CN101041733A

CN101041733A - Plastic elastomer compositions and air bag cover

Info

Publication number: CN101041733A
Application number: CNA2007100881358A
Authority: CN
Inventors: 古峰登; 中野贞之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2006-03-24
Filing date: 2007-03-15
Publication date: 2007-09-26

Abstract

The invention provides a strong low-temperature strength shockproof filmy resinoid combination and a safety air chamber cap made of the resinoid combination. The resinoid combination or a thermoplastic elastomer combination using for the shockproof film are made through the dynamic heating process of components in the existence of crosslinking agent: 15 to 40% weight component (A), 15 to 40% weight component (B) and 20 to 70% weight component (C) (the overall weight of components (A), (B) and (C) is considered as 100%). The components are specified as: the density of (A) ethylene-Alfa-alkene-non conjugated diene copolymer rubber is 850 to 900 kg/m3, the mooney viscosity (ML1+4 (100 degrees)) is 30 to 150 and the unit content of the ethylene is 30 to 90% weight; the density of (B) ethylene-Alfa-alkene-non conjugated diene copolymer rubber is 850 to 900 kg/m<3>, the mooney viscosity (ML1+4 (100 degrees)) is 30 to 150 and the unit content of the ethylene is 0.50 to 0.95 times of the unit content of ethylene of the component (A) or the iodine value is 0.25 to 0.95 times of the iodine value of the component (A); (C) acrylic resin.

Description

Composition for thermoplastic elastomer and air bag cover

Technical field

The present invention relates to have excellent low temperature impact strength and mobile composition for thermoplastic elastomer, and with the molded air bag cover that obtains of said composition.

Background technology

Need a kind of such air bag cover: under the situation that car collision takes place, it is explosion infallibly, so that air bag ejects immediately and open, and the fragment of air bag cover can not spread out; Need have enough low temperature intensity, even also can use in the area of cold with assurance; And, need be easy to moulding.As the material that is used for this air bag cover, for example, known have a resin combination that comprises polypropylene and linear low density polyethylene, the melt flow rate (MFR) (MFR) of wherein said polypropylene under 230 ℃ is 14g/10min, and described linear low density polyethylene is that 4g/10min and density are 915kg/m at 190 ℃ MFR ³The resin combination that comprises polypropylene and ethylene-octene copolymer rubber, wherein said polypropylene is that 30g/10min and ethylene content are 3 weight % at 230 ℃ MFR, and described ethylene-octene copolymer rubber is that 8g/10min and co-monomer content are 24 weight % at 230 ℃ MFR; And, another kind contains the resin combination of polypropylene and ethylene-octene copolymer rubber, wherein said polypropylene is 50g/10min at 230 ℃ MFR, and described ethylene-octene copolymer rubber is that 2.3g/10min and co-monomer content are 24 weight % at 230 ℃ MFR.Rigidity be about 150 to 400MPa and the material that retains of the Izod impact test under-40 ℃ also be suggested (referring to patent documentation 1, patent documentation 2 and patent documentation 3.)

[patent documentation 1] JP-A-8-27331

[patent documentation 2] JP-A-10-265628

[patent documentation 3] JP-A-2001-279030

Summary of the invention

Yet the problem that the air bag cover that is prepared by above-mentioned composition exists is that their low temperature impact strength makes us dissatisfied.

In view of such circumstances, the present invention provides the air bag cover with excellent low temperature impact strength perspectively and has been applicable to the composition for thermoplastic elastomer for preparing this air bag cover.

In one embodiment of the invention, provide a kind of by mixing the composition for thermoplastic elastomer that obtains to the following component of major general: the component (B1) of the component of 15 to 40 weight % (A1), 15 to 40 weight % and the component (C) of 20 to 70 weight % (component (A1), (B1) and total amount (C) are regarded as 100 weight %), described these components are prescribed as follows:

(A1): ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, iodine number is 0.1 to 40, acetate unit content is 30 to 90 weight %;

(B1): ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, iodine number is 0.1 to 40, acetate unit content is 0.50 to 0.95 times of acetate unit content of component (A1);

(C): acrylic resin.

In another embodiment of the invention, it provides a kind of by mixing the composition for thermoplastic elastomer that obtains to the following component of major general: the component (B2) of the component of 15 to 40 weight % (A2), 15 to 40 weight % and the component (C) of 20 to 70 weight % (component (A2), (B2) and total content (C) they are 100 weight %), and described these components are defined as follows:

(A2): ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, acetate unit content is 30 to 90 weight %, iodine number is 0.1 to 40;

(B2): ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, acetate unit content is 30 to 90 weight %, iodine number is 0.25 to 0.95 times of iodine number in the component (A2);

(C): acrylic resin.

The invention still further relates to air bag cover by any preparation in the described composition for thermoplastic elastomer.

(advantage of the present invention)

According to the present invention, its realizes providing the composition for thermoplastic elastomer with high low temperature impact strength, and by the air bag cover of this preparation of compositions.

Embodiment

First embodiment of the present invention is described below.

Composition for thermoplastic elastomer in the first embodiment of the invention comprises three kinds of components at least, that is, (A1) ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density is 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, iodine number is 0.1 to 40, acetate unit content is 30 to 90 weight %; (B1) ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, iodine number is 0.1 to 40, and acetate unit content is 0.50 to 0.95 times of acetate unit content in the component (A1); And (C) acrylic resin.

As being used as component of the present invention (A1) or ethylene-alpha-olefin-nonconjugated diene copolymer rubber (B1), it can use the mixture of ethylene-alpha-olefin-nonconjugated diene copolymer rubber and tenderizer (also being known as " extending oil "), i.e. the ethylene-alpha-olefin-nonconjugated diene copolymer rubber of tenderizer-filling.Can enumerate following method and be used for mixed ethylene-alpha-olefin-nonconjugated diene copolymer rubber and tenderizer: (1) will mix by known mixing machine as the ethylene-alpha-olefin-nonconjugated diene copolymer rubber (can be to be purchased product) and the tenderizer of the finished product; The solution of the intermediate product in the time of (2) will preparing ethylene-alpha-olefin-nonconjugated diene copolymer rubber mixes with tenderizer and forms mixture, removes from this mixture then and desolvates.

As tenderizer, what can exemplify has mineral oil such as paraffinic hydrocarbons, naphthenic hydrocarbon and aromatic mineral oil and preference chain alkane mineral oil.Should select the amount with described copolymer rubber blended tenderizer, so that after adding tenderizer, the mooney viscosity (ML of ethylene-alpha-olefin-nonconjugated diene copolymer rubber ₁₊₄(100 ℃)) will remain in 30 to 150 the scope.Do not comprise the ethylene-alpha-olefin-nonconjugated diene copolymer rubber of tenderizer with respect to per 100 weight parts, add tenderizer amount be generally 20 to 200 weight parts, preferred 20 to 150 weight parts, more preferably 20 to 120 weight parts.If the content of tenderizer is less than 20 weight parts, it is dissatisfied that the flowability that then prepared composition for thermoplastic elastomer provides may be made us.On the contrary, if the content of tenderizer surpasses 200 weight parts, the low temperature intensity of then prepared elastic composition may reduce.

Alpha-olefin in described copolymer rubber normally carbonatoms is 3 to 10 alpha-olefin.The example of this alpha-olefin is a linear alpha-olefin, such as propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and 1-decene; With the side chain alpha-olefin, as 3-methyl-1-butene and 3-Methyl-1-pentene.In these alpha-olefins, preferred propylene, 1-butylene, 1-hexene and 1-octene.

The example that can be used for the non-conjugated diene in the described copolymer rubber comprises the chain non-conjugated diene such as 1,4-hexadiene, 1,6-octadiene, 2-methyl isophthalic acid, 5-hexadiene, 6-methyl isophthalic acid, 5-heptadiene and 7-methyl isophthalic acid, 6-octadiene; With the ring-type non-conjugated diene, as cyclohexadiene, Dicyclopentadiene (DCPD), methyltetrahydro indenes, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene and 6-chloromethyl-5-isopropenyl-2-nirbornene.In these non-conjugated dienes, preferred 5-ethylidene-2-norbornene or Dicyclopentadiene (DCPD).

These non-conjugated dienes can with triolefin as 2,3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, 2-propenyl-2,2-norbornadiene, 1,3,7-sarohornene and 1,4,9-triolefin in the last of the ten Heavenly stems is used in combination.Under the situation of using such combination, copolymer rubber becomes ethylene-alpha-olefin-nonconjugated diene-non-conjugated triolefin copolymer rubber.

In the present invention, the example as component (A1) and ethylene-alpha-olefin-nonconjugated diene copolymer rubber (B1) is ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-1-butylene-5-ethylidene-2-norbornene copolymer rubber, ethene-1-hexene-5-ethylidene-2-norbornene copolymer rubber, ethene-1-octene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-Dicyclopentadiene (DCPD) copolymer rubber and ethene-1-butylene-Dicyclopentadiene (DCPD) copolymer rubber.Optimal ethylene-1-butylene-Dicyclopentadiene (DCPD) copolymer rubber.

Acetate unit content in the component (A1) is generally 30 to 90 weight %, preferred 35 to 80 weight %, and more preferably 40 to 70 weight %, and the unitary content of alpha-olefin is generally 10 to 70 weight %, preferred 20 to 65 weight %, more preferably 30 to 60 weight %.(herein, the unitary total amount of ethylene unit and alpha-olefin is regarded as 100 weight %).When using term " ethylene unit " in the present invention, the unit of its expression polymerization single polymerization monomer.If the content of ethylene unit surpasses 90 weight % or is lower than 30 weight %, then prepared composition for thermoplastic elastomer may reduce on low temperature intensity.

Acetate unit content in component (B1) is 0.50 to 0.95 times of acetate unit content in the component (A1), preferred 0.60 to 0.90 times, and the unitary content of alpha-olefin equals to deduct the surplus (the unitary total content of ethylene unit and alpha-olefin is considered to 100 weight %) that the weight percent content of ethylene unit obtains by 100 weight %.If the content of ethylene unit is lower than 0.5 times of acetate unit content in the component (A1) or surpasses 0.95 times, then prepared composition for thermoplastic elastomer may reduce on low temperature intensity.

Consider weather resistance, thermotolerance, low temperature intensity and the flowability of prepared composition for thermoplastic elastomer, iodine number according to ethylene-alpha-olefin-nonconjugated diene copolymer rubber (non-oil-extended rubber) is calculated, the unitary content of non-conjugated diene in component (A1) (is being used in combination under the situation of non-conjugated diene and non-conjugated triolefin, then be these two kinds monomeric unitary total contents) be 0.1 to 40, preferred 0.1 to 30, more preferably 1 to 30.If iodine number is less than 0.1, the shearing rate dependency of the viscosity of then prepared composition for thermoplastic elastomer may die down, and causes mobile variation.If iodine number surpasses 40, the low temperature intensity of then prepared composition for thermoplastic elastomer may reduce.

Consider weather resistance, thermotolerance, low temperature intensity and the flowability of prepared composition for thermoplastic elastomer, iodine number according to the ethylene-alpha-olefin-nonconjugated diene copolymer rubber (non-oil-extended rubber) in component (B1) is calculated, non-conjugated diene unit content in component (B1) (is being used in combination under the situation of non-conjugated diene and non-conjugated triolefin, these two kinds monomeric total unit content) be 0.1 to 40, preferred 0.1 to 30, more preferably 1 to 30.If iodine number is less than 0.1, the shearing rate dependent form of the viscosity of then prepared composition for thermoplastic elastomer may die down, and causes mobile variation.On the other hand, if iodine number surpasses 40, the low temperature intensity of then prepared composition for thermoplastic elastomer may reduce.

Component (A1) in the present composition that records under not having the annealed condition according to JIS K7112 and density (B1) are 850 to 900kg/m ³, preferred 850 to 890kg/m ³, more preferably 850 to 880kg/m ³If density surpasses 900kg/m ³, the low temperature intensity of then prepared composition for thermoplastic elastomer may descend.If density is less than 850kg/m ³, then may damage the hot strength of prepared composition for thermoplastic elastomer.

At the 100 ℃ of components (A1) measured according to JIS K6300 and mooney viscosity (ML (B1) ₁₊₄(100 ℃)) be 30 to 150, preferred 40 to 100, more preferably 50 to 80.Higher mooney viscosity may cause the flowability of prepared composition for thermoplastic elastomer to reduce than 150, or causes the outer light variation of described composition molded articles.Low mooney viscosity may cause the low temperature intensity of prepared composition for thermoplastic elastomer to reduce than 30.

Component (C) is a propene polymer, and the content of its propylene units is greater than 50 weight % but be 100 weight % or following, and it all is that the fusing point of measuring under the condition of 5 ℃/min is 100 ℃ or higher according to JIS K7121 at temperature rise rate and rate of temperature fall; Or propylene, ethene and/or carbonatoms be the random or segmented copolymer that 4 to 10 alpha-olefin forms, and the fusing point of described multipolymer is 100 ℃ or higher.Component (C) can be the combination of two or more described polymkeric substance, random copolymers and segmented copolymer.

As described random copolymers, consider the thermotolerance that improves prepared composition for thermoplastic elastomer, preferred (1) the propylene-ethylene random copolymers that uses, its propylene units content is 90 to 99.5 weight %, and acetate unit content is 0.5 to 10 weight % (total amount of propylene units and ethylene unit is regarded as 100 weight %); (2) propylene-ethylene-alpha-olefin random copolymers, its propylene units content are 90 to 99 weight %, and acetate unit content is 0.5 to 9.5 weight %, and C ₄-C ₁₀Alpha-olefin unit content is 0.5 to 9.5 weight % (the unitary total amount of propylene units, ethylene unit and alpha-olefin is regarded as 100 weight %); Or (3) propylene-alpha-olefin random copolymers, its propylene units content is 90 to 99.5 weight %, and C ₄-C ₁₀Alpha-olefin unit content is 0.5 to 10 weight % (the unitary total amount of propylene units and alpha-olefin is regarded as 100 weight %).

Described segmented copolymer is by first polymkeric substance of the prepared that comprises the steps and second mixture of polymers: prepare the step (1) of first polymkeric substance, described first polymkeric substance is the random copolymers that alfon or propylene, ethene and/or alpha-olefin form; And the step (2) for preparing second polymkeric substance, described second polymkeric substance is the random copolymers that propylene, ethene and/or alpha-olefin form in the presence of first polymkeric substance, the content (that is, the content of ethylene unit, the unitary content of alpha-olefin or ethylene unit and alpha-olefin unit the two content) that wherein is included in the monomeric unit except that propylene units in second polymkeric substance is higher than the content that is included in the monomeric unit except that propylene units in first polymkeric substance.Because step (1) and step (2) are in sequence, therefore above-mentioned product is commonly called segmented copolymer in the art, but it is not the typical segmented copolymer by Mode B BB---BBBSSS---SSS (BBB---BBB represents the segment of butadiene unit, and SSS---SSS represents the segment of styrene units) expression shown in relating to the textbook of polymkeric substance.That is to say that it is not the terminal covalently bound segmented copolymer by the end of first polymkeric substance and second polymkeric substance.

Consider the thermotolerance that improves prepared composition for thermoplastic elastomer, the preferred such multipolymer of described segmented copolymer: the content that wherein is included in the monomeric unit except that propylene units in first polymkeric substance is 0.5 to 10 weight % (total content that makes all monomeric units that contain in first polymkeric substance is 100 weight %); More select such multipolymer: the content of the monomeric unit except that propylene units that contains in second polymkeric substance is 5 to 50 weight % (total content that makes all monomeric units that contain in second polymkeric substance is 100 weight %); Also more preferably such polymkeric substance: wherein the content of second polymkeric substance is 5 to 70 weight % (content of described segmented copolymer is regarded as 100 weight %).

Described C ₄-C ₁₀The example of alpha-olefin comprises linear alpha-olefin, such as 1-butylene, 1-amylene, 1-hexene, 1-octene and 1-decene; The side chain alpha-olefin is as 3-methyl-1-butene and 3-Methyl-1-pentene; And two or more the combination in these alkene.

Consider the outward appearance when improving prepared composition for thermoplastic elastomer moulded product, according to JIS K7210 the melt flow rate (MFR) of the component of measuring under the load of 230 ℃ and 21.18N (C) be preferably 0.1g/10min or more than, more preferably 1g/10min or more than, but for improving the low temperature intensity of prepared composition for thermoplastic elastomer, 150g/10min should preferably be higher than, more preferably no higher than 100g/10min.

As component (C), can use for example alfon, ethylene-propylene random copolymer, ethylene-propylene-butene random copolymer, Ethylene-Propylene Block Copolymer and ethylene-propylene-butylene block-copolymer.Especially preferred alfon, ethylene-propylene random copolymer and Ethylene-Propylene Block Copolymer.

The content of component (A1) is 15 to 40 weight %, preferred 20 to 35 weight %, more preferably 25 to 35 weight %, the content of component (B1) is 15 to 40 weight %, preferred 20 to 35 weight %, more preferably 25 to 35 weight %, and the content of component (C) is 20 to 70 weight %, preferred 30 to 60 weight %, more preferably 30 to 50 weight % (making (A1)+(B1)+(C)=100 weight %).

Less than 15 weight %, then the low temperature intensity of the prepared composition for thermoplastic elastomer of susceptible of proof is low as fruit component (A1) or content (B1).And, surpassing 40 weight % as the content of fruit component (A1) or component (B1), the flowability of then prepared composition for thermoplastic elastomer may reduce, or the outward appearance of the molded product of prepared composition for thermoplastic elastomer may worsen.

Composition for thermoplastic elastomer of the present invention can be in the presence of linking agent constituent materials to be carried out dynamic heat to handle the composition that obtains.

As the example of operable linking agent herein, that can mention has organo-peroxide, sulfocompound and an alkyl phenol resin, in them, and preferred organo-peroxide.

The dynamic heat processing list is shown under the temperature that is applicable to crosslinking reaction, with all or part of fusion of the present composition and mix to carry out crosslinking reaction.Employed device comprises the device of knowing in dynamic heat is handled, such as twin screw extruder or Banbury mixer.Term " dynamic vulcanization " also is applicable to described processing.These methods have a detailed description in the document such as Thermoplastic Elastomers 2nd.Ed.153-190 (Hanser GardnerPublications 1996).

The example of organo-peroxide comprises ketone peroxide, diacyl peroxide, hydroperoxide, dialkyl peroxide, peroxy ketal class, crosses acid alkyl ester, peroxocarbonate, peroxide two carbonic ethers and peroxyesters.The more specifically example of such organo-peroxide is a dicumyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin, 1, two (t-butyl peroxy sec.-propyl) benzene of 3-, the tert-butyl peroxide cumyl, di-t-butyl peroxide, 2,2,4-tri-methyl-amyl-2-hydroperoxide, di-isopropyl benzo hydroperoxide, cumene peroxide, tert-butyl peroxide, 1,1-two (t-butyl peroxy)-3,5, the 5-trimethyl-cyclohexane, 1,1-di-t-butyl peroxy cyclohexane, the peroxidation isobutyl-, peroxidation 2,4 dichloro benzene formyl, peroxidation o-methyl-benzene formyl, peroxidation two-3,5, the 5-trimethyl acetyl, lauroyl peroxide, benzoyl peroxide and chloro benzoyl peroxide; And two or more the combination in these compounds.

The amount of the linking agent that uses in above-mentioned processing is generally 0.01 to 10 weight part, preferred 0.05 to 2 weight part, and more preferably 0.1 to 1 weight part, wherein component (A1), (B1) and total amount (C) are regarded as 100 weight parts.If the amount of linking agent is less than 0.01 weight part, the flowability of then prepared composition for thermoplastic elastomer may turn to reduction, and if its amount surpasses 10 weight parts, then the low temperature intensity possible deviation of prepared composition.

Linking agent can be used in combination with crosslinking coagent, to improve the low temperature intensity of prepared composition for thermoplastic elastomer.Preferred crosslinking coagent is to contain the strong compound of two or more pairs.The example of such crosslinking coagent is N, between N--and phenylene bismaleimides, tolylene bismaleimides, para-quinone dioxime, nitrosobenzene, vulkacit D, TriMethylolPropane(TMP), trimethylolpropane trimethacrylate and Vinylstyrene; And two or more combination in these compounds.

The amount of the crosslinking coagent that uses is preferably 0.01 to 10 weight part, and wherein said component (A1), (B1) and total amount (C) are regarded as 100 weight parts.If the amount of crosslinking coagent is less than 0.01 weight part, it is dissatisfied that the low temperature intensity of then prepared composition for thermoplastic elastomer may be made us, if its amount surpasses 10 weight parts, the required effect of the low temperature intensity of the prepared composition that then may not improve.

Component (A1), (B1) any and (C) can be used in combination with one or more additives, described additive such as mineral filler (for example, talcum, lime carbonate and calcined kaolin), organic filler (for example, fiber, wood powder and cellulose powder), antioxidant (for example, phenols, the sulphur class, Phosphorus, lactone and vitamins), protective agent, uv-absorbing agent (for example, benzotriazole category, three (diamines) class, N-anilide and benzophenone), thermo-stabilizer, photostabilizer (for example, hindered amines and benzoates), static inhibitor, nucleator, pigment, sorbent material (for example, metal oxide such as zinc oxide and magnesium oxide), metal chloride (for example, iron(ic) chloride and calcium chloride), hydrotalcite and aluminate.Can also be with these additives and prepared composition for thermoplastic elastomer blend.

When described composition for thermoplastic elastomer carries out when molded, it can combine with lubricant or silicone compounds, but with improve molded product leave release property and the wear resistance and the fracture-resistant (flaw resistance) of mould.As lubricant, can use for example laurylamide, palmitic amide, stearylamide, oleylamide, erucicamide, methylene-bis stearylamide, ethylenebisstearamide, ethylenebisoleoamide and stearyl diglycollic amide; And two or more combination in these compounds.Preferred stearylamide, oleylamide and erucicamide.

But consider the release property and the wear-resisting disruptiveness that undermines of membrane product, the add-on of lubricant is preferably 0.01 to 10 weight part, and more preferably 0.05 to 1 weight part, and component (A1), (B1) and total amount (C) are regarded as 100 weight parts.If the amount of lubricant is less than 0.01 weight part, then described character may affect adversely, and the adding of working as lubricant may cause the precipitating of lubricant on the molded article surface of prepared composition for thermoplastic elastomer above 10 weight parts.

The example of the silicone compounds that can use in the present invention comprises linear siloxanes, such as dimethyl siloxane, methylphenyl siloxane and methyl hydrogen siloxane (methylhydrodiene silicone); With the siloxanes of modification, such as amino modified siloxanes, epoxide modified siloxanes, carboxy-modified siloxanes, the siloxanes of methyl alcohol modification, the siloxanes of methacryloyl modification, sulfhydryl modified siloxanes, the siloxanes of phenol modification, polyether-modified siloxanes, the siloxanes of vinyl toluene base modification, alkyl-modified ester modified siloxanes, senior alkoxy-modified siloxanes and the siloxanes of fluorine modification of siloxanes, higher fatty acid.In these silicone compounds, preferred linear siloxanes.These silicone compounds can be to be purchased product.They can also be to have closely knit in advance the silicone oil in the olefin resin and/or the masterbatch of silicone rubber of being filled in.

But in view of the release property and the wear-resisting disruptiveness that undermines of membrane product, the amount of the silicone compounds that is added is preferably 0.01 to 10 weight part, and more preferably 0.1 to 5 weight part, and component (A1), (B1) and total amount (C) are regarded as 100 weight parts.If its amount is less than 0.01 weight part, then described character may affect adversely, and the adding of this compound surpasses 10 weight parts, may cause variable color on the molded article surface of prepared composition for thermoplastic elastomer.

Now, explain second embodiment of the present invention.

Composition for thermoplastic elastomer in second embodiment of the invention comprises following three kinds of components at least: (A2) ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, acetate unit content is 30 to 90 weight %, and iodine number is 0.1 to 40; (B2) ethylene-alpha-olefin-nonconjugated diene copolymer rubber, its density are 850 to 900kg/m ³, mooney viscosity (ML ₁₊₄(100 ℃)) be 30 to 150, acetate unit content is 30 to 90 weight %, and iodine number is 0.25 to 0.95 times of iodine number of component (A2); And (C) acrylic resin.

As being used as component of the present invention (A2) and ethylene-alpha-olefin-nonconjugated diene copolymer rubber (B2), can use the mixture of tenderizer (it also is known as " extending oil ") and ethylene-alpha-olefin-nonconjugated diene copolymer rubber, that is the ethylene-alpha-olefin-nonconjugated diene copolymer rubber of tenderizer-filling.For mixed ethylene-alpha-olefin-nonconjugated diene copolymer rubber and tenderizer, can utilize for example following method: mix by known mixing machine as the ethylene-alpha-olefin-nonconjugated diene copolymer rubber (it can be to be purchased product) and the tenderizer of the finished product (1); (2) will mix with tenderizer at the solution of the intermediate product of ethylene-alpha-olefin-nonconjugated diene copolymer rubber preparation process, form mixture, and then solvent is removed from this mixture.

The example that can be used for the tenderizer among the present invention comprises mineral oil, such as paraffinic hydrocarbons mineral oil, naphthenic mineral oil and aromatic mineral oil.The preferred paraffinic hydrocarbons mineral oil that uses.Under the situation of mixing tenderizer, need to regulate its amount, so that after adding tenderizer, the mooney viscosity (ML of ethylene-alpha-olefin-nonconjugated diene copolymer rubber ₁₊₄(100 ℃)) in 30 to 150 scope.With respect to the ethylene-alpha-olefin-nonconjugated diene copolymer rubber that does not contain tenderizer of per 100 weight parts, this regulated quantity of tenderizer is generally 20 to 200 weight parts, preferred 20 to 150 weight parts, more preferably 20 to 120 weight parts.If the content of tenderizer is less than 20 weight parts, the mobile possible deviation of then prepared composition for thermoplastic elastomer, and if its content surpass 200 weight parts, the low temperature intensity of then prepared composition may reduce.

The example of the non-conjugated diene in described copolymer rubber be the chain non-conjugated diene such as 1,4-hexadiene, 1,6-octadiene, 2-methyl isophthalic acid, 5-hexadiene, 6-methyl isophthalic acid, 5-heptadiene and 7-methyl isophthalic acid, 6-octadiene; With the ring-type non-conjugated diene, as cyclohexadiene, Dicyclopentadiene (DCPD), methyltetrahydro indenes, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene and 6-chloromethyl-5-isopropenyl-2-nirbornene.In these non-conjugated dienes, preferred 5-ethylidene-2-norbornene or Dicyclopentadiene (DCPD).

These non-conjugated dienes can with triolefin as 2,3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, 2-propenyl-2,2-norbornylene, 1,3,7-sarohornene and 1,4,9-triolefin in the last of the ten Heavenly stems is used in combination.Under the situation of using such combination, copolymer rubber becomes the copolymer rubber of ethylene-alpha-olefin-nonconjugated diene-non-conjugated triolefin.

In the present invention, the example as component (A2) and ethylene-alpha-olefin-nonconjugated diene copolymer rubber (B2) is ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-1-butylene-5-ethylidene-2-norbornene copolymer rubber, ethene-1-hexene-5-ethylidene-2-norbornene copolymer rubber, ethene-1-octene-5-ethylidene-2-norbornene copolymer rubber, ethylene-propylene-Dicyclopentadiene (DCPD) copolymer rubber and ethene-1-butylene-Dicyclopentadiene (DCPD) copolymer rubber.Optimal ethylene-1-butylene-Dicyclopentadiene (DCPD) copolymer rubber.

The content of the ethylene unit in the component (A2) is generally 30 to 90 weight %, preferred 35 to 80 weight %, more preferably 40 to 70 weight %, and the unitary content of alpha-olefin is generally 10 to 70 weight %, preferred 20 to 65 weight %, more preferably 30 to 60 weight % (the unitary total amount of ethylene unit and alpha-olefin is regarded as 100 weight %).If the content of ethylene unit surpasses 90 weight % or is lower than 30 weight %, the low temperature intensity possible deviation of then prepared composition for thermoplastic elastomer.

The content of the ethylene unit in component (B2) is generally 30 to 90 weight %, preferred 35 to 80 weight %, more preferably 40 to 70 weight %, and the unitary content of alpha-olefin is generally 10 to 70 weight %, preferred 20 to 65 weight %, more preferably 30 to 60 weight % (the unitary total amount of ethylene unit and alpha-olefin is regarded as 100 weight %).If the content of ethylene unit surpasses 90 weight % or is lower than 30 weight %, the low temperature intensity possible deviation of then prepared composition for thermoplastic elastomer.

Consider weather resistance, thermotolerance, low temperature intensity and the flowability of prepared composition for thermoplastic elastomer, pressing the iodine number of the ethylene-alpha-olefin-nonconjugated diene copolymer rubber (non-oil-extended rubber) of component (A2) calculates, the unitary content of non-conjugated diene in component (A2) (is being used in combination under the situation of non-conjugated diene and non-conjugated triolefin, be the total content of these two kinds of monomeric units) be 0.1 to 40, preferred 0.1 to 30, more preferably 1 to 30.If iodine number is less than 0.1, the shearing rate dependency of the viscosity of then prepared composition for thermoplastic elastomer may die down, and causes mobile the reduction.If iodine number surpasses 40, the low temperature intensity of then prepared composition may reduce.

Iodine number according to the ethylene-alpha-olefin-nonconjugated diene copolymer rubber (non-oil-extended rubber) of component (B2) is calculated, the unitary content of non-conjugated diene in component (B2) (is being used in combination under the situation of non-conjugated diene and non-conjugated triolefin, be the total content of these two kinds of monomeric units) be 0.25 to 0.95 times of the unitary content of non-conjugated diene in the component (A2), preferred 0.30 to 0.80 times.If the unitary content of non-conjugated diene that calculates according to iodine number is less than 0.25 times of non-conjugated diene unit content in the component (A2) or surpass 0.95 times, the low temperature intensity of then prepared composition for thermoplastic elastomer may reduce.

Component (A2) in the present composition that records under not having the annealed situation according to JIS K7112 and density (B2) are 850 to 900kg/m ³, preferred 850 to 890kg/m ³, more preferably 850 to 880kg/m ³If this density surpasses 900kg/m ³, the low temperature intensity of then prepared composition for thermoplastic elastomer may reduce, and if it is less than 850kg/m ³, the hot strength of then prepared composition may reduce.

Component (A2) in the present composition that under 100 ℃, records according to JIS K6300 and mooney viscosity (ML (B2) ₁₊₄(100 ℃)) be 30 to 150, preferred 40 to 100, more preferably 50 to 80.If mooney viscosity surpasses 150, the flowability of then prepared composition may affect adversely, and/or the outward appearance of said composition membrane product may be worsened.If mooney viscosity is lower than 30, then the low temperature intensity of the prepared composition of susceptible of proof reduces.

Component (C) is a propene polymer, the propylene units content that it has for greater than 50 weight % but be less than or equal to 100 weight %, and be 100 ℃ or higher with the fusing point that intensification or the rate of temperature fall of 5 ℃/min records according to JIS K7121; Or propylene, ethene and/or C ₄-C ₁₀Random or the segmented copolymer of alpha-olefin, its fusing point are 100 ℃ or higher.Component (C) can be two or more the combination in described polymkeric substance, random copolymers and the segmented copolymer.

In order to improve the thermotolerance of prepared composition, described random copolymers is preferably (1) propylene-ethylene random copolymers, the propylene units content that it has is 90 to 99.5 weight %, and the acetate unit content that has is 0.5 to 10 weight % (total amount of propylene units and ethylene unit is regarded as 100 weight %); (2) propylene-ethylene-alpha-olefin random copolymers, the propylene units content that it has are 90 to 99 weight %, and the acetate unit content that has is 0.5 to 9.5 weight %, and the C that has ₄-C ₁₀The unitary content of alpha-olefin is 0.5 to 9.5 weight % (the unitary total amount of propylene units, ethylene unit and alpha-olefin is regarded as 100 weight %); Perhaps (3) propylene-alpha-olefin random copolymers, the propylene units content that it has is 90 to 99.5 weight %, and the C that has ₄-C ₁₀Alpha-olefin unit content is 0.5 to 10 weight % (the unitary total amount of propylene units and alpha-olefin is regarded as 100 weight %).

Described segmented copolymer is by first polymkeric substance of the prepared that comprises the steps and second mixture of polymers: prepare the step (1) of first polymkeric substance, described first polymkeric substance is the random copolymers that alfon or propylene, ethene and/or alpha-olefin form; And the step (2) for preparing second polymkeric substance, described second polymkeric substance is the random copolymers that propylene, ethene and/or alpha-olefin form in the presence of first polymkeric substance, the content (that is, the content of ethylene unit, the unitary content of alpha-olefin or ethylene unit and alpha-olefin unit the two content) that wherein is included in the monomeric unit except that propylene units in second polymkeric substance is higher than the content that is included in the monomeric unit except that propylene units in first polymkeric substance.Because step (1) and step (2) are in sequence, therefore above-mentioned product is commonly called segmented copolymer in the art, but it is not the typical segmented copolymer as being represented by Mode B BB---BBBSSS---SSS (BBB---BBB represents the segment of butadiene unit, and SSS---SSS represents the segment of styrene units) shown in relating to the textbook of polymkeric substance.That is to say that it is not the terminal covalently bound segmented copolymer by the end of first polymkeric substance and second polymkeric substance.

Consider the thermotolerance that improves prepared composition for thermoplastic elastomer, the preferred such multipolymer of described segmented copolymer: the content that wherein is included in the monomeric unit except that propylene units in first polymkeric substance is 0.5 to 10 weight % (total content that makes all monomeric units that contain in first polymkeric substance is 100 weight %); More preferably such multipolymer: the content of the monomeric unit except that propylene units that contains in second polymkeric substance is 5 to 50 weight % (total content that makes all monomeric units that contain in second polymkeric substance is 100 weight %); Also more preferably such multipolymer: wherein the content of second polymkeric substance is 5 to 70 weight % (content that makes described segmented copolymer is 100 weight %).

Described C ₄-C ₁₀The example of alpha-olefin linear alpha-olefin is arranged, such as 1-butylene, 1-amylene, 1-hexene, 1-octene and 1-decene; The side chain alpha-olefin is such as 3-methyl-1-butene and 3-Methyl-1-pentene; And two or more the combination in these alkene.

Consider the outward appearance that improves prepared composition for thermoplastic elastomer moulded product, according to JIS K7210 the melt flow rate (MFR) of the component (C) that records under the load of 230 ℃ and 21.18N be preferably 0.1g/10min or more than, more preferably 1g/10min or more than, but for improving the low temperature intensity of prepared composition for thermoplastic elastomer, it should preferably not be higher than 150g/10min, more preferably no higher than 100g/10min.

The content of component (A2) is 15 to 40 weight %, preferred 20 to 35 weight %, more preferably 25 to 35 weight %, the content of component (B2) is 15 to 40 weight %, preferred 20 to 35 weight %, more preferably 25 to 35 weight %, and the content of component (C) is 20 to 70 weight %, preferred 30 to 60 weight %, more preferably 30 to 50 weight % (making (A2)+(B2)+(C)=100 weight %).

Less than 15 weight %, can confirm then that the low temperature intensity of prepared composition for thermoplastic elastomer is low as fruit component (A2) or content (B2).And the content of component (A2) or component (B2) surpasses 40 weight %, and the flowability of then prepared composition for thermoplastic elastomer may reduce, or the moulded product of prepared composition for thermoplastic elastomer may be worsened in appearance.

The amount of the linking agent that uses in above-mentioned processing is generally 0.01 to 10 weight part, preferred 0.05 to 2 weight part, and more preferably 0.1 to 1 weight part, wherein component (A2), (B2) and total amount (C) are regarded as 100 weight parts.If the amount of linking agent is less than 0.01 weight part, the flowability of then prepared composition for thermoplastic elastomer may turn to reduction, and if its amount surpasses 10 weight parts, the low temperature intensity possible deviation of then prepared composition.

The amount of the crosslinking coagent that uses is preferably 0.01 to 10 weight part, and wherein said component (A2), (B2) and total amount (C) are regarded as 100 weight parts.If the amount of crosslinking coagent is less than 0.01 weight part, it is dissatisfied that the low temperature intensity of then prepared composition for thermoplastic elastomer may be made us, if its amount surpasses 10 weight parts, the required effect of the low temperature intensity of the prepared composition that then may not improve.

When described composition for thermoplastic elastomer carries out when molded, it can combine with lubricant or silicone compounds, but with improve molded product leave release property and the wear resistance and the fracture-resistant of mould.As lubricant, can use for example laurylamide, palmitic amide, stearylamide, oleylamide, erucicamide, methylene-bis stearylamide, ethylenebisstearamide, ethylenebisoleoamide and stearyl diglycollic amide; And two or more combination in these compounds.Preferred stearylamide, oleylamide or erucicamide.

But consider the release property and the wear-resisting fracture-resistant that undermines of membrane product, the add-on of lubricant is preferably 0.01 to 10 weight part, more preferably 0.05 to 1 weight part (making (A2)+(B2)+(C)=100 weight part).If the amount of lubricant is less than 0.01 weight part, then described character may affect adversely, and the adding of working as lubricant may cause the precipitating of lubricant on the molded article surface of prepared composition for thermoplastic elastomer above 10 weight parts.

But in view of release property and the wearability and the fracture-resistant of membrane product, the amount of the silicone compounds that is added is preferably 0.01 to 10 weight part, and more preferably 0.1 to 5 weight part, and component (A2), (B2) and total amount (C) are regarded as 100 weight parts.If its amount is less than 0.01 weight part, then described character may affect adversely, and the adding of this compound surpasses 10 weight parts, then may cause variable color on the molded article surface of prepared composition for thermoplastic elastomer.

Component (A2), (B2) any and (C) can be used in combination with one or more additives, described additive such as mineral filler (for example, talcum, lime carbonate and calcined kaolin), organic filler (for example, fiber, wood powder and cellulose powder), antioxidant (for example, phenols, the sulphur class, Phosphorus, lactone and vitamins), protective agent, uv-absorbing agent (for example, benzotriazole category, three (diamines) class, N-anilide and benzophenone), thermo-stabilizer, photostabilizer (for example, hindered amines and benzoates), static inhibitor, nucleator, pigment, sorbent material (for example, metal oxide such as zinc oxide and magnesium oxide), metal chloride (for example, iron(ic) chloride and calcium chloride), hydrotalcite and aluminate.Can also be with these additives and prepared composition for thermoplastic elastomer blend.

In the present invention, can use and adopt known Ziegler-Natta catalyst, or slurry polymerization, solution polymerization, mass polymerization and the vapour phase polymerization of known complex catalyst such as metallocene class complex catalyst and Nonmetallocene class complex catalyst, with preparation component (A1), (B1), (A2) and (B2).

To mix by the ethylene-alpha-olefin-nonconjugated copolymer rubber that polymerization separately obtains, can prepare component (A1) and (B1) respectively, it is as follows that but the preparation method who preferably makes composition for thermoplastic elastomer is simplified to: use two polymerization reactors that are connected in serial or parallel with each other, in described one of them polymerization reactor, form component (A1), in another polymerization reactor, form simultaneously component (B1), make component (A1) and (B1) in solvent, mix to form mixing solutions, again solvent is removed from this mixing solutions, to obtain component (A1) and mixture (B1).When using component (A1) and this mixture (B1), because component (A1) and (B1) mixed, so, can easily produce the admixture of suitable (pertinent) when itself and component (C) when mixing.Especially under the situation of carrying out the dynamic heat processing in the presence of the linking agent, adopt component (A1) and this mixture (B1) can reduce mixing time.This situation also has such advantage: suppress to produce in the mixing process heat and have the product of good quality such as good appearance accessing.This is equally applicable to component (A2) and situation (B2).

In first and second embodiments of the present invention, in order to make the acrylic resin polymerization that is used as component (C), can use and adopt known Ziegler-Natta catalyst, or slurry polymerization, solution polymerization, mass polymerization or the vapour phase polymerization of known complex catalyst such as metallocene class complex catalyst and Nonmetallocene class complex catalyst.Component (C) can be to be purchased product.

By with described component (A1), (B1) and (C) or (A2), (B2) and (C) mix, in case of necessity with these components and other additive materials, and such as twin screw extruder or Banbury mixer, can obtain composition for thermoplastic elastomer of the present invention by known way.Mixing can be carried out in the presence of linking agent.

Composition for thermoplastic elastomer of the present invention is applicable to the preparation air bag cover., prepare such as the molded composition for thermoplastic elastomer of the present invention of injection molding by known method of moulding according to air bag cover of the present invention.Especially using rigidity is that the air bag cover that obtains of 100 to 400MPa composition for thermoplastic elastomer is well suited in driver's seat.

Embodiment

The present invention describes more specifically with reference to its embodiment, yet these embodiments are not counted as limitation of the scope of the invention.

[I] measures the method for character

(1) rigidity (stiffness)

Measure elastomeric modulus in flexure according to JIS K7203.

(2) low temperature intensity

Carry out Izod impact test according to JIS K6911 under-47 ℃, the result is divided into as follows:

NB: do not break

B: break

Based on following formula, total impact energy (kgf.cm) that test sample is absorbed calculates cantilever-type impact strength divided by the width of the barbed portion of test sample.

Cantilever-type impact strength=(total impact energy that test sample absorbs)/(width of the barbed portion of test sample)

(3) flowability

Use the thick oval helical flute of 2mm, under following condition, carry out molded, and from by this molded length computation flow process that obtains moulded product.

Flow process=length/thickness

Molded condition

Molding temperature: 50 ℃

Injector: Toshiba Machinery IS100-EN

Barrel temperature: HN=220 ℃; H3=220 ℃; H2=200 ℃; H1=190 ℃

Injection pressure: 116MPa

(4) melt flow rate (MFR) (MFR)

Measure under 230 ℃ and 21.18 N load according to JIS K7210.

(5) density

Measure under the annealed condition not having according to JIS K7112.

(6) mooney viscosity (ML ₁₊₄(100 ℃))

Is that 1 minute and rotor rotational time are to measure under 4 minutes the condition according to JIS K6300 at 100 ℃, warm up time.

(7) acetate unit content

By infrared absorption spectrometry.

(8) iodine number

By infrared absorption spectrometry.

[II] material

(1) oil

In following all embodiment and comparative example, all use Idemitsu Kosan ' s PW-380 as the oil ingredient that is comprised in oil-filled ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber.

(2) ethylene-propylene-non-conjugated diene copolymer rubber

A1-1: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 78; Ethylene unit: 67 weight %; Propylene units: 33 weight % (ethylene unit and propylene units the two total amount be regarded as 100 weight %); Iodine number: 3.9; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

A1-2: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 80; Ethylene unit: 64 weight %; Propylene units: 36 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 3.6; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

A1-3: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 75; Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 3.6; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

B1-1: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 78; Ethylene unit: 57 weight %; Propylene units: 43 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 4.4; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

B1-2: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 80; Ethylene unit: 51 weight %; Propylene units: 49 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 3.9; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

B1-3: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 75; Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 3.6: oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

A2-1: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880 kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 76; Ethylene unit: 62 weight %; Propylene units: 38 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 7.4; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

A2-2: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 80; Acetate unit content: 63 weight %; Propylene units content: 37 weight % (total amount of ethylene unit and propylene units is considered to 100 weight %); Iodine number: 4.9; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

A2-3: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 75; Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 3.6; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

B2-1: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 76; Ethylene unit: 62 weight %; Propylene units: 38 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 2.6; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

B2-2: its poly-type rubber of ethylene-propylene-5-ethylidene-2-norbornene

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 80; Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 2.7; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

B2-3: its poly-type rubber of ethylene-propylene-5-ethylidene-2-norbornene

Density: 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)): 75; Acetate unit content: 63 weight %; Propylene units content: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 3.6: oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts.

AB-1: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Use two polymerization reactors that are one another in series and connect, polymerization forms ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber in first polymerization reactor, and it is sent in the next polymerization reactor, herein, form ethylene-propylene-5-ethylidene-2-norbornene multipolymer that its structure is different from formed copolymer structure in first polymerization reactor by polymerization, thereby obtain having the mixture of the ethylene-propylene-5-ethylidene-2-norbornene multipolymer of different structure.To the ethylene-propylene-5-ethylidene-2-norbornene multipolymer of 100 weight parts of discharging from second stage polymerization reactor, the oil that adds 40 weight parts, after their uniform mixing, remove and desolvate and unreacted monomer, to obtain ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber.

Ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber as mixture:

Ethylene unit: 61 weight %; Propylene units: 39 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 4.2; Oil-contg: the multipolymer with respect to 100 weight parts is 40 weight parts; Density (containing oil condition): 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)) (containing oil condition): 78.

The ethylene-propylene that in first polymerization reactor, forms-5-ethylidene-2-norbornene copolymer rubber:

Ethylene unit: 57 weight %; Propylene units: 43 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 4.4; Density (containing the state of the oil of 40 weight parts): 880kg/m at ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts ³Mooney viscosity (ML ₁₊₄(100 ℃)) (in equal state): 78.

The ethylene-propylene that in second polymerization reactor, forms-5-ethylidene-2-norbornene copolymer rubber:

Ethylene unit: 67 weight %; Propylene units: 33 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 3.9; Density (containing the state of 40 weight part oil): 880kg/m at ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts ³Mooney viscosity (ML ₁₊₄(100 ℃)) (at described state): 78.

The amount of monomer of reacting in first polymerization reactor is 2: 1 with the weight ratio of the amount of monomer of reacting in second polymerization reactor.By in the structure of the resulting copolymer mixture of outlet of second polymerization reactor, at the ratio of the structure of the resulting multipolymer of outlet of first polymerization reactor and the amount of monomer of in each polymerization reactor, reacting, calculate the structure of determining formed multipolymer in second polymerization reactor.

AB-2: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Adopt two polymerization reactors that are connected in series, carry out used step, to obtain the mixture of the different ethylene-propylene of structure-5-ethylidene-2-norbornene copolymer rubber with AB-1.

Ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber as mixture:

Ethylene unit: 62 weight %; Propylene units: 38 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 4.2; Oil-contg: the ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts is 40 weight parts; Density (containing oil condition): 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)) (containing oil condition): 76.

Ethylene unit: 62 weight %; Propylene units: 38 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 2.6; Density (state that contains 40 weight part oil at multipolymer): 880kg/m with respect to 100 weight parts ³Mooney viscosity (ML ₁₊₄(100 ℃)) (at described state): 76.

Ethylene unit: 62 weight %; Propylene units: 38 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 7.4; Density (state that contains 40 weight part oil at multipolymer): 880kg/m with respect to 100 weight parts ³Mooney viscosity (ML ₁₊₄(100 ℃)) (at described state): 76.

AB-3: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Adopt two polymerization reactors that are connected in series, carry out used step, with the mixture of the different ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber of preparation structure with AB-1.

Ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber as mixture:

Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 4.2; Oil-contg: the ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts is 40 weight parts; Density (containing oil condition): 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)) (containing oil condition): 80.

Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 4.9; Density (containing the state of 40 weight part oil): 880kg/m at ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts ³Mooney viscosity (ML ₁₊₄(100 ℃)) (at described state): 80.

Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 2.7; Density (containing the state of 40 weight part oil): 880kg/m at ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts ³Mooney viscosity (ML ₁₊₄(100 ℃)) (at described state): 80.

AB-4: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Ethylene unit: 70 weight %; Propylene units: 30 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %); Iodine number: 7.5; Oil-contg: the ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts is 40 weight parts; Density (containing oil condition): 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)) (at described state): 78.

AB-5: ethylene-propylene-5-ethylidene-2-norbornene copolymer rubber

Ethylene unit: 63 weight %; Propylene units: 37 weight % (total amount of ethylene unit and propylene units is regarded as 100 weight %)); Iodine number: 3.6; Oil-contg: the ethylene-propylene-5-ethylidene-2-norbornene multipolymer with respect to 100 weight parts is 40 weight parts; Density (containing oil condition): 880kg/m ³Mooney viscosity (ML ₁₊₄(100 ℃)) (containing oil condition): 75.

(3) homo-polypropylene

The Norbrene Z101A of C-1:Sumitomo Chemical Co preparation.

MFR：25g/10min。

Embodiment 1

Pass through Banbury mixer, after trimethylolpropane trimethacrylate (crosslinking coagent) fusion of A1-1, the B1-1 of ratio of mixture shown in the table 1 and C-1 (total amount of A1-1, B1-1 and C-1 is regarded as 100 weight parts) and 0.18 weight part and mixing, carry out granulation.It is 47mm that these pellets are supplied to internal diameter, speed is the twin screw extruder of 50kg/hr, and mid-way (half-way spot) from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the A1-1+B1-1+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 1.

Embodiment 2

Pass through Banbury mixer, after trimethylolpropane trimethacrylate (crosslinking coagent) fusion of A1-2, the B1-2 of ratio of mixture shown in the table 1 and C-1 (total amount of A1-2, B1-2 and C-1 is regarded as 100 weight parts) and 0.18 weight part and mixing, carry out granulation.It is 47mm that these pellets are supplied to internal diameter, speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the A1-2+B1-2+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 1.

Comparative example 1

Pass through Banbury mixer, after trimethylolpropane trimethacrylate (crosslinking coagent) fusion of A1-3, the B1-3 of ratio of mixture shown in the table 1 and C-1 (total amount of A1-3, B1-3 and C-1 is regarded as 100 weight parts) and 0.18 weight part and mixing, carry out granulation.It is 47mm that these pellets are supplied to internal diameter, speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the A1-3+B1-3+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 1.

Table 1

	Ethylene content	Iodine number	Embodiment 1	Embodiment 2	Comparative example 1
	Ethylene content	Iodine number	Embodiment 1	Embodiment 2	Comparative example 1	A1-1	67	3.9	29
A1-2	64	3.6		29		A1-1	67	3.9	29
A1-2	64	3.6		29		A1-3	63	3.6			29
B1-1	57	4.4	29			A1-3	63	3.6			29
B1-1	57	4.4	29			B1-2	51	3.9		29
B1-3	63	3.6			29	B1-2	51	3.9		29
B1-3	63	3.6			29	C-1			42	42	42
Modulus in flexure			230	230	220	C-1			42	42	42
Modulus in flexure			230	230	220	Izod			NB	NB	B
Helical (Spiral)			523	547	505	Izod			NB	NB	B
Helical (Spiral)			523	547	505	MFR			9	12	7

Embodiment 3

Pass through Banbury mixer, after trimethylolpropane trimethacrylate (crosslinking coagent) fusion of A2-1, the B2-1 of ratio of mixture shown in the table 2 and C-1 (total amount of A2-1, B2-1 and C-1 is regarded as 100 weight parts) and 0.18 weight part and mixing, carry out granulation.It is 47mm that these pellets are supplied to internal diameter, speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the A2-1+B2-1+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 2.

Embodiment 4

Pass through Banbury mixer, after trimethylolpropane trimethacrylate (crosslinking coagent) fusion of A2-2, the B2-2 of ratio of mixture shown in the table 2 and C-1 (total amount of A2-2, B2-2 and C-1 is regarded as 100 weight parts) and 0.18 weight part and mixing, carry out granulation.It is 47mm that these pellets are supplied to internal diameter, speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the A2-2+B2-2+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 2.

Comparative example 2

Pass through Banbury mixer, after trimethylolpropane trimethacrylate (crosslinking coagent) fusion of A2-3, the B2-3 of ratio of mixture shown in the table 2 and C-1 (total amount of A2-3, B2-3 and C-1 is regarded as 100 weight parts) and 0.18 weight part and mixing, carry out granulation.It is 47mm that these pellets are supplied to internal diameter, speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the A2-3+B2-3+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 2.

Table 2

	Ethylene content	Iodine number	Embodiment 3	Embodiment 4	Comparative example 2
	Ethylene content	Iodine number	Embodiment 3	Embodiment 4	Comparative example 2	A2-1	62	7.4	29
A2-2	63	4.9		29		A2-1	62	7.4	29
A2-2	63	4.9		29		A2-3	63	3.6			29
B2-1	62	2.6	29			A2-3	63	3.6			29
B2-1	62	2.6	29			B2-2	63	2.7		29
B2-3	63	3.6			29	B2-2	63	2.7		29
B2-3	63	3.6			29	C-1			42	42	42
Modulus in flexure			220	230	220	C-1			42	42	42
Modulus in flexure			220	230	220	Izod			NB	NB	B
Cantilever-type impact strength			63	49	19	Izod			NB	NB	B
Cantilever-type impact strength			63	49	19	Helical			510	509	505
MFR			6	6	7	Helical			510	509	505

Embodiment 5

It is 47mm that the trimethylolpropane trimethacrylate (crosslinking coagent) of the AB-1 of ratio of mixture shown in the table 3 and C-1 (total amount of AB-1 and C-1 is regarded as 100 weight parts) and 0.18 weight part is supplied to internal diameter, total speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the AB-1+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 3.

Embodiment 6

It is 47mm that the trimethylolpropane trimethacrylate (crosslinking coagent) of the AB-2 of ratio of mixture shown in the table 3 and C-1 (total amount of AB-2 and C-1 is regarded as 100 weight parts) and 0.18 weight part is supplied to internal diameter, total speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the AB-2+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 3.

Embodiment 7

It is 47mm that the trimethylolpropane trimethacrylate (crosslinking coagent) of the AB-3 of ratio of mixture shown in the table 3 and C-1 (total amount of AB-3 and C-1 is regarded as 100 weight parts) and 0.18 weight part is supplied to internal diameter, total speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the AB-3+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 3.

Comparative example 3

It is 47mm that the trimethylolpropane trimethacrylate (crosslinking coagent) of the AB-4 of ratio of mixture shown in the table 3 and C-1 (total amount of AB-4 and C-1 is regarded as 100 weight parts) and 0.18 weight part is supplied to internal diameter, total speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the AB-4+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 3.

Comparative example 4

It is 47mm that the trimethylolpropane trimethacrylate (crosslinking coagent) of the AB-5 of ratio of mixture shown in the table 3 and C-1 (total amount of AB-5 and C-1 is regarded as 100 weight parts) and 0.18 weight part is supplied to internal diameter, total speed is the twin screw extruder of 50kg/hr, and mid-way from forcing machine, add 2.2 weight parts by paraffin oil (0.22 weight part, as linking agent) be diluted to 2 of 10% concentration, 5-dimethyl-2,5-two (t-butylperoxy) hexene (linking agent) (making the AB-5+C-1=100 weight part), and in the downstream end temperature of the linking agent supply unit of forcing machine is that the speed of rotation of 200 ℃ and screw rod is under the condition of 200rpm, this mixture is carried out dynamic heat handle, with the preparation composition for thermoplastic elastomer.This composite mold is made product, and measure the character of this product.The results are shown in the table 3.

Table 3

		Ethylene content	Iodine number	Embodiment 5	Embodiment 6	Embodiment 7	Comparative example 3	Comparative example 4
		Ethylene content	Iodine number	Embodiment 5	Embodiment 6	Embodiment 7	Comparative example 3	Comparative example 4	AB-1	A	57	4.4	58
B	67	3.9								A	57	4.4
B	67	3.9	AB-2	A	62	2.6		58
B	62	7.4		A	62	2.6
B	62	7.4		AB-3	A	63			4.9						58
B	63	2.7			A	63			4.9
B	63	2.7	AB-4			70	7.5				58
AB-5		63	AB-4	3.6		70	7.5				58						58
AB-5		63	C-1	3.6				42	42	42	42	42					58
Modulus in flexure			C-1					42	42	42	42	42	220	220	220	240	220
Modulus in flexure			Izod					NB	NB	NB	B	B	220	220	220	240	220
Cantilever-type impact strength			Izod					NB	NB	NB	B	B	55	72	83	6	33
Cantilever-type impact strength			MFR					9	5	7	24	6	55	72	83	6	33

Claims

1. composition for thermoplastic elastomer, it obtains by mixing to the following component of major general:

The component (B1) of the component of 15 to 40 weight % (A1), 15 to 40 weight % and the component (C) of 20 to 70 weight % (component (A1), (B1) and total amount (C) are regarded as 100 weight %), described these components are prescribed as follows:

(C): acrylic resin.

2. composition for thermoplastic elastomer, it obtains by mixing to the following component of major general:

The component (B2) of the component of 15 to 40 weight % (A2), 15 to 40 weight % and the component (C) of 20 to 70 weight % (component (A2), (B2) and total content (C) they are 100 weight %), and described these components are defined as follows:

(C): acrylic resin.

3. according to the composition for thermoplastic elastomer of claim 1 or 2, wherein said component (A1), (A2), (B1) and ethylene-alpha-olefin-nonconjugated diene copolymer rubber (B2) all are oil-filled ethylene-alpha-olefin-nonconjugated diene copolymer rubbers, the acetate unit content of described oil-filled ethylene-alpha-olefin-nonconjugated diene copolymer rubber is 40 to 80 weight %, iodine number is 1 to 30, and oil-filled rate is 20 to 120phr.

4. according to each composition for thermoplastic elastomer in the claim 1 to 3, it is handled and obtains by making constituent materials carry out dynamic heat in the presence of linking agent.

5. according to the composition for thermoplastic elastomer of claim 4, wherein said dynamic heat is handled and is carried out in the presence of organo-peroxide or in the presence of organo-peroxide and crosslinking coagent.

6. air bag cover, it is by carrying out molded obtaining with each described composition for thermoplastic elastomer in the claim 1 to 5.

7. method for preparing the composition for thermoplastic elastomer of claim 1, it comprises the steps:

Use two polymerization reactors that are connected in serial or parallel with each other;

In one of described polymerization reactor, form component (A1), in another polymerization reactor, form component (B1) simultaneously;

With component (A1) and (B1) in solvent, mix to form mixing solutions; Then,

From described mixing solutions, remove described solvent, to obtain component (A1) and mixture (B1); And

Mix in this mixture and kneading component (C), so that the content of component (A1) becomes 15 to 40 weight %, the content of component (B1) becomes 15 to 40 weight %, and the content of component (C) becomes 20 to 70 weight %.

8. method for preparing the composition for thermoplastic elastomer of claim 2, it comprises the steps:

In one of described polymerization reactor, form component (A2), in another polymerization reactor, form component (B2) simultaneously;

With component (A2) and (B2) in solvent, mix to form mixing solutions; Then,

From described mixing solutions, remove described solvent, to obtain component (A2) and mixture (B2); And

Mix in this mixture and kneading component (C), so that the content of component (A2) becomes 15 to 40 weight %, the content of component (B2) becomes 15 to 40 weight %, and the content of component (C) becomes 20 to 70 weight %.