JPH0372558A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent impact resistance and ductility by mixing a polymer obtained by hydrogenating a ring- opening polymer of a monomer comprising a norbornene derivative with a rubbery polymer. CONSTITUTION:The title composition comprises 10-99wt.% component (i) and 90-1wt.% component (ii). Component (i) is a hydrogenated polymer obtained by hydrogenating a ring-opening polymer which is produced by subjecting a monomer comprising at least one norbornene derivative of formula I, alone or together with a monomer copolymerizable therewith, to ring-opening polymerization. In formula I, A and B are each H or a 1-10C hydrocarbon group; X and Y are each H, a 1-10C hydrocarbon group, a halogen-substituted 1-10C hydrocarbon group, or a group of formula II-V (wherein R<1> is a 1-20C hydrocarbon group; and (n) is 0-10).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent impact resistance and ductility.

[Conventional technology]

Ring-opened polymers or ring-opened copolymers of norbornene derivatives have good optical properties, low hygroscopicity, and excellent heat resistance, and are therefore expected to be applied in various fields.

[Problem to be solved by the invention]

However, this ring-opened polymer (including ring-opened copolymer).

The same applies below. ) has the drawbacks of low impact resistance and poor ductility.

It is known, for example, from Japanese Patent Publication No. 57-3701, to mix rubbery polymers for the purpose of improving these drawbacks, but it is not always possible to obtain sufficient effects, and rather their properties are In some cases, it may decrease.

[Means to solve the problem]

The present invention was developed as a result of extensive research into the above problems.
According to a hydrogenated polymer obtained by further hydrogenating a monomeric ring-opening polymer made of a norbornene derivative having a specific polar substituent, by blending the specific polymer with the hydrogenated polymer, excellent durability can be obtained. It is confirmed that impact strength and ductility are reliably expressed, and that by blending a particularly selected polymer or a combination thereof, a thermoplastic resin M acid having even higher transparency or chemical resistance can be obtained. The heading is complete.

[Characteristics of the composition of the present invention]

Thermoplastic resin compositions according to the present invention are provided as the following compositions 1 to 2.

Composition ■: 10 to 99% by weight of the following (A) and 9% of the following (B)
0-1% by weight of a thermoplastic resin composition.

Component (A): A monomer consisting of at least one norbornene derivative represented by the following general formula (1), or obtained by ring-opening polymerization of this monomer and a copolymerizable monomer copolymerizable therewith. A hydrogenated polymer obtained by further hydrogenating a ring-opened polymer.

General formula (1) [wherein and B are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X and Y are a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms,
Halogen atom, 1 to 1 carbon atoms substituted with halogen atom
0 hydrocarbon group, +CHt)-COOR', +cH2)? 1OCOR',
+CH*)-OR', +CHJI, CN.

-(-CHj), C0NR"R", +CH2>-COO
Z.

+CH2)-0C'OZS+CHa)-02°+CH*
)-W or X and Y, in which at least one of A hydrocarbon group, Z is a hydrocarbon group substituted with a halogen atom, Wtt Si R'PDs-P(R'
lt carbon jl hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -0COR" or -OR@ (R@ is a carbon number 1 to 10
(represents a hydrocarbon group), p represents an integer of 0 to 3), n
represents an integer from 0 to 10. ), and m is 0 or 1. ].

(B) Component: Rubbery polymer.

Composition (2): A thermoplastic resin composition comprising (A) a tc content of 5 to 95% by weight and the following (C) a content of 95 to 5% by weight, similar to composition (2).

(C) a: Rubber reinforced thermoplastic resin.

Composition ■: 10 to 98% by weight of the same component (A) as in Composition I, and 2 to 90% of the following component (D-1) and/or (D-2)
% by weight.

(D-1) is divided into two molecules: block a (block with an aromatic vinyl compound content of 90% by weight or more) and block b (with a 1,2-vinyl bond content of 30 to 70% by weight). polybutadiene block) and block C (1
.
The proportion of block b is 10 to 50% by weight, and the proportion of block b is 30 to 50% by weight.
A polymer unit consisting of a block copolymer (i) or a 3-block copolymer (i) in which the proportion of 80% by weight and block C is 5 to 30% by weight, and the block a, block b and block C Regarding the propulsion copolymer <■> formed by bonding via a coupling agent residue with at least one polymer unit selected from the following, at least 80% or more of its olefinic unsaturated bonds are hydrogenated. The number average molecular weight is 40,000 to 700,000.
, a hydrogenated block copolymer having a difference in refractive index from that of (A) of 0.02 or less.

(D-2) is divided into block d (aromatic vinyl compound polymer block), block e (random copolymer block of aromatic vinyl compound and conjugated diene compound), and block f (aromatic vinyl compound polymer block). A tapered polymer block consisting of a conjugated diene compound and a tapered polymer block in which the proportion of an aromatic vinyl compound in the molecule gradually increases.
- an f-type block copolymer in which the ratio of aromatic vinyl compound/conjugated diene compound is from 5 to 40/95 by weight;
60, the total amount of aromatic vinyl compounds of block d and block f is 25% by weight or less of the total monomers, the vinyl bond content of the conjugated diene compound portion of block e is 15 to 60% by weight, and the conjugated diene A hydrogenated block obtained by hydrogenating at least 90% or more of the olefinic unsaturated bonds of a compound, having a number average molecular weight of so, ooo to 300.000, and a difference from the refractive index of the component (A) of 0.02 or less. Copolymer.

Composition ■: 10 to 93% by weight of component (A) similar to composition I, 2 to 40% by weight of component (E) below, and 5 to 88% of component (F) below
% by weight.

(E): A hydrogenated diene polymer which is a hydrogenated product of a polymer consisting of 50% by weight or less of an aromatic vinyl compound and 50% by weight or more of a conjugated diene compound.

(F) Component: Polyolefin.

Composition ■: 10 to 93% by weight of the same component (A) as in Composition I, 2 to 40% by weight of the following (G), and 5 to 88% of the following component (H)
% by weight.

0.01 to 10 parts of α,β-unsaturated carboxylic acid and/or its derivatives to 100 parts by weight of the hydrogenated diene polymer (G) and (E) according to composition (2). A modified hydrogenated diene polymer obtained by grafting.

(H): at least one polymer selected from polyolefin, polyamide, and polyester.

The present invention will be explained in detail below.

[Summary of the invention]

The present invention has the above (A) as an essential component, and this (A)
A thermoplastic resin composition (composition 1) having excellent impact resistance and ductility by blending the above component (B) in a specific proportion, or the above component (C) in a specific proportion. to provide a thermoplastic resin composition (composition ■) having excellent impact resistance and ductility; ) Component a and/or component (D-2) are blended in a specific ratio to provide a thermoplastic resin composition (composition ■) having even higher transparency; A thermoplastic resin composition (composition ■) which has excellent chemical resistance by blending component (E) of component (B) with component (F) in a specific ratio, or component (B) above. A thermoplastic resin composition (composition V) having excellent chemical resistance is provided by blending component (G) in (H) with component (a) in a specific ratio.

[Each composition component]

Next, each of the components used in the present invention will be specifically explained.

Component (A) This component (A) is a monomer consisting of a norbornene derivative represented by the above primary formula (1), hereinafter referred to as "specific monomer".
A ring-opening polymer obtained by ring-opening copolymerization of 〉 alone or by ring-opening copolymerization of a specific monomer with a copolymerizable monomer that can be copolymerized with the ring-opening polymer is further hydrogenated. It is a hydrogenated polymer obtained by, and hereinafter also referred to as "hydrogenated polymer (A)j."

The molecular weight of this hydrogenated polymer (A) is from 20.000 to 700.0 as a weight average molecular weight in terms of polystyrene.
00, especially from 30.000 to 500.000.

Among the specific monomers, the specific monomer in which the polar substituent X or ltY in the above general formula (I) is a carboxylic acid ester group represented by t + CH and C0OR' has a high glass transition temperature in the resulting polymer. It is preferable because it has low temperature and hygroscopicity.

In particular, the polar substituent consisting of this carboxylic acid ester group is
It is preferable that one monomer is contained per molecule of the specific monomer because the resulting polymer has low hygroscopicity.

Further, among the carboxylic acid ester groups represented by the formulas +CH, The polymer is preferred because it is easy to synthesize and the resulting polymer has good properties.

In the above formula, R' is a hydrocarbon group having 1 to 20 carbon atoms, and a larger number of carbon atoms is preferred because the resulting polymer has lower hygroscopicity. However, from the viewpoint of balance with the glass transition temperature of the obtained polymer, the number of carbon atoms is 1 to 1.
4 chain hydrocarbon group, or (poly)I having 5 or more carbon atoms
Preferably, it is an I-type hydrocarbon group.

Furthermore, a specific monomer in which a hydrocarbon group having 1 to 10 carbon atoms is simultaneously bonded as a substituent to the carbon atom to which a carboxylic acid ester group is bonded can be used without lowering the glass transition temperature of the resulting polymer. This is preferable because it reduces hygroscopicity. In particular, a specific monomer in which this substituent is a methyl group,
It is preferred because its synthesis is easy.

The ring-opening polymer according to the hydrogenated polymer (A) in the present invention may be one obtained by ring-opening polymerization of a specific monomer alone, but the ring-opening polymer related to the hydrogenated polymer (A) may be one obtained by ring-opening polymerization of a specific monomer alone. It may also be a product obtained by ring-opening copolymerization with the polymer. When a copolymerizable monomer is used in this way, the proportion of the specific monomer in the ring-opening polymer is 5 mol% or more, preferably 20 mol% or more. Examples of the copolymerizable monomers used include monomers that can be ring-opening polymerized by a metathesis polymerization catalyst and partially polymerized low polymers having a carbon-carbon double bond in the main chain of the polymer. be able to.

In addition, as a specific monomer, in the general formula (I) above, m
A tetracyclododecene derivative in which m is 1 is preferable to one in which m is 0 in that a polymer with a high glass transition point can be obtained, and when a specific monomer in which m is 1 is used, a cyclic olefin compound It is also possible to obtain a ring-opening polymer by carrying out ring-opening copolymerization with.

Specific examples of such cyclic olefin compounds include cycloolefins such as cyclopentene, cyclooctene, 1.5-cyclooctadiene, and 1.5.9-cyclododecatriene; bicyclo[2,2,1]-2 -Heptene, tricyclo[5,2,1,0'-"] -]8-decentric tricyclo[5,2,1,0"-"] -]3-decentric tricyclo[6,2,1,0 '-"] -]9-undecentric cyclo[6,2,1,0'-"] -]4
-undecenetetracyclo[4,4,0,1"1.1"
”] −]3-dodecenepentacy9 o [6,5
,1,1",0",0""]-4-pentadecene,pentacyclo[6,6,1,1'-',0"-'0
9.'']-4-hexadecene, pentacyclo[6゜5,
1.1"-', 0"-', O'-"]-]11-
pentadecene dicyclopentadiene, pentacyclo [6
, 5,1,1'' 02.ff, Pwll]-pentadeca-4,11-diene, and polycycloalkenes such as compounds in which m is 0 in the above general formula (I).

The polycycloalkenes described above are useful in reducing the hygroscopicity of the ring-opened polymer and controlling the glass transition temperature of the ring-opened polymer. For example, tetracyclodecene alone or a copolymer with bicycloheptene has too high a glass transition temperature and has no molding properties. : If undesirable silver streaks or molecular weight reduction occur, by copolymerizing with cycloolefin, the glass transition temperature can be lowered to a temperature at which the bottom shape can actually be easily formed. Furthermore, if the glass transition temperature of the resulting ring-opening polymer is low, below 100°C, it is possible to raise the glass transition temperature of the ring-opening polymer by copolymerizing polycycloalkene. Hygroscopicity can be lowered.

Copolymerizable monomers include carbon-carbon doubles in the main chain of polymers such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-propylene non-conjugated diene copolymer rubber, polynorbornene, and polypentenamer. Mention may also be made of unsaturated hydrocarbon polymers containing bonds.

The ring-opened polymer obtained as described above preferably has a saturated water absorption of 1.8% or less and a glass transition temperature of 100° C. or higher. The saturated water absorption rate is more preferably 1.2% or less, most preferably 0.8% or less. The glass transition temperature is more preferably 120°C or higher.

The metathesis polymerization catalyst used in the production of ring-opening polymers is usually a catalyst consisting of the following combinations of (a) Fy, min, and (b) min, but in order to increase the catalytic activity, it is further described below. Activating agents may be added.

(a) Component: At least one selected from WSMo and Re compounds (b) Component: IA, nA, IIB of Deming's periodic table
.

The amount of at least one component (a) and (b) selected from compounds of group IIIA, IVA, or IVB elements having at least one element-carbon bond or element-hydrogen bond. The metal atomic ratio (a):(b) is in the range of 1:1 to 1:20, preferably 1:2 to 1:10.

Metathesis polymerization catalysts prepared from component (a) and component (b) usually have high catalytic activity in the metathesis ring-opening polymerization reaction of specific monomers, but they also have the following (C) By adding an activator consisting of , it can be used as a catalyst with even higher activity.

Various compounds can be used as the (C) a component, and particularly preferably used compounds include the following.

(1) Elemental boron, BF,, Bcl,, B (On C
4Hs)s, BF30(CH3)2, BFsO(Ca
Hs)a, BF30(n C<HsL, BFs・2C
IH5O)ISBFa-2CH, +C0OH.

BFs/urea, BF1 triethanolamine, BFs'
Piperidine, B F s ' Cw Hs N H2,
Boron compounds such as B, 03, Hs B Oa, 5i (
Silicon compounds such as OC*Hs)a, Si(J4),
(2) Alcohols, hydroperoxides and peroxides, (3) Water, (4) Oxygen, (5) Carbonyl compounds such as aldehydes and ketones and their oligomers or polymers, (6) Ethylene oxide, shrimp chlorohydrin , cyclic ethers such as oxetane, (7) amides such as N,N-diethylformamide, N,N-dimethylacetamide, amines Ri6 such as aniline, morpholine, piperidine, and azo compounds such as azobenzene, (8) N- N-nitrone compounds such as nitrosodimethylamine and N-nitrone diphenylamine; (9) compounds containing an S-α group or N-α group such as trichloromelamine, N-chlorosuccinoimide, and phenylsulfenyl chloride; The quantitative relationship between component a) and component (C) cannot be uniformly defined because it varies greatly depending on the type of component (C) added, but in many cases,
)/(a) (% ratio) value is 0.005 to 10. It is preferably used in a range of 0.05 to 1.0.

In metathesis ring-opening polymerization reactions, the molecular weight of the resulting polymer can be adjusted by changing reaction conditions such as the type and concentration of metathesis polymerization catalyst, polymerization temperature, type and amount of solvent, and monomer concentration. However, it is usually preferable to adjust the molecular weight of the ring-opened polymer by adding an appropriate amount of a suitable molecular weight regulator to the polymerization reaction system. Such molecular weight regulators include α-olefins, α,
Examples include compounds having at least one carbon-carbon double bond or carbon-carbon triple bond in the molecule, such as ω-diolefins or acetylenes, or polar allyl compounds such as allyl chloride, allyl acetate, and trimethylallyloxysilane. can.

Examples of solvents used in the polymerization reaction include alkanes such as pentane, heptane, heptane, octane, nonane, and decane; cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin, and norbornane; Aromatic compounds such as benzene, toluene, xylene, ethylbenzene, and cumene; Chlorobutane,
Compounds such as halogenated alkanes and halogenated aryls such as bromhexane, dichloroethane, hexamethylene dipromide, and chlorobenzene; and saturated carboxylic acid esters such as ethyl acetate and methyl propionate.

The hydrogenation reaction of the ring-opened polymer obtained as described above can be carried out by a normal method, that is, a hydrogenation catalyst is added to a solution of the ring-opened polymer, and the hydrogenation reaction is carried out under normal pressure to 300 atm, preferably 300 atm.
~150 atmospheres of hydrogen gas at 0~180℃, preferably 2
It is carried out by acting at 0 to 150°C.

As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used.

As this hydrogenation catalyst, heterogeneous catalysts and homogeneous catalysts are known.

Heterogeneous catalysts include palladium, platinum, nickel,
Examples include solid catalysts in which a catalyst material such as rhodium or ruthenium is supported on a carrier such as carbon, silica, alumina, or titania. Homogeneous catalysts include nickel triethylaluminum naphthenate, nickel acetylacetonate-triethylaluminum, cobalt-n-butyllithium octenoate, titanocene dichloride-diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine)
Examples include rhodium.

Hydrogenated polymer (A) obtained in hydrogenation reaction
The hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 80% or more.

If the hydrogenation rate is less than 50%, the effect of improving impact resistance and ductility in the finally obtained thermoplastic resin composition will be reduced, which is not preferable.

Component (B) This component (B) is a rubbery polymer. A rubbery polymer containing this (B) (hereinafter referred to as "rubberous polymer (B)")
Includes conventional rubbery polymers and thermoplastic elastomers.

Examples of rubbery polymers include ethylene-α-olefin rubbery polymers; ethylene-α-olefin-polyene copolymer rubbers; combinations of ethylene and unsaturated carboxylic acid esters such as ethylene-methyl methacrylate and ethylene-butyl acrylate. Copolymers: Copolymers of ethylene and vinyl fatty acids, such as ethylene-vinyl acetate; Polymers of alkyl acrylates, such as ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate. Coalescing; polybutadiene, styrene-butadiene random copolymers and block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, butadiene-(
- Diene rubbers such as meth)acrylic acid alkyl ester copolymer, butadiene-(meth)acrylic acid alkyl ester-acrylonitrile copolymer, butadiene-(meth)acrylic acid alkyl ester-acrylonitrile-styrene copolymer, and these Hydrogenated products include butylene-isoprene copolymers, hydrogenated products of block copolymers of aromatic hydrocarbon compounds such as styrene and aliphatic diene hydrocarbon compounds such as butadiene and isoprene, etc. Not only one type but two or more types can also be used.

The rubbery polymer (B) may be obtained by crosslinking the above rubbery polymer using a known crosslinking agent such as divinylbenzene.

The above-mentioned butadiene-styrene copolymers include styrene-butadiene copolymers having at least one styrene block and hydrogenated products thereof.

In the above ethylene-α-olefin rubbery polymer, the ratio of ethylene and α-olefin is 95:5 by weight.
~5:95, preferably 95:5~20:80, more preferably 92:8~60:40. Particularly preferably 85
: 15-70 : 30.

The α-olefin used here has 3 to 20 carbon atoms.
It is an unsaturated hydrocarbon compound, and specific examples thereof include:
Propylene, butene-1, pentene-1, hexene-1
, heptene-1,4-methyl 1f7-1,4-methylpentene-1, and the like. Particularly preferred is propylene.

The cyclohexane-insoluble component in the ethylene-α-olefin rubbery polymer is a component that affects the processability and impact resistance of the final thermoplastic resin composition, and this has been taken into consideration. , the proportion thereof is 50% by weight or less, preferably 5% by weight or less.

The polyene compound for the ethylene-α-olefin-polyene copolymer includes 1,4-pentadiene,
L5-hexadiene, 2-methyl-1,5-hexadiene, 3.3-dimethyl-1,5-hexadiene, 1.7
-octadiene, 1,9-decadiene, 6-methyl-1
, 5-hexadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene, 9-methyl-1,9-undecadiene, isoprene, l,3-pentadiene, 1.
4.9-decatriene, 4-vinyl-1-cyclohexadiene, cyclopentadiene, 2-methyl-2,5-norbornadiene, 5-methyl-2-norbornadiene,
Examples include 5-ethylidene-2-norbornene, 5-impropylidene-2-norbornene, 5-isopropenyl-2-norbornene, dicyclopentadiene, and tricyclopentadiene.

The rubbery polymer (B) made of the above rubbery polymer has a Mooney viscosity (ML+.1.100°C) of 5 to 200.
It is preferable that

Examples of the thermoplastic elastomer used as the rubbery polymer (B) include styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, styrene-isoprene block copolymer, and hydrogenated styrene-isoprene block copolymer. Examples include aromatic vinyl-conjugated diene block copolymers such as block copolymers, low-crystalline polybutadiene resins, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and ethylene-based ionomer resins. .

The aromatic vinyl-conjugated diene block copolymer is AB
type, ABA type, ABA taper type, radial teleblock type, etc.

In order to obtain a thermoplastic resin composition particularly excellent in transparency, a preferred rubbery polymer (B) is hydrogenated styrene-
Random copolymers, block copolymers or block-random copolymers of butadiene with a styrene content of 20 to 45% by weight, and copolymers of butadiene and acrylic esters, in which butadiene and The weight ratio of acrylic acid ester is 10-90:90-1O
Examples include those in which styrene and/or acrylonitrile are copolymerized with 100 parts by weight of these in a proportion of 0 to 30 parts by weight, and hydrogenated products thereof.

The rubbery polymer (B) contains specific functional groups such as epoxy groups, carboxyl groups, hydroxyl groups, amino groups, acid anhydride groups, and oxazoline groups for the purpose of improving compatibility with the hydrogenated polymer (A). It may be modified with a group. The modified rubbery polymer can be obtained by copolymerizing an unsaturated compound having the above-mentioned specific functional group with a monomer that provides the above-mentioned rubbery polymer, or by copolymerizing the above-mentioned rubbery polymer with the above-mentioned specific unsaturated compound. Examples include a method of mixing and melt-kneading an unsaturated compound having a functional group and, if necessary, an organic peroxide for modification.

The amount of the unsaturated compound having a specific functional group used for modifying the rubbery polymer is preferably within the range of 0.01 to 30% by weight of the entire thermoplastic resin composition.

(C) Component (C) is a rubber-reinforced thermobreathable resin. The rubber-reinforced heat-recoverable resin (hereinafter also referred to as "rubber-reinforced heat-recoverable resin (C)") as component (C) is a monomer that can be copolymerized with the rubbery polymer in the presence of the rubber-like polymer. Alternatively, it is a copolymer formed by copolymerizing a monomer mixture such as an aromatic vinyl compound, a maleimide compound, a vinyl cyanide compound, and another vinyl monomer copolymerizable with these.

Examples of the rubbery polymer' for obtaining the rubber-reinforced thermoplastic resin (C) include ethylene-propylene random and block copolymers, ethylene-butene random and block copolymers, etc. Copolymers with α-olefins; copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-methacrylate and ethylene-butyl acrylate; copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate;
Ethylene-propylene-nonconjugated polymers such as propylene-ethylidene norbornene copolymer and ethylene-propylene-hexadiene copolymer; random and block copolymers of polybutadiene, isoprene, styrene-butadiene, and random and block copolymers thereof; Hydrogenated polymers; diene rubbers such as acrylonitrile-butadiene copolymer, butadiene-imprene copolymer; butylene-isoprene copolymer, etc.; not only one type but two or more of these can be used. You can also do it.

Among these, preferable rubbery polymers in terms of physical properties are diene rubber, ethylene-propylene rubber, and ethylene-propylene-nonconjugated genter polymer.

Examples of aromatic vinyl compounds copolymerized in the presence of the rubbery polymer include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, These include p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, dimethylstyrene, etc., and not only one type thereof but two or more types thereof can also be used.

Among these, the aromatic vinyl compound preferably used is styrene.

Examples of maleimide compounds include maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-0-chlorophenylmaleimide, N-cyclohexylmaleimide, and preferably N-phenylmaleimide, N-0 -Chlorphenylmaleimide, N
-cyclohexylmaleimide, etc., and not only one type thereof but two or more types thereof can also be used.

Examples of vinyl cyanide compounds are acrylonitrile, methacrylatetrile, etc., of which acrylonitrile is preferred.

Examples of other copolymerizable vinyl compounds include: alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate, propyl acrylate; alkyl esters of methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate; maleic anhydride, anhydrous Unsaturated acid anhydrides such as itaconic acid and citraconic anhydride can be mentioned, and not only one type but two or more types of these can also be used.

Specific examples of the rubber-reinforced thermoplastic resin (C) as described above include acrylonitrile-butadiene-styrene resin (
ABS resin>, acrylonitrile-ethylene-propylene-styrene IHII (AES resin>1. Methyl methacrylate-butadiene-styrene resin (MBS resin),
Acrylonitrile-butadiene-methyl methacrylate-styrene resin (ABMS resin), acrylonitrile-
n-butyl acrylate-styrene resin (AAS resin)
, rubber-modified polystyrene (high-impact styrene), etc., and not only one type but two or more types of these can also be used.

Component (D-1) Component (D-1) is a specific hydrogenated block copolymer and is included within the scope of component (B) above. The hydrogenated block copolymer (hereinafter also referred to as "hydrogenated block copolymer (D-1) J") with (D-1) as a component is: ■ Mainly composed of aromatic vinyl compounds, the proportion of which is 90% by weight. % or more of the polymer block a.

(2) Block b made of polybutadiene having a medium content of 1.2-vinyl bonding metal of 30 to 70% by weight.

and ■ 1. Obtained by further hydrogenating a block copolymer (unhydrogenated block copolymer) consisting of block C consisting of polybutadiene having a low content of 2-vinyl bond metals of less than 30% by weight. It is a copolymer.

That is, the molecule has at least one block a, one block b, and one or more blocks C, and the content ratio of block a is 10 to 50% by weight, and the content ratio of block b is 3% by weight.
0 to 80% by weight and the content of block C is 5 to 30%
% by weight of the block copolymer (i) or the polymer unit consisting of the block copolymer (i) forms the block a through the coupling agent residue.

Regarding the block copolymer (ii), which is bonded to a polymer unit consisting of at least one selected from b and C, and whose polymer molecular chain is extended or branched, the contained olefinic inorganic Number average molecular weight obtained by hydrogenating at least 80% or more of the saturated bonds, from 40.000 to TO0,00
0 hydrogenated block copolymer.

The above-mentioned unhydrogenated block copolymer contains at least one each of blocks a, b, and C as an essential component, and therefore the simplest one is a block having the structure (a-b-c). It is a copolymer. Furthermore, in addition to this basic structural arrangement, it may be a block copolymer in which all or part of the above three types of blocks are arranged regularly or irregularly.

In addition, in the unhydrogenated block copolymer, the polymer unit consisting of the above block copolymer (i) is bonded to 1 to 3 other blocks via coupling agent residues, thereby forming a polymer. The combined molecular chain may be extended or branched. The partner block to be joined here is block a
, b and C.

Blocks a, b and C as described above are bonded via a coupling agent residue, for example (a-b-
c) Those having the structure r+X (however, n = 2 to 4) are treated with diethyl adipate, divinylbenzene, silicon tetrachloride, tin tetrachloride, dimethyl dichlorosilicate L after block copolymerization as described below. It can be obtained by adding a coupling agent such as 1,2-dibromoethane or 1,4-chloromethylbenzene. However, if one block combination contains blocks a, b, and C, there is no need for another block combination to contain all three, for example (a- It may have a structure like b-c)X(a-b).

<Block a> Block a is a polymer of one or more aromatic vinyl compounds selected from aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, and p-tert-butylstyrene. Alternatively, it is made of a copolymer with 1,3-butadiene having an aromatic vinyl compound content of 90% by weight or more. More than 80% of the olefinically unsaturated bonds in block a are later hydrogenated.

The proportion of aromatic vinyl compounds in this block a is 9
If the amount is 0% by weight, the refractive index of the resulting hydrogenated block copolymer (D-1) will be low, making it impossible to obtain high transparency in the composition with the hydrogenated polymer (A). . This block a has a number average molecular weight of 5.000 to
Preferably it is 70.000.

The content of block a in the unhydrogenated block copolymer is 10 to 50% by weight, preferably 15 to 45% by weight. If this proportion exceeds 50% by weight, the thermoplastic resin composition finally obtained will have a reduced effect of improving transparency and impact resistance at low temperatures.

Block b> Block b has a 1,2-vinyl bond content of 30 to 70
It consists of a polybutadiene polymer of 40% to 60% by weight, and 80% or more of its olefinic unsaturated bonds are subsequently hydrogenated.

When 100% of the olefinically unsaturated bonds are hydrogenated, the eukaryotic block b becomes identical to a polymer in which ethylene and butene-1 are randomly copolymerized. This block b has a number average molecular weight of 30,000 to 300.
Preferably, it is 000.

In the unhydrogenated block copolymer, if the amount of 1,2-vinyl bond metal in block b is less than 30% by weight, polyethylene chains are generated during hydrogenation, so that the hydrogenated block copolymer obtained Rubbery properties are lost during coalescence, and if the amount exceeds 70% by weight, the glass transition point of the hydrogenated block copolymer obtained becomes high, and rubbery properties are also lost, which is not preferable.

In the unhydrogenated block copolymer, the content of block b is 30 to 80% by weight, preferably 35 to 70% by weight.
It is. If this proportion is less than 30% by weight, (A)
In a composition containing 100% or more, the effect of modifying low-temperature impact resistance is lost, while if this proportion exceeds 80% by weight, the hydrogenated block copolymer does not form into pellets and processability decreases.

Block C〉 Block C has a 1,2-vinyl bond content of 30% by weight.
%, preferably 3 to 20% by weight of polybutadiene polymer, of which 80% or more of the olefinically unsaturated bonds are subsequently hydrogenated.

This block C has a number average molecular weight of 10.000 to
Preferably, it is 300,000.

In an unhydrogenated block copolymer, if the amount of 1,2-vinyl bond gold in block C exceeds 30% by weight, the resinous properties are lost even after hydrogenation, and the block copolymer loses its thermal properties. The plastic elastomer properties are lost. Moreover, it is difficult to produce polybutadiene having a 1,2-vinyl bond content of less than 3% by weight.

The content of block C in the unhydrogenated block copolymer is 5 to 30% by weight, preferably 5 to 25% by weight. If this proportion is less than 5% by weight, the effect of improving the impact resistance at low temperatures will be insufficient in the final composition, and if it exceeds 30% by weight, the effect of improving the impact resistance at low temperatures will be insufficient. Inferior, undesirable.

The hydrogenated block copolymer (D
-1) has a number average molecular weight of 40.000 to TO0,
It is 000. Then, the hydrogenated block copolymer (
It is important for D-1) that its olefinic unsaturated bonds are hydrogenated by at least 80% or more, preferably 90% or more, and the difference in refractive index with respect to component (A) is 0.02 or less. It needs to be sufficiently small. That is, in the hydrogenated block copolymer (D-1),
If the proportion of olefinic unsaturated bonds to be hydrogenated is less than 80%, the weather resistance and thermal stability of the final composition will be insufficient, and the difference in refractive index will exceed 0.02. In this case, high transparency cannot be obtained in the final thermoplastic resin composition.

In addition, the hydrogenated block copolymer (D-1) contains an epoxy group, a carboxyl group, a hydroxyl group, an amine 7 group, an acid anhydride, and an oxazoline for the purpose of improving compatibility with the hydrogenated polymer (A). It may be modified with a specific functional group such as a group. For denaturation, use (B) above.
A method similar to that described for minutes can be used.

(D-2) Component This (D-2) component is the same as the (D-1) component.
It consists of a specific hydrogenated diene block copolymer included within the scope of component B). This (D-2)a
Hydrogenated diene block copolymer (hereinafter also referred to as "hydrogenated diene block copolymer (D-2) J")
is a gutter bottom made of ■block d made of an aromatic vinyl compound, ■block e made of a random copolymer of an aromatic vinyl compound and a conjugated diene compound, and ■an aromatic vinyl compound and a conjugated diene compound. A block copolymer consisting of a tapered polymer in which the proportion of an aromatic vinyl compound gradually increases; The ratio is 5 to 40/95 to 60, and the total amount of aromatic vinyl compound components in blocks d and f is 25% by weight or less of the total monomers, and the conjugated diene compound portion in block e. A hydrogenated diene block obtained by hydrogenating a diene block copolymer having a vinyl bond metal content of 15 to 60% by weight, so that at least 90% of the olefinic unsaturated bonds are hydrogenated by a conjugated diene compound. It is a copolymer. This hydrogenated diene block copolymer (D-2) has a number average molecular weight of 50.000 to 300.0 in terms of polystyrene.
Preferably it is 00.

Aromatic vinyl compounds for blocks d, e and f include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene,
1.1-Diphenylstyrene, N,N-diethyl-p-
Examples include aminoethylstyrene and vinylpyridine, among which styrene and α-methylstyrene are particularly preferred.

Moreover, as a conjugated diene compound, 1,3-butadiene,
Isoprene, 2,3-dimethyl-1,3-butadiene,
1.3-pentadiene, 2-methyl-1,3-pentadiene, 1.3-hexadiene, 4.5-diethyl-1,
Examples include 3-octadiene, 3-butyl-1,3-octadiene, and chloroprene. Among these, the hydrogenated diene block copolymer (D-2) is industrially advantageous and has excellent physical properties. Since we obtain, 1.3-
Butadiene, isoprene and 1,3-pentadiene are preferred, and 1,3-butadiene is particularly preferred.

As mentioned above, the diene block copolymer to be hydrogenated has a weight ratio of aromatic vinyl compound to conjugated diene compound of 5 to 40/95 to 60, preferably 7 to 40/ It needs to be between 93 and 60. When the proportion of the aromatic vinyl compound is less than 5% by weight, the obtained hydrogenated diene block copolymer (D-2) and (A
) It is not possible to obtain sufficient properties in a composition with components.

On the other hand, when the proportion of the aromatic vinyl compound exceeds 40% by weight, the resulting hydrogenated diene block copolymer (
D-2) becomes resinous and loses its rubbery properties,
A composition containing component (A) a has insufficient impact resistance, especially impact resistance at low temperatures.

The total amount of aromatic vinyl compound components in block d and block f is 25% by weight or less, preferably 3% by weight of the total monomers.
-25% by weight, particularly preferably 5-20% by weight.

When this proportion exceeds 25% by weight, the hydrogenated diene block copolymer (D-2) becomes resinous, and (A)
Compositions with these components result in insufficient impact resistance, particularly at low temperatures. In addition, if this proportion is less than 3% by weight, blocking will occur easily when the obtained hydrogenated diene copolymer is pelletized, and (A)
Compositions with other components tend to result in molded articles having poor appearance. Further, the proportion of the aromatic vinyl compound component in block d is preferably at least 3% by weight, particularly preferably from 5 to 15% by weight.

In block e consisting of a random copolymer of an aromatic vinyl compound and a conjugated diene compound, the vinyl bond content of the conjugated diene compound component is 15 to 60% by weight, preferably 20 to 55% by weight. This proportion is 15% by weight
The non-droplet type requires severe polymerization conditions in its production, which is not only industrially disadvantageous in terms of production, but also makes the resulting hydrogenated diene block copolymer (D-2) and (
A composition containing A) has insufficient impact resistance. On the other hand, if this proportion exceeds 60% by weight, the composition containing (A) will have too low rigidity even if it is attempted to satisfy both impact resistance and rigidity.

The above hydrogenated diene block copolymer (D-2
) has at least 90% of the olefinically unsaturated bonds due to its conjugated diene compound component, preferably 93 to 100%
% is required to be hydrogenated and saturated. If the degree of hydrogenation is less than 90%, the thermoplastic resin composition finally obtained will have poor thermal stability, weather resistance, and ozone resistance.

This hydrogenated diene block copolymer (D-2) has a polystyrene equivalent number average molecular weight of 50.000 to 300.
000, preferably from 70.000 to 250.000, and if it is outside this range, sufficient effects cannot be obtained in the final thermoplastic resin composition.

For example, when the number average molecular weight is less than 50.000, the resulting composition has low impact resistance, while aoo, oo
If it exceeds o, the surface appearance will deteriorate.

Further, the hydrogenated diene block copolymer (D-2) needs to have a sufficiently small difference in refractive index with respect to (A) of 0.02 or less. If it exceeds 20%, high transparency cannot be obtained in the final thermoplastic resin composition.

In addition, the hydrogenated diene block copolymer (D-2) is
Even if it has been modified with a specific functional group such as an epoxy group, carboxyl group, hydroxyl group, amino group, acid anhydride, or oxazoline group for the purpose of improving compatibility with the hydrogenated polymer (A). good. For modification, a method similar to that described for (B) above can be used.

Component (E) This tc component is a hydrogenated diene polymer obtained by hydrogenating a diene polymer containing an aromatic vinyl compound and a conjugated diene compound.

Examples of the conjugated diene compound for obtaining the hydrogenated diene polymer (hereinafter also referred to as "hydrogenated diene polymer (E)J") as (E) ff1 include butadiene, isoprene, pentadiene, 2.3 -dimethylbutadiene and the like.

Examples of aromatic vinyl compounds include styrene, paramethylstyrene, and α-methylstyrene.

Particularly preferred diene polymers are those obtained from butadiene and styrene.

The diene polymer to be hydrogenated may be a block copolymer of a conjugated diene compound and an aromatic vinyl compound, a random copolymer, or a mixture thereof.

As this component (E), a mixture of a plurality of hydrogenated diene polymers of different types can be used, but in order to obtain the mixture, a mixture of a plurality of diene polymers may be hydrogenated. However, a plurality of hydrogenated diene polymers may be mixed.

The proportion of aromatic vinyl compounds in the diene polymer is 5
It is 0% by weight or less, preferably 40 to 5% by weight. If this proportion exceeds 50% by weight, the hydrogenated diene polymer obtained will take on resinous properties,
Compositions with component (A) are not preferred because impact resistance decreases.

The diene polymer has a 1.2-
The vinyl binder content such as 13.4- is preferably IO weight % or more, more preferably 20 to 80 weight %, particularly preferably 30 to 60 weight %. This ratio is 10
If it is less than % by weight, the obtained hydrogenated diene polymer will take on resinous properties and the impact resistance of the finally obtained thermoplastic resin composition will decrease, which is not preferable.

The number average molecular weight of this diene polymer is preferably 5.
000~1.000. Goo, more preferably 30.
000 to 300.000. If this value is less than 5.000, the obtained hydrogenated diene polymer will not be rubber-like but will become liquid, while if it exceeds 1.000.000, processability tends to decrease, which is not preferable.

Specifically, the diene polymer includes at least one block α or block γ below and at least one block α or γ below.
A copolymer comprising the following block β or block α/β, or a diene polymer comprising blocks β or α/β.

The specific composition is as follows: α: Aromatic vinyl compound polymer β: Conjugated diene compound polymer βl: Conjugated diene compound polymer β with a vinyl bound metal content of 20% by weight or more, : Vinyl bound gold alloy content 0 weight % undropped conjugated diene compound polymer α/β: random copolymer of aromatic vinyl compound/conjugated diene compound γ: copolymer of conjugated diene compound and aromatic vinyl compound, and aromatic vinyl compound gradually increases Examples of tapered polymers include diene polymers having the following skeletons.

(1) α−β (2) α−β−α (3) α-β-γ (4) α−β, −β.

(5) β (6) α/β (7) α−α/β (8) α-α/β-γ (9) α-α/β-α αOβ2-β1-β.

αυ γ-β 02r-β-γ α3 T-α/β-γ αυ T-α-β Copolymers having these basic skeletons repeatedly can also be mentioned, and dienes obtained by coupling them can also be mentioned. It may be a type polymer.

The above (4) α-β Peng-β structure is disclosed in Japanese Patent Application No. 63-285774, and the β (5) and (6) α/β structures are disclosed in Japanese Patent Application No. 63-285774. 12740
This is shown in Publication No. 0.

Also, α-α/β in (7) and α-α/β-T in (8)
For those having the structure, preferably the ratio of aromatic vinyl compound/conjugated diene compound is 5 to 40/60 to 95% by weight, and the total weight of the aromatic vinyl compound of α or α and γ is the total copolymer. 3 to 25% by weight, the vinyl bond content of the conjugated diene compound part in the α/β structure is 15% or more,
Particularly preferably 30 to 80%.

According to the hydrogenated diene polymer (E) according to the above (4), (5), (6), (7) or (8), in the finally obtained thermoplastic resin composition, - This is preferable because much better characteristics can be achieved. Of these, (6)
, (7) or (8), even better low-temperature properties and fatigue properties can be obtained.

The hydrogenated diene polymer (E) is obtained by hydrogenating the above-mentioned diene polymer.

Here, the hydrogenation rate is 70% or more, preferably 90% or more. If the hydrogenation rate is less than 70%, the weather resistance of the finally obtained thermoplastic resin composition will deteriorate, which is not preferable.

The above-mentioned method for polymerizing diene polymers and hydrogenation method for diene polymers are described in, for example, Japanese Patent Application No. 1983-
No. 104256.

Component (F) This component (F) consists of a polyolefin. This (F)
T? Polyolefins (hereinafter also referred to as "polyolefins (F)") include homopolymers such as polyethylene and polypropylene, ethylene, propylene,
Copolymers of other α-olefins may also be mentioned. Specific examples include copolymers of ethylene and propylene, ethylene or propylene and 1-butene,
-There are copolymers with pentene, l-hexene, and 4-methylpentene-1. Among these, polyethylene and polypropylene are preferred, and highly crystalline polypropylene is particularly preferred, with a density of 0.89 to
0.93 g/c- and melt flow rate (
ASTM D1238L) is 0.1-70g/
10 m1n is preferable.

Component (G) This component (G) is a modified water S-added diene polymer. This (G)t? , the modified hydrogenated diene polymer (hereinafter also referred to as "modified hydrogenated diene polymer (G)") as (E) Fft, 100 weight of the hydrogenated diene polymer used as the minute. part, from 0.01 to
It is obtained by grafting reaction with 10 parts by weight of α,β-unsaturated carboxylic acid and/or its derivative.

Here, specific examples of α,β-unsaturated carboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride. acid,
Aconitic anhydride, maleimide, N-phenylenemaleimide, N-methylmaleimide, N-ethylmaleimide,
glycidyl acrylate, glycidyl methacrylate,
Examples include acrylamide.

The amount of grafting of these α,β-unsaturated carboxylic acid derivatives is 0 to 100 parts by weight of the hydrogenated diene polymer.
．． 01-10 parts by weight, preferably 0.05
~7 parts by weight. If the amount of grafting is less than 0.01 part by weight, the obtained modified hydrogenated diene polymer (G) has low compatibility with component (A) and (H), so that the final thermoplastic The impact resistance of the resin composition becomes low.

On the other hand, when the amount of grafting exceeds 10 parts by weight, the resulting modified hydrogenated diene polymer (G) tends to deteriorate, and therefore the impact resistance of the final thermoplastic resin composition is sex becomes lower.

Examples of the method of grafting an α,β-unsaturated carboxylic acid derivative onto a hydrogenated diene polymer include a method of reacting in a solution state as shown in Japanese Patent Publication No. 44-15422, and Japanese Patent Publication No. 43-18144. There are a method of reacting in a slurry state as shown in the publication, a method of reacting in a molten state using an extruder as shown in Japanese Patent Publication No. 43-27421, and others, and any method can be used. .

Specifically, a hydrogenated diene polymer and α.

A mixture of a β-unsaturated carboxylic acid derivative and a small amount of organic peroxide is heated to
By melt-kneading and reacting at a temperature of 0° C., the desired modified hydrogenated diene polymer (G) can be obtained.

(H) component This component (H) consists of at least one polymer selected from the following polymers consisting of polyolefins, polyamides, and polyesters (the polymers as component (H) are as follows: (Also referred to as "polymer (H)").

Polyolefin> This polyolefin is exactly the same as that used as the component (F) described above.

<Polyamide> This polyamide is not particularly limited, and includes ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2.2.4- and 2.4.4-trimethylhexamethylenediamine. , 1,3- and 1,4-bis(aminomethyl>cyclohexane), bis(p-aminocyclohexyl)methane, m-xylylenediamine, p-xylylenediamine and other aliphatic, alicyclic or aromatic diamines. and polyamides derived from aliphatic, alicyclic or aromatic dicarboxylic acids such as adipic acid, superric acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid; epsilon-caprolactam, ω-dodecalactam, etc. Polyamides obtained by ring-opening polymerization of lactams; boria-based acids derived from 6-aminocaproic acid, 1,1-aminoundecanoic acid, 1,2-aminododecanoic acid, etc., and copolymerized polyamides or mixed polyamides thereof Among these, nylon-6 (
Polycaproamide), Nylon-66 (Polyhexamethylene adipamide), Nylon-12 (Polydodecaamide), Nylon-610 (Polyhexamethylenediamine)
, nylon-46 and copolymers and mixtures thereof are useful.

There are no particular restrictions on the degree of polymerization of this polyamide.
Normally, any relative viscosity (measured at 25°C for a solution obtained by dissolving 1 g of polymer in 98% sulfuric acid 100%) within the range of S ~ 6.0 can be used. Particularly, using a polyamide having this value in the range of 2 to 5, it is possible to obtain a thermoplastic resin composition with an excellent balance between impact resistance and moldability.

Further, the molecular structure of this polyamide is not limited either, and it may be either a linear polyamide or a branched polyamide.

Polyester> The polyester is not particularly limited, but it is preferably one obtained by polycondensation of a dicarboxylic acid or a derivative such as an alkyl ester of a dicarboxylic acid and a diol. Of the composition of this polyester, 70 to 100 mol% of the portion composed of dicarboxylic acid
is composed of terephthalic acid, and 30 to 0 mol% of isophthalic acid, terephthalenedicarboxylic acid,
Particularly preferred are those that are laterally squeezed with adipic acid, sebacic acid, or the like. The part composed of glycol is
ethanediol, propanediol, butanediol,
It may be composed of one or more of bentanediol, hexanediol, and the like. Further, there may be a portion laterally squeezed with oxybenzoic acid or bisphenol 8, and mixed polyesters containing one or more of these polyesters are also included in the scope of this polyester.

Examples of such polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, and copolymers and mixtures thereof.

[Thermoplastic resin composition]

Next, the proportions and characteristics of the constituent components of each of the thermoplastic resin compositions of the present invention will be explained.

Composition I> This composition (1) is the composition according to claim 1. This composition I consists of a hydrogenated polymer (A) and a rubbery polymer (B).
).

The ratio of hydrogenated polymer (A) to rubbery polymer (B) is 10 to 99:90 to 1, preferably 10 to 95 by weight.
: 90-5, more preferably 20-95:80-5
, particularly preferably 30-90:70-1O.

If the proportion of the rubbery polymer (B) is too small, the resulting thermoplastic resin composition will not have good [rIi resistance and ductility; on the other hand, if the proportion is too large, the hydrogenated polymer There is a possibility that the excellent properties of (A) will not be exhibited.

This composition I can be obtained by kneading the hydrogenated polymer (A) and the rubbery polymer (B) at a temperature of 250 to 350°C using various extruders, Banbury mixers, Nigu rolls, etc. can. More simply, each component can be directly melted and kneaded in a molding machine to form a bottom shape.

In order to improve the compatibility between the two during this melt-kneading process, unsaturated compounds having specific functional groups such as epoxy groups, carboxyl groups, hydroxyl groups, amino groups, acid anhydrides, oxazoline groups, etc. Organic peroxides can be added. The addition ratio of the unsaturated compound having this specific functional group is 0.01 to 3% of the total composition.
It is preferably within the range of 0% by weight.

When melt-kneading the hydrogenated polymer (A) and the rubbery polymer (B), the rubbery polymer (B) should be dynamically crosslinked with a crosslinking agent, and the hydrogenated polymer (
Additives that form chemical bonds between A) and the rubbery polymer (B) can be added. Generally known means can be used to crosslink rubbery polymers, such as peroxide crosslinking method using a combination of organic peroxide and a polyfunctional compound such as divinylbenzene, sulfur crosslinking method, A resin crosslinking method using a phenol resin or the like, and others can be used.

The thermoplastic resin composition of Composition (1) is characterized by having excellent impact resistance and ductility.

<Composition (2)> This composition (2) is the composition according to claim 2. This composition (2) is composed of a hydrogenated polymer (A) and a rubber-reinforced thermoplastic resin (C).

The ratio of the hydrogenated polymer (A) to the rubber reinforced thermoplastic resin (C) is 5 to 95:95 to 5, preferably 8 to 95:95 by weight.
92:, 92-8, more preferably lO-90:90-
If the proportion of the rubber-reinforced thermoplastic resin (C) is too small, the composition (2) will not have sufficient impact resistance, while if it is too large, the tensile strength will decrease. do.

The proportion of the rubbery polymer in the entire composition (1) is 2 to 2.
50% by weight, preferably 3-45% by weight, more preferably 5-40% by weight. If this proportion is less than 2% by weight, the composition (2) will have low impact resistance, and if this proportion is greater than 50% by weight, the tensile strength will be reduced.

The mixing method for obtaining Composition (1) and the possibility of using specific additives to improve compatibility during melt-kneading are the same as in the case of Composition I.

The thermoplastic resin composition of Composition (1) is characterized by having excellent impact resistance and ductility.

Composition (2) This composition (2) is the composition according to claim 3. This composition (1) is composed of a hydrogenated polymer (A) and a hydrogenated block copolymer (D-1) and/or a hydrogenated diene block copolymer (D-2).

The proportion of the hydrogenated polymer (A) in this composition ① is 1
0 to 98% by weight, preferably 15 to 95% by weight,
More preferably, it is 20 to 90% by weight. Also, the composition ■
(D-1) component and/or (D-2) li in
The proportion of t is 2 to 90% by weight, preferably 5 to 8% by weight.
It is 5% by weight, more preferably 10 to 80% by weight. When this proportion is less than 2% by weight, Composition (1) has low impact resistance, and when it exceeds 90% by weight, it has low heat resistance.

The mixing method for obtaining Composition (1) and the possibility of using specific additives to improve compatibility during melt-kneading are the same as in the case of Composition I.

This m-acid (2) is characterized by its excellent impact resistance and ductility, as well as its high transparency.

<Composition (2)> This composition (2) is the composition according to claim 4. This composition (2) is composed of a hydrogenated polymer (A), a hydrogenated diene polymer (E), and a polyolefin (F).

The proportion of the hydrogenated polymer (A) in this composition ① is 1
0 to 93% by weight, preferably 13 to 90% by weight,
More preferably, it is 15 to 90% by weight. This ratio is 1
If the amount is 0% by weight, sufficient heat resistance will not be obtained in the resulting composition (2), while if it exceeds 98% by weight, it will be difficult to develop sufficient impact resistance.

The proportion of the hydrogenated diene polymer (E) in this composition (2) is 2 to 40% by weight, preferably 3 to 38% by weight, and more preferably 5 to 35% by weight. When this proportion is less than 2% by weight, composition (2) has low impact resistance, with 9%
If it exceeds 0% by weight, heat resistance will be low.

The proportion of polyolefin (F) in this composition (■) is 5
-88% by weight, preferably 7-85% by weight, more preferably 10-85% by weight. When this proportion is less than 5% by weight, composition (1) has poor chemical resistance, and when it exceeds 88% by weight, it has low heat resistance.

The mixing method for obtaining Composition (1) and the possibility of using specific additives to improve compatibility during melt-kneading are the same as in the case of Composition I.

This composition ■ has excellent impact resistance and ductility, and
Another feature is that it has excellent chemical resistance.

Composition V> This composition V is the composition according to claim 5. This composition V is composed of a hydrogenated polymer (A), a modified hydrogenated diene polymer (G), and a polymer (H).

The proportion of hydrogenated polymer (A) in this composition V is 1
0 to 93% by weight, preferably 13 to 90% by weight,
More preferably, it is 15 to 90% by weight. This ratio is l
If O is present in an amount of % by weight, sufficient heat resistance will not be obtained in the resulting composition V, while if it exceeds 98% by weight, sufficient impact resistance will be difficult to develop.

The modified hydrogenated diene polymer (G
) is 2 to 40% by weight, preferably 3 to 38% by weight.
% by weight, more preferably 5 to 35% by weight. When this proportion is less than 2% by weight, composition (2) has low impact resistance, and when it exceeds 40% by weight, it has low heat resistance.

The proportion of the polymer (H) in this composition V is 5 to 88% by weight, preferably 7 to 85% by weight, and more preferably 10 to 85% by weight. If this proportion is less than 5% by weight, Composition V will have poor chemical resistance, and if it exceeds 88% by weight, it will have low heat resistance.

The mixing method for obtaining Composition V and the possibility of using specific additives to improve compatibility during melt-kneading are the same as in the case of Composition (2).

This composition V is characterized by excellent impact resistance and ductility, as well as excellent heat resistance and chemical resistance.

The thermoplastic resin composition of the present invention described above, that is, each of the above compositions Coalescence can be blended as appropriate. Such polymers are
For example, polystyrene, polyethylene, polypropylene,
Polymethyl methacrylate, styrene-methyl methacrylate copolymer, polycarbonate, polyamide, thermoplastic polyamide elastomer, thermoplastic polyamide-polyester elastomer, thermoplastic polyester elastomer, polybutylene terephthalate, polyethylene terephthalate, ABS resin, AS resin, HIPS, It is selected from polysulfone, polyphenylene ether, polyether sulfone polyimide, polyphenyl sulfide, polyether ether ketone, vinylidene fluoride polymer, etc.

Moreover, various additives can be added to the thermoplastic resin composition of the present invention as necessary.

Examples of additives include antioxidants, such as 2°6-di-t-butyl-4-methylphenol, 2-(1-methylcyclohexyl)-4,6-dimethylphenol,
．． 2-methylene-bis-(4-ethyl-6-t-butylphenol), tris(dinonylphenyl>phosphite; ultraviolet absorber, e.g. pt-butylphenyl salicylate), 2,2'-dihydroxy-4 -methoxybenzophenone, 2-(2″-hydroxy-4°-m-octoxyphenyl>benzotriazole; lubricants such as paraffin wax, stearic acid, hydrogenated oils, stearamide, methylene bisstearamide, n-butyl stearate, Ketone wax, octyl alcohol, hydroxystearic acid triglyceride; flame retardants such as antimony oxide, aluminum hydroxide, zinc oxalate, tricresyl phosphate, tris<dichloropropyl>phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene , tetrabromobisphenol A;
Antistatic agents, e.g. stearamidopropyl dimethyl-
Examples include β-hydroxyethyl, ammonium drate; coloring agents such as titanium oxide, carbon black; and pigments. Furthermore, known plasticizers and the like can also be used.

Furthermore, the thermoplastic resin composition of the present invention includes glass fiber, carbon fiber, glass beads, asbestos, wollastonite, calcium carbonate, talc, barium sulfate, mica, potassium titanate, fluorine resin, Fillers such as molybdenum sulfide can be used alone or in combination of two or more. Among these, glass fiber and carbon fiber have a fiber diameter of 6 to 60 m and a diameter of 30 JIm.
It is preferable to have a fiber length of the above length. These fillers are contained in an amount of 1 to 150 parts by weight per 100 parts by weight of the thermoplastic resin composition.
It is preferably contained in the proportion of parts by weight.

The thermoplastic resin composition of the present invention can be made into various molded products by injection molding method, sheet extrusion method, vacuum forming method, irregular bottom foaming method, press molding method, stun molding method, etc. can.

The various molded products obtained here can be used for automobile exterior parts, interior parts, various electrical and electronic parts, housings, optical materials, etc. by utilizing their excellent properties.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

In the following, "parts" indicate parts by weight.

In addition, the measurement of each characteristic was performed according to the following conditions.

Hydrogenation rate: Based on 60MHz NMR.

Impact resistance: Izot impact strength (according to ASTM D256, with 178″ notch) Heat resistance: Heat distortion temperature (according to ASTM D 648).

18.6Kg/cm2.1/4") Ductility: Tensile elongation (A tensile test was performed on a small dumbbell test piece at a tensile speed of 50 mm/min using an autograph,
(Measure the rate of elongation) Tensile strength: Based on a tensile test under the same conditions as for the ductility above. ) Total light transmittance: (according to ASTM D 2003).

Thickness: 3 mm> Chemical resistance: A constant strain of 1% strain rate was applied to the test piece, brake fluid was applied to the flexed part, and the time until breakage was measured after being left at 23°C.

In the evaluation, "◎" means until 100 hours have passed,
Indicates that no abnormalities such as breaks or cracks occurred.

Composition I> The following polymer (A) and rubbery polymer (B) were prepared.

Hydrogenated polymer (A) *Polymer A-1 A hydrogenated polymer produced by the method below.

In a reaction vessel purged with nitrogen gas, 500 g of a specific monomer 8-carboxymethylteto5 Schifo [4,4,0,121,1'''-3-dodecene represented by the following structural formula (1), 1,2-dichloroethane 2000-, l-hexene 3.8 g as a molecular weight regulator, chlorobenzene solution 91,6- of tungsten hexachloride with a concentration of 0.05 M/j as a catalyst, and paraaldehyde with a concentration of 0. 1
The intrinsic viscosity (ηl+h )0.78a/g
(450 g of a ring-opened polymer was obtained at a concentration of 0.5 g/di in chloroform at 30° C.).

This ring-opening polymer was dissolved in 9,000 g of tetrahydrofuran, 45 g of palladium-alumina catalyst with a palladium concentration of 5% was added, and hydrogen gas was added to a pressure of 100 g of 7 cm.
” and hydrogenation reaction was carried out at 150°C for 5 hours.

After the hydrogenation reaction, the catalyst was filtered off, and the filtrate was poured into a large excess of methanol acidified with hydrochloric acid to produce a hydrogenated polymer.

The hydrogenation rate of this polymer A-1 is virtually 100%, and the refractive index is nl! =1.511.

*Polymer A-2 As a specific monomer, 8-methyl-8-carboxymethyltetracyclo[4,4,0
,1"-', l'・"]-]3-dodecene was used in the same manner as in the production of polymer A-1, and the intrinsic viscosity (η5hh) was 0.56 dl/g (in chloroform, at 30°C , a ring-opened polymer with a concentration of 0.5 g/d1) was obtained,
A hydrogenated polymer obtained by subjecting this to a hydrogenation reaction in the same manner as Polymer A-1.

The hydrogenation rate of this polymer A-2 was essentially 100%, and the refractive index was nl = 1.512.

*Polymer A-3 As a specific monomer, it is represented by the following structural formula <3) 5-
Polymer A-1 was obtained in the same manner as in the production of polymer A-1, except that carboxymethyl-bicyclo[2,2,11-2-heptene was used. Hydrogenated polymer at 30°C, concentration 0.5 g/a).

The hydrogenation rate of this polymer A-3 is substantially 100%, and the refractive index is II = 1. It was '510.

Comparative Ring-Opening Polymer*Polymer A-4 A non-hydrogenated ring-opening polymer produced in the same manner as in the production of Polymer A-1. The refractive index of this polymer A-4 was nl = 1.542.

The structural formula of the specific monomer used above is as follows.

Structural formula (1) Structural formula (2) Structural formula (3) Rubber polymer (B) *Rubber polymer B-1 A polymer produced by the method below.

In an autoclave with a capacity of 5 Il, 2500 g of degassed and dehydrated cyclohexane, 160 g of styrene, and 1.3
After charging 340 g of -butadiene, 2.5 g of tetrahydrofuran and 0.34 g of n-butyllithium were added to carry out a polymerization reaction. The polymerization temperature increased from 30°C to 80°C.

At the point when the conversion rate is almost 100%, 2゜6-
Add sheet tert-butylcatechol, remove the solvent by steam stripping, and dry with a hot roll at 120°C to obtain a vinyl bond amount of 30% and a styrene content of 3.
A 2% styrene-butadiene copolymer was obtained.

This styrene-butadiene copolymer was charged into an autoclave with a capacity of 31 cm to form a cyclohexane solution with a concentration of 15%. After purging the inside with nitrogen gas, a catalyst solution of nickel naphthenate: n-butyl lithium: tetrahydrofuran = l: 3:20 (mole ratio) prepared in advance in a separate vessel was added to a catalyst solution with a ratio of nickel to 2000 moles of olefin part. 1
It was prepared in a ratio of moles.

Thereafter, hydrogen gas was introduced into the reaction system, and a hydrogenation reaction was carried out at 70°C. After controlling the hydrogenation rate based on the amount of hydrogen gas absorbed and consumed, the hydrogen gas in the system was replaced with nitrogen gas, and the anti-aging agent 2,6-di-tert-butyl para-cresol was added at a rate of 1%. After repeating catalyst removal and coagulation, roll drying was performed by a conventional method to obtain a hydrogenated diene copolymer with a hydrogenation rate of 95%.

*Rubbery polymer B-2 n-butyl acrylate obtained by emulsion polymerization of 60 parts of n-butyl acrylate, 15 parts of butadiene, 22 parts of acrylonitrile, and 3 parts of divinylbenzene.
Butadiene-acrylonitrile copolymer.

*Rubber polymer B-3 A copolymer obtained by emulsion polymerization of 60 parts of n-butyl acrylate, 15 parts of butadiene, and 25 parts of acrylonitrile was coagulated and dried, and after dissolving it in a solvent, A copolymer obtained by hydrogenation reaction.

*Rubber polymer B-4 Hydrogenated styrene-butadiene-styrene block copolymer "Krayton G 1650J (manufactured by Shell).

*Rubber polymer B-5 Hydrogenated styrene-isoprene block copolymer "Krayton 01701J (manufactured by Shell).

*Rubber polymer B-6 Hydrogenated butadiene-acrylonitrile copolymer "Tilmer 1707J (Bayer AG II).

*Rubber polymer B-7 Styrene-butadiene-styrene block copolymer rJ
sRTR2000J (manufactured by Japan Synthetic Rubber Co., Ltd.).

*Rubber polymer B-8 1,2-polybutadiene rJsRRB 820J (
Manufactured by Japan Synthetic Rubber.

*Rubber polymer B-9 Acrylic rubber obtained by emulsion polymerization of 97 parts of 2-ethylhexyl acrylate and 3 parts of divinylbenzene.

Examples 1-1 to! -14 and Comparative Example 1-1 and!
-2 The above polymers A-1 to A-4, rubbery polymers B-1 to B-9, and additives are mixed according to the formulation shown in Table 1, kneaded using a Nigu roll, and then crushed. A molded article of a thermoplastic resin composition as Composition I was obtained by an injection molding method. A test piece was prepared from the thermoplastic resin composition and its impact resistance and ductility were evaluated. The results are shown in Table 1.

From the results in Table 1, it can be seen that rubbery polymer (B
) is not mixed, the impact strength and tensile elongation of the resin composition are low, and as in Comparative Example 2,
It is clear that when a non-hydrogenated polymer is used, the impact resistance and ductility are not improved even when the rubbery polymer (B) is mixed.

(Effect of the invention according to claim 1) The thermoplastic resin composition which is the composition I according to the present invention has good optical properties, low hygroscopicity and excellent heat resistance due to the hydrogenated polymer (A). However, it also has superior impact resistance and ductility.

Composition ■> Hydrogenated polymer (A) The above polymers A-1 to A-3 and non-hydrogenated polymer A-4 Rubber-reinforced thermoplastic resin (C) *Rubber-reinforced thermoplastic resin C- 1 Hydrogenated block copolymer rKRATO with a refractive index of 1.507 was prepared in advance into a homogeneous solution state in a stainless steel autoclave with an internal volume of 10 mm equipped with a paddle type stirring device.
NG-1650J (Shell Chemical Co., Ltd. 5EBS
)1ON, X tyrene lO,8Is, and toluene 100
and 0.1 B of t-dodecyl mercaptan,
Raise the temperature while stirring and add methyl methacrylate at 50°C.
．． 0.5 fl of 211t-butylperoxyisopropyl carbonate was added. After replacing the system with nitrogen, see page 9.
The temperature was raised to 0°C, and polymerization was continued at this temperature with stirring until the polymerization conversion rate reached 74%. When the polymerization conversion rate reached 74%, the polymerization was stopped and an antiaging agent was added. Thereafter, the contents were taken out from the autoclave, unreacted monomers and solvent were removed by steam distillation, and the obtained polymer was finely ground, dried, and pelletized using a vented extruder with a diameter of 40 mm.

This rubber reinforced thermoplastic resin C-2 Hydrogenated block copolymer rK with a refractive index of 1.5105
A polymerization reaction was carried out using 15 parts of RATON G-1701XJ (5EBS manufactured by Shell Chemical Co., Ltd.), 12.8 parts of styrene, and 72.2 parts of methyl methacrylate in the same manner as rubber reinforced thermoreproducible resin C-1. I did it.

After stopping the polymerization when the polymerization conversion rate reached 70%,
Post-treated in the same manner as rubber-reinforced thermoplastic resin C-1,
A graft copolymer was obtained.

The rubbery polymer content of the obtained graft copolymer was 20
% by weight, and the refractive index of the copolymer consisting only of the monomer mixture was 1.5113.

*Rubber-reinforced thermoplastic resin C-3 Two reactors each consisting of a stainless steel autoclave with an internal volume of 30 cm equipped with a paddle-type stirring device, with the supply to each reactor being carried out from the bottom of the reactor, and the top Polymerization was carried out according to the recipe and conditions shown below using a polymerization reactor connected in an overflow manner.

Feedstock to the first reactor: Hydrogenated block copolymer rKRATONG-165D
J...20 parts styrene
...11 parts Methyl methacrylate ...64 parts t-dodecyl mercaptan ... o,tgt-butylperoxyisopropyl carbonate
... 0.5 parts Polymerization conditions in the first reactor Polymerization temperature 90°C Polymerization conversion rate 50% Average residence time M 3 hours Polymerization conditions in the second reactor Polymerization temperature 90°C Polymerization conversion rate 75% Average residence time 3 hours Then, the polymerization solution overflowing from the second reactor was temporarily held in a tank, and then introduced into an extruder with an open vent of 65 mm diameter to separate and remove volatile components and form pellets.

The rubbery polymer content of the obtained graft copolymer was 24
．． 8% by weight, and the refractive index of the copolymer fat consisting only of the monomer mixture was 1.5066.

This rubber-reinforced thermoplastic resin C-4 was polymerized in the same manner as the rubber-reinforced thermoplastic resin C-1, except that polybutadiene (PBD) was used instead of the hydrogenated block copolymer as the base rubber. , a rubber-reinforced thermoplastic resin obtained by post-treatment.

*Rubber reinforced heat transferable resin C-5 Ethylene-propylene copolymer rubber r as base rubber
JSREPOIPJ (Japan Synthetic Rubber Company m1) iof1
6, rubber reinforced thermoplastic resin C except that 81 parts of methyl methacrylate and 9 parts of methyl acrylate were used.
Rubber-reinforced thermoreproducible resin obtained by polymerization and post-treatment in the same manner as -1.

Examples 11-1 to 11-7 and Comparative Examples 11-1 to 11-4 The above polymers A-1 to A-4 and rubber-reinforced thermoplastic resins C-1 to C-5 were prepared in the formulations shown in Table 3. Mix, diameter 2
The molded product was molded at a temperature of 260° C. using a 0+11111 extruder to obtain a molded article of a thermoplastic resin composition as Composition (2). A test piece was prepared from the mononuclear thermoplastic resin composition, and its impact resistance and ductility were evaluated. The results are shown in Table 2.

From the results in Table 2, Comparative Example [-1 and Comparative Example n-2 have a small proportion of rubber-reinforced thermoplastic resin (C), so impact resistance, tensile strength, and elongation are low. -3 has a low tensile strength and elongation due to a small proportion of hydrogenated polymer (A), and the polymer corresponding to component (A) of Comparative Example IF-4 is not hydrogenated. It is obvious that the impact resistance and tensile strength and elongation are low.

(Effects of composition (2)) The thermobreathable resin composition which is composition (2) according to the present invention has good optical properties, low hygroscopicity and excellent heat resistance due to the hydrogenated polymer (A). However, it has even better impact resistance and ductility.

Composition ■> The following polymers (A>, hydrogenated block copolymer (D-1)
) and a hydrogenated block copolymer (D-2) were prepared.

Hydrogenated polymer (A) The above polymers A-1 to A-3 and non-hydrogenated polymer A-4 Hydrogenated block copolymer (D-1) *Hydrogenated block copolymer D-1 -1 Hydrogenated block copolymer obtained by the following (1> and (2)).

(1) After charging 2500 g of degassed and dehydrated cyclohexane and 350 g of 1,3-butadiene into a No. 51 autoclave, 0.50 g of n-butyllithium was added.
Isothermal polymerization was carried out at 50°C. After the conversion rate reached 31%, 12.5 g of tetrahydrofuran was added and polymerization was carried out at elevated temperature from 50°C to 80°C. After the conversion rate reached approximately 100%, 150 g of styrene was added and polymerization was carried out for 15 minutes to obtain an a-b-C) IJ block copolymer. Its molecular properties are shown in Table 3-1.

(2> Next, in another container, titanocene dichloride 1.95
g to 30stl of cyclohexane! and reacted with 2.68 g of triethylaluminum at room temperature.

The obtained dark blue, apparently fine solution was added to the polymer solution obtained in (1) above, and 5.0 kg f was added at 50°C.
The hydrogenation reaction was carried out for 2 hours at a hydrogen pressure of /c-.

After that, the solvent was removed with methanonyl/hydrochloric acid, and the 2.6-sheet
Ert-butylcatechol was added and drying was performed under reduced pressure to obtain a hydrogenated a-b-c)Q block copolymer. Its molecular properties are shown in Table 3-2.

*Hydrogenated block copolymer D-1-2 A hydrogenated block copolymer obtained by the following (1) and (2).

(1> Using the same equipment as for hydrogenated block copolymer D-1-1, 2500 g of cyclohexane, 350 g of 1,3-butadiene, and 0.25 g of tetrahydrofuran
After charging, 0.50 g of n-butyllithium was added and polymerization was carried out isothermally at 50°C. After the conversion rate reached 11%, 12.5 g of tetrahydrofuran was added, and polymerization was carried out at elevated temperature from 50°C to 80°C. After the conversion rate reached approximately 100%, 150 g of styrene was added and polymerization was carried out for 15 minutes to obtain an a-b-c)'J block copolymer. Its molecular properties are shown in Table 3-1.

(2) Hydrogenate the a-b-C) rib block copolymer obtained in (1) above in the same manner as hydrogenated block copolymer D-1-1, and hydrogenate a1)-c triblock copolymer. A block copolymer was obtained. Its molecular properties are shown in Table 3-2.

*Hydrogenated block copolymer D-1-3 A hydrogenated block copolymer obtained by the following (1) and (2>).

<1> Using the same apparatus as hydrogenated block copolymer D-1-1, a-b was obtained by increasing the amount of n-butyllithium and decreasing the amount of tetrahydrofuran from the hydrogenated block copolymer D-1-1. -c) A rib block copolymer was obtained. Its molecular properties are shown in Table 3-1.

(2) Hydrogenate the a-b-c) rib block copolymer obtained in (1) above in the same manner as hydrogenated block copolymer D-1-1, and hydrogenate the a-b-c) A rib block copolymer was obtained. Its molecular properties are shown in Table 3-2.

*Hydrogenated block copolymer D-1-4 A hydrogenated block copolymer obtained by the following (1> and (2)).

(1> Same as D-1-1 except that the same equipment as hydrogenated block copolymer D-1-1 was used and the amount of n-butyllithium was increased from that of hydrogenated block copolymer D-1-1. A b-b-c) rib block copolymer was obtained. This a-
b-C) Dimethyldichlorosilane was added to the block copolymer in an amount of 0.5 molar equivalent to n-butyllithium, and a coupling reaction was performed (a-b-c) to form an X-type block copolymer. Obtained.

The obtained block copolymer had a vinyl content of C block of 13% by weight and a number average molecular weight of 11.000, a vinyl content of B block of 51% by weight and a number average molecular weight of 32.
．． 000, the styrene content of the a block was 100% by weight and the number average molecular weight was 18.000.

(2> Hydrogenated block copolymer D-1-
Hydrogenated (
ab C) A 2X type block copolymer was obtained.

This hydrogenated block copolymer has a hydrogenation rate of 96% for the butadiene unit and 1% for the styrene unit.
They were as follows. The molecular properties of this hydrogenated block copolymer are shown in Table 3-2.

*Hydrogenated block copolymer D-1-5 A hydrogenated block copolymer obtained by the following (1> and (2)).

(1) Using the same equipment as for hydrogenated block copolymer D-1-1, 2500 g of cyclohexane and 350 g of 1,3-butadiene were charged, and then 1 g of tetrahydrofuran was charged.
2.5 g and 0.50 g of n-butyllithium were added and polymerization was carried out at elevated temperature from 50°C to 80°C. After the conversion reached approximately 100%, 150 g of styrene was added and polymerization was continued for an additional 15 minutes to obtain an a-b block copolymer.

The molecular properties of the obtained polymer are shown in Table 13-1.

<2> The a-b block copolymer obtained in the above (1) was hydrogenated in the same manner as hydrogenated block copolymer D-1-1 to obtain a hydrogenated a-b block copolymer. Its molecular properties are shown in Table 3-2.

Hydrogenated block copolymer (D-2) Hydrogenated diene block copolymer D-2-1 below (1
) and a hydrogenated diene block copolymer obtained by (2).

(1) After charging 2500 g of degassed and dehydrated cyclohexane and 50 g of styrene into an autoclave with an internal volume of 51 cm, 9.8 g of tetrahydrofuran and 0.2 g of n-butyllithium were added, and isothermal polymerization was performed at 50°C. 1st stage polymerization).

After the polymerization conversion rate reached almost 100%, 1.3
- while continuously adding a mixture of 350 g of butadiene and 100 g of styrene at a rate of 75 g per 10 minutes,
Polymerization was carried out at 70°C (second stage polymerization).

Sampling was performed every 10 minutes during the polymerization, and the content of bound styrene and the microstructure of 1°3-butadiene in the successively produced polymers were measured.

(2) After the conversion rate of the added monomer reached almost 100%, the reaction solution was cooled to 70°C, and n-butyllithium 0,6
g, 0.6 g of 2.6-t-butylcresol, and 0.6 g of bis(cyclopentagenyl>titanium dichloride).
28 g of diethylaluminum and 1.1 g of diethylaluminium were added, and a hydrogenation reaction was carried out for 1 hour while maintaining the hydrogen gas pressure at 1.0 kg/ca+2. Next, the reaction solution was cooled to room temperature and taken out from the autoclave, and then the solvent was removed by steam stripping and dried with a roll at 120° C. to obtain a hydrogenated diene block copolymer D-2-1.

As a result of measuring the properties of the obtained hydrogenated diene block copolymer D-2-1 by the above-mentioned analytical method, the total bound styrene content in the copolymer before hydrogenation was 30% by weight.
The bound styrene content of the polymer obtained in the first stage polymerization is 100% by weight, and from the monomer conversion rate and the amount of the copolymer finally obtained, it accounts for 100% by weight in the total copolymer. The ratio is 1
It was 0% by weight. Let this component be block d.

Next, as a result of sequential analysis, polymerization proceeded while the composition of styrene and 1,3-butadiene in the second stage product remained constant, and as a result of GPC measurement, low molecular weight products were partially released as the reaction progressed. It was confirmed that the living reaction had progressed, as the molecular weight was gradually increasing without any presence of the compound. This 1.
The vinyl bond content of 3-butadiene was analyzed to be 40% by weight. Let this component be block e.

In addition, this hydrogenated diene block copolymer Riichi 2-1
Analysis of the residual double bonds in the conjugated diene moiety revealed that the hydrogenation rate was 98%. Also, its molecular weight is 150.0
00, and the melt flow rate at 230° C. and a load of 5 kg was 40 g/10 m1n. The molecular properties of this copolymer D-2-1 are shown in Table 4.

Present hydrogenated diene block copolymer D-2-2 Hydrogenated diene block copolymer obtained by the following method.

First stage polymerization: Styrene: 25 g Tetrahydrofuran: 9.8 g Second stage polymerization: Styrene: 50 g, 3-butadiene: 425 g or more Copolymerization was used except when a polymerization recipe of 425 g or more was used. Hydrogenated diene-based block copolymer D-2-2 was obtained in the same manner as Coalesce D-2-1. This copolymer D
Table 4 shows the molecular properties of -2-2.

*Hydrogenated diene block copolymer D-2-3 A hydrogenated diene block copolymer obtained by the following method.

1st stage polymerization: Styrene...25 g Tetrahydrofuran...3g 2nd stage polymerization: Styrene...100g 1,3-butadiene...350g or more Copolymer D except for the polymerization recipe used Hydrogenated diene block copolymer D-2-3 was obtained in the same manner as in -2-1. The molecular properties of this copolymer D-2-3 are shown in Table 4.

*Hydrogenated diene block copolymer D-2-4 A hydrogenated diene block copolymer obtained by the method below.

First stage polymerization: Styrene: 100g Tetrahydrofuran: 9.8g Second stage polymerization: Styrene: 75 g, 3-butadiene: 325g or more Copolymers except for those using polymerization formulations Hydrogenated diene block copolymer D-2-4 was obtained in the same manner as D-2-1. The molecular properties of this copolymer D-2-4 are shown in Table 4.

*Hydrogenated diene block copolymer D-2-5 A hydrogenated diene block copolymer obtained by the method below.

First stage polymerization: Styrene: 50 g Tetrahydrofuran: 9.8 g Second stage polymerization: Styrene: 200 g 1,3-butadiene: 250 g or more Copolymer Hydrogenated diene block copolymer D-2-5 was obtained in the same manner as D-2-1. The molecular properties of this copolymer D-2-5 are shown in Table 4.

Examples DI-l to lll-14 and comparative examples m-1 to II! -8 The above hydrogenated polymers A-1 to A-4, hydrogenated block copolymers D-1-1 to D-1-5, and hydrogenated diene block copolymers D-2-1 to D- 2-5 to 5th
The formulations shown in Tables and Table 6 were mixed and pellets were produced using an extruder with a diameter of 50III at a temperature of 280°C. This pellet was molded into a bottom shape using an injection molding machine rIS-80AJ (manufactured by Toshiba Corporation) at a molding temperature of 280°C to obtain a molded article of a thermoplastic resin composition as Composition ①. A test piece was prepared, and its impact resistance, heat resistance, ductility, and total light transmittance were measured.The results are shown in Tables 5 and 6.

(Effects of Composition (2)) The thermoplastic resin composition that is Composition (2) according to the present invention has good optical properties and low moisture absorption due to the hydrogenated polymer (A), and also has excellent impact resistance. It has ductility, high transparency and even better heat resistance.

Composition (2) The following polymer (A), hydrogenated diene polymer (E), and polyolefin (F) were prepared.

Hydrogenated polymer (A) Above polymer A-1 Hydrogenated diene polymer (E) *Hydrogenated diene polymer E-1 rKARATON G1650J (manufactured by Shell Chemical Co.) *Hydrogenated diene polymer E- 2 A random copolymer of butadiene with a vinyl bond content of 30% by weight, a styrene content of 30% by weight, and a number average molecular weight of 200.000, with a double bond of 98%.
% hydrogenated diene polymer.

*Hydrogenated diene polymer E-3 A block copolymer consisting of α-β-T, where α is a styrene block, β is a random co-block of styrene and butadiene, and γ is a co-block of styrene and butadiene in which styrene gradually increases. The styrene content in the block copolymer is 30% by weight, the total styrene content of α and T in the block copolymer is 15% by weight, and the styrene content of α in the block copolymer is 15% by weight. 5% by weight, the vinyl bond metal content in the butadiene portion of β is 40% by weight, and the number average molecular weight of the entire block copolymer is iao, ooo. Hydrogenation in which 98% of the double bonds are hydrogenated Diene polymer.

Polyolefin (F) *Polyolefin F-1 Polyethylene (manufactured by Mitsubishi Yuka Co., Ltd.) *Polyolefin F-2 Polypropylene (manufactured by Chisso Chemical Co., Ltd.) Examples mV-l to rV-8 and comparative examples TV-l to -6 40 aue extruder Pellets were prepared by kneading at a temperature of 280° C. according to the formulation shown in Table 9. This pellet was molded into a bottom shape using an injection molding machine RLS-80AJ (manufactured by Toshiba Corporation) at a molding temperature of 280°C to obtain a molded article of a thermoplastic resin composition as composition (2).The thermoplastic resin composition was then tested. A piece was prepared and its impact resistance, ductility, heat resistance and chemical resistance were measured.The results are shown in Table 7.

(Effects of Composition (2)) The thermoplastic resin composition which is Composition (2) according to the present invention has good optical properties and low moisture absorption due to the hydrogenated polymer (A), and also has excellent impact resistance. It has properties such as strength and ductility, as well as excellent heat resistance and chemical resistance.

<Composition V> The following polymer (A), modified hydrogenated diene polymer (G
) and polymer (H) were prepared.

Hydrogenated polymer (A) Above polymer A-1 Modified hydrogenated diene polymer (G) *Modified hydrogenated diene polymer G-1 to G-3 Above hydrogenated diene polymer E- A modified hydrogenated diene polymer obtained by pelletizing each of 1 to E-3 and 10.2 parts by weight of anhydrous maleic W per 100 parts by weight using a 40a+m extruder at 230°C.

Polymer (H) *Polymer H-1 Nylon-6 "Amilan CM1017J (manufactured by Toshi Co., Ltd.) *Polymer H-2 PBT (manufactured by Polyplastics Co., Ltd.) *Polymer H-3 Polypropylene (manufactured by Chisso Kagaku Co., Ltd., above) Examples V- to V-8 and Comparative Examples V-1 to -4 (same as polyolefin F-2) were kneaded using a 4Qmm extruder at a temperature of 280°C according to the formulation shown in Table 8 to form pellets. This pellet was molded into a bottom shape using an injection molding machine m1s-80AJ (manufactured by Toshiba Corporation) at a molding temperature of 280°C to obtain a molded article of a thermoplastic resin composition as Composition V. A test piece was prepared from the resin composition, and its impact resistance, ductility, heat resistance and chemical resistance were measured.The results are shown in Table 8.

(Effects of composition V) The thermoplastic resin composition which is composition It has impact resistance and ductility, and also has excellent heat resistance and chemical resistance.

〔Effect of the invention〕

The thermoplastic resin compositions of Composition I to Composition II according to the present invention all contain a hydrogenated polymer (A
), it has good optical properties, low moisture absorption, and excellent heat resistance, as well as excellent impact resistance and ductility, and is expected to be developed as a new molding material.

In addition, the thermoplastic resin composition of composition (1) has higher transparency and even better heat resistance in addition to the above-mentioned properties, and the thermoplastic resin composition of composition (2) and composition (V) have even higher transparency and even better heat resistance. In addition to the above-mentioned properties, it has even better chemical resistance and even better heat resistance.

Because of these excellent properties, the thermoplastic resin composition of the present invention can be suitably used for automobile exterior and interior parts, various electrical and electronic parts, housings, optical materials, and the like.

Claims (1)

[Scope of Claims] 1) A thermoplastic resin composition comprising 10 to 99% by weight of the following component (A) and 90 to 1% by weight of the following component (B). Component (A): A monomer consisting of at least one norbornene derivative represented by the following general formula (I), or obtained by ring-opening polymerization of this monomer and a copolymerizable monomer copolymerizable therewith. A hydrogenated polymer obtained by further hydrogenating a ring-opened polymer. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, A and B are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, and hydrocarbon group,
Halogen atom, 1 to 1 carbon atoms substituted with halogen atom
0 hydrocarbon group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. consisting of X and Y. Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. At least one of Y is a group other than a hydrogen atom and a hydrocarbon group {where R^1, R^2, R^3 and R^4 are a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group substituted with a halogen atom, W is SiR^5_pD_3_-_p
(R^5 is a hydrocarbon group having 1 to 10 carbon atoms, D is a halogen atom, -OCOR^6 or -OR^6 (R^6 is a hydrocarbon group having 1 to 10 carbon atoms), p is 0 ~3), n represents an integer of 0 to 10. }, and m is 0 or 1. ]. (B) Component: Rubbery polymer. 2) A thermoplastic resin composition comprising 5 to 95% by weight of component (A) according to claim 1 and 95 to 5% by weight of component (C) below. (C) Component: Rubber reinforced thermoplastic resin. 3) 10 to 98% by weight of component (A) according to claim 1;
The following (D-1) component and/or (D-2) component 2~
90% by weight of a thermoplastic resin composition. (D-1) Component: Block a (block with aromatic vinyl compound content of 90% by weight or more) and block b (1,2-vinyl bond content of 30 to 70% by weight) in the molecule.
polybutadiene block) and block c(1,
2-vinyl bond content of less than 30% by weight), the proportion of block a is 10 to 50% by weight, and the proportion of block b is 30 to 8% by weight.
A block copolymer (i) in which the proportion of 0% by weight and block c is 5 to 30% by weight, or a polymer unit consisting of the block copolymer (i), and the blocks a, b, and c. A block copolymer (ii) in which at least one selected polymer unit is bonded via a coupling agent residue, and at least 80% or more of its olefinic unsaturated bonds are hydrogenated. , number average molecular weight is 40,000 to 700,000
, a hydrogenated block copolymer having a difference in refractive index from the component (A) of 0.02 or less. (D-2) Components: block d (aromatic vinyl compound polymer block), block e (random copolymer block of aromatic vinyl compound and conjugated diene compound), block f (aromatic vinyl compound and conjugated diene compound and a tapered polymer block in which the proportion of aromatic vinyl compound in the molecule gradually increases.
- an f-type block copolymer in which the ratio of aromatic vinyl compound/conjugated diene compound is from 5 to 40/95 by weight;
60, the total amount of aromatic vinyl compounds in block d and block f is 25% by weight or less of the total monomers, the vinyl bond content of the conjugated diene compound portion in block e is 15 to 60% by weight, and the conjugated diene compound A hydrogenated block having a number average molecular weight of 50,000 to 300,000 and a refractive index difference of 0.02 or less from the refractive index of the component (A) obtained by hydrogenating at least 90% or more of the olefinic unsaturated bonds of the component (A). Polymer. 4) 10 to 93% by weight of component (A) according to claim 1;
2 to 40% by weight of the following component (E) and 5 to 40% of the following component (F)
88% by weight of a thermoplastic resin composition. Component (E): A hydrogenated diene polymer which is a hydrogenated product of a polymer consisting of 50% by weight or less of an aromatic vinyl compound and 50% by weight or more of a conjugated diene compound. (F) Component: Polyolefin. 5) 10 to 93% by weight of component (A) according to claim 1;
2 to 40% by weight of the following component (G) and 5 to 40% of the following component (H)
88% by weight of a thermoplastic resin composition. Component (G): 0.01 to 10 parts by weight of an α,β-unsaturated carboxylic acid and/or a derivative thereof is grafted onto 100 parts by weight of the hydrogenated diene polymer which is the component (E) according to claim 4. A modified hydrogenated diene polymer obtained by reaction. Component (H): at least one polymer selected from polyolefin, polyamide, and polyester.