JP4522728B2 - Thermoplastic polymer composition - Google Patents

Description

  The present invention relates to a thermoplastic polymer composition. The thermoplastic polymer composition of the present invention is excellent in flexibility, heat resistance such as strain recovery under high temperature conditions (for example, 120 ° C.), molding processability, tear resistance and oil resistance, and is effective for various applications. A molded body that can be used for the above can be obtained.

  In recent years, thermoplastic elastomers, which are rubber-like soft materials that do not require a vulcanization process and have the same molding processability as thermoplastic resins, have become automotive parts, home appliance parts, electric wire coatings, medical parts, footwear, and miscellaneous goods. It is used in various fields. Among these, a block copolymer having an aromatic vinyl compound polymer block-conjugated diene compound polymer block or a styrene thermoplastic elastomer that is a hydrogenated product thereof is used as a material excellent in flexibility, moldability, and the like. However, in recent years, with the expansion of application fields such as home appliance parts, automobile parts, building material parts, etc., improvement in heat resistance is particularly demanded. Styrenic thermoplastic elastomers are inferior in tear strength compared to vulcanized rubber, so when used in window frames, door seals, various packings, etc., the sealability will be reduced in long-term use. Improvement is also an issue. Furthermore, in automotive parts, when used as parts in the engine room, when exposed to various lubricating oils, or used as exterior materials such as window frames and door seals, molding materials, wax and wax removers. It is often exposed to oils such as, and improving oil resistance is also a problem.

Regarding the provision of heat resistance to a polymer composition mainly composed of a styrenic thermoplastic elastomer, [1] a block copolymer having a polymer block composed of an aromatic vinyl compound and a polymer block composed of a conjugated diene compound. A hydrogenated product, a non-aromatic rubber softener, a peroxide-decomposable olefin resin, and a compound containing a specific amount of an inorganic filler as required are kneaded in advance, and then an organic peroxide and a crosslinking aid. and if the production method of the elastomeric composition, characterized in that partially crosslinked by the addition of an anti-oxidant is disclosed by, the elastomeric composition excellent in physical properties such as high temperature compression set only can be obtained (JP 1);
[2] Hydrogenated block copolymer and rubber softener having a specific weight average molecular weight range and a specific distribution having a polymer block composed of an aromatic vinyl compound and a polymer block composed of a conjugated diene compound The ratio is 20/80 to 80/20 (mass ratio), and a mixture obtained by blending a specific amount of the olefin polymer with respect to 100 parts by mass of the total amount of the two components is moved in the presence of a crosslinking agent. A thermoplastic elastomer composition obtained by heat treatment (see Patent Document 2) has been proposed. However, in these compositions, since only the soft segment composed of the conjugated diene compound polymer block of the hydrogenated block copolymer is crosslinked, rubber elasticity (compression set) at 100 ° C. or higher is not good. It is sufficient and has not reached the level achieved with vulcanized rubber.

  On the other hand, [3] (A) 10-80% by weight of a crosslinkable diene rubber and / or crosslinkable thermoplastic elastomer, (B) 20-80% by weight of an aromatic vinyl compound thermoplastic resin such as polystyrene, and (C) It is obtained by adding a cross-linking agent of component (A) to 0 to 40% by weight of a plasticizer [provided that (A) + (B) + (C) = 100% by weight], melt-kneading, A dynamic crosslinking composition characterized in that the gelation rate of the component A) is 30 to 100% is disclosed, and it is described that the tear strength is good (see Patent Document 3). In addition, for the purpose of improving the above-mentioned compression set (rubber elasticity) at 100 ° C. or higher, [4] block copolymer having one or more aromatic vinyl compound polymer blocks and one or more conjugated diene compound polymer blocks. In the blend, a specific amount of a block copolymer having a specific crosslinked structure or a hydrogenated product thereof, a polyolefin, and, optionally, a rubber softener, crosslinked at least at an aromatic vinyl compound polymer block portion forming a hard segment. A thermoplastic elastomer composition is disclosed, and it is disclosed that such a thermoplastic elastomer composition is excellent in strain recovery (heat resistance) at high temperatures (see Patent Document 4).

JP 59-131613 A JP 2000-109640 A JP-A-10-195241 International Publication No. 02/090433 Pamphlet

However, the dynamic cross-linking composition of Patent Document 3 does not describe any effect of improving heat resistance and oil resistance. Moreover, since there is much content of aromatic vinyl compound type thermoplastic resins with high lipophilicity, such as a polystyrene, in a composition, it is anticipated that it is inferior to oil resistance. Furthermore, in the thermoplastic elastomer composition of Patent Document 4, since the hard segment of the hydrogenated block copolymer has a crosslinked structure, the amount of the crosslinking agent and crosslinking aid used is increased in order to further improve heat resistance. When the degree of cross-linking is increased, the elongation at break and tear strength are particularly markedly lowered and may not be practically used. Moreover, when the degree of crosslinking is too high, the fluidity of the thermoplastic elastomer composition is lowered, and the molding processability in various moldings such as injection molding and extrusion molding tends to be reduced.
Thus, the object of the present invention is to solve such conventional problems, and is excellent in flexibility, strain recovery at high temperatures (heat resistance), and excellent in moldability, tear resistance and oil resistance. It is to provide a plastic polymer composition.

According to the present invention, the above object is
(1) It has one or more polymer blocks A mainly composed of aromatic vinyl compound units and one or more polymer blocks B mainly composed of conjugated diene compound units, and at least the polymer block A part is crosslinked. An addition polymerization block copolymer (a) selected from the block copolymers or hydrogenated products thereof, and one or more polymer blocks A ′ mainly composed of aromatic vinyl compound units, and conjugated diene compound units With respect to 100 parts by mass of the total amount ((a) + (a ₁ )) of the addition polymerization block copolymer (a ₁ ) composed of a block copolymer having at least one polymer block B ′ mainly composed of the olefin resin (b) contained in the range of 10 to 300 parts by weight,
The addition polymerization block copolymer (a) comprises a structural unit (I) and a functional group (II) based on an alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring in the polymer block A. And at least the polymer block A moiety is crosslinked by the structural unit (I) and / or the functional group (II),
Based on the total mass of the polymer block B constituting the addition polymerization block copolymer (a) in the polymer block B, the structural unit composed of the other polymerizable monomer composed of the conjugated diene compound. It is a thermoplastic polymer composition that is 10% by mass or less and has a hydrogenation rate of carbon-carbon double bonds in the polymer block B of 95 mol% or more , wherein the functional group (II) is a hydroxyl group A functional group having an active hydrogen atom selected from (—OH), —SH, —NH ₂ , —NHR, —CONH ₂ , —CONHR, —CONH— , —SO ₃ H, —SO ₂ H and —SOH, carboxyl A thermoplastic polymer composition which is a functional group selected from a group as well as an epoxy group ;
(2) One or more polymer blocks A mainly composed of aromatic vinyl compound units and one or more polymer blocks B mainly composed of conjugated diene compound units, and at least the polymer block A part is crosslinked. An addition polymerization block copolymer (a) selected from the block copolymers or hydrogenated products thereof, and one or more polymer blocks A ′ mainly composed of aromatic vinyl compound units, and conjugated diene compound units With respect to 100 parts by mass of the total amount ((a) + (a ₁ )) of the addition polymerization block copolymer (a ₁ ) composed of a block copolymer having at least one polymer block B ′ mainly composed of The olefin-based resin (b) is contained in the range of 10 to 300 parts by mass, the rubber softener (c) is contained in the range of 300 parts by mass or less, and the addition polymerization block copolymer (a) is a polymer block. A has at least one selected from the structural unit (I) and the functional group (II) based on alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring, and the structure At least the polymer block A part is crosslinked by the unit (I) and / or the functional group (II),
Based on the total mass of the polymer block B constituting the addition polymerization block copolymer (a) in the polymer block B, the structural unit composed of the other polymerizable monomer composed of the conjugated diene compound. It is a thermoplastic polymer composition that is 10% by mass or less and has a hydrogenation rate of carbon-carbon double bonds in the polymer block B of 95 mol% or more , wherein the functional group (II) is a hydroxyl group A functional group having an active hydrogen atom selected from (—OH), —SH, —NH ₂ , —NHR, —CONH ₂ , —CONHR, —CONH— , —SO ₃ H, —SO ₂ H and —SOH, carboxyl A thermoplastic polymer composition which is a functional group selected from a group as well as an epoxy group ;
(3) The thermoplastic polymer composition of (1) or (2), wherein the structural unit (I) is a structural unit based on p-methylstyrene and the functional group (II) is a hydroxyl group;
(4) Any of (1) to (3), wherein the mass ratio of the addition polymerization block copolymer (a) and the addition polymerization block copolymer (a ₁ ) is in the range of 10:90 to 95: 5. A thermoplastic polymer composition of

(5) It has one or more polymer blocks A mainly composed of aromatic vinyl compound units and one or more polymer blocks B mainly composed of conjugated diene compound units, and the structural unit ( I) and a block copolymer having at least one selected from functional groups (II) or an addition polymerization block copolymer (a ₀ ) selected from hydrogenated products thereof, and an aromatic vinyl compound unit as a main component Amount of addition polymerization block copolymer (a ₁ ) composed of a block copolymer having one or more polymer blocks A ′ and one or more polymer blocks B ′ mainly composed of conjugated diene compound units ((A ₀ ) + (a ₁ )) 100 parts by mass of olefin resin (b) in the range of 10 to 300 parts by mass and cross-linking agent (d) in the range of 0.01 to 20 parts by mass Become The compound, a method for producing a thermoplastic polymer composition characterized by dynamic crosslinking in the molten condition (1), polymer block B of the addition polymerization-based block copolymer (a ₀₎ Among them, the structural unit composed of another polymerizable monomer composed of the conjugated diene compound is 10% by mass based on the total mass of the polymer block B constituting the addition polymerization block copolymer (a ₀ ). less and, and the carbon of the polymer block in B - hydrogenation of the carbon double bonds Ri der least 95 mol%, further functional groups (II) is a hydroxyl group (-OH), - SH, -NH 2 , —NHR, —CONH ₂ , —CONHR, —CONH— , —SO ₃ H, —SO ₂ H and —SOH, a functional group having an active hydrogen atom, a functional group selected from a carboxyl group and an epoxy group There is thermoplasticity Production method of polymer composition ;
(6) One or more polymer blocks A mainly composed of aromatic vinyl compound units and one or more polymer blocks B mainly composed of conjugated diene compound units, and structural units ( Addition polymerization block copolymer (a ₀ ) selected from a block copolymer having at least one of I) and functional group (II) or a hydrogenated product thereof, and a polymer mainly composed of an aromatic vinyl compound unit Total amount of addition polymerization block copolymer (a ₁ ) composed of a block copolymer having at least one block A ′ and at least one polymer block B ′ mainly comprising a conjugated diene compound unit ((a ₀ ) + (a ₁ )) 100 parts by mass of the olefin resin (b) in the range of 10 to 300 parts by mass and the rubber softener (c) in the range of 300 parts by mass or less, d) 0. (2) The method for producing a thermoplastic polymer composition according to (2), wherein the mixture comprising 1 to 20 parts by mass is dynamically cross-linked under melting conditions. In the polymer block B of the polymer (a ₀ ), a polymer in which a structural unit composed of another polymerizable monomer composed of a conjugated diene compound constitutes an addition polymerization block copolymer (a ₀ ) or less 10% by weight based on the total weight of the block B, and the carbon of the polymer block in B - hydrogenation of the carbon double bonds Ri der least 95 mol%, further functional groups (II) is a hydroxyl group A functional group having an active hydrogen atom selected from (—OH), —SH, —NH ₂ , —NHR, —CONH ₂ , —CONHR, —CONH— , —SO ₃ H, —SO ₂ H and —SOH, carboxyl Groups and epoxy groups A method for producing a thermoplastic polymer composition, which is a functional group selected from : and ( 7 ) a molded article comprising the thermoplastic polymer composition according to any one of (1) to (4);
Is achieved by providing

The present invention is described in detail below.
The addition polymerization block copolymer (a) constituting the thermoplastic polymer composition of the present invention comprises one or more polymer blocks A mainly composed of aromatic vinyl compound units and mainly composed of conjugated diene compound units. The polymer block B has at least one polymer block B, and at least the polymer block A portion is crosslinked.
The addition polymerization block copolymer (a) may be crosslinked at both the polymer block A part and the polymer block B part, but is not crosslinked at the polymer block B part. It is more preferable that the resin is crosslinked only at the portion because of excellent rubber elasticity.

In the addition polymerization block copolymer (a), the polymer block A constitutes a hard segment, and the polymer block B constitutes a soft segment. The addition polymerization block copolymer (a) suitably used in the thermoplastic polymer composition of the present invention is selected from the structural unit (I) and the functional group (II) in the polymer block A forming the hard segment. It has at least one kind, and at least the polymer block A portion is crosslinked by the structural unit (I) and / or the functional group (II).

  Examples of the alkyl styrene constituting the structural unit (I) that the polymer block A of the addition polymerization block copolymer (a) may have include, for example, o-alkyl styrene whose alkyl group has 1 to 8 carbon atoms. M-alkyl styrene, p-alkyl styrene, 2,4-dialkyl styrene, 3,5-dialkyl styrene, 2,4,6-trialkyl styrene, one of the hydrogen atoms of the alkyl group in the aforementioned alkyl styrenes or Examples thereof include halogenated alkylstyrenes in which two or more are substituted with a halogen atom. More specifically, examples of the alkylstyrene constituting the structural unit (I) include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2 , 4,6-trimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4,6-triethylstyrene, o-propylstyrene M-propyl styrene, p-propyl styrene, 2,4-dipropyl styrene, 3,5-dipropyl styrene, 2,4,6-tripropyl styrene, 2-methyl-4-ethyl styrene, 3-methyl- 5-ethylstyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, 2,4- (Chloromethyl) styrene, 3,5-bis (chloromethyl) styrene, 2,4,6-tri (chloromethyl) styrene, o-dichloromethylstyrene, m-dichloromethylstyrene, p-dichloromethylstyrene, etc. Can be mentioned.

  The polymer block A can have a unit composed of one or more of the aforementioned alkylstyrene and halogenated alkylstyrene as the structural unit (I). Among them, the structural unit (I) is a structural unit based on p-methylstyrene, which is excellent in reactivity with a crosslinking agent (d) such as a bismaleimide compound and an organic peroxide described later, and is a polymer block. A is preferable because a crosslinked structure can be reliably introduced into A. In addition, when carbon number of the alkyl group couple | bonded with the benzene ring of structural unit (I) becomes 9 or more, it will be inferior to the reactivity with a crosslinking agent (d), and it will become difficult to form a crosslinked structure.

On the other hand, examples of the functional group (II) (functional group before cross-linking) that the polymer block A of the addition polymerization block copolymer (a) may have include a functional group having an active hydrogen atom [for example, the formula: − A functional group represented by OH, —SH, —NH ₂ , —NHR, —CONH ₂ , —CONHR—, —CONH—, —SO ₃ H, —SO ₂ H, —SOH (wherein R is a hydrocarbon group) shown), etc.]; functional group having a nitrogen atom (for example, the _{formula: -NR 2,> C = NH} ,> C = N -, - CN, -NCO, -OCN, -SCN, -NO, -NO 2 , —NCS, —CONR ₂ , —CONR— or the like (wherein R represents a hydrocarbon group) or the like; a functional group having a carbonyl group or a thiocarbonyl group [eg, formula:> C═ O,> C = S, -CH = O, -CH = S, -COOR, -C OR (wherein, R represents a hydrocarbon group), etc.]; epoxy group, and the like thioepoxy group. The addition polymerization block copolymer (a) has one or more of these functional groups in the polymer block A, and can be crosslinked at that portion. Among these, the functional group (II) that the polymer block A may have is preferably a hydroxyl group (formula: —OH) from the viewpoint of easy formation of crosslinking.

The addition polymerization block copolymer (a) can have an aromatic vinyl compound unit other than the structural unit (I) as the aromatic vinyl compound unit constituting the polymer block A. Other aromatic vinyl compound units, for example, styrene, alpha-methyl styrene, beta-methyl styrene, mono-fluorostyrene, difluoro styrene, monochlorostyrene styrene, dichloro styrene, methoxy styrene, vinyl naphthalene, vinyl anthracene, indene, Asetonafuchiren The unit which consists of these etc. can be mentioned and can have these 1 type, or 2 or more types of units. Especially, as another aromatic vinyl compound unit, the structural unit based on styrene is preferable.

  When the polymer block A has another aromatic vinyl compound unit together with the structural unit (I) and / or the functional group (II), the structural unit (I) and / or the functional group (II) and the other aromatic group The bonding form of the vinyl compound unit may be any form such as random, block, or tapered.

  The polymer block A may have a small amount of structural units based on other polymerizable monomers as necessary, together with the structural units based on the aromatic vinyl compound. In that case, the proportion of the structural unit based on the other polymerizable monomer is preferably 30% by mass or less, more preferably 10% by mass or less, based on the total mass of the polymer block A. Examples of other polymerizable monomers in that case include methacrylic acid esters, acrylic acid esters, 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. The bonding form of these other polymerizable monomers may be any form such as random, block, or tapered.

  When the polymer block A of the addition polymerization block copolymer (a) has the structural unit (I) and is crosslinked at that portion, the content of the structural unit (I) in the polymer block A is: The number of bond blocks in the addition polymerization block copolymer (a), the number average molecular weight of the addition polymerization block copolymer, the polymer block A has only the structural unit (I), or the structural unit (I) It may differ depending on whether it has a functional group (II).

  The addition polymerization block copolymer (a) does not have the functional group (II) in the polymer block A, has only the structural unit (I), and is crosslinked by the structural unit (I) portion. In the case of a polymer or a hydrogenated product thereof [hereinafter sometimes referred to as “addition polymerization block copolymer (aI)”], the content of the structural unit (I) in the polymer block A is determined by addition polymerization. 1 mass relative to the mass of the polymer block A constituting the system block copolymer (aI) [the total mass when the addition polymerization system block copolymer (aI) has two or more polymer blocks A] % Or more, preferably 5% by mass or more, and more preferably 10% by mass or more. In some cases, all the units constituting the polymer block A may be composed of the structural unit (I). In the addition polymerization block copolymer (aI) having only the structural unit (I) in the polymer block A, the content ratio of the structural unit (I) to the mass of the polymer block A is less than 1% by mass. Further, it is difficult for the polymer block A portion to form a cross-link, and the thermoplastic polymer composition containing such an addition polymerization block copolymer tends to be inferior in heat resistance.

  On the other hand, when the polymer block A of the addition polymerization block copolymer (a) has a functional group (II) and is crosslinked at that portion, the content of the functional group (II) in the polymer block A Is the number of binding blocks, number average molecular weight of addition block copolymer (a), polymer block A has only functional group (II) or structural unit (I) together with functional group (II). It may vary depending on whether you have it.

  The addition polymerization system block copolymer (a) does not have the structural unit (I) in the polymer block A, has only the functional group (II), and is crosslinked at the functional group (II) portion. When the copolymer or its hydrogenated product (hereinafter sometimes referred to as “addition polymerization block copolymer (aII)”) is not crosslinked in the polymer block B, the addition polymerization block copolymer The content of the functional group (II) per molecule of the polymer (aII) is preferably in the range of 1.2 to 1000, and more preferably in the range of 1.6 to 200.

  Further, the addition polymerization block copolymer (a) does not have the structural unit (I), and both the polymer block A and the polymer block B have the functional group (II), and the polymer block A and the polymer When the block B is cross-linked, the content of the functional group (II) per molecule of the addition polymerization block copolymer (aII) is in the range of 2.2 to 1100. Is preferable, and the range of 1.6 to 230 is more preferable. At that time, the content of the functional group (II) in the polymer block B is preferably 0.5 to 30 per molecule of the addition polymerization block copolymer (aII).

  Further, when the addition polymerization block copolymer (a) has both the structural unit (I) and the functional group (II) in the same or different polymer block A, the content of the structural unit (I) is It is preferable that the content of the functional group (II) is 1 to 90% by mass with respect to the mass of the polymer block A and the range of 1 to 1000 per molecule of the addition polymerization block copolymer (a).

  The number (number) of crosslinks in the polymer block A portion of the addition polymerization block copolymer (a) is preferably 2 or more per molecule of the addition polymerization block copolymer (a). The number of crosslinks in the polymer block A can be changed by adjusting the number of structural units (I) and / or functional groups (II) introduced into the polymer block A and the amount of the crosslinking agent (d) to be used. Can do.

  Next, in the addition polymerization block copolymer (a), the conjugated diene compound constituting the polymer block B includes isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3- Examples thereof include pentadiene. The polymer block B may be composed of only one kind of these conjugated diene compounds or may be composed of two or more kinds, among which butadiene, isoprene, or a mixture of butadiene and isoprene. Is preferred. When the polymer block B has a structural unit derived from two or more kinds of conjugated diene compounds, their bonding form is random, block, tapered, or a combination of two or more thereof. Can do.

  The polymer block B may have a small amount of a structural unit composed of another polymerizable monomer as necessary, together with a structural unit composed of a conjugated diene compound. The proportion of the other polymerizable monomer in that case is preferably 30% by mass or less based on the total mass of the polymer block B constituting the addition polymerization block copolymer (a), and is preferably 10% by mass. The following is more preferable. Examples of the other polymerizable monomer in that case include styrene, α-methylstyrene, and the above-described alkylstyrene (preferably p-methylstyrene) constituting the structural unit (I). Further, the polymer block B may have a functional group (II).

  The polymer block B includes a polyisoprene block composed of isoprene units or a hydrogenated polyisoprene block in which part or all of carbon-carbon double bonds based on the isoprene units are hydrogenated; a polybutadiene block composed of butadiene units or the butadiene Hydrogenated polybutadiene block in which some or all of the carbon-carbon double bonds based on the unit are hydrogenated; or a copolymer block composed of a mixture of isoprene and butadiene composed of isoprene units and butadiene units; It is a copolymer block made of a mixture of isoprene and butadiene in which some or all of the carbon-carbon double bonds are hydrogenated, and the weather resistance, heat resistance, etc. of the thermoplastic polymer composition of the present invention From the point of view, it is preferable.

In the above-described polyisoprene block that can be a constituent block of the polymer block B, before the hydrogenation, the unit derived from isoprene is a 2-methyl-2-butene-1,4-diyl group [—CH ₂ —C (CH ₃ ) ═CH—CH ₂ —; 1,4-bonded isoprene unit], isopropenyl ethylene group [—CH (C (CH ₃ ) ═CH ₂ ) —CH ₂ —; 3,4-bonded isoprene Unit] and 1-methyl-1-vinylethylene group [—C (CH ₃ ) (CH═CH ₂ ) —CH ₂ —; 1,2-bonded isoprene unit]. The ratio of each unit is not particularly limited.

In the above-mentioned polybutadiene block which can be a building block of the polymer block B, before hydrogenation, 70 to 20 mol%, particularly 65 to 40 mol% of the butadiene unit is a 2-butene-1,4-diyl group ( _{-CH 2 -CH = CH-CH 2} -; 1,4- bond is butadiene units), 30 to 80 mol%, in particular 35 to 60 mol% ethylene vinyl group [-CH (CH = CH) -CH 2 -; 1,2-bonded butadiene unit] is preferable. When the 1,4-bond amount in the polybutadiene block is within the range of 70 to 20 mol%, the rubber elasticity is improved.

  In the above-described copolymer block composed of a mixture of isoprene and butadiene which can be a building block of the polymer block B, the unit derived from isoprene is 2-methyl-2-butene-1,4-diyl before hydrogenation. Group, isopropenylethylene group and 1-methyl-1-vinylethylene group, and units derived from butadiene are composed of 2-butene-1,4-diyl group and vinylethylene group. The ratio is not particularly limited. In a copolymer block composed of a mixture of isoprene and butadiene, the arrangement of isoprene units and butadiene units may be random, block, or tapered. And in the copolymer block which consists of a mixture of isoprene and butadiene, it is preferable that the molar ratio of isoprene unit: butadiene unit is 10: 90-90: 10 from the point of the improvement effect of rubber elasticity, 30: 70- More preferably, it is 70:30.

  In the polymer block B of the addition polymerization block copolymer (a), the thermoplastic polymer composition containing the addition polymerization block copolymer (a) has good heat resistance and weather resistance. Part or all of the carbon-carbon double bond is preferably hydrogenated (hereinafter sometimes referred to as “hydrogenation”). In this case, the hydrogenation rate of the polymer block B composed of the conjugated diene compound unit is preferably 60 mol% or more, more preferably 80 mol% or more, and further preferably 95 mol% or more. In particular, when the hydrogenation rate is close to 100 mol%, the reaction rate between the polymer block B and the cross-linking agent (d) is reduced when the thermoplastic polymer composition of the present invention is produced. Proportion of crosslinking introduced into the polymer block A forming the hard segment by promoting the reaction between at least one of the structural unit (I) and / or the functional group (II) of the block A and the crosslinking agent (d) Is preferable because of high.

Addition polymerized block copolymer (a) has at least one selected from structural units only polymer block A (I) and functional groups (II), the polymer block B and one of them The polymer block A is preferably crosslinked only at the portion of the polymer block A, but the polymer block A has at least one selected from the structural unit (I) and the functional group (II), and a polymer. The block B may have a functional group (II) and may be crosslinked by both the polymer block A and the polymer block B. In addition, in the addition polymerization block copolymer (a) crosslinked at both the polymer block A and the polymer block B, the crosslinking at the polymer block B is performed by the structural unit (I) and / or the functional group ( It may be crosslinked with other than II).

In the polymer block A having at least one structural unit (I) and functional groups (II), structural units (I) and / or functional groups (II) can also be present at the terminal of the polymer block A It may be present in the middle of the molecular chain of the polymer block A, or may be present both at the end of the polymer block A and in the middle of the molecular chain. Therefore, the polymer block A may be cross-linked at the end portion of the polymer block A, may be cross-linked in the middle of the molecular chain of the polymer block A, or the end of the polymer block A It may be cross-linked both in the middle of the molecular chain. The addition block copolymer (a) is a diblock copolymer (AB) having one polymer block A, and a triblock copolymer (BAB) having one polymer block A. ) or a hydrogenated product thereof, at least one selected from the structural units (I) and functional groups (II) is present in the one polymer block a, crosslinking at that portion is formed Yes.

When the addition polymerization block copolymer (a) is a triblock having two or more polymer blocks A, a tetrablock or more multiblock copolymer, or a hydrogenated product thereof, two or more it may be one in the structural unit (I) and at least one of the cross-linked with that portion be present structure selected from the functional groups (II) of the polymer block a, or two or more Or at least 1 sort (s) selected from structural unit (I) and functional group (II) may exist in all the polymer blocks A, respectively, and you may make it the structure bridge | crosslinked by the several polymer block A part.

Polymer block having at least one selected the polymer block A nor have any of the structural units (I) or functional group (II) A _0, the structural units (I) and functional groups (II) When A is represented by A ₁ and the polymer block B is represented by B, the above-mentioned diblock copolymer, triblock copolymer, or those in which the addition polymerization block copolymer (a) has only one polymer block A If it is the hydrogenated product, the addition polymerized block copolymer (a) is crosslinked with at least a polymer block a ₁ moiety, or a diblock copolymer represented by a 1 _-B, B It is a triblock copolymer represented by -A ₁ -B, or a hydrogenated product thereof. In this case, the addition polymerization block copolymer (a) is desirably crosslinked at the polymer block B portion from the viewpoint of improving heat resistance and rubber elasticity.

In addition, when the addition polymerization block copolymer (a) is a triblock or more multiblock copolymer having two or more polymer blocks A, for example, A ₁ − crosslinked at least in the block A ₁ portion. B-A ₀ , A ₁ -B-A ₁ , A ₁ -B-A ₀ -B, A ₁ -B-A ₁ -B, A ₁ -A ₀ -B-A ₀ -A ₁ , A _0- A ₁ -B-A ₁ -A ₀ , A ₁ -BA-A ₀ -BA ₁ , (A ₁ -B) _j (j represents an integer of 3 or more), (A ₁ -B) _k − A ₁ (k represents an integer of 2 or more), (B-A ₁ ) _m -B (m represents an integer of 2 or more), (A ₁ -B) _n -X (n is an integer of 2 or more, X represents a coupling agent residue), etc., and / or hydrogenated products thereof. It may be.

Among them, the addition polymerization block copolymer (a) is a hydrogenated product of a triblock copolymer represented by A ₁ -B-A ₁ cross-linked at least with a block A ₁ part, or A ₁ -A. _{0 -B-a 0} -A hydrogenated product of pentablock copolymer represented by _1, especially of triblock copolymers in which at least blocks _{a 1} moiety is represented by _a 1 _{-B-a 1} crosslinked A cross-linked product of a hydrogenated product is preferable because the effect of improving physical properties by introduction of cross-linking is high, and the resulting thermoplastic polymer composition has more excellent heat resistance.

  The degree of crosslinking in the addition polymerization block copolymer (a) can be adjusted according to the composition, use, etc. of the thermoplastic polymer composition of the present invention containing the addition polymerization block copolymer (a). Generally, when the addition polymerization block copolymer (a) after crosslinking is subjected to Soxhlet extraction treatment with cyclohexane for 10 hours, the mass ratio (gel fraction) of the gel remaining without being dissolved in cyclohexane is extracted. It is preferable that the degree of crosslinking is 80% or more with respect to the mass of the addition-polymerized block copolymer (a) after the previous crosslinking from the viewpoint of excellent heat resistance.

  The addition polymerization type block copolymer (a) constituting the thermoplastic polymer composition of the present invention has at least a conjugated diene compound polymer block part in that a crosslinking is formed at least in the polymer block A part. This is different from a cross-linked product of a block copolymer comprising a cross-linked aromatic vinyl compound polymer block and a conjugated diene compound polymer block. In the thermoplastic polymer composition of the present invention, as described above, the heat resistance is excellent by using the addition polymerization block copolymer (a) that is at least crosslinked at the polymer block A portion forming the hard segment. This makes it possible to provide a thermoplastic polymer composition having good rubber properties.

In the addition polymerization block copolymer (a), the number average molecular weight of the polymer block A is 2500 to 75000 as the state before crosslinking [that is, corresponding to the addition polymerization block copolymer (a ₀ )], preferably Is in the range of 5,000 to 50,000, the number average molecular weight of the polymer block B is in the range of 10,000 to 400,000, preferably in the range of 30,000 to 350,000, and the number average molecular weight of the entire addition polymerization block copolymer (a ₀ ). Is in the range of 12,500 to 2,000,000, preferably 50,000 to 1,000,000, from the viewpoint of the mechanical properties and molding processability of the resulting thermoplastic polymer composition. In addition, the number average molecular weight (Mn) as used in this specification says the value calculated | required from the standard polystyrene calibration curve by the gel permeation chromatography (GPC) method.

The above addition polymerization block copolymer (a ₀ ) used for the production of the thermoplastic polymer composition of the present invention is crosslinked with the structural unit (I) and / or the functional group (II) of the polymer block A. Except for the point that it is a non-addition polymerization block copolymer, the cross-linked addition polymerization block copolymer (a) described above constituting the thermoplastic polymer composition of the present invention and its contents (For example, the type and composition of the monomer constituting the block copolymer, the molecular weight, etc.).

The production method of the addition polymerization type block copolymer (a ₀ ) before crosslinking used for the production of the thermoplastic polymer composition of the present invention is not limited at all, and the structural unit (I) and the functional group (II) are added to the polymer block A. ) of long as the method can produce addition polymerized block copolymer (a ₀₎ having at least one, it may be prepared by employing any method. For example, the addition polymerization block copolymer (a ₀ ) can be produced by performing a known polymerization method such as an ionic polymerization method such as anionic polymerization or cationic polymerization, or a radical polymerization method. For example, the addition polymerization block copolymer (a ₀ ) having the structural unit (I) in the polymer block A is polymerized with n-hexane, cyclohexane or the like using an alkyl lithium compound as an initiator when an anionic polymerization method is used. In an organic solvent inert to the reaction, block copolymerization is achieved by sequentially polymerizing the alkylstyrene constituting the structural unit (I), the mixture of the alkylstyrene and vinyl aromatic compound constituting the structural unit (I), and the conjugated diene compound. A coalescence (that is, an unhydrogenated addition polymerization block copolymer (a ₀ )) is formed.

In addition, an addition polymerization block copolymer (a ₀ ) having a functional group (II) in the polymer block A is produced by applying a termination reaction, an initiation reaction, a copolymerization of a functional monomer, a polymer reaction, and the like. can do. For example, when an addition polymerization type block copolymer is synthesized using a bifunctional anionic polymerization initiator, oxirane, carbonyl group, thiocarbonyl group, acid anhydride, aldehyde group, thioaldehyde group, carbon Polymers by functionalizing compounds with acid ester groups, amide groups, sulfonic acid groups, sulfonic acid ester groups, amino groups, imino groups, nitrile groups, epoxy groups, sulfide groups, isocyanate groups, isothiocyanate groups, etc. An addition polymerization type block copolymer (a ₀ ) having a functional group (II) at the terminal of the block A (that is, an unhydrogenated addition polymerization type block copolymer (a ₀ )) can be produced. Furthermore, an addition polymerization type block copolymer (a ₀ ) having a functional group (II) in the middle of the molecular chain of the polymer block A is, for example, Macromolecules, Vol. 28, 8702 (1995). ).
The number of functional groups in the addition polymerized block copolymer _{(a 0)} (II) can be calculated using NMR, titration, and the like.

In addition, the addition polymerization block copolymer (a ₀ ) having at least one of the structural unit (I) and the functional group (II) in the polymer block A can be further hydrogenated as necessary. can do. Such a hydrogenation reaction is carried out, for example, by using the block copolymer in a saturated hydrocarbon solvent such as cyclohexane, Raney nickel; a metal such as Pt, Pd, Ru, Rh, or Ni as a support such as carbon, alumina, or diatomaceous earth. A heterogeneous catalyst supported on a Ziegler catalyst comprising a combination of an organometallic compound comprising a Group 8-10 metal such as nickel or cobalt and an organoaluminum compound or organolithium compound such as triethylaluminum or triisobutylaluminum Presence of hydrogenation catalysts such as metallocene catalysts composed of combinations of bis (cyclopentadienyl) compounds of transition metals such as titanium, zirconium and hafnium and organometallic compounds such as lithium, sodium, potassium, aluminum, zinc or magnesium; Under normal reaction temperature As a hydrogenated product of the block copolymer (that is, a hydrogenated addition polymerization block copolymer). Combined (a ₀ )) can be obtained.

The addition polymerization block copolymer (a ₁ ) constituting the thermoplastic polymer composition of the present invention comprises at least one polymer block A ′ mainly comprising an aromatic vinyl compound unit, and a conjugated diene compound unit. It has one or more polymer blocks B ′ as a main component.

Examples of the aromatic vinyl compound unit constituting the polymer block A ′ of the addition polymerization block copolymer (a ₁ ) include aromatic vinyl compound units other than the structural unit (I), such as styrene, α-methylstyrene, β - methyl styrene, mono-fluorostyrene, difluoro styrene, monochlorostyrene styrene, dichloro styrene, methoxy styrene, vinyl naphthalene, vinyl anthracene, indene, it may be mentioned a unit made of Asetonafuchiren, these one or more unit Can have. Among these, a structural unit based on styrene is preferable.

  The polymer block A ′ may have a small amount of structural units based on other polymerizable monomers as necessary, together with the structural units based on the aromatic vinyl compound. In this case, the proportion of structural units based on other polymerizable monomers is preferably 30% by mass or less, more preferably 10% by mass or less based on the total mass of the polymer block A ′. Examples of other polymerizable monomers in that case include methacrylic acid esters, acrylic acid esters, 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. The bonding form of these other polymerizable monomers may be any form such as random, block, or tapered.

Next, in the addition polymerization block copolymer (a ₁ ), the conjugated diene compound constituting the polymer block B ′ is isoprene, butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1, 3-pentadiene and the like can be mentioned. The polymer block B ′ may be composed of only one of these conjugated diene compounds or may be composed of two or more kinds, among which butadiene, isoprene, or a mixture of butadiene and isoprene. Is preferred. When the polymer block B ′ has a structural unit derived from two or more kinds of conjugated diene compounds, the bonding form thereof is random, tapered, block-like, or a combination of two or more thereof. be able to.

In the above-mentioned polyisoprene block that can be a constituent block of the polymer block B ′, the unit derived from isoprene is a 2-methyl-2-butene-1,4-diyl group [—CH ₂ —C (CH ₃ ) ═CH. —CH ₂ —; 1,4-bonded isoprene unit], isopropenylethylene group [—CH (C (CH ₃ ) ═CH ₂ ) —CH ₂ —; 3,4-bonded isoprene unit] and 1-methyl 1-vinylethylene group [—C (CH ₃ ) (CH═CH ₂ ) —CH ₂ —; 1,2-bonded isoprene unit], consisting of at least one group selected from the group consisting of The ratio of the unit is not particularly limited.

In the above-mentioned polybutadiene block which can be a building block of the polymer block B ′, 70 to 10 mol%, particularly 65 to 20 mol% of the butadiene unit is a 2-butene-1,4-diyl group (—CH ₂ —CH═ CH—CH ₂ —; 1,4-bonded butadiene unit), and 30 to 80 mol%, particularly 35 to 60 mol% are vinylethylene groups [—CH (CH═CH) —CH ₂ —; 1,2- Bonded butadiene units] are preferred. When the 1,4-bond amount in the polybutadiene block is in the above-described range of 70 to 10 mol%, rubber elasticity is improved.

  In the above-described copolymer block composed of a mixture of isoprene and butadiene which can be a building block of the polymer block B ′, the unit derived from isoprene is 2-methyl-2-butene-1,4- before hydrogenation. It consists of diyl group, isopropenylethylene group and 1-methyl-1-vinylethylene group, and the unit derived from butadiene consists of 2-butene-1,4-diyl group and vinylethylene group. The ratio is not particularly limited. In a copolymer block composed of a mixture of isoprene and butadiene, the arrangement of isoprene units and butadiene units may be random, block, or tapered. And in the copolymer block which consists of a mixture of isoprene and butadiene, it is preferable that the molar ratio of isoprene unit: butadiene unit is 10: 90-90: 10 from the point of the improvement effect of rubber elasticity, 30: 70- More preferably, it is 70:30.

When the polymer block A ′ is represented by A ′ and the polymer block B ′ is represented by B ′, the addition polymerization block copolymer (a ₁ ) is a diblock copolymer represented by A′-B ′, A Triblock copolymer represented by '-B'-A', B'-A'-B ', A'-B'-A'-B', A'-B'-A'-B'- A ', (A'-B') _p (p represents an integer of 3 or more), (A'-B ') _q- A' (q represents an integer of 2 or more), (B'-A ' ) _R -B '(r represents an integer of 2 or more), (A'-B') _n -X (n represents an integer of 2 or more, X represents a coupling agent residue), and the like. And any of them may be used. Among them, the addition polymerization block copolymer (a ₁ ) is particularly a triblock copolymer represented by A′-B′-A ′, which is highly effective in improving the physical properties and is obtained as a thermoplastic. It is preferable because the heat resistance of the polymer composition becomes more excellent.

In the addition polymerization block copolymer (a ₁ ), the number average molecular weight of the polymer block A ′ is 2500 to 75000, preferably 5000 to 50000, and the number average molecular weight of the polymer block B ′ is 10,000 to 10000. The heat obtained is in the range of 400,000, preferably in the range of 30000-350,000, and the number average molecular weight of the whole addition polymerization block copolymer (a ₁ ) is in the range of 12500-2000000, preferably in the range of 50000-1000000. It is suitable from the viewpoints of mechanical properties and moldability of the plastic polymer composition. In addition, the number average molecular weight (Mn) as used in this specification says the value calculated | required from the standard polystyrene calibration curve by the gel permeation chromatography (GPC) method.

The production method of the addition polymerization block copolymer (a ₁ ) is not limited at all, and can be produced by performing a known polymerization method such as an ionic polymerization method such as anionic polymerization or cationic polymerization, or a radical polymerization method. For example, in the case of anionic polymerization, an addition polymerization system is obtained by sequentially polymerizing a vinyl aromatic compound and a conjugated diene compound in an organic solvent inert to a polymerization reaction such as n-hexane or cyclohexane using an alkyl lithium compound as an initiator. A block copolymer (a ₁ ) is formed.

The addition polymerization block copolymer (a ₀ ) and the addition polymerization block copolymer (a ₁ ) are both essential components of the thermoplastic polymer composition of the present invention. By including the addition-polymerized block copolymer (a ₁ ), which is an unhydrogenated product, as a constituent component, the thermoplastic polymer composition of the present invention is imparted with tear resistance and oil resistance, although the reason is not clear. Is done. The mixing ratio of the two is not strictly limited, but is usually added from the viewpoint of high temperature strain recovery (heat resistance), flexibility, molding processability, etc. of the obtained thermoplastic polymer composition. The polymerization block copolymer (a ₀ ): addition polymerization block copolymer (a ₁ ) is preferably in the range of 10:90 to 95: 5, and preferably 30:70 to 90:10. The range is more preferable, and the range of 40:60 to 85:15 is more preferable.

Examples of the olefin resin (b) constituting the thermoplastic polymer composition of the present invention include an ethylene polymer, a propylene polymer, poly (1-butene), poly (4-methyl-1-pentene), and the like. 1 type, or 2 or more types of these can be used.
Examples of the ethylene polymer include ethylene homopolymers such as high density polyethylene, medium density polyethylene, and low density polyethylene, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-heptene. Copolymer, ethylene-1-octene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer , Ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, and the like. Examples of the propylene polymer include propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer, propylene-1-butene copolymer, propylene-ethylene-1-butene copolymer, propylene. Examples include -4-methyl-1-pentene copolymer. Among these, from the viewpoint of moldability, ethylene polymers such as high density polyethylene, medium density polyethylene and / or low density polyethylene; propylene homopolymer, ethylene-propylene random copolymer and / or ethylene-propylene block A propylene polymer such as a copolymer is preferred, and a propylene polymer is more preferred.

The blending amount of the olefin resin (b) is 100 parts by mass of the total amount of the addition polymerization block copolymer (a) and the addition polymerization block copolymer (a ₁ ) ((a) + (a ₁ )). On the other hand, it is necessary to be in the range of 10 to 300 parts by mass, preferably in the range of 15 to 200 parts by mass, and more preferably in the range of 20 to 100 parts by mass. The blending amount of the olefin resin (b) with respect to 100 parts by mass of the total amount of the addition polymerization block copolymer (a) and the addition polymerization block copolymer (a ₁ ) ((a) + (a ₁ )) is 10 If it is less than part by mass, the molding processability of the resulting thermoplastic polymer composition will be poor, while if it exceeds 300 parts by mass, the flexibility and rubber elasticity of the resulting thermoplastic polymer composition will be poor.

In the thermoplastic polymer composition of the present invention, the rubber softener (c), which is a component further contained as necessary, includes petroleum softeners such as paraffinic and naphthenic process oils; liquid paraffin; Examples include vegetable oil-based softeners such as peanut oil and rosin; synthetic softeners such as ethylene-α-olefin oligomers, liquid polybutene, and low molecular weight polybutadiene. The rubber softener (c) is preferably a softener having a kinematic viscosity of 20 to 800 mm ² / s at 40 ° C., particularly a paraffinic oil. These rubber softeners (c) can be used alone or in combination of two or more. Examples of the rubber softener (c) that can be suitably used in the present invention include paraffinic process oils in the product name “Diana Process Oil” series marketed by Idemitsu Kosan Co., Ltd.

When the rubber softener (c) is further contained, the blending amount is the total amount of the addition polymerization block copolymer (a) and the addition polymerization block copolymer (a ₁ ) ((a) + (a ₁₎₎ in the range below 300 parts by weight per 100 parts by weight, it is preferably in the range of 30 to 250 parts by weight, and more preferably in the range of 50 to 200 parts by weight. The blending amount of the rubber softener (c) is 100 parts by mass of the total amount of the addition polymerization block copolymer (a) and the addition polymerization block copolymer (a ₁ ) ((a) + (a ₁ )). On the other hand, if it exceeds 300 parts by mass, the mechanical properties of the resulting thermoplastic polymer composition will be reduced, and the rubber softener (c) bleed out from the molded product obtained from such thermoplastic polymer composition. Becomes remarkable and is not preferable.

  As the cross-linking agent (d), it reacts with a cross-linking agent that acts on the structural unit (I) present in the polymer block A to form a cross-link [hereinafter referred to as cross-linking agent (dI)] or a functional group (II). Thus, a cross-linking agent (d) having a reactive group that forms a cross-linkage [hereinafter referred to as cross-linking agent (dII)] is used.

As the crosslinking agent (dI), it acts on the structural unit (I) present in the polymer block A of the addition polymerization block copolymer (a ₀ ) during the dynamic crosslinking treatment under melting conditions, Any crosslinking agent may be used as long as the polymer block A can be crosslinked at a portion. An appropriate crosslinking agent (dI) can be selected in consideration of reactivity and the like according to the processing conditions (for example, processing temperature and processing time) at the time of such dynamic crosslinking treatment, and among them, a bismaleimide compound One or more organic peroxides are preferably used as the crosslinking agent (dI).

  As the bismaleimide compound, any bismaleimide compound can be used as long as it can cause crosslinking at the alkyl group moiety and carbon-carbon double bond moiety bonded to the benzene ring. For example, N, N′-m-phenylene Bismaleimide, N, N′-p-phenylenebismaleimide, N, N′-p-phenylene (1-methyl) bismaleimide, N, N′-2,7-naphthene bismaleimide, N, N′-m- Examples thereof include naphthene bismaleimide, N, N′-m-phenylene-4-methyl bismaleimide, N, N′-m-phenylene (4-ethyl) bismaleimide, and toluylene bismaleimide. These can be used individually by 1 type or in mixture of 2 or more types. Of these, N, N′-m-phenylenebismaleimide is preferable from the viewpoint of reactivity.

  Examples of the organic peroxide include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4 Bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, t-butyl group Such as mill peroxide. . These can be used individually by 1 type or in mixture of 2 or more types. Of these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and dicumyl peroxide are preferably used from the viewpoint of reactivity.

When an addition polymerization block copolymer (a ₀ ) is used in which all of the carbon-carbon double bonds of the polymer block B are hydrogenated, and a bismaleimide compound is used as the crosslinking agent (dI), Addition in which the polymer block B in the polymer block copolymer (a ₀ ) is not crosslinked but is selectively crosslinked only in the structural unit (I) portion existing in the polymer block A, that is, only in the hard segment portion. A polymerization block copolymer (a) is formed. Further, when an addition polymerization block copolymer (a ₀ ) having a carbon-carbon double bond in the polymer block B is used and a bismaleimide compound is used as the crosslinking agent (dI), a structural unit ( An addition-polymerized block copolymer (a) crosslinked with both the polymer block A portion and the polymer block B portion having I) is formed.

Further, when an organic peroxide is used as the crosslinking agent (dI), a carbon-carbon double bond may or may not be present in the polymer block B in the addition polymerization block copolymer (a ₀ ). Then, an addition polymerization type block copolymer (a) crosslinked with both the polymer block A portion and the polymer block B portion having the structural unit (I) is formed.

As the crosslinking agent (dII) used corresponding to the type of the functional group (II), the functional group (II) is a hydroxyl group (—OH), —SH, —NH ₂ , —NHR, —CONH ₂ , —CONHR, In the case of a functional group having an active hydrogen atom such as —CONH—, —SO ₃ H, —SO ₂ H, —SOH, etc., a monomer having an isocyanate group, an isocyanate adduct (aliphatic, aliphatic having a cyclic group) , Aromatic and biphenyl isocyanate adducts, etc.), isocyanate compounds such as blocked isocyanates can be used, and polyisocyanate compounds having 2 or more, especially 3 or more isocyanate groups, such as hexamethylene diisocyanate, are used as raw materials. A polyisocyanate having an isocyanurate bond is preferably used. At that time, in order to increase the reactivity between the functional group (II) and the isocyanate compound, a tin-based catalyst, a titanium-based catalyst, or the like may be used in combination.

  When the functional group (II) is a hydroxyl group, in addition to the isocyanate compound described above, for example, a polycarboxylic acid anhydride such as a polyepoxy compound, maleic anhydride, pyromellitic anhydride or the like is used as a crosslinking agent (dII). Can be used as

  When the functional group (II) is a carboxyl group, for example, a polyepoxy compound, polyamine or the like can be used as the crosslinking agent (dII). Moreover, when functional group (II) is an epoxy group, polycarboxylic acid, polyamine, etc. can be used as a crosslinking agent (dII), for example.

The use amount of the crosslinking agent (d) [the total use amount of both when the crosslinking agent (dI) and the crosslinking agent (dII) are used in combination] is the same as the addition polymerization block copolymer (a ₀ ) and the addition polymerization block in the range of 0.01 to 20 parts by mass relative to the total 100 parts by weight of polymer _{(a 1),} and more preferably in the range of 0.01 to 10 parts by weight. When the amount of the crosslinking agent (d) used is less than 0.01 parts by mass, sufficient crosslinking cannot be formed. On the other hand, when the amount exceeds 20 parts by mass, the softener for rubber (c) Bleed out, deterioration of mechanical properties, etc. occur.

  Moreover, when the usage-amount of crosslinking agent (dII) is seen from the equivalent of functional group (II), the usage-amount of crosslinking agent (dII) is the functional group (II) [polymer block B is also functional in the polymer block A. In the case of having the group (II), the ratio is preferably from 0.1 to 100 equivalents, more preferably from 0.1 to 10 equivalents per 1 equivalent.

  In addition to the above-mentioned crosslinking agent (d), if necessary, disulfide compounds such as benzothiazyl disulfide and tetramethylthiuram disulfide, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, etc. The crosslinking aid (e) may be used.

The thermoplastic polymer composition of the present invention can contain other polymers as long as the effects of the present invention are not impaired. Examples of other polymers that can be contained include polyphenylene ether resins; polyamide 6, polyamide 6 · 6, polyamide 6 · 10, polyamide 11, polyamide 12, polyamide 6 · 12, polyhexamethylenediamine terephthalamide, polyhexamethylene Polyamide resins such as diamine isophthalamide and xylene group-containing polyamide; Polyester resins such as polyethylene terephthalate and polybutylene terephthalate; Acrylic resins such as polymethyl acrylate and polymethyl methacrylate; Polyoxymethylene homopolymer, Polyoxymethylene Polyoxymethylene resins such as copolymers; Styrene resins such as styrene homopolymers, acrylonitrile / styrene resins, acrylonitrile / butadiene / styrene resins; Bonate resin; ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM); styrene / butadiene copolymer rubber, styrene / isoprene copolymer rubber or hydrogenated product thereof or modification thereof Natural rubber; synthetic isoprene rubber, liquid polyisoprene rubber and its hydrogenated product or modified product; chloroprene rubber; acrylic rubber; butyl rubber; acrylonitrile-butadiene rubber; epichlorohydrin rubber; silicone rubber; Urethane rubber; polyurethane elastomer; polyamide elastomer; polyester elastomer; soft vinyl chloride resin.
In addition, when other polymers are contained, the content thereof is preferably within a range in which the mechanical properties of the obtained thermoplastic polymer composition are not impaired, and the addition polymerization block copolymer (a ₀ ) and addition polymerization are added. preferably not more than 200 parts by mass of the total amount 100 parts by weight of the system the block copolymer (a _1).

  Moreover, the thermoplastic polymer composition of this invention can contain an inorganic filler as needed. Examples of the inorganic filler include calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate, mica, glass fiber, whisker, carbon fiber, magnesium carbonate, glass powder, metal powder, kaolin, graphite, two Examples thereof include molybdenum sulfide and zinc oxide, and one or more of these can be contained. When blending an inorganic filler, the content is preferably in a range where the effects of the present invention are not impaired, and is generally 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic polymer composition. Preferably there is.

  Furthermore, the thermoplastic polymer composition of the present invention may be a reinforcing resin such as α-methylstyrene resin, a flame retardant, a lubricant, a light stabilizer, a pigment, a heat stabilizer, an antifogging agent, an antistatic agent, if necessary. 1 type (s) or 2 or more types, such as a silicone oil, an antiblocking agent, a ultraviolet absorber, a heat stabilizer, antioxidant, and a coloring agent, can be contained. Among these, examples of the antioxidant include hindered phenols, hindered amines, phosphoruss, and sulfurs.

The thermoplastic polymer composition of the present invention is prepared by previously producing an addition polymerization block copolymer (a) crosslinked at least in the polymer block A portion, and with respect to the crosslinked addition polymerization block copolymer (a). The addition polymerization block copolymer (a ₁ ), the olefin resin (b), the rubber softener (c), if necessary, and other optional additives are mixed and heated and kneaded. Also good.
However, the thermoplastic polymer composition of the present invention has one or more polymer blocks A mainly composed of aromatic vinyl compound units and one or more polymer blocks B mainly composed of conjugated diene compound units, And at least one addition polymerization block copolymer (a ₀ ) selected from a block copolymer having at least one of structural unit (I) and functional group (II) in the polymer block A and a hydrogenated product thereof. (Addition polymerization block copolymer before crosslinking), addition polymerization block copolymer (a ₁ ), olefin resin (b), rubber softener (c) if necessary, and other It is preferable to prepare a mixture obtained by mixing optional components and mixing the mixture with the crosslinking agent (d) and / or the crosslinking assistant (e) and dynamically crosslinking the mixture under melting conditions. By adopting such a method, an addition polymerization block copolymer in which the respective components are uniformly mixed and is crosslinked with at least one part of the structural unit (I) and the functional group (II) in the polymer block A is used. The thermoplastic polymer composition of the present invention containing the coalescence (a) can be produced smoothly.
As used herein, “dynamic crosslinking under melting conditions” means that the mixture in a molten state is crosslinked while being subjected to shear stress by kneading.

As a method for producing the thermoplastic polymer composition of the present invention, a method used for producing a normal resin composition or polymer composition can be employed. That is, using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a heating roll, various kneaders, the addition polymerization block copolymer (a ₀ ) (addition polymerization block copolymer before crosslinking) A polymer), an addition polymerization block copolymer (a ₁ ), a polyolefin resin (b), a rubber softener (c), if necessary, and other optional components, and a crosslinking agent ( The mixture obtained by mixing d) and / or the crosslinking aid (e) can be produced by a dynamic crosslinking method under melting conditions. The temperature at this time is preferably in the range of 150 to 250 ° C.

  The thermoplastic polymer composition of the present invention is, for example, a sheet, a film, a tube, a hollow molded body, using a conventionally known method such as extrusion molding, injection molding, hollow molding, compression molding, press molding, calender molding, It can be formed into a molded product and other various molded products. It can also be compounded with other members (for example, polymer materials such as polyethylene, polypropylene, olefin elastomer, ABS resin, polyamide, metal, wood, cloth, etc.) by a two-color molding method.

  The thermoplastic polymer composition of the present invention is an automotive interior / exterior material part, a tube in an engine room, a hose, a wire covering material used for wiring such as electrical / electronic equipment parts, a power cord, a plug, an adapter, etc. Covering material for electrical insulation parts; flooring for flooring of houses, condominiums, etc., floor sheets for protection, tent sheets, etc .; door materials, window frame sealing materials, blinders blinders, etc. It can be effectively used as a building material; a laminated structure used as an interior material for vehicles;

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these Examples. The thermoplastic polymer compositions obtained in the following examples and comparative examples were evaluated as follows.

[1] Hardness (JIS-A)
The thermoplastic polymer compositions obtained in the examples or comparative examples were injection molded at 230 ° C. to obtain a sheet having a length of 110 mm × width of 110 mm × thickness of 2 mm. Six sheets were stacked to a thickness of 12 mm, and the A hardness was measured according to JIS K 6253.

[2] Compression set A sheet having a length of 150 mm, a width of 150 mm, and a thickness of 2 mm was obtained by injection molding of the thermoplastic elastomer composition obtained in the examples or comparative examples at 230 ° C. Six sheets of this sheet are stacked and placed in a frame of length 150 mm × width 150 mm, pressed at 200 ° C. for 5 minutes, then a test piece is obtained according to JIS K 6262, and the amount of compressive deformation is 25 under the temperature condition of 120 ° C. % Compression set after standing for 22 hours. The smaller this value, the better the strain recovery at high temperatures.

[3] Tear Strength The thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to obtain a sheet having a length of 110 mm × width of 110 mm × thickness of 2 mm. Using this sheet, an angle-type test piece without cut was prepared in accordance with JIS K 6252, and a tear test was performed at 23 ° C. and a moving speed of the test gripper of 500 mm / min to measure the tear strength.

[4] Oil resistance The thermoplastic polymer compositions obtained in Examples and Comparative Examples were injection molded at 230 ° C. to obtain a sheet having a length of 110 mm × width of 110 mm × thickness of 2 mm. Using this sheet, a test piece having a length of 40 mm, a width of 20 mm and a thickness of 2 mm was prepared, and immersed in rubber processing oil (Sunoco Rubber Processing Oil IRM903 manufactured by Nippon San Oil Co., Ltd.) at 100 ° C. for 70 hours. The mass change rate of the test piece was measured according to the equation and used as an index of oil resistance.
Mass change rate (%) = 100 × (A ₁ −A ₀ ) / A ₀
A ₀ : Mass of the test piece before the test (g)
A ₁ : Mass of the test piece after the test (g)

Further, the addition polymerization block copolymer (a ₀ ), the addition polymerization block copolymer (a ₁ ), the polyolefin resin (b), the rubber softening agent (c) used in the following examples or comparative examples, The contents of the crosslinking agent (d) and the crosslinking assistant (e) are as follows.

Addition polymerized block copolymer _(a 0)
Reference example 1
In a pressure vessel with a stirrer, 30 kg of cyclohexane, 20 ml of sec-butyllithium (1.3 M cyclohexane solution) and 600 g of a mixture of p-methylstyrene / styrene = 50/50 (mass ratio) are added, and 120 ° C. is added at 120 ° C. Then, 2800 g of a mixture mixed with isoprene / butadiene = 50/50 (mass ratio) was added, and polymerization was performed at the same temperature for 120 minutes. Thereafter, 600 g of a mixture mixed with p-methylstyrene / styrene = 50/50 (mass ratio) was further added and polymerized at the same temperature for 120 minutes to obtain poly (p-methylstyrene / styrene) -poly (isoprene / butadiene). A reaction mixture containing a poly (p-methylstyrene / styrene) triblock copolymer was obtained. A hydrogenation catalyst prepared by adding 200 g of triisopropylaluminum (20% by mass, cyclohexane solution) to 30 g of nickel octylate (64% by mass, cyclohexane solution) is added to the reaction mixture containing the triblock copolymer, The hydrogenation reaction was performed at 80 ° C. and a hydrogen pressure of 1 MPa for 5 hours, and the poly (p-methylstyrene / styrene) -poly (isoprene / butadiene) -poly (p-methylstyrene / styrene) triblock copolymer described above was used. A hydrogenated product [hereinafter referred to as addition polymerization block copolymer (a ₀ -1)] was obtained. The number average molecular weight of the resulting addition polymerization block copolymer (a ₀ -1) is 260000; the proportion of poly (p-methylstyrene) block is 35% by mass; the hydrogenation rate of the poly (isoprene / butadiene) block is 99%.

Reference example 2
Add 30 kg of cyclohexane, 20 ml of sec-butyllithium (1.3 M cyclohexane solution) and 700 g of p-methylstyrene in a pressure-resistant vessel equipped with a stirrer, polymerize at 50 ° C. for 120 minutes, then add 63 g of tetrahydrofuran and 2600 g of butadiene for 120 minutes. Polymerized. Thereafter, 700 g of p-methylstyrene was further added and polymerized for 120 minutes, methanol was added to terminate the polymerization, and a poly (p-methylstyrene) -polybutadiene-poly (p-methylstyrene) triblock copolymer was obtained. A reaction mixture containing was obtained. A hydrogenation catalyst separately prepared from nickel octylate and triisopropylaluminum was added to the resulting reaction mixture, and a hydrogenation reaction was performed in a hydrogen atmosphere at 80 ° C. and 1 MPa for 5 hours to obtain poly (p-methylstyrene). -A hydrogenated product of polybutadiene-poly (p-methylstyrene) triblock copolymer [hereinafter referred to as a block copolymer (a ₀ -2)] was obtained. The number average molecular weight (Mn) of the obtained block copolymer (a ₀ -2) was 260000; the proportion of the poly (p-methylstyrene) block was 35% by mass; the hydrogenation rate of the polybutadiene block was 99% by mol. It was.

Reference example 3
In a pressure vessel equipped with a stirrer, 30 kg of cyclohexane, 64 g of tetrahydrofuran, 3300 g of butadiene and 58 g of dilithiopolybutadiene as a bifunctional initiator were added and polymerized at 50 ° C. for 120 minutes, and then 1440 g of styrene was added and polymerized at 50 ° C. for 60 minutes. . Next, 12 g of ethylene oxide was added, methanol was added to stop the polymerization, and a reaction mixture containing a polystyrene-polybutadiene-polystyrene triblock copolymer having hydroxyl groups at both ends was obtained. A hydrogenation catalyst prepared separately from nickel octylate and triisopropylaluminum was added to the resulting reaction mixture, and a hydrogenation reaction was carried out in a hydrogen atmosphere at 80 ° C. and 1 MPa for 5 hours. - polybutadiene - polystyrene triblock copolymer hydrogenation product of the following, a block copolymer (a 0 _-3) referred to as this] was obtained. Mn of the obtained block copolymer (a ₀ -3) is 200000; hydroxyl group content = 1.7 per molecule; ratio of polystyrene block is 30% by mass; hydrogenation rate of polybutadiene block is 99 mol% there were.

Addition polymerization block copolymer (a ₁ )
Reference example 4
Add 30 kg of cyclohexane, 80 ml of sec-butyllithium (1.3 M cyclohexane solution) and 860 g of styrene in a pressure-resistant vessel equipped with a stirrer, polymerize at 50 ° C. for 30 minutes, then add 50 g of tetramethylethylenediamine, and then add 6.8 kg of isoprene. And polymerized for 30 minutes. Thereafter, 860 g of styrene was further added for polymerization for 30 minutes, methanol was added to stop the polymerization, and a reaction mixture containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. [Hereinafter, this is referred to as a block copolymer (a ₁ -1)]. Mn of the obtained block copolymer (a ₁ -1) is 136000; the proportion of polystyrene block is 20% by mass, and the total of 1,2-bond amount and 3,4-bond amount of the polyisoprene block is 65 mol%. Met.

Reference Example 5
Add 30 kg of cyclohexane, 80 ml of sec-butyllithium (1.3M cyclohexane solution) and 860 g of styrene in a pressure vessel equipped with a stirrer, polymerize at 50 ° C. for 30 minutes, then add 170 g of tetrahydrofuran, and then add 6.8 kg of isoprene. For 30 minutes. Thereafter, 860 g of styrene was further added for polymerization for 30 minutes, methanol was added to stop the polymerization, and a reaction mixture containing a polystyrene-polyisoprene-polystyrene triblock copolymer was obtained. [Hereinafter, referred to as block copolymer _(a 1 -2)] was obtained. Mn of the obtained block copolymer (a _1-2 ) is 132000; the proportion of polystyrene block is 20% by mass, and the total of 1,2-bond amount and 3,4-bond amount of the polyisoprene block is 55 mol%. Met.

Reference Example 6
Add 30 kg of cyclohexane, 80 ml of sec-butyllithium (1.3M cyclohexane solution) and 860 g of styrene in a pressure-resistant vessel equipped with a stirrer, polymerize at 50 ° C. for 30 minutes, then add 170 g of tetrahydrofuran, then add 6.8 kg of butadiene and add 30 Polymerized for minutes. Thereafter, 860 g of styrene was further added for polymerization for 30 minutes, methanol was added to stop the polymerization, and a reaction mixture containing a polystyrene-polybutadiene-polystyrene triblock copolymer was obtained. [Hereinafter, referred to as block copolymer _(a 1 -3)] was obtained. The resulting block copolymer number average molecular weight of _(a 1 -3) _(Mn) is 132000; the proportion of the polystyrene blocks was 20 mass%, 1,2-bond content of the polybutadiene blocks was 55 mol%.

Olefin resin (b):
(B) -1: “Grand Polypro B101” (trade name) manufactured by Sumitomo Mitsui Polyolefin Co., Ltd., [polypropylene (homopolymer), MFR: 1 g / 10 min (230 ° C., 21 N)]
Rubber softener (c):
(C) -1: Idemitsu Kosan Co., Ltd., trade name “PW-380”
[Paraffinic process oil, kinematic viscosity: 381.6 mm ² / s (40 ° C.)]
Crosslinking agent (d):
(D) -1: Product name “BALNOCK PM” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
[N, N′-m-phenylene bismaleimide]
(D) -2: Product name “Perhexa 25B-40” manufactured by NOF Corporation
[2,5-Dimethyl-2,5-di (t-butylperoxy) hexane]
(D) -3: Nippon Polyurethane Industry Co., Ltd., trade name “Coronate HX”
[Isocyanurate bond made from hexamethylene diisocyanate
Polyisocyanate, number of isocyanate groups = 3 / molecule]
Crosslinking aid (e):
(E) -1: Nippon Kasei Co., Ltd. product name "TAIC WH-60"
(Triallyl isocyanurate)
(E) -2: Product name “Noxeller DM-P” manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
(Di-2-benzothiazyl disulfide)

<Examples 1-7, Comparative Examples 1-3>
Block copolymers (a ₀ -1) to (a ₀ -3) obtained in Reference Examples 1 to 3 and addition polymerization block copolymers (a ₁ -1) obtained in Reference Examples 4 to 6 _(a 1 -3), olefin resin (b), rubber softener (c), a crosslinking agent (d) and cross-linking aid (e), in the formulation shown in Table 1 and Table 2 (all parts by weight) After premixing, using a twin screw extruder (manufactured by Technobel Co., Ltd.), melt kneading at a temperature of 160 to 200 ° C. and a screw rotation speed of 200 rpm, extruding the strand, and then cutting the strand with a pelletizer to form a pellet A thermoplastic polymer composition was obtained. Each physical property evaluation was performed by the above-mentioned method using the pellet of the obtained thermoplastic polymer composition. The results are shown in Tables 1 and 2.

  From the results of Tables 1 and 2, the thermoplastic polymer compositions obtained in each example have a low strain at 120 ° C. compared to the comparative example, so that strain recovery at high temperatures (heat resistance) is achieved. It is excellent in oil resistance because of its excellent tear strength and small change in weight after immersion in rubber processing oil.

The thermoplastic polymer composition of the present invention is excellent in flexibility, strain recovery at high temperatures (heat resistance), and excellent in moldability, tear resistance and oil resistance. Taking advantage of these properties, the thermoplastic polymer composition of the present invention is an automotive interior / exterior material part, a tube in an engine room, a hose, a wire covering material used for wiring of electrical / electronic equipment parts, Cover materials for electrical insulation parts such as power cords, plugs, adapters, etc .; floor sheets for flooring in houses and condominiums, floor sheets for protection, floor sheets in buildings, tent sheets, etc .; door materials, sealing materials for window frames, It can be used effectively as a building material such as a blindfold of a belander; a laminated structure used as an interior material for a vehicle, or the like.

Claims (7)

A block having at least one polymer block A mainly composed of an aromatic vinyl compound unit and at least one polymer block B mainly composed of a conjugated diene compound unit, wherein at least the polymer block A part is crosslinked. An addition polymerization block copolymer (a) composed of a hydrogenated copolymer and at least one polymer block A ′ mainly composed of an aromatic vinyl compound unit and a polymer composed mainly of a conjugated diene compound unit; For 100 parts by mass of the total amount ((a) + (a ₁ )) of the addition polymerization block copolymer (a ₁ ) composed of a block copolymer having one or more combined blocks B ′, an olefin resin (b ) In the range of 10 to 300 parts by mass ,
The addition polymerization block copolymer (a) comprises a structural unit (I) and a functional group (II) based on an alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring in the polymer block A. And at least the polymer block A moiety is crosslinked by the structural unit (I) and / or the functional group (II),
Based on the total mass of the polymer block B in the polymer block B, the structural unit composed of another polymerizable monomer composed of the conjugated diene compound constitutes the addition polymerization block copolymer (a). A thermoplastic polymer composition having a mass% or less and a hydrogenation rate of carbon-carbon double bonds in the polymer block B of 95 mol% or more , wherein the functional group (II) is a hydroxyl group ( _{-OH), - SH, -NH 2} , -NHR, -CONH 2, -CONHR, -CONH -, - SO 3 H, functionality, carboxyl group having an active hydrogen atom selected from -SO ₂ H and -SOH And a thermoplastic polymer composition which is a functional group selected from epoxy groups. A block having at least one polymer block A mainly composed of an aromatic vinyl compound unit and at least one polymer block B mainly composed of a conjugated diene compound unit, wherein at least the polymer block A part is crosslinked. An addition polymerization block copolymer (a) composed of a hydrogenated copolymer and at least one polymer block A ′ mainly composed of an aromatic vinyl compound unit and a polymer composed mainly of a conjugated diene compound unit; For 100 parts by mass of the total amount ((a) + (a ₁ )) of the addition polymerization block copolymer (a ₁ ) composed of a block copolymer having one or more combined blocks B ′, an olefin resin (b ) In the range of 10 to 300 parts by mass, and the rubber softener (c) in the range of 300 parts by mass or less ,
The addition polymerization block copolymer (a) comprises a structural unit (I) and a functional group (II) based on an alkylstyrene in which at least one alkyl group having 1 to 8 carbon atoms is bonded to a benzene ring in the polymer block A. And at least the polymer block A moiety is crosslinked by the structural unit (I) and / or the functional group (II),
Based on the total mass of the polymer block B in the polymer block B, the structural unit composed of another polymerizable monomer composed of the conjugated diene compound constitutes the addition polymerization block copolymer (a). A thermoplastic polymer composition having a mass% or less and a hydrogenation rate of carbon-carbon double bonds in the polymer block B of 95 mol% or more , wherein the functional group (II) is a hydroxyl group ( _{-OH), - SH, -NH 2} , -NHR, -CONH 2, -CONHR, -CONH -, - SO 3 H, functionality, carboxyl group having an active hydrogen atom selected from -SO ₂ H and -SOH And a thermoplastic polymer composition which is a functional group selected from epoxy groups .   The thermoplastic polymer composition according to claim 1 or 2, wherein the structural unit (I) is a structural unit based on p-methylstyrene, and the functional group (II) is a hydroxyl group. The mass ratio of the addition polymerization block copolymer (a) and the addition polymerization block copolymer (a ₁ ) is in the range of 10:90 to 95: 5. The thermoplastic polymer composition described. It has 1 or more polymer blocks A mainly composed of aromatic vinyl compound units and 1 or more polymer blocks B mainly composed of conjugated diene compound units, and the polymer block A has 1 to 8 carbon atoms. Addition polymerization block comprising a hydrogenated product of a block copolymer having at least one selected from structural units (I) and functional groups (II) based on alkylstyrene having at least one alkyl group bonded to a benzene ring Copolymer (a ₀ ) and block copolymer having one or more polymer blocks A ′ mainly composed of aromatic vinyl compound units and one or more polymer blocks B ′ mainly composed of conjugated diene compound units the total weight of the addition polymerized block copolymer comprising a polymer _{(a 1) ((a 0} ) + (a 1)) with respect to 100 parts by mass of 10 to 300 mass olefin resin (b) The thermoplastic heavyweight according to claim 1, wherein the mixture comprising the crosslinking agent (d) in the range of 0.01 to 20 parts by mass is dynamically crosslinked under melting conditions. A method for producing a coalescence composition, in which a structural unit composed of another polymerizable monomer composed of a conjugated diene compound in a polymer block B of an addition polymerization block copolymer (a ₀ ) is subjected to addition polymerization. 10 mass% or less based on the total mass of the polymer block B constituting the system block copolymer (a ₀ ), and the hydrogenation rate of the carbon-carbon double bond in the polymer block B is 95 mol%. der is, further functional groups (II) is a hydroxyl group _(-OH), a more - SH, -NH 2, -NHR, -CONH 2, -CONHR, -CONH -, - SO 3 H, -SO 2 H and -An government having an active hydrogen atom selected from SOH Group is a functional group selected from carboxyl group and an epoxy group, method for producing a thermoplastic polymer composition. It has 1 or more polymer blocks A mainly composed of aromatic vinyl compound units and 1 or more polymer blocks B mainly composed of conjugated diene compound units, and the polymer block A has 1 to 8 carbon atoms. Addition polymerization block copolymer selected from block copolymers having at least one of structural units (I) and functional groups (II) based on alkylstyrene having at least one alkyl group bonded to a benzene ring, or hydrogenated products thereof Polymer (a ₀ ) and a block copolymer having at least one polymer block A ′ mainly composed of aromatic vinyl compound units and at least one polymer block B ′ mainly composed of conjugated diene compound units 10 to 300 olefin resin (b) with respect to 100 parts by mass of the total amount ((a ₀ ) + (a ₁ )) of the addition polymerization block copolymer (a ₁ ) comprising A mixture containing rubber softener (c) in the range of 300 parts by mass or less and crosslinking agent (d) in the range of 0.01 to 20 parts by mass within the range of parts by weight is operated under melting conditions. The method for producing a thermoplastic polymer composition according to claim 2, wherein the polymer block B of the addition polymerization block copolymer (a ₀ ) comprises a conjugated diene compound. The structural unit composed of the other polymerizable monomer of the structural unit is 10% by mass or less based on the total mass of the polymer block B constituting the addition polymerization block copolymer (a ₀ ), and the polymer block carbon in B - hydrogenation of the carbon double bonds Ri der least 95 mol%, further functional groups (II) is a hydroxyl group _{(-OH), - SH, -NH} 2, -NHR, -CONH 2, _{-CONHR, -CONH -, - SO 3} H, -SO 2 H And a functional group having an active hydrogen atom selected from the -SOH, is a functional group selected from carboxyl group and an epoxy group, method for producing a thermoplastic polymer composition. The molded object which consists of a thermoplastic polymer composition of any one of Claims 1-4.