-30≤t a≤ T h+ 30 scope, dynamic crosslinking is carried out with equidirectional rotation twin screw extruder in the limit, wherein, when the fusing point of ethylene series resin is designated as T m, 1 minute half life temperature of organo-peroxide is T hThe time, organo-peroxide satisfies T m≤ T h≤ T m+ 50 (℃).
In this manufacture method, the melting mixing of the polymer composition of in continous way opposite spin twin shaft mixing roll, supplying with, and the blending dispersion of linking agent, the mixing thing that is controlled in below the certain temperature is supplied with in the equidirectional rotation twin screw extruder, thereby the dynamic crosslinking reaction is finished.The temperature t of the mixing thing of the outlet of continous way opposite spin twin shaft mixing roll aBecause of the difference of the ethylene series resin that uses and linking agent is different, but must be controlled at certain temperature, under the state that the crosslinking reaction that this temperature can be carried out is inhibited, carry out the melting mixing of polymer composition in continous way opposite spin twin shaft mixing roll.Therefore, be necessary for and suppress below the temperature that crosslinking reaction carries out.When using organo-peroxide at least, 1 fen half life temperature is designated as T as linking agent h, it must be at T h-30≤t a≤ T h+ 30 (℃) (preferred T h-20≤t a≤ T h+ 25 (℃), more preferably T h-10≤t a≤ T hThe scope of+20 (℃)).If the temperature t of the mixing thing of the outlet of continous way opposite spin twin shaft mixing roll aSurpass T h+ 30 (℃), because in continous way opposite spin twin shaft mixing roll, mixing thing is fed in the equidirectional rotation twin screw extruder under the state that the state that crosslinking reaction is acutely carried out or crosslinking reaction end, so the mechanical properties of composition for thermoplastic elastomer, forming process deterioration.On the other hand, if temperature t aNot enough T h-30 (℃), melting mixing deficiency then, the tendency that exists the physical strength of composition for thermoplastic elastomer to reduce.
As continous way opposite direction twin shaft mixing roll, can exemplify CIM, the Mixtron FCM/NCM/LCM/ACM (being trade mark) that Kobe Steel, Ltd society makes etc. that society of JSW makes.
In addition, equidirectional rotation twin screw extruder and indefinite, particularly preferably using L/D (ratio of effectively long L of screw rod and outer diameter D) is more than 30, more preferably 36～60 twin screw extruder.
The supply method of linking agent is not particularly limited, can supply with in the polymer composition or in the blending dispersion operation, supply with by being mixed in, specifically, comprise: 1. use blend mixing machine and the polymer composition of supplying with crosslinking reaction to be pre-mixed, supply with the method for continous way opposite spin twin shaft mixing roll, 2. get the method that the hopper of a mixing roll is supplied with from the continous way opposite spin.In addition, also comprise 3. and can supply with from the machine barrel peristome between the outlet of the hopper that is arranged on continous way opposite spin twin shaft mixing roll and mixing roll.
When in the banded device, making composition for thermoplastic elastomer, tenderizer, the supply method of weighting agent etc. also is not particularly limited, can exemplify and 1. use blend mixing machine and rubber and the ethylene series resin of supplying with crosslinking reaction to be pre-mixed, supply with the method for continous way opposite spin twin shaft mixing roll, 2. from continous way opposite spin twin shaft mixing roll, the method that equidirectional rotation twin screw extruder or both hoppers are supplied with, 3. from continous way opposite spin twin shaft mixing roll, the method that the machine barrel peristome that is provided with between equidirectional rotation twin screw extruder or both hoppers and the die head is supplied with, 4. use the sidepiece feeder to supply to method of equidirectional rotation twin screw extruder etc.
In addition, particularly contain in the manufacturing of composition [D] at polysiloxane, when making composition for thermoplastic elastomer with the continous way forcing machine, as supply method unmodified and the modification organopolysiloxane, when it is powder, can exemplify the method for using mixing tank and the polymer composition of supplying with crosslinking reaction to be pre-mixed, to supply with the continous way forcing machine; When it is liquid, can exemplifies the polymer composition that uses mixing tank and supply with crosslinking reaction and be pre-mixed, supply with the method for continous way forcing machine or the method for supplying with from the barrel peristome that is arranged between hopper and the die head.
As the prilling process of the composition for thermoplastic elastomer made from these methods, can use strand cutting (strand cut), the known prilling granulators such as cutting, thermal cutting that cut, spray under water, be not particularly limited.
Optimum implementation of the present invention
Below, in conjunction with the embodiments the present invention is carried out specific description.Only otherwise surmount its purport, the present invention is not limited to these following embodiment.
1. the embodiment that relates to the composition [A] that contains the specified particle diameter rubber particles
Following described as rubber, crystallinity ethylene series resin, noncrystalline ethylene series resin, tenderizer and linking agent etc. that raw material uses.
[1] raw material
(1) rubber
1. EPDM (a11): ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber, ethylene content is 66 quality %, 5-ethylidene-2-norbornene content is 4.5 quality %, the limiting viscosity of 135 ℃ of mensuration is 4.7dl/g in the naphthane solvent, mineral oil softener (trade(brand)name: Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd. makes) amount is 50 quality %;
2. EPDM (a12): ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber, ethylene content is 66 quality %, 5-ethylidene-2-norbornene content is 4.5 quality %, the limiting viscosity of 135 ℃ of mensuration is 3.8dl/g in the naphthane solvent, mineral oil softener (trade(brand)name: Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd. makes) amount is 40 quality %;
3. EPDM (a13): ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber, ethylene content is 66 quality %, 5-ethylidene-2-norbornene content is 4.5 quality %, the limiting viscosity of 135 ℃ of mensuration is 2.8dl/g in the naphthane solvent, mineral oil softener (trade(brand)name: Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd. makes) amount is 20 quality %.
(2) ethylene series resin
1. crystallinity olefin resin (b11): propene polymer, density are 0.90g/cm 3, MFR (230 ℃ of temperature, the heavy 2.16kg of load) is 5g/10 branch (trade(brand)name: Novatec PP MA4, Nippon Polychem Co. manufacturing);
2. crystallinity olefin resin (b12): propylene-ethylene random copolymer, density are 0.90g/cm 3, MFR (230 ℃ of temperature, the heavy 2.16kg of load) is 3g/10 branch (trade(brand)name: Novatec PP BC5CW, Nippon Polychem Co. manufacturing);
3. crystallinity olefin resin (b13): propylene-ethylene random copolymer, density are 0.90g/cm 3, MFR (230 ℃ of temperature, the heavy 2.16kg of load) is 23g/10 branch (trade(brand)name: Novatec PP FL25R, Nippon Polychem Co. manufacturing);
4. noncrystalline olefin resin (b2): the noncrystalline multipolymer of propylene/1-butene, propylene content are 71 moles of %, and melt viscosity is 8Pa s, and density is 0.87g/cm 3, Mn is 6500 (trade(brand)names: APAO UT2780, Ube Industries Ltd. manufacturing).
(4) linking agent
1. linking agent (h1): 2,5-2-3,1 minute half life temperature is 194.3 ℃ (trade(brand)names: Perhexa 25B-40, NOF Corp. make);
2. linking agent (h2): 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3,1 minute half life temperature are 179.8 ℃ (trade(brand)names: Perhexa 25B-40, NOF Corp. make);
3. linking agent (h3): Vinylstyrene (purity 55%) (Sankyo Kasei Co. manufacturing).
(5) anti-aging agent (j1): commodity are called Irganox 1010 (Ciba Specialty ChemicalsCo. manufacturing).
(6) lubricant (silicone oil (k1)): polydimethyl organo-siloxane (trade(brand)name: SH-200 (100cSt), Toray Dow Corning Silicone Ltd. makes).
[2] contain the manufacturing of the composition [A] of specified particle diameter rubber particles
(1) manufacture method (manufacture method 1) of use closed mixing machine+continous way forcing machine
Embodiment 1,3,5
According to the cooperation shown in the table 1, the feedstock composition input that does not comprise linking agent has been heated in 150 ℃ the pressurization kneader (Moriyama Company Ltd. manufacturing), carry out mixingly disperseing in 15 minutes with 40rpm up to each uniform component.Use be set at 180 ℃, the feeder-ruder (Moriyama Company Ltd. manufacturing) of 40rpm the composition of molten state carried out granulation thereafter.The linking agent (h1)～(h3) that cooperates ratio in the pellet that makes shown in the interpolation table 1 uses the Henshel agitator to mix for 30 seconds.Then, operating weight formula feeder (trade(brand)name: KF-C88, Kubota Co. manufacturing) output with 40kg/hr supplies to twin screw extruder (equidirectional non-engagement type screw rod, L/D (ratio of effectively long L of external diameter 45mm, screw rod and outer diameter D)=38.5, trade(brand)name " PCM-45 ", Ikegai Ltd. make), the limit is implemented dynamic thermal treatment limit and is extruded under 200 ℃ of design temperatures, screw rod revolution 300rpm, make the composition [A] that obtains containing the specified particle diameter rubber particles.
(2) used the manufacture method (manufacture method 2) of continous way opposite spin twin shaft mixing roll+two coupling devices of equidirectional rotation twin screw extruder
Embodiment 2,4,6 and comparative example 4
Use the Henshel agitator to cooperate the feedstock composition of ratio to mix for 30 seconds shown in the table 1.Then, use 2 weight-type feeder (trade(brand)names " KF-C88 ", Kubota Co. makes), with the output of 40kg/hr from continous way in the other direction the material-guiding inlet of twin shaft mixing roll above-mentioned raw materials mixed constituent is supplied at continous way opposite spin twin shaft mixing roll (engagement type 2 rotors in the other direction, L/D=10, trade(brand)name " Mixtron LCM ", Kobe SteelLtd. manufacturing) back has connected equidirectional rotation twin screw extruder (equidirectional non-engagement type screw rod, L/D=42, trade(brand)name " TEX 44SS ", Japan Steel Work Co. manufacturing) in the device, sets 80 ℃ at barrel zone temperature, rotor revolution number 350～800rpm, gatage 1～40%, the hole aperture is to carry out melting mixing 100% time.Then, the composition of molten state is supplied in the equidirectional twin screw extruder that directly links to each other with continous way opposite spin twin shaft mixing roll, enforcement is made the composition [A] that obtains containing the specified particle diameter rubber particles owing to the crosslinking reaction that dynamic thermal treatment produces under 200 ℃ of barrel zone temperature settings, screw rod revolution 400rpm.In addition, mineral oil softener is pressed into from the 1st mixing rotor portions machine barrel of continous way opposite spin twin shaft mixing roll.
(3) used the manufacture method (manufacture method 3) of continous way forcing machine
Comparative example 1～3
After using the Henshel agitator that the feedstock composition that cooperates ratio shown in the table 1 was mixed for 30 seconds, use 2 weight-type feeder (trade(brand)names " KF-C88 ", Kubota Co. makes), the rubber and the ethylene series resin that will mix various additives with the output of 40kg/hr supply to twin screw extruder (equidirectional non-engagement type screw rod, L/D=38.5, trade(brand)name " P CM-45 ", Ikegai Ltd. makes) in, be set at 200 ℃ at barrel zone temperature, screw rod revolution 300rpm bottom carries out dynamic thermal treatment limit and extrudes, and makes the composition [A] that obtains containing the specified particle diameter rubber particles.
In addition, in these three methods of use are made, the temperature of the mixing thing of the mixing thing temperature of the outlet of continous way opposite spin twin shaft mixing roll and the outlet of equidirectional rotation twin screw extruder uses non-contact thermometer (trade(brand)name: PT-3LF, Optex Co. makes) to measure.
[3] contain the evaluation of the composition [A] of specified particle diameter rubber particles
For the composition that contains the specified particle diameter rubber particles [A] that makes is as mentioned above estimated, carry out the mensuration of following project.
(1) melt flow index (MFR): 230 ℃, the following mensuration of load weight 10kg.
(2) hardness: according to JIS K 6253.
(3) tensile break strength and tension fracture elongation: according to JIS K 6251.
(4) compression permanentset: according to JIS K 6262.
(5) extrude processibility: use Labplastmill forcing machine (external diameter=20mm, L/D=25, Toyo Seiki Co. make), carry out flat board under the following conditions and extrude (mouthful the mould width 25mm of portion, thickness 1.5mm), its outward appearance is estimated with visual.Smooth surface and marginately be designated as zero, all be designated as in addition *.
(setting of Labplastmill forcing machine)
Machine barrel C1:180 ℃
Machine barrel C2:190 ℃
Machine barrel C3:210 ℃
Mouth mould: 205 ℃
Screw rod revolution: 40rpm
(6) particle
As the index of melting mixing, measure " particle " of the composition [A] that contains the specified particle diameter rubber particles.So-called " particle ", be meant that rubber and ethylene series resin do not have abundant melting mixing, the huge gel of visual visible that generates when carrying out dynamichandling in the presence of linking agent, the not melts or the fish eyes etc. of ethylene series resin when manufacturing contains the composition [A] of specified particle diameter rubber particles.The evaluation of " particle " is to use 6 inches rollers of Electric heating (Kansai RollCo. manufacturing), being set at 180 ℃, roller spacing in temperature is to make the composition [A] that contains the specified particle diameter rubber particles become thin slice under the 0.5mm, and " particle " that exist on the thin slice with visual counting 20 * 20cm size carries out.Judgment standard is as described below.
30 of 0～less thaies: few; 30～less than 100: few; More than 100: many
(7) gel fraction: measure according to aforesaid method.
(8) take the TEM photo
The TEM photo that contains the composition [A] of specified particle diameter rubber particles is to thinly slice with the composition [A] that freezing shave machine will contain the specified particle diameter rubber particles, use ruthenium tetroxide to dye, use infiltration type electron microscope (trade(brand)name: H-7500, Hitachi Ltd. make) to obtain being amplified to take pictures under 2000 times then.
When the TEM photo being drawn a portrait parsing, use Image-Pro Plus Ver.4.0forWindows (manufacturing of MediaCybernetics company) to resolve the area that software is asked for the cross-linked rubber particle as portrait.
Use aforementioned formula, try to achieve number average particle diameter dn and volume average particle size dv from the area of the cross-linked rubber particle asked for, thereby calculate dv/dn.
Table 1
Oil-extended rubber Limiting viscosity (dl/g) Mineral oil softener content (quality %) Embodiment Comparative example
??1 ??2 ??3 ??4 ??5 6 ??1 ??2 3 ??4
Oil-filled EPDM (a11) ??4.7 ??50 ??- ??- ??- ??- ??75(37.5) 75(37.5) ??- ??- 75(37.5) ??-
Oil-filled EPDM (a12) ??3.8 ??40 ??80(48) ??80(48) ??- ??- ??- - ??80(48) ??80(48)
Oil-filled EPDM (a13) ??2.8 ??20 ??- ??- ??75(60) ??75(60) ??- - ??- ??75(60) ??- ??-
Crystallinity ethylene series resin (b11) ??- ??- ??25 ??25 ??- - ??- ??25 ??- ??-
Crystallinity ethylene series resin (b12) ??20 ??20 ??- ??- ??- - ??20 ??- ??20
Crystallinity ethylene series resin (b13) ??- ??- ??- ??- ??7 7 ??- ??- ??7 ??-
Noncrystalline ethylene series resin (b2) ??- ??- ??- ??- ??7 7 ??- ??- ??7 ??-
Mineral oil softener (g1) is added in the back ??- ??- ??- ??- ??11 11 ??- ??- ??11 ??-
The amount of tenderizer (mass parts) when rubber is 100 mass parts ??66.7 ??66.7 ??25 ??25 ??129 129 ??66.7 ??25 ??129 ??66.7
Rubber and ethylene series resin add up to the amount (mass parts) of 100 mass parts ??EPDM ??70.6 ??70.6 ??70.6 ??70.6 ??72.8 72.8 ??70.6 ??70.6 ??70.6 ??70.6
The ethylene series resin adds up to ??29.4 ??29.4 ??29.4 ??29.4 ??27.2 27.2 ??29.4 ??29.4 ??27.2 ??29.4
Linking agent (h1) ??1 ??1 ??- ??- ??- - ??- ??- ??- ??1
Linking agent (h2) ??- ??- ??0.7 ??0.7 ??1 1 ??- ??0.7 ??1 ??-
Linking agent (h3) ??1.2 ??1.2 ??0.7 ??0.7 ??1.2 1.2 ??1.2 ??0.7 ??1.2 ??1.2
The total amount (mass parts) of linking agent when rubber and ethylene series resin add up to 100 mass parts ??3.2 ??3.2 ??1.6 ??1.6 ??4.3 4.3 ??1.8 ??1.6 ??4.3 ??3.2
Anti-aging agent (j1) ??0.1 ??0.1 ??0.1 ??0.1 ??0.1 0.1 ??0.1 ??0.1 ??0.1 ??0.1
Silicone oil (k1) ??0.2 ??0.2 ??0.2 ??0.2 ??0.2 0.2 ??0.2 ??0.2 ??0.2 ??0.2
Manufacture method ??1 ??2 ??1 ??2 ??1 2 ??3 ??3 ??3 ??2
The gatage (%) of continuous opposite spin twin shaft mixing roll ??- ??40 ??- ??15 ??- 1 ??- ??- ??- ??10
The hole aperture (%) of continuous opposite spin twin shaft mixing roll ??- ??100 ??- ??100 ??- 100 ??- ??- ??- ??30
The rotor revolution number (rpm) of continuous opposite spin twin shaft mixing roll ??- ??750 ??- ??350 ??- 800 ??- ??- ??- ??500
The mixing thing temperature of continuous opposite spin twin shaft mixing roll outlet (℃) ??- ??194 ??- ??196 ??- 169 ??- ??- ??- ??261
The mixing thing temperature of equidirectional rotation twin screw extruder outlet (℃) ??225 ??222 ??266 ??275 ??251 247 ??246 ??273 ??244 ??251
＜rerum natura〉MFR (g/10min) ??25 ??10 ??17 ??10 ??75 120 ??46 ??25 ??143 ??5
Hardness (A type Shore hardness) ??73 ??75 ??86 ??87 ??49 50 ??73 ??87 ??49 ??75
Tensile break strength (MPa) ??8.1 ??9.9 ??9.8 ??9.9 ??3.9 4.3 ??7 ??9.2 ??3.2 ??5.4
Tension fracture elongation (%) ??600 ??640 ??650 ??670 ??620 650 ??590 ??630 ??600 ??530
Compression permanentset (%) ??38 ??34 ??45 ??49 ??38 33 ??45 ??56 ??40 ??39
Extrude processibility ??○ ??○ ??○ ??○ ??○ ○ ??× ??× ??× ??×
Particle Few Seldom Few Seldom Few Few Many Many Many Many
Gel fraction (%) ??97.4 ??98.7 ??97.8 ??98.9 ??99.4 99.3 ??97.9 ??98.5 ??99.1 ??98.1
The portrait analysis result of TEM photo Number average particle diameter dn (μ m) ??0.773 ??0.567 ??0.672 ??0.598 ??0.729 0.644 ??1.304 ??1.228 ??1.173 ??2.134
Volume average particle size dv (μ m) ??1.016 ??0.722 ??0.885 ??0.718 ??0.938 0.759 ??2.127 ??1.998 ??1.862 ??3.677
??dv/dn ??1.314 ??1.273 ??1.317 ??1.201 ??1.287 1.179 ??1.631 ??1.627 ??1.587 ??1.723
In the oil-filled EPDM hurdle bracket is the amount (mass parts) of EPDM.
[4] effect of embodiment
As can be seen from Table 1, the rerum natura of the composition that contains the specified particle diameter rubber particles [A] (embodiment 1,3 and 5) that obtains with manufacture method 1 and extrude excellent in workability, particle is few in its formed body.In addition, in the composition that contains the specified particle diameter rubber particles [A] that obtains with manufacture method 2, the mixing thing temperature t of the outlet of continuous opposite spin twin shaft mixing roll in the comparative example 4 aHigher than 250 ℃, extrude poor in processability.In addition, finding on its formed body has a plurality of particles, and the median size of cross-linked rubber particle is big, and dv/dn is higher than also.On the other hand, in embodiment 2,4 and 6, the mixing thing temperature t of the outlet of continuous opposite spin twin shaft mixing roll aAll low than 250 ℃, in addition, with 1 fen half life temperature T of linking agent hConcern T h-30≤t a≤ T h+ 30 set up.In addition, extrude excellent in workability, particle is few on its formed body, and particularly in embodiment 2 and 4, particle is considerably less.In addition, number average particle diameter dn is 0.55～0.65 μ m, and dv/dn is 1.18～1.27 than also, and is all good.
In addition, with the composition that contains the specified particle diameter rubber particles [A] (comparative example 1～3) that manufacture method 3 obtains, it extrudes poor in processability, and particle is also many, and the median size of cross-linked rubber particle is big, and dv/dn is higher than also.
2. the related embodiment of composition [B] that contains the acrylic ester resin
Following described as rubber, crystallinity ethylene series resin, noncrystalline ethylene series resin, tenderizer and linking agent etc. that raw material uses.
[1] raw material
(1) ethene-alpha-olefin is random copolymerization rubber (a11): ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber, the ethene amount is 66 quality %, the 5-ethylidene-2-norbornene amount is 4.5 quality %, 135 ℃ of limiting viscosity [η]=4.7dl/g that measure down in the naphthane solvent, mineral oil softener (trade(brand)name: Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd. makes) amount is 50 quality %.
(2) ethylene series resin
1. crystallinity olefin resin (b13): propylene-ethylene random copolymer, density are 0.90g/cm 3, MFR (230 ℃ of temperature, the heavy 2.16kg of load) is 23g/10 branch (trade(brand)name: Novatec PP FL25R, Nippon Polychem Co. manufacturing);
2. noncrystalline olefin resin (b2): the noncrystalline multipolymer of propylene/1-butene, propylene content are 71 moles of %, and melt viscosity is 8Pa s, and density is 0.87g/cm 3, Mn is 6500 (trade(brand)names: APAO UT2780, Ube Industries Ltd. manufacturing).
(3) (methyl) acrylic ester resin (c1): methyl methacrylate/methyl acrylate copolymer, density are 1.19g/cm 3, MFR (230 ℃ of temperature, the heavy 3.8kg of load) is 8g/10min (trade(brand)name: Parapet G, Kuraray Ltd. manufacturing).
(4) hydrogenated diene polymer (d1)
According to the synthesizing hydrogenated diene polymer of following method.In addition, various mensuration are undertaken by following method.
1. aromatic vinyl compound content: with 679cm -1Phenyl be absorbed as the basis, measure with infrared analysis.
2. the ethylenic linkage content of conjugated diolefine: use infrared analysis, calculate with the Morello method.
3. hydrogenation ratio: with tetracol phenixin as solvent, by 90MHz, 1The H-NMR spectrogram is calculated.
4. weight-average molecular weight: as solvent, use gel infiltration vapor-phase chromatographies (GPC) down with tetrahydrofuran (THF), try to achieve by polystyrene conversion at 38 ℃.
The synthetic method of hydrogenated diene polymer
It is that carrying out polymerization under 50 ℃ is more than 98% up to polymerisation conversion in 5 liters the autoclave that hexanaphthene 2.5kg, tetrahydrofuran (THF) 15g, vinylbenzene (block A composition) 110g, n-Butyl Lithium 0.55g are joined internal volume., add 1,3-butadiene (B block composition) 220g, carry out polymerization and reach more than 98%, add vinylbenzene (block A composition) 110g again, carry out polymerization and reach 100% until polymerisation conversion until polymerisation conversion thereafter.
After polymerization is over, make reaction solution remain on 70 ℃, add n-Butyl Lithium 0.33g, t-hydroxy-4-methyl-2 pentanone 0.61g, two (cyclopentadienyl) titanium dichloride 0.21g and diethyl aluminum chloride 0.76g, at hydrogen pressure 10kg/cm 2Under make its reaction 1 hour, carry out hydrogenation.Mix in the methyl alcohol that this reaction solution input is a large amount of, reclaim the solid matter of separating out, obtain segmented copolymer thereby carry out drying.This hydrogenated diene polymer (d1) is the A-B-A type, and hydrogenation ratio is 95%, and in the butadiene unit of B block 1,2-ethylenic linkage content is 80%, and the mass ratio of block A/ B block is 50/50, and weight-average molecular weight is 100000.
(5) linking agent and crosslinking coagent
1. linking agent (h1): 2, the 5-2 (trade(brand)name: Perhexa 25B-40, NOF Corp. makes);
2. crosslinking coagent (i1): Vinylstyrene (purity 55%), Sankyo Kasei Co. makes;
3. crosslinking coagent (i2): commodity are called Vulnoc PM, Ouchishinko ChemicalIndustries Co., and Ltd. makes.
(6) other additives
1. anti-aging agent (j1): commodity are called Irganox 1010, and Ciba Specialty ChemicalsCo. makes;
2. silicone oil (k1): polydimethyl organo-siloxane, commodity are called SH-200 (100cSt), Toray Dow-Corning Silicone Co. and make.
Embodiment 7
[2] contain the manufacturing of the composition [B] of acrylic ester resin
With ethene-alpha-olefin be random copolymerization rubber (a11) 80 mass parts, crystallinity olefin resin (b13) 10 mass parts, noncrystalline olefin resin (b2) 5 mass parts, (methyl) acrylic ester resin (c1) 5 mass parts, hydrogenated diene polymer (d1) 2 mass parts, anti-aging agent (j1) 0.1 mass parts and silicone oil (k1) 0.2 mass parts input to be heated to 150 ℃ capacity be in two wrist types pressurization kneaders (Moriyama Company Ltd. manufacturing) of 10 liters, with 40rpm mixing 20 minutes.Thereafter, with being set at the composition granulation of 180 ℃, the feeder-ruder (Moriyama Company Ltd. manufacturing) of 40rpm with molten state.Then, in the particle that obtains, cooperate linking agent (h2) 0.5 mass parts and crosslinking coagent (i2) 0.5 mass parts, mixed for 30 seconds with the Henshel mixing machine.Then, (IkegaiLtd. makes with twin screw extruder, trade(brand)name: PCM-45, be equidirectional complete engagement type screw rod, the ratio L/D of screw flight partial-length L and screw diameter D is 33.5), extrude on the following dynamic thermal treatment limit of implementing of 230 ℃, 300rpm, 2 minutes condition of delay, make the composition that contains the acrylic ester resin [B] that obtains to granular dynamic crosslinking type composition for thermoplastic elastomer.
[3] making of test film
Use the particle injection molding of injection moulding machine (trade(brand)name: N-100, Japan Steel Work Co. make), make the sheet material of thick 2mm, long 120mm, wide 120mm, for various evaluations uses with the thermoplastic elastomer that makes.
[4] contain the evaluation of the composition [B] of acrylic ester resin
(1) flowability: under 230 ℃ of temperature, the heavy 10kg of load, measure melt flow index, as the index of flowability.
(2) hardness:, measure according to JIS K 6253 as the index of flexibility.
(3) tensile break strength and tension fracture elongation: measure according to JIS K 6251.
(4) compression permanentset: as the index of caoutchouc elasticity, according to JIS K 6262, under 70 ℃, 22 hours condition, measure.
(5) scratch resistance test 4.: use Toyo Seiki Mfg., the Tai Shi scratch test machine (Taber scratch tester) that Co. makes makes to hang with certain load weight and (load is increased from the 10g at initial stage with the weight of each 10g.) metal claw (by wolfram varbide system) is at moulding product surface scan, mensuration produces the load weight value when scratching.The load weight value is big more, and then scratch resistance is just excellent more.
(6) the scratch resistance test 2.: the nail with thumb is drawn on the matrix band surface, and visual judgement scratches degree.
Metewand is: zero expression does not have scuffing, and △ represents slight scuffing, and * expression cut is dark.
Above measurement result is shown in table 2.
Embodiment 8～10 and comparative example 5～10
With the cooperation ratio shown in the table 2, make granular composition [B] and the test film that contains the acrylic ester resin similarly to Example 7.The evaluation result of the composition that contains the acrylic ester resin [B] that obtains is shown in table 2.
Table 2
Embodiment Comparative example
7 8 9 10 5 6 7 8 9 10
Oil-filled EPDM (a11) (mineral oil softener amount 50 quality %) 80(40) 65(32.5) 70(35) 60(30) 70(35) 85(42.5) 80(40) 65(32.5) 70(35) 60(30)
Crystallinity ethylene series resin (b13) 10 20 10 22 25 13 20 22 22 22
Noncrystalline ethylene series resin (b2) 5 - 5 3 5 2 - 3 3 3
(methyl) acrylic ester resin (c1) 5 10 10 10 - - - 10 - 10
Hydrogenated diene polymer (d1) 2 5 5 5 - - ?- - 5 5
Amount (quality %) when rubber, ethylene series resin, (methyl) acrylic ester resin and hydrogenated diene polymer add up to 100 quality % EPDM 64.5 48.1 53.8 42.9 53.8 73.9 66.7 48.1 53.8 42.9
The ethylene series resin adds up to 24.2 29.6 23.1 35.7 46.2 26.1 33.3 37 38.5 35.7
(methyl) acrylic ester resin 8.1 14.8 15.4 14.3 - - - 14.9 - 14.3
Hydrogenated diene polymer 3.2 7.5 7.7 7.1 - - - - 7.7 7.1
Linking agent (h1) 0.5 1 ?1 1 1 1 1 1 1 -
Crosslinking coagent (i1) - 1.25 1.25 - 0 1.25 1.25 - - -
(i2) 0.5 - - 0.5 0.5 - - 0.5 0.5 -
Anti-aging agent (j1) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Silicone oil (k1) 0.2 0.2 0.2 0.2 1.2 0.2 0.2 0.2 0.2 0.2
Mobile MFR(190℃×21.1N)(g/10min) 3 10 4 32 35 2 6 30 ?39 ?14
Mechanical characteristics Hardness (A type Shore hardness) 60 80 68 88 86 60 74 86 82 86
Tensile break strength (MPa) 6.2 7 5.4 8.5 10.3 7 8.2 5.1 9.8 4.1
Tension fracture elongation (%) 740 650 720 650 760 600 650 660 680 720
The compression permanentset CS(701℃×22hr)(％) 45 51 50 61 51 58 40 65 61 90
The damage resistant test ① 40 50 40 50 Below 10 Below 10 Below 10 40 Below 10 Below 10
② ○ ○ ○ ○ × × × ○ × ×
In the oil-filled EPDM hurdle bracket is the amount (mass parts) of EPDM.
(6) effect of embodiment
As can be seen from Table 2, embodiment 7～10 has excellent scratch resistance, mechanical characteristics, caoutchouc elasticity.In addition, because comparative example 5～7 does not contain (methyl) acrylic ester resin and hydrogenated diene polymer, so scratch resistance is poor.In addition, because comparative example 8 does not contain hydrogenated diene polymer, so mechanical properties.In addition, because comparative example 9 do not contain (methyl) acrylic ester resin, so scratch resistance is poor, because that comparative example 10 does not carry out is crosslinked, so mechanical characteristics, caoutchouc elasticity and scratch resistance are poor.
3. the composition [C] that contains maleimide compound
Following described as rubber, crystallinity ethylene series resin, noncrystalline ethylene series resin, tenderizer and linking agent etc. that raw material uses.
[1] raw material
(1) ethene-alpha-olefin is a random copolymerization rubber
With weight ratio is that 50/50 ratio contains ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber (a11) (ethene amount 66 quality %, 5-ethylidene-2-norbornene amount 4.5 quality %, (the trade(brand)name: Diana Process Oil PW-380 of limiting viscosity of 135 ℃ of mensuration [η]=4.7dl/g) and mineral oil softener in the naphthane solvent, Idemitsu KosanCo., Ltd. makes) oil-filled ethene-alpha-olefin be random copolymers.
(2) ethylene series resin
1. crystallinity olefin resin (b13): propylene-ethylene random copolymer, density are 0.90g/cm 3, MFR (230 ℃ of temperature, the heavy 2.16kg of load) is 23g/10 branch (trade(brand)name: Novatec PP FL25R, Nippon Polychem Co. manufacturing);
2. noncrystalline olefin resin (b2): the noncrystalline multipolymer of propylene/1-butene, propylene content are 71 moles of %, and melt viscosity is 8Pa s, and density is 0.87g/cm 3, Mn is 6500 (trade(brand)name: APAO UT2780 ", Ube Industries Ltd. make).
(3) (methyl) acrylic ester resin
Methyl methacrylate methyl acrylate copolymer (c1): density is 1.19g/cm 3, MFR (230 ℃ of temperature, the heavy 3.8kg of load) is 8g/10min (trade(brand)name: Parapet G, Kuraray Ltd. manufacturing).
(4) hydrogenated diene polymer (d1)
According to the synthesizing hydrogenated diene polymer of following method.In addition, various mensuration are undertaken by following method.
1. aromatic vinyl compound content: with 679cm -1Phenyl be absorbed as the basis, measure with infrared analysis.
2. the ethylenic linkage content of conjugated diolefine: use infrared analysis, calculate with the Morello method.
3. hydrogenation ratio: with tetracol phenixin as solvent, by 90MHz, 1The H-NMR spectrogram is calculated.
4. weight-average molecular weight: as solvent, use gel infiltration vapor-phase chromatographies (GPC) down with tetrahydrofuran (THF), try to achieve by polystyrene conversion at 38 ℃.
The synthetic method of hydrogenated diene polymer
It is that carrying out polymerization under 50 ℃ is more than 98% up to polymerisation conversion in 5 liters the autoclave that hexanaphthene 2.5kg, tetrahydrofuran (THF) 15g, vinylbenzene (block A composition) 110g, n-Butyl Lithium 0.55g are joined internal volume., add 1,3-butadiene (B block composition) 220g, carry out polymerization and reach more than 98%, add vinylbenzene (block A composition) 110g again, carry out polymerization and reach 100% until polymerisation conversion until polymerisation conversion thereafter.
After polymerization is over, make reaction solution remain on 70 ℃, add n-Butyl Lithium 0.33g, t-hydroxy-4-methyl-2 pentanone 0.61g, two (cyclopentadienyl) titanium dichloride 0.21g and diethyl aluminum chloride 0.76g, at hydrogen pressure 10kg/cm 2Under make its reaction 1 hour, carry out hydrogenation.Mix in the methyl alcohol that this reaction solution input is a large amount of, reclaim the solid matter of separating out, obtain segmented copolymer thereby carry out drying.This hydrogenated diene polymer (d1) is the A-B-A type, and hydrogenation ratio is 95%, and in the butadiene unit of B block 1,2-ethylenic linkage content is 80%, and the mass ratio of block A/ B block is 50/50, and weight-average molecular weight is 100000.
(5) linking agent
1. organo-peroxide (h1): 2, the 5-2 (trade(brand)name: Perhexa 25B-40, NOF Corp. makes);
2. crosslinking coagent (i1): Vinylstyrene (purity 55%), Sankyo Kasei Co. makes.
(6) maleimide compound (e1): N, and a N '-benzene bismaleimides (trade(brand)name: Vulnoc PM, Ouchishinko Chemical Industries Co., Ltd. makes).
(7) other additives
1. anti-aging agent (j1): commodity are called Irganox 1010, and Ciba Specialty ChemicalsCo. makes;
2. silicone oil: polydimethyl organo-siloxane, commodity are called SH-200 (viscosity=100cSt), Toray Dow-Corning Silicone Co. make.
Embodiment 11
[2] contain the manufacturing of the composition [C] of maleimide compound
With ethene-alpha-olefin be random copolymerization rubber (a11) 80 mass parts, crystallinity olefin resin (b13) 15 mass parts, noncrystalline olefin resin (b2) 5 mass parts, maleimide compound (e1) 0.5 mass parts and anti-aging agent (j1) 0.1 mass parts input to be heated to 150 ℃ capacity be in two wrist types pressurization kneaders (Moriyama Company Ltd. manufacturing) of 10 liters, with 40rpm mixing 20 minutes.Thereafter, with being set at the composition granulation of 180 ℃, the feeder-ruder (Moriyama Company Ltd. manufacturing) of 40rpm with molten state.Then, in the particle that obtains, cooperate organo-peroxide (h2) 1 mass parts and silicone oil (k1) 0.2 mass parts, mixed for 30 seconds with the Henshel mixing machine, (Ikegai Ltd. makes to use twin screw extruder then, trade(brand)name: PCM-45, be equidirectional complete engagement type screw rod, the ratio L/D of screw flight partial-length L and screw diameter D is 33.5), at 230 ℃, 300rpm, extrude on the following dynamic thermal treatment limit of being detained 2 minutes of implementing of condition, makes the composition that contains maleimide compound [C] that obtains to granular dynamic crosslinking type thermoplastic elastomer composition.
[3] test film that contains the composition [C] of maleimide compound is made
The particle injection molding of the composition that contains maleimide compound [C] that use injection moulding machine (trade(brand)name: N-100, Japan Steel Work Co. make) will make, make the sheet material of thick 2mm, long 120mm, wide 120mm, use for various evaluations.
[4] contain the evaluation of the composition [C] of maleimide compound
(1) flowability: under 230 ℃ of temperature, the heavy 10kg of load, measure melt flow index, as the index of flowability.
(2) hardness:, measure according to JIS K 6253 as the index of flexibility.
(3) tensile break strength and tension fracture elongation: measure according to JIS K 6251.
(4) compression permanentset: as the index of caoutchouc elasticity, according to JIS K 6262, under 70 ℃, 22 hours condition, measure.
(5) injection weldability: used on ethylene series vulcanized rubber test film injection welding and contained the test film of the composition [C] of maleimide compound, with the composition [C] that contains maleimide compound and the joint of adherend is starting point, carry out bending with 180 ° angles, the then state of peeling off at interface after the visual observation alternating bending 10 times.
Metewand: zero expression does not have and to peel off, and △ represents to find that a part peels off, and * expression is peeled off and produced fracture.
1. the making of adherend
Make following ethylene series vulcanized rubber sheet as adherend, use for test.
For ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber (72 moles of % of ethylene content, 28 moles of % of propylene content, mooney viscosity 92, iodine value 15, trade(brand)name " EP103A ", JSR Corp. makes) 100 weight parts, with carbon black (trade(brand)name: Seast 116, Tokai Carbon Co. makes) 145 mass parts, mineral oil softener (g1) (trade(brand)name: Diana Process Oil PW380, Idemitsu Kosan Co., Ltd. make) 85 mass parts, active zinc white (Sakai Chemical Industry Co. manufacturing) 5 mass parts, stearic acid (Asahi Denka Corp. manufacturing) 1 mass parts, processing aid (trade(brand)name: Hitanol 1501, Hitachi Chemical Co. makes) 1 mass parts, releasing agent (trade(brand)name: Structol WB212, Syl and Zilaher Co. makes) 2 mass parts and softening agent (polyoxyethylene glycol) 1 mass parts, with capacity is 3 liters Banbury mixer (Kobe Steel Ltd. manufacturing), at 50 ℃, 70rpm, carry out mixing under the condition of 2.5 minutes time.Then, add dewatering agent (trade(brand)name: Vesta PP, Inoue Sekkai Kogyo Co. manufacturing) 10 mass parts, vulcanization accelerator (trade(brand)name M:1 mass parts, trade(brand)name PX:1 mass parts, trade(brand)name TT:0.5 mass parts, trade(brand)name D:1 mass parts, by Ouchishinko ChemicalIndustries Co., Ltd. makes) and sulphur 2.2 mass parts, use 6 inches to open and refine roller (Kansai Roll Co. manufacturing) and under 50 ℃, carry out mixing.Then, vulcanized 10 minutes down, obtain the ethylene series vulcanized rubber sheet of 120mm pros, thick 2mm at 170 ℃.With the dumbbell shaped cutting knife this sheet is washed into long 60mm, wide 50mm, makes adherend.
2. on the ethylene series vulcanized rubber injection welding making of test film of thermoplastic elastomer
(the test film shape of 120 * 120 * 2mm) attaches above-mentioned adherend (60 * 50 * 2mm) in advance in the split mould of injection moulding machine (N-100 type, Japan Steel Work Co. make), each composition for thermoplastic elastomer injection molding of making to adherend, is made the square plate (120 * 120 * 2mm) of composition for thermoplastic elastomer and ethylene series vulcanized rubber (adherend) welding.
(6) 2. 1. the damage resistant test reach: adopt method as hereinbefore to estimate.Metewand is also identical.
Above table 3 and the table 4 of the results are shown in.
Embodiment 12～18, comparative example 11～15
With the cooperation ratio shown in table 3 and the table 4, make the composition [C] that granulous contains maleimide compound similarly to Example 11, make test film.In addition, similarly the composition [C] that contains maleimide compound is estimated.The results are shown in table 3 and table 4.
Table 3
Embodiment Comparative example
11 ??12 13 14 15 11 12 13
Cooperate Oil-filled EPDM (a11) (mineral oil softener amount 50 quality %) 80(40) ??80(40) 70(35) 75(37.5) 65(32.5) 80(40) 80(40) 80(40)
Crystallinity ethylene series resin ??(b13) 15 ??15 25 20 10 15 15 15
Noncrystalline ethylene series resin ??(b2) 5 ??5 5 5 10 5 5 5
Maleimide compound ??(e1) 0.5 ??0.5 0.5 1 0.5 - 0.25 -
The amount (mass parts) of maleimide compound when rubber, ethylene series resin and tenderizer add up to 100 mass parts 0.5 ??0.5 0.5 1 0.5 - 0.25 -
Mineral oil softener is added in the back ??(g1) - ??- - - 15 - - -
Amount (quality %) when rubber, ethylene series resin and tenderizer add up to 100 quality % ??EPDM 40 ??40 35 37.5 32.5 40 40 40
The ethylene series resin adds up to 20 ??20 30 25 20 20 20 20
Mineral oil softener 40 ??40 35 37.5 47.5 40 40 40
Linking agent ??(h1) 1 ??1 1 1 1 1 1 1
Crosslinking coagent ??(h3) - ??- - - - - - 1.25
Anti-aging agent ??(f1) 0.1 ??0.1 0.1 0.1 0.1 0.1 0.1 0.1
Silicone oil ??(K1) 0.2 ??0.2 0.2 0.2 0.2 0.2 0.2 0.2
Rerum natura Mobile ??MFR(230℃×5kg)(g/10min) 101 ??106 120 110 102 52 80 42
Mechanical characteristics Hardness (A type Shore hardness) 67 ??65 8.6 78 49 67 68 57
Tensile break strength (MPa) 6.5 ??6.2 9.7 8 3.5 5 6 8.8
Tension fracture elongation (%) 740 ??570 680 640 660 810 780 720
The compression permanentset ??CS(701℃×22hr)(％) 50 ??47 59 49 61 65 57 45
The injection weldability Warpage separability, 180 ° (visual) ○ ??○ ○ ○ ○ × × ×
In the oil-filled EPDM hurdle bracket is the amount (mass parts) of EPDM.
Table 4
Embodiment Comparative example
??16 ??17 ??18 ??14 ??15
Cooperate Oil-filled EPDM (a11) (mineral oil softener amount 50 quality %) ??70(35) ??80(40) ??64(32) ??70(35) ??70(35)
Crystallinity ethylene series resin ??(b13) ??26 ??14 ??32 ??26 ??26
Noncrystalline ethylene series resin ??(b2) ??4 ??6 ??4 ??4 ??4
Amount (quality %) when rubber, ethylene series resin and tenderizer add up to 100 quality % ??EPDM ??35 ??40 ??32 ??35 ??35
The ethylene series resin adds up to ??30 ??20 ??36 ??30 ??30
Mineral oil softener ??35 ??40 ??32 ??35 ??35
Maleimide compound ??(e1) ??0.6 ??1.2 ??0.6 ??- ??-
The amount (mass parts) of maleimide compound when rubber, ethylene series resin and tenderizer add up to 100 mass parts ??0.6 ??1.2 ??0.6 ??- ??-
(methyl) acrylic ester resin ??(c1) ??12 ??12 ??12 ??12 ??12
The amount (mass parts) of (methyl) acrylic ester resin when rubber, ethylene series resin and tenderizer add up to 100 mass parts ??12 ??12 ??12 ??12 ??12
Hydrogenated diene polymer ??(d1) ??6(0.5) ??6(0.5) ??6(0.5) ??6(0.5) ??6(0.5)
Linking agent ??(h1) ??1.2 ??1.2 ??1.2 ??- ??1.2
Crosslinking coagent ??(h3) ??- ??- ??- ??- ??1.5
Anti-aging agent ??(j1) ??0.12 ??0.12 ??0.12 ??0.12 ??0.12
Silicone oil ??(k1) ??0.24 ??0.24 ??0.24 ??0.24 ??0.24
Rerum natura Mobile ??MFR(230℃×5kg)(g/10min) ??35 ??5 ??45 ??3 ??16
Mechanical characteristics Hardness (A type Shore hardness) ??88 ??70 ??92 ??89 ??88
Breaking tenacity (MPa) ??7.4 ??5.8 ??8 ??7.2 ??8
Extension at break (%) ??850 ??730 ??600 ??1120 ??720
The compression permanentset ??CS(701℃×22hr)(％) ??59 ??55 ??66 ??88 ??56
The injection weldability Warpage separability, 180 ° (visual) ??○ ??○ ??○ ??× ??×
Scratch resistance (1) ??50 ??40 ??50 Below 10 ??50
Scratch resistance (2) ??○ ??○ ??○ ??× ??○
In the oil-filled EPDM hurdle bracket is the amount (mass parts) of EPDM.In addition, in the hydrogenated diene polymer hurdle bracket be mass ratio with respect to (methyl) acrylic ester resin.
(6) effect of embodiment
As can be seen from Table 3, embodiment 11～15 has excellent mechanical characteristics, caoutchouc elasticity, injection weldability.Because the addition of the maleimide compound of comparative example 11 and comparative example 12 is in the application's scope, so processibility, mechanical characteristics, caoutchouc elasticity, injection weldability are poor.Because comparative example 13 has used the crosslinking coagent beyond the maleimide compound, it is poor therefore to inject weldability.In addition, as can be seen from Table 4, embodiment 16～18 has excellent scratch resistance, mechanical characteristics, caoutchouc elasticity, injection weldability.In addition, because that comparative example 14 does not carry out is crosslinked, so mechanical characteristics, caoutchouc elasticity, scratch resistance, injection weldability are poor.In addition, because comparative example 15 has used maleimide compound crosslinking coagent in addition, it is poor therefore to inject weldability.
4. the related embodiment of composition [D] that contains polysiloxane
Following described as rubber, crystallinity ethylene series resin, noncrystalline ethylene series resin, tenderizer and linking agent etc. that raw material uses.
[1] raw material
(1) oil-extended rubber
1. oil-extended rubber (a11): ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber, ethylene content is 66 quality %, 5-ethylidene-2-norbornene content is 4.5 quality %, the limiting viscosity of 135 ℃ of mensuration is 4.7dl/g in the naphthane solvent, mineral oil softener (trade(brand)name: Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd. makes) amount is 50 quality %;
2. oil-extended rubber (a12): ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber, ethylene content is 66 quality %, 5-ethylidene-2-norbornene content is 4.5 quality %, the limiting viscosity of 135 ℃ of mensuration is 3.8dl/g in the naphthane solvent, mineral oil softener (trade(brand)name: Diana Process Oil PW-380, Idemitsu Kosan Co., Ltd. makes) amount is 40 quality %.
(2) ethylene series resin
1. propylene-ethylene random copolymer (b13): density is 0.90g/cm 3, MFR (230 ℃ of temperature, the heavy 2.16kg of load) is 23g/10 branch (trade(brand)name: Novatec PP FL25R, Nippon Polychem Co. manufacturing);
2. the noncrystalline multipolymer of propylene/1-butene (b2): propylene content is 71 moles of %, and melt viscosity is 8Pa s, and density is 0.879g/cm 3, Mn is 6500 (trade(brand)names: APAO UT2780, Ube Industries Ltd. manufacturing).
(3) unmodified organopolysiloxane
1. polydimethylsiloxane (f11): viscosity 100cSt (trade(brand)name: silicone oil SH-200, Toray Dow-Corning Silicone Co. makes);
2. polydimethylsiloxane (f12): viscosity 1000cSt (trade(brand)name: silicone oil SH-200, Toray Dow-Corning Silicone Co. makes);
3. polydimethylsiloxane (f13): viscosity 5000cSt (trade(brand)name: silicone oil SH-200, Toray Dow-Corning Silicone Co. makes);
4. polydimethylsiloxane (f14): viscosity 12500cSt (trade(brand)name: silicone oil SH-200, Toray Dow-Corning Silicone Co. makes);
5. (trade(brand)name: BY 16-140, Toray Dow-Corning Silicone Co. manufacturing) more than ultra-high molecular weight silicon rubber (f15): the viscosity 1000000cSt.
(4) modification organopolysiloxane
Acrylic acid modified silicone resin (f2): commodity are called x-22-8171, Shin-Etsu ChemicalCo., and Ltd. makes.
(5) mineral oil softener (g1): commodity are called Diana Process Oil PW-380, Idemitsu Kosan Co., and Ltd. makes.
(6) linking agent and crosslinking coagent
1. 2,5-2 (h1), commodity are called Perhexa 25B-40, and NOF Corp. makes;
2. N, a N '-benzene bismaleimides (h2), commodity are called Vulnoc PM, Ouchishinko Chemical Industries Co., Ltd. makes;
3. crosslinking coagent (h3): Vinylstyrene (Sankyo Kasei Co. manufacturing).
(6) aging additive (j1): commodity are called Irganox 1010, and Ciba SpecialtyChemicals Co. makes.
[2] contain the manufacturing of the composition [D] of polysiloxane
Embodiment 19～25 and comparative example 16～20 (making) with closed mixing machine+continous way mixing roll
According to the cooperation shown in table 5 and 6, the feedstock composition input that does not comprise linking agent has been heated in 150 ℃ the pressurization kneader (Moriyama Company Ltd. manufacturing), carry out mixingly disperseing in 15 minutes with 40rpm up to each uniform component.Use feeder-ruder (Moriyama Company Ltd. manufacturing) composition of molten state carried out granulation thereafter.Then, in this pellet, add linking agent and crosslinking coagent, use the Henshel agitator to mix for 30 seconds with cooperation ratio shown in table 5 and 6.Then, operating weight formula feeder supplies to twin screw extruder (equidirectional non-engagement type screw rod, L/D=38.5, trade(brand)name " PCM-45 ", Ikegai Ltd. make) with the output of 40kg/hr, the limit is implemented dynamic thermal treatment limit down at 200 ℃, screw rod revolution 300rpm, 2 minutes residence times and is extruded, and makes the composition that contains polysiloxane [D] that obtains to dynamic crosslinking type composition for thermoplastic elastomer.
[3] contain the evaluation of the composition [D] of polysiloxane
For the composition that contains polysiloxane [D] that makes is as mentioned above estimated, carry out the mensuration of following project.
1. melt flow index (MFR): under 230 ℃ of temperature, the heavy 10kg of load, measure.
2. hardness, tensile break strength and tension fracture elongation: measure according to JIS K 6301.
3. compress permanentset: according to JIS K 6301,70 ℃, 22 hours, 25% the compression condition under measure.
4. initial stage sliding and durable sliding
The use trier (Tosoku Seimitsu Co. manufacturing) that reciprocatingly slides is at the heavy 233g/3cm of load 2(face is pressed 78g/cm 2), under the glass ring test film sliding velocity 100mm/min (1 stroke 50mm), measure the test film (long 110mm, wide 61mm, thick 2mm) that constitutes by the composition that contains polysiloxane [D] static friction coefficient and kinetic friction coefficient with respect to the round tube type glass ring test film of external diameter 25.7mm, internal diameter 20mm, high 16.5mm, weight 9.6g.The initial stage sliding is the test film that will use after the test film injection molding through 1 day, at room temperature measures.In addition, durable sliding is to use after the injection molding test film being statically placed in the test film of gear baking oven (gear oven) after 500 hours, at room temperature measures.
5. separate out test: will contain in the gear baking oven (Toyo Seiki Co. manufacturings) that test film that the composition [D] of polysiloxane constitutes is statically placed in 100 ℃ of temperature 120 hours, the condition of surface of usefulness visual observation test film.
6. extrude processibility: use Labplastmill forcing machine (external diameter=20mm, L/D=25, Toyo Seiki Co. make), carry out flat board under the following conditions and extrude (mouthful the mould width 25mm of portion, thickness 1.5mm), its outward appearance is estimated with visual.Smooth surface and marginately be designated as zero, all be designated as in addition *.
Machine barrel C1=180 ℃, machine barrel C2=190 ℃, machine barrel C3=210 ℃, mouthful mould=205 ℃, screw rod revolution: 40rpm.
7. inject weldability: having used the injection welding and contained the test film of the composition [D] of polysiloxane, is starting point with the composition [D] that contains polysiloxane and the joint of adherend, the state of peeling off when visual observation is carried out warpage with 180 ° angle.
Metewand: zero expression does not have and to peel off, and △ represents to find that a part peels off, and * expression is peeled off and produced fracture.
In addition, for 2. above-mentioned～5., the composition [D] that will contain polysiloxane with injection moulding machine (commodity be called N-100, JapanSteel Work Co. make) is made into the injection molding test film of 120 * 120 * 2mm size.
[4] making of adherend
7. for above-mentioned, the adherend that making as described below is made of the ethylene series vulcanized rubber uses for test.
For ethylene/propene/5-ethylidene-2-norbornene terpolymer rubber (72 moles of % of ethylene content, 28 moles of % of propylene content, mooney viscosity 92, iodine value 15, trade(brand)name " EP103A ", JSR Corp. makes) 100 weight parts, cooperate carbon black (trade(brand)name: Seast 116, Tokai Carbon Co. makes) 145 mass parts, mineral oil softener (g1) (trade(brand)name: Diana Process Oil PW380, Idemitsu Kosan Co., Ltd. make) 85 mass parts, active zinc white (Sakai Chemical Industry Co. manufacturing) 5 mass parts, stearic acid (Asahi Denka Corp. manufacturing) 1 mass parts, processing aid (trade(brand)name: Hitanol 1501, Hitachi Chemical Co. makes) 1 mass parts, releasing agent (trade(brand)name: Structol WB212, Syl and Zilaher Co. makes) 2 mass parts and softening agent (polyoxyethylene glycol) 1 mass parts, modulating mixture.
Then, use Banbury mixer, under 50 ℃, 70rpm, 2.5 minutes condition of mixing time, carry out mixing this mixture.Then, add dewatering agent (trade(brand)name: Vesta PP, Inoue Sekkai Kogyo Co. manufacturing) 10 mass parts, vulcanization accelerator (trade(brand)name M:1 mass parts, trade(brand)name PX:1 mass parts, trade(brand)name TT:0.5 mass parts, trade(brand)name D:1 mass parts, by Ouchishinko Chemical Industries Co., Ltd. makes) and sulphur 2.2 mass parts, use is opened the refining roller and is carried out mixing under 50 ℃.Then, vulcanized 10 minutes down, obtain the vulcanized rubber sheet of 120mm pros, thick 2mm at 170 ℃.With the dumbbell shaped cutting knife this sheet is washed into long 60mm, wide 50mm, makes adherend.
[5] on the ethylene series vulcanized rubber injection welding making of test film of thermoplastic elastomer
(the test film shape of 120 * 120 * 2mm) attaches above-mentioned adherend (60 * 50 * 2mm) in advance in the split mould of injection moulding machine (N-100 type, Japan Steel Work Co. make), each composition for thermoplastic elastomer injection molding of making to adherend, is made the square plate (120 * 120 * 2mm) of composition for thermoplastic elastomer and ethylene series vulcanized rubber (adherend) welding.
The results are shown in table 5～6.
Table 5
Embodiment
Oil-extended rubber Limiting viscosity (dl/g) Mineral oil softener content (quality %) ??19 ??20 ??21 ??22 ??23 ??24 ??25
Oil-filled EPDM (a11) 4.7 50 ??30 ??32.5 ??40 ??70 ??70 ??70 ??70
Oil-filled EPDM (a12) 3.8 40 ??30 ??32.5 ??40 ??- ??- ??- ??-
Amount (quality %) when contained EPDM of oil-extended rubber and tenderizer add up to 100 quality % EPDM ??45 ??45 ??55 ??50 ??50 ??50 ??50
Mineral oil softener ??55 ??55 ??45 ??50 ??30 ??50 ??50
Crystallinity ethylene series resin (b13) ??5 ??5 ??75 ??25 ??25 ??30 ??30
Noncrystalline ethylene series resin (b2) ??5 ??5 ??75 ??5 ??5 ??- ??-
Mineral oil softener (g1) is added in the back ??25 ??15 ??5 ??- ??- ??- ??-
Oil-extended rubber, the amount (mass parts) when ethylene series resin and back interpolation tenderizer add up to 100 mass parts Oil-filled EPDM ??63.2 ??72.2 ??80 ??70 ??70 ??70 ??70
The ethylene series resin adds up to ??10.5 ??11.1 ??15 ??30 ??30 ??30 ??30
Tenderizer is added in the back ??26.3 ??16.7 ??5 ??- ??- ??- ??-
The unmodified organopolysiloxane of low viscosity Viscosity 100cSt (f11) ??- ??- ??- ??- ??0.5 ??- ??0.5
Viscosity 1000cSt (f12) ??- ??3 ??3 ??15 ??15 ??-
Viscosity 5000cSt (f13) ??1.5 ??- ??- ??- ??- ??- ??-
The unmodified organopolysiloxane of high viscosity Viscosity 12500cSt (f14) ??1.5 ??3 ??3 ??1.5 ??- ??1.5 ??-
Viscosity 1000000cSt (f15) ??- ??- ??- ??- ??2.5 ??- ??2.5
Acrylic acid modified organopolysiloxane (f2) ??1 ??1 ??1 ??1 ??0.5 ??1 ??0.5
Amount (mass parts) when oil-extended rubber, ethylene series resin and back interpolation tenderizer add up to 100 mass parts The unmodified organopolysiloxane of low viscosity ??1.6 ??3.7 ??3 ??15 ??0.5 ??1.5 ??0.5
The unmodified organopolysiloxane of high viscosity ??1.6 ??3.7 ??3 ??1.5 ??2.5 ??1.5 ??2.5
Acrylic acid modified organopolysiloxane ??1.1 ??1.1 ??1 ??1 ??0.5 ??1 ??0.5
Linking agent (h1) ??1 ??1 ??1 ??0.5 ??0.5 ??0.5 ??0.5
Linking agent (h2) ??- ??- ??- ??1 ??1 ??1 ??1
Crosslinking coagent (h3) ??1.3 ??1.3 ??1.3 ??- ??- ??- ??-
Anti-aging agent (j1) ??0.1 ??0.1 ??0.1 ??0.1 ??0.1 ??0.1 ??0.1
MFR(g/10min) ??330 ??520 ??280 ??300 ??285 ??285 ??270
Hardness (JIS-A hardness) ??42 ??41 ??51 ??85 ??87 ??87 ??87
Tensile break strength (MPa) ??3.9 ??3.7 ??4.6 ??10 ??9.8 ??9.8 ??10.1
Tension fracture elongation (%) ??800 ??770 ??760 ??740 ??710 ??710 ??720
Compression permanentset (%) ??42 ??43 ??46 ??59 ??60 ??60 ??60
The initial stage sliding Static friction coefficient ??0.61 ??0.45 ??0.32 ??0.29 ??0.3 ??0.45 ??0.31
Kinetic friction coefficient ??0.63 ??0.38 ??0.29 ??0.25 ??0.26 ??0.34 ??0.28
Durable sliding Static friction coefficient ??0.57 ??0.52 ??0.62 ??0.3 ??0.35 ??0.52 ??0.36
Kinetic friction coefficient ??0.57 ??0.35 ??0.25 ??0.28 ??0.3 ??0.43 ??0.32
Separate out test (zero=do not have, *=have) ??○ ??○ ??○ ??○ ??○ ??○ ??○
Extrude processibility ??○ ??○ ??○ ??○ ??○ ??○ ??○
The injection weldability ??○ ??○ ??○ ??○ ??○ ??○ ??○
Table 6
Comparative example
Oil-extended rubber Limiting viscosity (dl/g) Mineral oil softener content (quality %) ??16 ??17 ??18 ??19 ??20
Oil-filled EPDM (a11) 4.7 50 ??32.5 ??32.5 ??32.5 ??32.5 ??32.5
Oil-filled EPDM (a12) 3.8 40 ??32.5 ??32.5 ??32.5 ??32.5 ??32.5
Amount (quality %) when contained EPDM of oil-extended rubber and tenderizer add up to 100 quality % EPDM ??45 ??45 ??45 ??45 ??45
Mineral oil softener ??55 ??55 ??55 ??55 ??55
Crystallinity ethylene series resin (b13) ??5 ??5 ??5 ??5 ??5
Noncrystalline ethylene series resin (b2) ??5 ??5 ??5 ??5 ??5
Mineral oil softener (g1) is added in the back ??15 ??15 ??15 ??15 ??15
Amount (mass parts) when oil-extended rubber, ethylene series resin and back interpolation tenderizer add up to 100 mass parts Oil-filled EPDM ??72.2 ??72.2 ??72.2 ??72.2 ??72.2
The ethylene series resin adds up to ??11.1 ??11.1 ??11.1 ??11.1 ??11.1
Tenderizer is added in the back ??16.7 ??16.7 ??16.7 ??16.7 ??16.7
The unmodified organopolysiloxane of low viscosity Viscosity 100cSt (f11) ??3 ??- ??- ??- ??-
Viscosity 1000cSt (f12) ??- ??3 ??- ??- ??3
Viscosity 5000cSt (f13) ??- ??- ??3 ??- ??-
The unmodified organopolysiloxane of high viscosity Viscosity 12500cSt (f14) ??- ??- ??- ??3 ??3
Viscosity 1000000cSt (f15) ??- ??- ??- ??- ??-
Acrylic acid modified organopolysiloxane (f2) ??- ??- ??- ??- ??-
Amount (mass parts) when oil-extended rubber, ethylene series resin and back interpolation tenderizer add up to 100 mass parts The unmodified organopolysiloxane of low viscosity ??3.3 ??3.3 ??3.3 ??- ??3.3
The unmodified organopolysiloxane of high viscosity ??- ??- ??- ??3.3 ??3.3
Acrylic acid modified organopolysiloxane ??- ??- ??- ??- ??-
Linking agent (h1) ??1 ??1 ??1 ??1 ??1
Linking agent (h2) ??- ??- ??- ??- ??-
Crosslinking coagent (h3) ??1.3 ??1.3 ??1.3 ??1.3 ??1.3
Anti-aging agent (j1) ??0.1 ??0.1 ??0.1 ??0.1 ??0.1
MFR(g/10min) ??200 ??130 ??290 ??250 ??280
Hardness (JIS-A hardness) ??43 ??43 ??42 ??42 ??42
Tensile break strength (MPa) ??4 ??3.9 ??4.2 ??4.1 ??3.7
Tension fracture elongation (%) ??760 ??760 ??780 ??770 ??680
Compression permanentset (%) ??39 ??40 ??43 ??45 ??43
The initial stage sliding Static friction coefficient ??0.55 ??0.81 ??0.93 ??0.97 ??0.6
Kinetic friction coefficient ??0.53 ??0.67 ??0.72 ??0.7 ??0.59
Durable sliding Static friction coefficient ??1.5 ??1.48 ??1.16 ??0.88 ??1.25
Kinetic friction coefficient ??1.1 ??1 ??0.73 ??0.69 ??1.1
Separate out test (zero=do not have, *=have) ??× ??× ??× ??○ ??×
Extrude processibility ??○ ??○ ??○ ??○ ??×
The injection weldability ??○ ??○ ??○ ??○ ??×
(6) effect of embodiment
Can see that from table 5～6 16～18 of comparative examples have used the unmodified organopolysiloxane of low viscosity, and do not use acrylic acid modified organopolysiloxane.Therefore, though extrude processibility and injection weldability excellence, initial stage and durable sliding are poor, separate out generation.In addition, 19 of comparative examples have used the unmodified organopolysiloxane of high viscosity, and do not use acrylic acid modified organopolysiloxane.Therefore, though extrude processibility and injection weldability excellence, initial stage and durable sliding are poor.In addition, comparative example 20 contains low viscosity and full-bodied unmodified organopolysiloxane, but does not contain acrylic acid modified organopolysiloxane.Therefore, initial stage and durable sliding, extrude processibility, the injection weldability poor, separate out generation.On the other hand, the composition that contains polysiloxane [D] of embodiment 19～25, its initial stage and durable sliding and extrude excellent in workability, organopolysiloxane does not have separates out.In addition, generations such as nothing is peeled off, fracture have excellent injection weldability.

Claims (7)

1, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, the polymer composition that contains rubber, ethylene series resin, tenderizer, (methyl) acrylic ester resin and maleimide compound is carried out dynamic thermal treatment and form, wherein, when this rubber, this ethylene series resin and this tenderizer are added up to 100 mass parts, this maleimide compound is 0.3～10 mass parts, should (methyl) acrylic resin be 1～30 mass parts.
2, according to the composition for thermoplastic elastomer of claim 1 record, wherein, described polymer composition also contains hydrogenated diene polymer, and this hydrogenated diene polymer is 0.1～1 with respect to the mass ratio of described (methyl) acrylic resin.
3, composition for thermoplastic elastomer, it is characterized in that: in the presence of linking agent, be that the polymer composition of copolymer rubber, ethylene series resin, tenderizer and maleimide compound carries out dynamic thermal treatment and forms containing ethene-alpha-olefin, this ethene-alpha-olefin is that copolymer rubber is being 2.0～6.8dl/g with naphthane as solvent, 135 ℃ of limiting viscosities [η] of measuring down, wherein, when this rubber, this ethylene series resin and this tenderizer added up to 100 mass parts, this maleimide compound was 0.3～10 mass parts.
4, the manufacture method of composition for thermoplastic elastomer, it is the method for making the composition for thermoplastic elastomer of each record of claim 1～3, it is characterized in that: the polymer composition that will contain rubber and ethylene series resin with closed mixing machine reaches other additives that do not comprise linking agent, or contain the polymer composition of rubber and ethylene series resin, at least a portion of linking agent reaches other additive melting mixings that do not comprise linking agent, become the melting mixing thing, this melting mixing thing or this melting mixing thing and the additive that at least contain linking agent supplied in continous way forcing machine, carry out dynamic thermal treatment thereafter.
5, the manufacture method of composition for thermoplastic elastomer, it is the method for making the composition for thermoplastic elastomer of each record of claim 1～3, it is characterized in that: in the polymer composition that contains rubber and ethylene series resin, cooperate linking agent, thereafter, supply in interconnective a plurality of continous way mixing roll, carry out dynamic thermal treatment.
6, the manufacture method of composition for thermoplastic elastomer, it is the method for making the composition for thermoplastic elastomer of each record of claim 1～3, it is characterized in that: the polymer composition that will contain rubber and ethylene series resin is supplied with from the raw material introduction part of this continous way opposite spin twin-screw mixer machine of the extrusion device of the continous way opposite spin twin-screw mixer machine at upper reaches and dirty equidirectional rotation twin screw extruder configured in series, by this continous way opposite spin twin-screw mixer machine that this polymer composition is mixing, the mixing thing temperature that the limit exports this continous way opposite spin twin-screw mixer machine remains on and is less than or equal to 250 ℃, the limit should supply to this equidirectional rotation twin screw extruder by mixing thing, carried out dynamic crosslinking.
7, the manufacture method of composition for thermoplastic elastomer, it is the method for making the composition for thermoplastic elastomer of each record of claim 1～3, it is characterized in that: will contain rubber, the polymer composition of ethylene series resin and organo-peroxide is supplied with from the raw material introduction part of this continous way opposite spin twin-screw mixer machine of the extrusion device of the continous way opposite spin twin-screw mixer machine at upper reaches and dirty equidirectional rotation twin screw extruder configured in series, by this continous way opposite spin twin-screw mixer machine that this polymer composition is mixing, the limit is with the mixing thing temperature (t of this continous way opposite spin twin-screw mixer machine outlet a) be controlled at T h-30≤t a≤ T h+ 30 (℃) scope, the limit should supply to this equidirectional rotation twin screw extruder by mixing thing, carried out dynamic crosslinking, wherein, and when the fusing point of this ethylene series resin is T mThe time, 1 minute half life temperature T of organo-peroxide h(℃) at T m≤ T h≤ T m+ 50 (℃) scope.
CNB2005100779577A 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same Expired - Fee Related CN100500755C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2001283462 2001-09-18
JP2001283462A JP3694789B2 (en) 2001-09-18 2001-09-18 Thermoplastic elastomer composition and molded article
JP2001369528 2001-12-04

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CNB028183312A Division CN100434464C (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same

Publications (2)

Publication Number Publication Date
CN1693354A true CN1693354A (en) 2005-11-09
CN100500755C CN100500755C (en) 2009-06-17

Family

ID=19106942

Family Applications (4)

Application Number Title Priority Date Filing Date
CNB2005100779543A Expired - Lifetime CN100358942C (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same
CNB2005100779562A Expired - Lifetime CN100366669C (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same
CN2005100779558A Expired - Fee Related CN101085844B (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same
CNB2005100779577A Expired - Fee Related CN100500755C (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same

Family Applications Before (3)

Application Number Title Priority Date Filing Date
CNB2005100779543A Expired - Lifetime CN100358942C (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same
CNB2005100779562A Expired - Lifetime CN100366669C (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same
CN2005100779558A Expired - Fee Related CN101085844B (en) 2001-09-18 2002-06-27 Thermoplastic elastomer composition and process for producing the same

Country Status (2)

Country Link
JP (1) JP3694789B2 (en)
CN (4) CN100358942C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103131090A (en) * 2011-11-25 2013-06-05 住友化学株式会社 Rubber composition
CN111448253A (en) * 2017-12-11 2020-07-24 三井化学株式会社 Polymer composition and use thereof

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005075555A1 (en) * 2004-02-03 2005-08-18 Jsr Corporation Thermoplastic elastomer composition, formed article and sealing material having low hardness
JP4904685B2 (en) * 2004-11-22 2012-03-28 日油株式会社 Composition for improving surface properties of resin moldings
JP4720204B2 (en) * 2005-02-15 2011-07-13 住友化学株式会社 Method for producing thermoplastic elastomer composition
US7319121B2 (en) * 2005-10-07 2008-01-15 Advanced Elestomer Systems, Inc. Microcellular foams of thermoplastic vulcanizates
WO2010008003A1 (en) * 2008-07-16 2010-01-21 東レ株式会社 Separator for electricity storage device
EP2847265B1 (en) 2012-05-10 2016-05-25 ExxonMobil Chemical Patents Inc. Compositions and methods for making them
CN102875879B (en) * 2012-10-18 2014-01-22 湖北超洁汽车用品有限公司 Method for producing modified thermoplastic elastomer
JP6203047B2 (en) * 2013-12-27 2017-09-27 オリンパス株式会社 Resin composition, medical tube forming material, and medical tube
JP6213235B2 (en) * 2013-12-27 2017-10-18 住友化学株式会社 Method for producing flame retardant thermoplastic elastomer composition
EP3279252B1 (en) * 2015-03-30 2020-04-22 Mitsui Chemicals, Inc. Thermoplastic elastomer composition and method for producing same
CN107129623B (en) * 2016-02-29 2020-12-15 住友化学株式会社 Thermoplastic elastomer composition
WO2017209108A1 (en) 2016-06-02 2017-12-07 日立化成株式会社 Thermosetting resin compositin, prepreg, laminated board, printed wiring board, and high-speed communication-compatible module
CN111094446B (en) * 2017-09-20 2023-04-14 北川工业株式会社 Composition, method for producing heat-resistant vibration-proof material, and heat-resistant vibration-proof material
CN109721858B (en) * 2018-12-05 2021-07-09 湖北航天化学技术研究所 Medium-temperature repairing rubber material, preparation method thereof and application thereof in propellant
JP2021046490A (en) * 2019-09-18 2021-03-25 横浜ゴム株式会社 Thermoplastic resin composition for refrigerant transportation piping and refrigerant transportation piping
CN112592461B (en) * 2020-12-14 2022-02-11 北京化工大学 Modified hydrogenated nitrile rubber material and preparation method and application thereof

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0215959B1 (en) * 1985-04-16 1993-01-13 Mitsui Petrochemical Industries, Ltd. Particulate, crosslinked amorphous copolymer, process for its production, and use thereof
JPS63110228A (en) * 1986-10-28 1988-05-14 Sumitomo Chem Co Ltd Thermoplastic elastomer composition and production thereof
WO1990005165A1 (en) * 1988-10-28 1990-05-17 Exxon Chemical Patents Inc. Dynamically vulcanized alloys of crystalline polyolefin resin and halobutyl rubber material
US4985502A (en) * 1988-12-23 1991-01-15 Showa Denko K.K. Thermoplastic elastomer
JP3209643B2 (en) * 1994-08-19 2001-09-17 住友ベークライト株式会社 Method for producing thermoplastic elastomer for airbag cover material
JP3597578B2 (en) * 1994-10-27 2004-12-08 東レ・ダウコーニング・シリコーン株式会社 Method for producing polypropylene resin composition
JP3201206B2 (en) * 1995-03-01 2001-08-20 住友化学工業株式会社 Rubber-modified styrenic resin composition and molded article thereof
JPH08291239A (en) * 1995-04-21 1996-11-05 Mitsui Petrochem Ind Ltd Thermoplastic elastomer composition
JP3652788B2 (en) * 1996-06-11 2005-05-25 電気化学工業株式会社 Method for producing molded thermoplastic resin
JP3240621B2 (en) * 1997-04-14 2001-12-17 旭化成株式会社 Olefin-based thermoplastic elastomer composition
CA2266506C (en) * 1997-07-29 2005-09-27 Kaneka Corporation Graft copolymer particles and thermoplastic resin compositions
DE69915900T3 (en) * 1998-01-20 2008-06-26 Jsr Corp. Thermoplastic elastomer composition
JP2000026668A (en) * 1998-07-13 2000-01-25 Mitsui Chemicals Inc Surface member resin composition and laminate thereof
JP3952350B2 (en) * 1998-07-21 2007-08-01 三井化学株式会社 Resin composition for skin member, laminated body thereof, method for reducing the amount of creaking at the time of extrusion molding of the composition, and method for producing molded body
JP3437466B2 (en) * 1998-11-10 2003-08-18 信越ポリマー株式会社 Olefin-based thermoplastic elastomer composition
DE10081095B4 (en) * 1999-04-13 2006-04-13 Asahi Kasei Kabushiki Kaisha Process for the preparation of a rubber composition

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103131090A (en) * 2011-11-25 2013-06-05 住友化学株式会社 Rubber composition
CN103131090B (en) * 2011-11-25 2018-03-30 住友化学株式会社 Rubber composition
CN111448253A (en) * 2017-12-11 2020-07-24 三井化学株式会社 Polymer composition and use thereof

Also Published As

Publication number Publication date
CN1693353A (en) 2005-11-09
CN101085844B (en) 2011-07-20
CN100500755C (en) 2009-06-17
CN100366669C (en) 2008-02-06
CN100358942C (en) 2008-01-02
CN101085844A (en) 2007-12-12
JP3694789B2 (en) 2005-09-14
CN1693352A (en) 2005-11-09
JP2003089732A (en) 2003-03-28

Similar Documents

Publication Publication Date Title
CN1555395A (en) Thermoplastic elastomer composition and process for producing the same
CN1155629C (en) Unsaturated copolymers, processes for preparing same, and compositions containing the same
CN1693354A (en) Thermoplastic elastomer composition and process for producing the same
CN1046460C (en) Thermoplastic elastomer laminates and glass run channels molded therefrom
CN1154690C (en) Crosslinked olefine elastomer foamable composition and elastomer composition used for manufacturing said foamable composition
CN1154670C (en) Crystalline polypropylene, process for preparing same, polypropylene composition, and thermoformed article
CN1235920C (en) Olefin series thermoplastic elastomer and its producing method and use
CN1922261A (en) Thermoplastic elastomer composition and molded article thereof
CN1191286C (en) Ethylene copolymer rubber, process for producing same and use
CN1191285C (en) Ethylene/alpha-olefin/unconjugated polyene copolymer rubber, rubber composition for sealing, molded rubber for sealing, and process for producing the molded rubber
CN1476452A (en) Hydrogenated copolymer
CN85109582A (en) Dynamiically cured thermoplastic olefin polymers
CN1630669A (en) Modified hydrogenated copolymer
CN1660928A (en) Rubber compositions and uses thereof
CN1312322A (en) Low-atomizing thermoplastic elastic composition and production process and use of said composition
CN1670071A (en) Polypropylene resin compositions
CN1119373C (en) Propylene resin composition and process for producing same
CN1761712A (en) Pellet comprising ethylene-alpha-olefin-non-conjugated polyene copolymer, method for producing thermoplastic elastomer and method for producing pellet comprising ethylene-alpha-olefin-non-conjugated p
CN1141933A (en) Thermoplastic and high-elastic composition
CN1296201C (en) Laminated products and building spacer of olefinic thermolplastic elastomer
CN1068893C (en) Ethylene/alpha-olefin/nonconjugated polyene copolymer rubber composition
CN1208050A (en) Olefin thermoplastic elastomer composition
CN1289590C (en) Polypropylene-base resin composition, process for proudcing the said composition and injection moulding products
CN1187404C (en) Flexible syndiotactic polypropylene compositions and molded object
CN1109696C (en) Ethylenic random copolymer, process for preparing the same and rubber composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090617

Termination date: 20210627