JP4973843B2 - Thermoplastic elastomer composition - Google Patents

Description

  The present invention relates to a thermoplastic elastomer composition having an excellent balance of flexibility, strength and compression set, and excellent wear resistance, and more specifically, a modified conjugated diene polymer containing a specific functional group and a functional group containing The present invention relates to a thermoplastic elastomer composition comprising an olefin polymer.

Vulcanized rubber is flexible and rubber-elastic, has excellent compression set and mechanical strength, and is widely used in fields such as automobile interior and exterior parts, home appliance parts, building materials, medical parts, footwear, toys, and sundries. Yes.
However, vulcanized rubber is not necessarily a material suitable for life cycle assessment in terms of recycling. In recent years, as a substitute for vulcanized rubber, the use of a recyclable thermoplastic elastomer that does not require a vulcanization step and can be molded in the same manner as a thermoplastic resin has been increasing year by year.
Among thermoplastic elastomers, styrene-butadiene block copolymer (SBS) and styrene-isoprene block copolymer (SIS), which are styrenic thermoplastic elastomers, are rich in flexibility and excellent in rubber elasticity at room temperature. Due to its excellent processability, it is used in a wide range of applications as a substitute for vulcanized rubber.
However, a soft material having a Shore A hardness of 60 or less is inferior in mechanical strength and workability only with a styrenic thermoplastic elastomer.
On the other hand, an olefinic thermoplastic elastomer (Patent Document 1) blended with an elastomer and an olefinic resin and a highly crosslinked thermoplastic elastomer (Patent Document 2, Patent Document 3) for improving mechanical strength are also known. . Since this elastomer has a relatively high hardness, a plasticizer is generally used when used for a soft material. However, the addition of a plasticizer is not preferred because of bleeding problems.
JP 62-62847 A JP-A 64-24839 JP 2006-2085 A

  By adding a modified conjugated diene polymer containing a functional group to a functional group-containing olefin polymer using a specific production method, the present invention has an excellent balance of flexibility, strength, and compression set, and is further resistant to resistance. An object of the present invention is to provide a thermoplastic elastomer composition having excellent wear characteristics.

That is, this invention consists of the following structures.
[1] (A) having at least one group selected from the group consisting of alkoxysilyl group, amino group, acid anhydride group, and carboxyl group, and selected from the following groups (a) to (d) 5 to 95% by weight of a modified conjugated diene polymer (hereinafter also referred to as “(a) modified conjugated diene polymer”) and (b) a functional group-containing olefin polymer of 5 to 95%. % (However, (A) + (B) = 100 wt%).
(A) A polymer produced by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound and reacting the resulting conjugated diene polymer with an alkoxysilane compound.
(B) A polymer produced by polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound having an amino group.
(C) A polymer produced by polymerizing an unsaturated monomer having a conjugated diene and an amino group or these and an aromatic vinyl compound in the presence of an organic alkali metal compound.
(D) By polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, the resulting conjugated diene polymer is reacted with a compound represented by the following general formula (1). Manufactured polymer.
R ¹ R ² C = N−Y (1)
[In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon number. 1 to 100 organosiloxy groups. Y represents a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 100 carbon atoms. Of the organosiloxy group. ]
(E) A conjugated diene or a conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is reacted with a ketone compound and / or an ester compound and / or an aldehyde compound. Thereafter, a polymer produced by reacting with an acid anhydride and / or acid halide.
[2] The total content of at least one group selected from the group consisting of an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group in the (a) modified conjugated diene polymer is 0.0001 to The thermoplastic elastomer composition according to the above [1], which is 5 mmol / g.
[3] (A) The modified conjugated diene polymer is a modified conjugated diene polymer having both an alkoxysilyl group and an amino group, and at least one selected from the following groups (f) to (h): The thermoplastic elastomer composition according to [1] or [2], which is a modified conjugated diene polymer produced by a seed method.
(F) A conjugated diene or a conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound having an amino group, and the resulting conjugated diene polymer is represented by the following general formula (2) Modified polymer obtained by reacting
R ³ _(4-mn) Si (OR ⁴ ) _m X _n (2)
[Wherein, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms, and a plurality of R ³ In some cases, each R ³ may be the same or different group. R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ^{if R 4} have more than one purpose, each ^{R 4} is different even in the same group group Good. X is a substituent having a polar group containing at least one of O atom and Si atom. When there are a plurality of X, each X may be the same or different, and each X is an independent substituent. Even a group may form a cyclic structure. m is 1, 2 or 3, and n is an integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. ]
(G) An unsaturated monomer having a conjugated diene and an amino group, or these and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is represented by the above general formula (2). A modified polymer obtained by reacting a compound represented by the formula:
(H) Modification in which conjugated diene or conjugated diene and aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is reacted with a compound represented by the following general formula (7) Polymer.
R ¹² _(4-pq) Si (OR ¹³ ) _p Z _q (7)
^{Wherein, R 12} is an alkyl group, an aryl group having 6 to 20 carbon atoms, organo siloxy group aralkyl group or 1 to 100 carbon atoms having 7 to 20 carbon atoms having 1 to 20 carbon ^{atoms, R 12} is more In some cases, each R ¹² may be the same or different group. R ¹³ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon ^{atoms, if R 13} have more than one purpose, each ^{R 13} is different even in the same group group Good. Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same or different, and each Z may be an independent substituent and form a cyclic structure. Also good. p is 1, 2 or 3, and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. ]
[4] A block copolymer in which the (b) modified conjugated diene polymer includes one or more polymer blocks selected from the following polymer blocks (A), (B), and (C): The thermoplastic elastomer composition according to any one of the above [1] to [3].
(A) Aromatic vinyl compound polymer block whose aromatic vinyl compound is 80% by weight or more (B) Conjugated diene polymer block (C) Random copolymer block of aromatic vinyl compound and conjugated diene [5] ( (B) A functional group-containing olefin polymer is mainly composed of a binary comprising an olefin unit and an unsaturated compound unit having at least one functional group selected from a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group; The thermoplastic elastomer composition according to the above [1], which is a multi-component copolymer.
[6] The thermoplastic elastomer composition according to [5], wherein the (b) functional group-containing olefin polymer is a maleic anhydride-modified ethylene-propylene copolymer.
[7] The thermoplastic elastomer composition according to [5], wherein the (b) functional group-containing olefin polymer is an ethylene-glycidyl methacrylate copolymer.
[8] A thermoplastic elastomer composite in which (c) 1 to 300 parts by weight of a reinforcing agent is blended with 100 parts by weight of the thermoplastic elastomer composition according to any one of the above [1] to [7].
[9] The thermoplastic elastomer composite according to [8], wherein the (c) reinforcing agent is carbon black.
[10] The thermoplastic elastomer composite according to the above [8], wherein the (c) reinforcing agent is silica.
[11] The thermoplastic elastomer composite according to the above [8], wherein the (c) reinforcing agent is magnesium hydroxide.

  According to the present invention, the functional group-containing olefin polymer is blended with a modified conjugated diene polymer having at least one group selected from the group consisting of an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group. By doing so, a thermoplastic resin elastomer having an excellent balance between strength and compression set, flexibility (low hardness) and excellent wear resistance can be obtained.

The embodiment of the thermoplastic elastomer composition of the present invention will be specifically described below.
The thermoplastic elastomer composition of the present invention comprises (a) at least one group selected from the group consisting of an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group obtained by using a specific production method. And 5 to 95% by weight of a modified conjugated diene polymer having (b) a functional group-containing olefin polymer [provided that (b) + (b) = 100% by weight]. To do.
Hereinafter, each component will be described more specifically.

(I) Modified conjugated diene polymer A modified conjugated diene polymer having an alkoxysilyl group, which is one of the present invention, comprises (a) a conjugated diene or a conjugated diene and an aromatic vinyl compound in an inert organic solvent. It can be easily obtained by polymerizing an organic alkali metal compound as a polymerization initiator and reacting the resulting conjugated diene polymer with an alkoxysilane compound. The “alkoxysilyl group” is a group in which at least one alkoxy group selected from alkyloxy having 1 to 20 carbon atoms, aryloxy having 6 to 20 carbon atoms, and aralkyloxy having 7 to 20 carbon atoms is bonded to a silicon atom. Specific examples thereof include alkoxy groups such as methoxy, ethoxy, butoxy, propoxy, pentyloxy, neopentyloxy, hexyloxy, amyloxy, phenoxy and the like. Among these, those in which an alkoxy group such as methoxy, ethoxy, amyloxy, phenoxy and the like are bonded to a silicon atom are preferable.

  Examples of the “conjugated diene” include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, 1,3- Examples include hexadiene, 1,3-cyclohexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, myrcene, chloroprene, and the like. Among these, 1,3-butadiene and isoprene are preferable.

  Examples of the “aromatic vinyl compound” include styrene, tert-butylstyrene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylstyrene, vinylnaphthalene, vinylanthracene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned. Of these, styrene and tert-butylstyrene are preferred. In this case, the “conjugated diene”, the “aromatic vinyl compound”, and other unsaturated compounds such as acrylonitrile and methyl methacrylate may be added and polymerized in an amount of about 5% by weight or less based on the total monomers. .

  Examples of the “organic alkali metal compound” that is a polymerization initiator include organic lithium compounds and organic sodium compounds, and organic lithium compounds are particularly preferable. There is no particular limitation on the amount of the organic alkali metal compound used, and various amounts can be used as necessary. Usually, the amount is 0.02 to 15% by weight, preferably 0.03 to 100% by weight per 100% by weight of the monomer. Used in an amount of 5% by weight.

The alkoxysilane compound reacted with the conjugated diene polymer is not limited in its structure as long as it can react with the conjugated diene polymer and can be a modified polymer, but the following general formula (2) The alkoxysilane compound represented by these is used.
R ³ _(4-mn) Si (OR ⁴ ) _m X _n (2)
[Wherein, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms, and a plurality of R ³ In some cases, each R ³ may be the same or different group. R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, ^{if R 4} have more than one purpose, each ^{R 4} is different even in the same group group Good. X is a substituent having a polar group containing at least one of O atom and Si atom. When there are a plurality of X, each X may be the same or different, and each X is an independent substituent. Even a group may form a cyclic structure. m is 1, 2 or 3, and n is an integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. In particular, m is preferably 2 or 3, and n is preferably 0 or 1. ]

  Examples of the alkoxysilane compound represented by the general formula (2) include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltriphenoxysilane, dimethyldi Phenoxysilane, 1-trimethylsilyl-2-dimethoxy-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-diethoxy-1-aza-2-silacyclopentane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltri Tokishishiran, trimethylsiloxy triphenoxy silane, trimethylsiloxy trimethoxysilane, trimethylsiloxy triethoxysilane, trimethylsiloxy tributoxysilane silane, and 1,1,3,3-tetramethyl-1-phenoxy Siji siloxanes.

  The modification method using the alkoxysilane compound is modified by adding the alkoxysilane compound into the polymerization system when the polymerization conversion rate of the polymerization reaction for producing the conjugated diene polymer reaches 90% to 100%. It is preferable to carry out the reaction. The addition method may be added before the polymerization conversion rate reaches 90%, or the silane compound may be added intermittently or continuously during the polymerization reaction to carry out the modification reaction. Good.

  The amount of the alkoxysilane compound used is preferably 0.05 to 5 times mol, more preferably 0.1 to 1.5 times mol, based on the number of moles of active sites derived from the organic alkali metal compound. .

  The content of the alkoxysilyl group in the resulting conjugated diene polymer is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol / g, and more preferably 0.003 to 0.1 mmol / g. It is. The alkoxysilyl group is usually present at the end of the polymer chain, but may be present at the side chain. When the content of the alkoxysilyl group is less than 0.0001 mmol / g, the effect of improving compression set and wear resistance is not manifested. On the other hand, even if it exceeds 5 mmol / g, the effect does not increase proportionally, which is uneconomical and undesirable.

Further, the modified conjugated diene polymer having an amino group which is one of the present invention is not particularly limited in the method for introducing an amino group, but can be easily obtained by, for example, the following methods (b) to (d). Obtainable.
(B) It is produced by polymerizing conjugated diene or conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound having an amino group.
(C) It is produced by polymerizing a conjugated diene and an unsaturated monomer having an amino group or these and an aromatic vinyl compound in the presence of an organic alkali metal compound.
(D) By polymerizing a conjugated diene or a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, the resulting conjugated diene polymer is reacted with a compound represented by the following general formula (1). Manufactured.
R ¹ R ² C = N−Y (1)
[In General Formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a carbon number. 1 to 100 organosiloxy groups. Y represents a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or 1 to 100 carbon atoms. Of the organosiloxy group. ]

  Examples of the organic alkali metal compound having an amino group used in the method (b) include the following general formula (3) or (4).

[In the above general formula (3), R ⁵ and R ⁶ are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group and the other is 1 to 3 carbon atoms. A 20-alkyl group, an aryl group having 6-20 carbon atoms, an aralkyl group having 7-20 carbon atoms, or an organosiloxy group having 1-100 carbon atoms. R ⁷ in the general formulas (3) and (4) is an alkylene group or alkylidene group having 1 to 20 carbon atoms. Further, R ⁸ in the general formula (4) is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. is there. ]

Examples of the organic alkali metal compound represented by the general formula (3) or (4) include 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane and 2-lithio-1- [N, N -Bis (trimethylsilyl)] aminoethane, 3-lithio-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5-tetramethyl-1- (3-lithio Propyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-lithio-2,2-dimethyl-propyl) -1-aza-2,5 -Disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-lithioethyl) -1-aza-2,5-disilacyclopentane, 3-lithio-1- [N- (tert- Butyl-dimethylsilyl) -N- Trimethylsilyl] aminopropane, 3-lithio-1-(N-methyl -N- trimethylsilyl) aminopropane, 3-lithio-1-(N-ethyl--N- trimethylsilyl) amino propane.
The amount of the organic alkali metal compound represented by the general formula (3) or (4) is generally 0.05 to 50% by weight, preferably 0.07 to 10% by weight per 100% by weight of the monomer. Used in the amount of%.

  Examples of the unsaturated monomer having an amino group used in the method (c) include the following general formula (5) or (6).

[In the general formulas (5) and (6), R ⁹ and R ¹⁰ are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, and the other Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms. Further, in the general formula ^{(6), R 11} is an alkylene or alkylidene group having 1 to 20 carbon atoms. Furthermore, n ′ in the general formulas (5) and (6) is 1 to 3. ]

Examples of the unsaturated monomer represented by the general formula (5) or (6) include p- [N, N-bis (trimethylsilyl) amino] styrene and p- [N, N-bis (trimethylsilyl) aminomethyl. ] Styrene, p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene, m- [N, N-bis (trimethylsilyl) amino] styrene, p- (N-methyl-N-trimethylsilylamino) Examples include styrene and p- (N-methyl-N-trimethylsilylaminomethyl) styrene.
The amount of the unsaturated monomer represented by the general formula (5) or (6) is 0.01 to 100 times mol, preferably 0.01 to the mol number of the active site derived from the organic alkali metal. It is added at a ratio of 10 times mol, particularly preferably 1.0 to 3.0 times mol.
The reaction time is preferably in the range of 1 second to 2 hours. Further, the unsaturated monomer can be added at any time such as at the start of polymerization, during polymerization, before completion of polymerization, or after completion of polymerization.

  Examples of the compound of the general formula (1) used in the method (d) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, and N-benzylideneaniline. The amount used when the compound represented by the general formula (1) is modified by reacting with the conjugated diene polymer is not particularly limited, but is usually based on the number of moles of active sites derived from the organic alkali metal compound. It is added at a ratio of 0.2 to 3 times mol, preferably 0.3 to 1.5 times mol, more preferably 0.4 to 1.3 times mol.

  The amino group content in the resulting modified conjugated diene polymer is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol / g, and more preferably 0.003 to 0.1 mmol / g. It is. The position of the amino group is not particularly limited, and may be present at the end of the polymer chain or may be present at the side chain. The amino group is preferably a primary amino group and / or a secondary amino group. If the content of the amino group is out of the above range, it is not preferable because the reason is the same as in the case of the alkoxysilyl group.

The production method of the modified conjugated diene polymer having both an alkoxysilyl group and an amino group, which is one of the present invention, is not particularly limited. For example, it can be easily obtained by the following methods (f) to (h). it can.
(F) A conjugated diene or a conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound having an amino group, and the resulting conjugated diene polymer is represented by the above general formula (2) It is manufactured by making the modified polymer made to react.
(G) An unsaturated monomer having a conjugated diene and an amino group, or these and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is represented by the above general formula (2). It is manufactured by making it the modified polymer which made the compound represented by react.
(H) Modification in which conjugated diene or conjugated diene and aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is reacted with a compound represented by the following general formula (7) It is manufactured by making a polymer.
R ¹² _(4-pq) Si (OR ¹³ ) _p Z _q (7)
^{Wherein, R 12} is an alkyl group, an aryl group having 6 to 20 carbon atoms, organo siloxy group aralkyl group or 1 to 100 carbon atoms having 7 to 20 carbon atoms having 1 to 20 carbon ^{atoms, R 12} is more In some cases, each R ¹² may be the same or different group. R ¹³ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon ^{atoms, if R 13} have more than one purpose, each ^{R 13} is different even in the same group group Good. Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same or different, and each Z may be an independent substituent and form a cyclic structure. Also good. p is 1, 2 or 3, and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. In particular, p is preferably 2 or 3, and q is preferably 1. ]

  Examples of the alkoxysilane compound represented by the general formula (7) include N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis ( Trimethylsilyl) aminopropyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane, N, N-bis (trimethylsilyl) aminoethyldimethylethoxysilane, N-bis (trimethylsilyl) aminoethyldimethylmethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N-methyl-N-trimethylsilylamino Propyltrimethoxysilane, N-methyl-N-trimethylsilylaminopropyltriethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylmethoxysilane, N-methyl-N- Trimethylsilylaminopropylmethyldiethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, , N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropyldimethylethoxysilane, N, N-dimethylaminopropyldimethylmethoxysilane, N, N-dimethylaminopropylmethyldiethoxysilane, N, N-dimethylamino Propylmethyldimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (triethoxysilyl) -1-propane Amine, N-ethylidene-3- (triethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (triethoxysilyl) -1-propanamine, N- (4-N, N -Dimethylaminobenzylidene) -3- (triethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (trimethoxysilyl) -1-propanamine, N-ethylidene -3- (trimethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (trimethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (trimethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (Methyldimethoxysilyl) -1-propanamine, N-ethylidene-3- (methyldimethoxysilyl) -1-propanamine, N- (1-methylpropylide) ) -3- (methyldimethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (methyldimethoxysilyl) -1-propanamine, N- (1,3-dimethyl) Butylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (methyldiethoxysilyl) -1-propanamine, N-ethylidene-3- (methyldi) Ethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3- (methyldiethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- ( Methyldiethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (dimethylmethoxysilyl) -1-propanamine N- (1-methylethylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N-ethylidene-3- (dimethylmethoxysilyl) -1-propanamine, N- (1-methylpropylidene) -3 -(Dimethylmethoxysilyl) -1-propanamine, N- (4-N, N-dimethylaminobenzylidene) -3- (dimethylmethoxysilyl) -1-propanamine, N- (1,3-dimethylbutylidene) -3- (dimethylethoxysilyl) -1-propanamine, N- (1-methylethylidene) -3- (dimethylethoxysilyl) -1-propanamine, N-ethylidene-3- (dimethylethoxysilyl) -1- Propanamine, N- (1-methylpropylidene) -3- (dimethylethoxysilyl) -1-propanamine, N- (4- N, N-dimethylaminobenzylidene) -3- (dimethylethoxysilyl) -1-propanamine and the like.

  The total content of alkoxysilyl groups and amino groups in the resulting conjugated diene polymer is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol / g, more preferably 0.003 to 0.003. 0.1 mmo1 / g. These groups are usually present at the polymer chain end, but may be present in the side chain. If the total content of the alkoxysilyl group and the amino group is out of the above range, the reason is the same as in the case of the alkoxysilyl group, which is not preferable.

Next, the production method of the modified conjugated diene polymer having an acid anhydride group and / or carboxyl group, which is one of the present invention, is not particularly limited. For example, it can be easily obtained by the following method (e). it can.
(E) A conjugated diene or a conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer was selected from the group of ketone compounds, ester compounds, and aldehyde compounds. It is easily produced by reacting one or more compounds and then reacting with an acid anhydride and / or acid halide.

  The structure of the “ketone compound” is not limited. For example, acetone, diethyl ketone, n-butyl ethyl ketone, ethyl amyl ketone, isophorone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, methyl isopropyl ketone, methyl cyclohexanone. 4-acetodiphenyl, methyl ethyl ketone, benzophenone, cyclohexyl phenyl ketone, 4-methylbenzophenone, 4-octylbenzophenone, propiophenone and the like.

  The structure of the “ester compound” is not limited, and examples thereof include ethyl acetate, methyl acetate, propyl acetate, methyl benzoate, methyl toluate, phenyl benzoate, benzyl benzoate, and γ-butyrolactone.

  The structure of the “aldehyde compound” is not limited, but examples include formaldehyde, acetaldehyde, butyraldehyde, n-octylaldehyde, benzaldehyde, phthalaldehyde, tolylaldehyde, o-tolualdehyde, p-tolylacetaldehyde, 4-isopropyl. Examples include benzaldehyde, aldehyde pyridine, α-naphthaldehyde, furfural and the like.

  The amount of one or more compounds selected from the group of ketone compounds, ester compounds, and aldehyde compounds is preferably 0.1 to 2 times the number of moles of active sites derived from the organic alkali metal compound. Mol, more preferably 0.5 to 1.3 times mol.

The structure of the “acid anhydride” is not limited, and examples thereof include propionic anhydride, lactic anhydride, caproic anhydride, maleic anhydride, phthalic anhydride, 3-methylphthalic anhydride, and 4-methylphthalic anhydride. Acid, cis-hexahydrophthalic anhydride, trans-hexahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, cis-1,2,3,6-tetrahydrophthalic anhydride, 1,2,4-benzenetricarboxylic anhydride And pyromellitic dianhydride.
The “acid halide” is not limited in its structure, and examples thereof include benzene dicarboxylic acid chloride, phthalic acid chloride, isophthalic acid dichloride, and trimellitic acid trichloride.
Moreover, as a compound which has both an acid anhydride and an acid halide, there is no limitation in the structure, For example, anhydrous trimellitic acid chloride etc. are mentioned.

  The amount of the acid anhydride and / or acid chloride to be used is preferably 0.05 to 5 times mol, more preferably 0.1 to 1.5 mol, based on the number of moles of active sites derived from the organic alkali metal compound. Double mole.

  The content of acid anhydride groups and / or carboxyl groups in the resulting conjugated diene polymer is usually 0.0001 to 5 mmol / g, preferably 0.001 to 1 mmol / g, more preferably 0.003. ~ 0.1 mmo1 / g. If the content of the acid anhydride group and / or the carboxyl group is out of the above range, the reason is the same as in the case of the alkoxysilyl group.

The (a) modified conjugated diene polymer having at least one group selected from the group consisting of an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group includes the following (A), (B) and ( A block copolymer containing one or more polymer blocks selected from the polymer blocks of C) is preferred.
(A) Aromatic vinyl compound polymer block whose aromatic vinyl compound is 80% by weight or more (B) Conjugated diene polymer block (C) Random copolymer block of aromatic vinyl compound and conjugated diene

The random copolymer block (C) may include a so-called tapered type in which the aromatic vinyl compound content continuously changes in one molecule.
Examples of the “block copolymer containing one or more polymer blocks selected from the polymer blocks (A) and (B) to (C)” include (A)-(B) , (A)-(C), [(A)-(B)] x-Y ', [(A)-(C)] x-Y', (A)-(B)-(A), ( A)-(C)-(A), [(A)-(B)-(C)] x-Y ', [(A)-(B)-(A)] x-Y', [(A )-(C)-(A)] x-Y ', (A)-(B)-(A)-(B), (B)-(A)-(B)-(A), (A) -(C)-(A)-(C), (C)-(A)-(C)-(A), (A)-(B)-(C)-(A), etc. , X is an integer from 2 to 8, and Y ′ is the residue of the coupling agent).
In the case of a pellet shape, it is preferable to include at least one (A) polymer block as a block component outside the modified conjugated diene polymer.

  Examples of the inert organic solvent include aliphatic, alicyclic, alkyl-substituted alicyclic, aromatic and alkyl-substituted aromatic hydrocarbons, ethers, and mixtures thereof. Specifically, aliphatic hydrocarbons (eg, butane, pentane, hexane, heptane, etc.), alicyclic hydrocarbons (eg, cyclopentane, cyclohexane, cycloheptane, etc.), alkyl-substituted alicyclic hydrocarbons (eg, Methylcyclohexane, methylcycloheptane, etc.), aromatic hydrocarbons (eg, benzene), alkyl-substituted aromatic hydrocarbons (eg, toluene, xylene, etc.), and ethers (eg, tetrahydrofuran, diethyl ether, di-n-butyl ether, etc.) ) Is included.

Further, the composition ratio of the “conjugated diene” and the “aromatic vinyl compound” in the “conjugated diene polymer” is not particularly limited, but is usually 5 to 90% by weight of the conjugated diene and the aromatic vinyl compound 95. 10 to 10% by weight, preferably 5 to 80% by weight and 95 to 20% by weight, more preferably 10 to 75% by weight of the conjugated diene and 90 to 25% by weight of the aromatic vinyl compound.
The vinyl bond (1,2- and 3,4-bond) content of the conjugated diene of the “conjugated diene polymer” is less than 80% by weight, preferably 3 to 60% by weight, more preferably 5 to 55% by weight. It is.
In order to adjust the vinyl bond content, polar compounds such as ethers, tertiary amines and alkali metal alkoxides can usually be used.
For example, diethyl ether, ethylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl propyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxybenzene, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, potassium tert -Amyl oxide, potassium tert-butyl oxide, etc. are mentioned, These compounds can be used individually or in mixture of 2 or more types. The usage-amount of this polar compound is 0 mol or more with respect to 1 mol of organolithium compounds, Preferably it is 0-300 mol.

  Examples of the coupling agent include halogen compounds, epoxy compounds, carbonyl compounds, and polyvinyl compounds. Specifically, for example, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, tetrachlorosilane, dibromoethane, and bisphenol. A diglycidyl ether, bisphenol F diglycidyl ether, epoxidized soybean oil, divinylbenzene, tetrachlorotin, butyltrichlorotin, tetrachlorogermanium, bis (trichlorosilyl) ethane, diethyl adipate, dimethyl adipate, dimethyl terephthalic acid, Examples include diethyl terephthalic acid and polyisocyanate.

  The resulting modified conjugated diene polymer is prepared by removing the catalyst residue or adding a phenol-based or amine-based anti-aging agent as necessary, and then modifying the modified conjugated diene polymer solution from the modified conjugated diene polymer solution. The polymer is isolated. Isolation of the modified conjugated diene polymer can be achieved, for example, by adding acetone or alcohol to the modified conjugated diene polymer solution and precipitating it, or adding the modified conjugated diene polymer solution in hot water with stirring and distilling the solvent. The removal can be performed by a method of removing the solvent by distilling the modified conjugated diene polymer solution with a vented extruder. The molecular weight of the modified conjugated diene polymer having at least one kind of alkoxysilyl group, amino group, acid anhydride group and carboxyl group of the present invention is not particularly limited, but is 3 in terms of weight average molecular weight in terms of polystyrene in the GPC method. It is 10,000 to 2,000,000, preferably 40,000 to 1,000,000, and more preferably 50,000 to 500,000.

(B) Functional group-containing olefin polymer The (B) functional group-containing olefin polymer of the present invention comprises at least one functional group selected from an olefin unit and a carboxyl group, an acid anhydride group, an oxazoline group, and an epoxy group. It is a binary or multi-component copolymer mainly composed of an unsaturated compound unit.
Here, the content of the functional group in the (b) functional group-containing olefin polymer is 0.1 to 20% by weight.
(B) Typical examples of the olefin in the functional group-containing olefin polymer include ethylene, propylene, butene, pentene, hexene, heptene, methylbutene, and methylpentene, and ethylene and propylene are preferable. (B) Typical examples of the carboxyl group-containing unsaturated compound in the functional group-containing olefin polymer include acrylic acid, methacrylic acid, maleic acid, and the like, and typical examples of the acid anhydride group-containing unsaturated compound As maleic anhydride, itaconic anhydride and the like, typical examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline, and typical examples of the epoxy group-containing unsaturated compound include glycidyl methacrylate. And acrylic glycidyl ether. Examples of the functional group preferably used in the present invention include an acid anhydride group and an epoxy group.
(B) Preferable specific examples of the functional group-containing olefin polymer include anhydrous maleic modified ethylene-propylene copolymer, ethylene-glycidyl methacrylate copolymer and the like.

Furthermore, (c) as a reinforcing agent to be blended in the thermoplastic elastomer composition mainly composed of the components (a) to (b) of the present invention, flame retardancy, conductivity, mechanical properties, etc. are added. It is a substance that exerts a reinforcing effect such as easy and uniform dispersion during kneading and improved workability. For example, carbon black, zinc white, magnesium carbonate, silicic acid and silicic acid compound, calcium carbonate, clay, silica, talc, aluminum sulfate, mica, glass fiber, antimony compound, magnesium hydroxide, phosphorus compound, aluminum hydroxide, etc. It is.
Among these, as component (c), aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, tin oxide hydrate, borax, etc. The flame retardancy is improved by using an inorganic flame retardant such as a hydrate of an inorganic metal compound. Of these, magnesium hydroxide and aluminum hydroxide are preferable.
In the present invention, the surface of the inorganic flame retardant is coated with a fatty acid such as stearic acid, oleic acid, or palmitic acid or a metal salt thereof; paraffin, wax, polyethylene wax, or a modified product thereof; organic such as organic borane or organic titanate. Metal compounds; those treated with a silane coupling agent or the like may be used. Among them, the surface treated with a silane coupling agent is preferable because the effect of improving the tensile strength is remarkable.

When magnesium hydroxide or aluminum hydroxide is used as the inorganic flame retardant, it is preferable that the crystal grows well and has little aggregation. The BET specific surface area is 20 m ² / g or less, particularly preferably in the range of 3 to 10 m ² / g, and the average secondary particle diameter is in the range of 0.2 to 5 μm, particularly preferably in the range of 0.5 to 3 μm. Magnesium oxide or aluminum hydroxide. Magnesium hydroxide or aluminum hydroxide may be either a synthetic product or a natural product as long as it satisfies the above characteristics. A synthetic product of magnesium hydroxide is obtained by contacting in an aqueous medium under conditions that allow magnesium chloride or magnesium nitrate and ammonia or potassium hydroxide to sufficiently contact, and then heating under pressure.

The amount of silane coupling agent added to magnesium hydroxide or aluminum hydroxide is 0.1 to 3% by weight, preferably 0.3 to 1% by weight. When the amount is less than the lower limit of the above range, the cohesive strength of magnesium hydroxide or aluminum hydroxide is strong, and the dispersibility in the composition tends to be poor. Even if the upper limit of the above range is exceeded, the dispersibility is not further improved, which is economically undesirable. As a surface treatment method of magnesium hydroxide or aluminum hydroxide with a silane coupling agent, a known method, that is, a dry method or a wet slurry method can be used. The wet slurry method is more preferable in terms of uniform treatment. Moreover, since the surface treatment of magnesium hydroxide or aluminum hydroxide is performed by hydrolyzing a silane coupling agent in an aqueous solution thereof, those soluble in ordinary water are preferable. Some types of silane coupling agents do not hydrolyze unless the pH is lowered to about 4 with acetic acid or the like. When such a silane coupling agent is used, the surface of the magnesium hydroxide or aluminum hydroxide is eroded by acid during the surface treatment, resulting in poor acid resistance, or when used for electric wires, This is not preferable because the volume resistivity of the coating material is lowered.
In the wet slurry method, magnesium hydroxide or aluminum hydroxide is dispersed in water, and a required amount of a silane coupling agent dissolved in ion-exchanged water to a concentration of 5% by weight or less is gradually added under high-speed stirring. After the dropping, high-speed stirring is continued for about 15 to 30 minutes. The treated slurry may be filtered off and dried at about 120 ° C., or the treated slurry may be spray dried as it is.

  In the case of surface treatment with higher fatty acid or alkali metal salt thereof, spray higher fatty acid or alkali metal salt dissolved in magnesium hydroxide or aluminum hydroxide with heat or solvent and dry method using Henschel mixer etc. Can be surface treated. The amount of higher fatty acid or alkali metal salt thereof added to magnesium hydroxide or aluminum hydroxide may be 10-80%, preferably 15-50% of the specific surface area by the BET method. As the higher fatty acid and its alkali metal salt, stearic acid, oleic acid, palmitic acid, lauric acid, arachidic acid and their sodium salt, potassium salt and the like are used. Magnesium hydroxide or aluminum hydroxide treated by other methods can also be used. For example, nitrogen compound treatment, silicone polymer treatment, zinc stannate treatment, nickel compound treatment, cationic polymer treatment, multilayer (combination treatment such as fatty acid treatment, silane coupling agent treatment, silicone compound treatment, zinc stannate treatment), etc. .

  Further, in the present invention, in order to enhance the flame retardant effect of the inorganic flame retardant, an ammonium polyphosphate flame retardant, a phosphorus flame retardant such as a phosphate ester, a silicone compound; In addition, antimony trioxide, zinc stannate, zinc borate, calcium borate, red phosphorus, water glass, frit, etc. may be used as a flame retardant aid. It may be used.

The conductivity is improved by using conductive carbon black such as furnace black, channel black, gas black, acetylene black, and arc black as the component (c). Among these, furnace black, particularly ketjen black, which has a large specific surface area and excellent conductivity, is preferable. Further, a conductive composite carbon black obtained by combining these conductive carbon blacks may be used. The specific surface area of the conductive carbon black is preferably about 100 to 1,500 m ² / g, particularly about 500 to 1,500 m ² / g. The average particle diameter of the conductive carbon black has a close relationship with the proportion of the component (A) and cannot be defined unconditionally, but is usually 1 nm to 10 μm, preferably 5 nm to 1 μm, more preferably about 10 to 100 nm. It is.

(C) Tensile properties are improved by using silica such as dry silica, wet silica, and synthetic silicate silica as the component. Among these, wet silica having a large specific surface area is preferable. The specific surface area of silica is preferably about 20 to 400 m ² / g, particularly about 50 to ²⁰⁰ m ² / g. The average particle diameter of the silica has a close relationship with the ratio of the component (A) and cannot be generally defined, but is usually 1 nm to 30 μm, preferably 10 nm to 25 μm, and more preferably about 100 nm to 20 μm.

(A) / (B) of the thermoplastic elastomer composition of the present invention is 5 to 95% by weight / 5 to 95% by weight, preferably 10 to 90% by weight / 10 to 90% by weight, and more preferably 20 to 80%. % By weight / 20 to 80% by weight (where (A) + (B) = 100% by weight). By setting the content ratio as described above, the required performance can be satisfied.
In the thermoplastic elastomer composite of the present invention, the compounding amount of (c) the reinforcing agent is 1 to 300 parts by weight, preferably 2 to 250 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer composition. If the amount is less than 1 part by weight, the effect of improving the tensile strength is small. On the other hand, if it exceeds 300 parts by weight, fine dispersion in the elastomer composition becomes difficult and the tensile strength is poor.

  In addition to the above components, various additives other than the reinforcing agent can be added to the thermoplastic elastomer composition of the present invention as necessary. For example, an inorganic filler can be added. By containing an inorganic filler, preferable properties such as flame retardancy, strength and rigidity can be imparted to the thermoplastic elastomer composition, which is preferable. Moreover, there is no limitation in particular about content of an inorganic filler, In order to satisfy the performance requested | required, it can be set as various content. The content of the inorganic filler is usually 1 to 300 parts by weight, preferably 2 to 250 parts by weight, particularly preferably 5 to 200 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer composition. By setting it as this range, since properties, such as a flame retardance and intensity | strength, can be provided, without inhibiting the physical property of a thermoplastic elastomer composition, it is preferable.

  Other additives include anti-aging agents, weathering agents, metal deactivators, light stabilizers, UV absorbers, heat stabilizers and other stabilizers, antibacterial / antifungal agents, dispersants, softeners, plasticizers, Crosslinking agents, co-crosslinking agents, vulcanizing agents, vulcanization aids, foaming agents, foaming aids, and the like can be used.

<Method for producing thermoplastic elastomer composition (and thermoplastic elastomer composite)>
There is no restriction | limiting in particular as a manufacturing method of the thermoplastic elastomer composition (and thermoplastic elastomer composite) of this invention, A well-known method can be used. Examples thereof include known kneaders such as various extruders, Banbury mixers, kneaders, and rolls, a melt kneading method using a kneading machine combining them, and a dry blending method using an injection molding machine.

The kneading temperature and kneading time can be arbitrarily selected depending on conditions such as the desired thermoplastic elastomer composition (and the thermoplastic elastomer composite) and the type of kneader, but the kneading temperature in the extruder is 150 to 250 ° C., The kneading time is preferably from 30 seconds to 20 minutes, and the shear rate is preferably from 100 to 10,000 seconds- ¹ . When the kneading temperature is 250 ° C. or the kneading time exceeds 20 minutes, the thermal deterioration of the polar resin becomes a problem, and the physical properties of the molded product may be deteriorated or the appearance may be deteriorated. If the kneading time is less than 30 seconds, the kneading is insufficient.

  The thermoplastic elastomer composition (and thermoplastic elastomer composite) thus obtained is known in the art such as injection molding, extrusion molding, inflation molding, rotational molding, press molding, hollow molding, calendar molding, and blow molding. It is possible to mold by a method.

  The thermoplastic elastomer composition (and the thermoplastic elastomer composite) of the present invention includes various industrial parts such as precision parts, civil engineering / housing-related building materials such as window sashes, hangers, chairs, and household goods such as trash cans. Used for etc.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.

<Production of Modified Conjugated Diene Polymer>
A modified conjugated diene polymer was produced by the methods 1) to 4) described below.
Various measurements were performed according to the following methods.

(I) Content of vinyl bonds (1, 2, and 3, 4 bonds) Determined by an infrared absorption spectrum method (Morello method).
(Ii) Bound styrene content A calibration curve was prepared and determined by infrared absorption spectroscopy.
(Iii) Weight average molecular weight It calculated | required in polystyrene conversion using the gel permeation chromatography (GPC) (the Tosoh company make, HLC-8120).
(Iv) Carboxyl group and / or acid anhydride group content (mmol / g)
It was determined by quantification by chromatographic analysis described in JP-A 59-98106, page 6, right lower orchid, line 10 to page 7, lower left orchid, line 5.
(V) Alkoxysilyl group content (mmol / g)
The infrared absorption spectrum was quantified from a calibration curve created by the amount of absorption near 1,250 cm ⁻¹ due to the Si—OC ₆ H ₅ bond present in the modifier. Further, when the alkoxysilyl group present in the modifier is a Si—OCH ₃ , Si—OC ₂ H ₅ , or Si—OC (CH ₃ ) ₂ (C ₂ H ₅ ) bond, absorption near 1,100 cm ^−1. It was quantified from a calibration curve prepared by the amount. However, the content of the alkoxysilyl group was determined by dividing the quantified value by the polystyrene-equivalent number average molecular weight Mn obtained by the GPC method and the molecular weight of the alkoxysilyl group to obtain the number of moles (content) of the alkoxysilyl group.
(Vi) Amino group content (mmol / g)
Analy. Chem. It was determined by quantification by the amine titration method described on page 564 (1952). That is, the modified polymer was purified, dissolved in an organic solvent, and methyl violet was used as an indicator, and titration was performed by titrating HCLO ₄ / CH ₃ COOH until the color of the solution changed from purple to light blue.
(Vii) MFR (melt flow rate)
According to JIS K7210, it measured on the conditions of 230 degreeC and a 21.2N load.

1) Production of Modified Conjugated Diene Polymer (I-1) Into a reaction vessel having an internal volume of 100 liters purged with nitrogen, 50 kg of cyclohexane, 1.25 kg of styrene and 7.0 g of sec-butyllithium were added, and a polymerization initiation temperature of 50 The first stage polymerization was carried out at 0 ° C., and after completion of the reaction, the temperature was set to 70 ° C., 7.4 kg of 1,3-butadiene was added, and the second stage polymerization was carried out with heat insulation. After 30 minutes, 1.25 kg of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 0.1 kg of 1,3-butadiene was added to carry out a fourth stage polymerization. In this system, 31.7 g of methyltriphenoxysilane was added and reacted for 30 minutes. After the reaction, the reaction solution was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain a polymer (I-1). The obtained polymer (I-1) contained 12% of vinyl bonds, and the weight average molecular weight measured by GPC was about 150,000. The alkoxysilyl group content was 0.0125 mmol / g.
Further, the polymer (HI-1) is an unmodified conjugated diene polymer obtained by polymerization according to the polymer (A-1) except that methyltriphenoxysilane is not used.

2) Production of Modified Conjugated Diene Polymer (I-2) In a reaction vessel with an internal volume of 100 liters purged with nitrogen, 50 kg of cyclohexane, 1.25 kg of styrene and 3-lithio-1-N, N-bis (trimethylsilyl) 22.9 g of aminopropane was added, and the first stage polymerization was carried out at a polymerization start temperature of 50 ° C. After completion of the reaction, the temperature was set to 70 ° C., 7.5 kg of 1,3-butadiene was added, and the second stage polymerization was carried out with heat insulation. . After 30 minutes, 1.25 kg of styrene was added to carry out the third stage polymerization. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel, and then the reaction solution is stirred into water and the solvent is removed by steam distillation to obtain the polymer (I-2) shown in Table 1. Obtained. The amino group content of the obtained polymer (I-2) was 0.0061 mmol / g.

3) Production of Modified Conjugated Diene Polymer (I-3) In a reaction vessel having an internal volume of 100 liters purged with nitrogen, 50 kg of cyclohexane, 1.25 kg of styrene, and 2,2,5,5-tetramethyl-1- (3-Lithiopropyl) -1-aza-2,5-disilacyclopentane (22.7 g) was added, and the first stage polymerization was carried out at a polymerization initiation temperature of 50 ° C. After completion of the reaction, the temperature was adjusted to 70 ° C. and 1,3 -7.5 kg of butadiene was added and second-stage polymerization was performed with heat insulation. After 30 minutes, 1.25 kg of styrene was added to carry out the third stage polymerization. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel, and then the reaction solution is stirred into water and the solvent is removed by steam distillation to obtain the polymer (I-3) shown in Table 1. Obtained. The amino group content of the obtained polymer (I-3) was 0.0060 mmol / g.

4) Production of Modified Conjugated Diene Polymer (A-4) 50 kg of cyclohexane, 1.25 kg of styrene and 7.0 g of sec-butyllithium were added to a reaction vessel having an internal volume of 100 liters purged with nitrogen, and a polymerization initiation temperature of 50 The first stage polymerization was carried out at 0 ° C., and after completion of the reaction, the temperature was set to 70 ° C., 7.5 kg of 1,3-butadiene was added, and the second stage polymerization was carried out with heat insulation. After 30 minutes, 1.25 kg of styrene was added to carry out the third stage polymerization. Thereafter, 64 g of p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene was added to the active site of the polymer and reacted for 30 minutes. After the reaction, the reaction solution is returned to room temperature and normal pressure and extracted from the reaction vessel, and then the reaction solution is stirred into water and the solvent is removed by steam distillation to obtain the polymers (i-4) shown in Table 1. Obtained. The amino group content of the obtained polymer (I-4) was 0.014 mmol / g.

5) Production of Modified Conjugated Diene Polymer (A-5) Using sec-butyllithium as a polymerization initiator, the amount of the polymerization initiator so as to have a copolymer structure shown in (A-5) of Table 2 The monomer type, monomer amount, polymerization temperature, polymerization time, etc. were changed to obtain a polymer according to the production method of 1) above. Next, 11.7 g of N-benzylideneethylamine was added to the active site of the polymer and reacted for 30 minutes. After the reaction, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a polymer (I-5). The amino group content of the obtained polymer (I-5) was 0.0063 mmol / g.

6) Production of Modified Conjugated Diene Polymer (A-6) To a reaction vessel having an internal volume of 100 liters purged with nitrogen, 50 kg of cyclohexane, 1.25 kg of styrene and 7 g of sec-butyllithium are added, and the polymerization start temperature is 50 ° C. And polymerized. After completion of the reaction, the temperature was set to 80 ° C., 7.5 kg of butadiene was slowly added, and the second stage polymerization was carried out isothermally. After 30 minutes, 1.25 kg of styrene was added and the third stage polymerization was performed. After completion of the reaction, benzaldehyde was added as a ketone compound and / or ester compound and / or aldehyde compound until the orange color of living lithium became colorless, and 10.4 g was required. Thereafter, 16.1 g of phthalic anhydride was added. After the reaction, the reaction solution was returned to normal temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a polymer (I-6). This block polymer contained 12% of vinyl bonds, the weight average molecular weight measured by GPC was about 150,000, and the carboxyl group content was 0.0062 mmol / g.

7) Production of Modified Conjugated Diene Polymer (A-7) 50 kg of cyclohexane, 1.25 kg of styrene, and 7 g of sec-butyllium are added to a reaction vessel having an internal volume of 100 liters purged with nitrogen, and the polymerization start temperature is 50 ° C. And polymerized. After completion of the reaction, the temperature was set to 80 ° C., 7.5 kg of butadiene was slowly added, and the second stage polymerization was carried out isothermally. After 30 minutes, 1.25 kg of styrene was added and the third stage polymerization was performed. After completion of the reaction, acetone was added as a ketone compound and / or ester compound and / or aldehyde compound until the orange color of living lithium became colorless, and 5.7 g was required. Thereafter, 20.7 g of trimellitic anhydride chloride was added. After the reaction, the reaction solution was returned to room temperature and normal pressure and extracted from the reaction vessel. Then, the reaction solution was stirred into water and the solvent was removed by steam distillation to obtain a polymer (I-7). This block polymer contained 12% of vinyl bonds, the weight average molecular weight measured by GPC was about 150,000, and the carboxyl group content was 0.012 mmol / g.

8) Production of modified conjugated diene polymer (I-8) After polymerization according to polymer (I-3), 31.7 g of methyltriphenoxysilane was added to the system and reacted for 30 minutes. After the reaction, the reaction solution was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain a polymer (I-8). The obtained polymer (I-8) had an alkoxysilyl group content of 0.0125 mmol / g and an amino group content of 0.0060 mmol / g.

9) Production of Modified Conjugated Diene Polymers (A-9) to (A-12) Modified conjugated diene heavy polymers having an alkoxysilyl group as shown in Tables 2 and 3 in accordance with the polymer (A-1) Polymers (A-9) to (A-12) were obtained by changing the kind of the modifier, the monomer, and the like so as to be combined. The polymer (H-2) is an unmodified conjugated diene polymer obtained by polymerizing according to the polymer (I-12) except that N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane is not used. It is a polymer.

10) Modified conjugated diene polymer (A-13)
Isoprene is used in place of butadiene as the conjugated diene, and the others are modified in accordance with the polymer (a-1) so as to be a modified conjugated diene polymer having an alkoxysilyl group as shown in Table 3, The monomer (a) was changed to obtain a polymer (A-13).

11) Modified conjugated diene polymers (A-14) to (A-15)
50 kg of cyclohexane, 1.25 kg of styrene, 1.0 g of ethylene glycol diethyl ether and 7.0 g of sec-butyl lithium are added to a reaction vessel having an internal volume of 100 liters purged with nitrogen, and the first stage polymerization is performed at a polymerization start temperature of 50 ° C. After completion of the reaction, the temperature was set to 70 ° C., 7.4 kg of butadiene was slowly added, and the second stage polymerization was performed with heat insulation. After 30 minutes, 1.25 kg of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 0.1 kg of 1,3-butadiene was added to carry out a fourth stage polymerization. To this system, 21.7 g of methyldiethoxy (t-amyloxy) silane was added and reacted for 30 minutes. After the reaction, the reaction solution was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain a polymer (I-14). The obtained polymer (I-14) had a vinyl bond of 25%, a weight average molecular weight of about 150,000, and an alkoxysilyl group content of 0.0124 mmol / g.
(I-15) is an ethylene glycol diethyl ether, a modifier type, a monomer, etc. so as to be a modified conjugated diene polymer having an alkoxysilyl group as shown in Table 4 according to (i-14). Was changed to obtain a polymer (I-15). The polymer (HI-3) is an unmodified conjugated diene polymer obtained by polymerizing according to the polymer (I-15) except that N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane is not used. It is a polymer.

12) Modified conjugated diene polymer (A-16)
Add 50 kg of cyclohexane, 1.0 kg of styrene, and 6.5 g of sec-butyllithium to a reaction vessel with an internal volume of 100 liters purged with nitrogen, and perform the first stage polymerization at a polymerization start temperature of 50 ° C. At 80 ° C., 6.9 kg of butadiene and 1 kg of styrene were slowly added, and the second stage polymerization was carried out isothermally. After 30 minutes, 1.0 kg of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 0.1 kg of 1,3-butadiene was added to carry out a fourth stage polymerization. Then, 29.4 g of methyltriphenoxysilane was added to the system and reacted for 30 minutes. After the reaction, it was returned to room temperature and normal pressure, extracted from the reaction vessel, stirred into water, and the solvent was removed by steam distillation to obtain a polymer (I-16). The obtained polymer (I-16) had a weight average molecular weight of about 150,000 and an alkoxysilyl group content of 0.0125 mmol / g. The polymer (HI-4) is an unmodified conjugated diene polymer obtained by polymerization according to the polymer (A-16) except that methyltriphenoxysilane is not used.

(A) methyltriphenoxysilane (b) 3-lithio-1-N, N-bis (trimethylsilyl) aminopropane (c) 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1 -Aza-2,5-disilacyclopentane (d) p- {2- [N, N-bis (trimethylsilyl) amino] ethyl} styrene

(A) Methyltriphenoxysilane (c) 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5-disilacyclopentane (e) N-benzylideneethylamine ( f) Phthalic anhydride (g) Trimellitic anhydride chloride (h) Methyldiethoxy (t-amyloxy) silane

(A) Methyltriphenoxysilane (i) N, N-bis (trimethylsilyl) aminopropyltriethoxysilane (j) N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane (k) N, N-bis (trimethylsilyl) Aminopropylmethyldiethoxysilane

(A) Methyltriphenoxysilane (h) Methyldiethoxy (t-amyloxy) silane (k) N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane

(2) Various components Various components used in Examples and Comparative Examples are as follows.
(B) the modified conjugated diene polymer Tables 1 co auditors that having a structure shown in 4 diene polymer (a-1) - (b -16)
(B) Functional group-containing olefin polymer (b-1): Maleic anhydride-modified ethylene / propylene copolymer: manufactured by JSR Corporation
"EP T7711"
(B-2): Ethylene / glycidyl methacrylate copolymer: manufactured by Sumitomo Chemical Co., Ltd.
"Bond Fast E"
(C) Reinforcing agent (C-1): Conductive carbon Kato Ketjen Black EC
(C-2): Magnesium hydroxide Kyowa Chemical Industry Co., Ltd. Kisuma 5P
(C-3): Silica Tosoh Corporation nip seal ER

<Physical property evaluation>
(1) Tensile breaking strength and tensile breaking elongation According to ASTM D-638, a test piece was subjected to a tensile test under a temperature condition of 23 ° C. and measured.
(2) Compression set According to JIS K6262, the compression set was measured at 70 ° C., 22 hours, 25% compression.
(3) Hardness Measured according to JIS K6253 as an index of flexibility.
(4) Wear test Based on JIS K6264, it measured by grinding wheel H22, continuous 1,000 times, and load 4.9N.
(5) Conductivity According to JIS K7194, the surface resistance value was measured using a low resistivity meter.
(6) Flame retardance Measured by an inclination test according to JIS C3005. Those that disappeared naturally within 60 seconds were considered acceptable.
(7) Removability of reinforcing agent A sheet of 15 cm in length × 15 cm in width is fixed, and the copy paper is reciprocated 10 times with 20 sm span on it, and the deposits on the copy paper due to friction are visually observed. Evaluation based on the criteria.
○: There is no adhesion of the reinforcing agent.
X: A reinforcing agent adheres.

Example 1
(A) 30 parts of (a-1) as component and 70 parts of (b-1) as component (b) are melt-kneaded using a lab plast mill set at 180 ° C., and 150 parts are kneaded. A test piece for evaluating physical properties was produced by molding with a hot press set to ° C., and physical properties were evaluated by the method described above. The results are shown in Table 5.

Examples 2-24, Comparative Examples 1-4
Using the formulation shown in Tables 5 to 8, test pieces were prepared in the same manner as in Example 1, and the physical properties were evaluated. The results are shown in Tables 5 to 8 below.

From Tables 5 to 8, it can be seen that Examples 1 to 24, which are compositions of the present invention, are thermoplastic elastomer compositions and composites having high tensile strength and good wear compression set.
On the other hand, from Table 9, in Comparative Examples 1 to 4, which are compositions using an unmodified polymer that is not the modified conjugated diene polymer of the present invention, the tensile strength is low and the heat is inferior to the wear compression set. It turns out that it is a plastic elastomer composition and a composite.

The thermoplastic elastomer composition of the present invention includes an instrument panel skin, automotive interior and exterior parts such as a handle, home appliance parts such as a soft keyboard, building materials such as joints for window frames, medical parts such as medicine plugs, footwear, toys, miscellaneous goods, Used as various industrial parts such as tool grips.

Claims (9)

(A) A modified non-hydrogenated conjugated diene polymer having an amino group, a modified non-hydrogenated conjugated diene polymer having an acid anhydride group and a carboxyl group , or a modified non-water having both an alkoxysilyl group and an amino group A modified non-hydrogenated conjugated diene produced by at least one selected from the group consisting of (c), (e), (f), (g) and (h) (B) Functional group-containing olefin polymer 5 to 95% by weight (however, (ii) + (b) = 100% by weight)
A thermoplastic elastomer composition comprising as a main component,
(B) A thermoplastic elastomer composition, wherein the functional group-containing olefin polymer is a maleic anhydride-modified ethylene-propylene copolymer or an ethylene-glycidyl methacrylate copolymer.
(C) A polymer produced by polymerizing a conjugated diene, an unsaturated monomer having an amino group, and an aromatic vinyl compound in the presence of an organic alkali metal compound.
(E) A conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene-based polymer is at least one selected from the group of ketone compounds, ester compounds, and aldehyde compounds. A polymer produced by reacting a compound and then reacting with an acid anhydride and / or acid halide.
(F) A conjugated diene and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound having an amino group, and the resulting conjugated diene polymer is reacted with a compound represented by the following general formula (2). Modified polymer.
R ³ _(4-mn) Si (OR ⁴ ) _m X _n (2)
[Wherein, R ³ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to 100 carbon atoms, and a plurality of R ³ In some cases, each R ³ may be the same or different group. R ⁴ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. When there are a plurality of R ^{4 s} , each R 4 may be the same group or a different group. . X is a substituent having a polar group containing at least one of O atom and Si atom. When there are a plurality of X, each X may be the same or different, and each X is an independent substituent. Even a group may form a cyclic structure. m is 1, 2 or 3, and n is an integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. ]
(G) A conjugated diene, an unsaturated monomer having an amino group, and an aromatic vinyl compound are polymerized in the presence of an organic alkali metal compound, and the resulting conjugated diene polymer is represented by the above general formula (2). Modified polymer obtained by reacting a compound to be reacted.
(H) A modified polymer obtained by polymerizing a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound and reacting the resulting conjugated diene polymer with a compound represented by the following general formula (7).
R ¹² _(4- pq ₎ Si (OR ¹³ ) pZq (7)
^{Wherein, R 12} is an alkyl group, an aryl group having 6 to 20 carbon atoms, organo siloxy group aralkyl group or 1 to 100 carbon atoms having 7 to 20 carbon atoms having 1 to 20 carbon ^{atoms, R 12} is more In some cases, each R ¹² may be the same or different group. R ¹³ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon ^{atoms, if R 13} have more than one purpose, each ^{R 13} is different even in the same group group Good. Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same or different, and each Z may be an independent substituent and form a cyclic structure. Also good. p is 1, 2 or 3, and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. ]   (I) The total content of at least one group selected from the group of alkoxysilyl groups, amino groups, acid anhydride groups, and carboxyl groups in the modified non-hydrogenated conjugated diene polymer is 0.0001 to 5 mmol. The thermoplastic elastomer composition according to claim 1, which is / g. (A) The modified non-hydrogenated conjugated diene polymer is a block copolymer containing one or more polymer blocks selected from the following polymer blocks (A), (B), and (C): The thermoplastic elastomer composition according to claim 1 or 2.
(A) Aromatic vinyl compound polymer block whose aromatic vinyl compound is 80% by weight or more (B) Conjugated diene polymer block (C) Random copolymer block of aromatic vinyl compound and conjugated diene (I) The modified non-hydrogenated conjugated diene polymer is obtained by modifying a styrene-butadiene block copolymer (SBS) or a styrene-isoprene block copolymer (SIS). The thermoplastic elastomer composition as described.   A thermoplastic elastomer composite comprising (c) 1 to 300 parts by weight of a reinforcing agent with respect to 100 parts by weight of the thermoplastic elastomer composition according to any one of claims 1 to 4.   (C) The thermoplastic elastomer composite according to claim 5, wherein the reinforcing agent is carbon black.   (C) The thermoplastic elastomer composite according to claim 5, wherein the reinforcing agent is silica.   (C) The thermoplastic elastomer composite according to claim 5, wherein the reinforcing agent is magnesium hydroxide. The heat according to any one of claims 5 to 8, which is used for an application selected from the group consisting of automotive interior / exterior parts, home appliance parts, building materials, medical parts, footwear, toys, tool grips, precision parts, household goods. Plastic elastomer composite.