JP2884675B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for preparing a specific monomer in the presence of a diene polymer comprising 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene. Thermoplastic resin excellent in impact resistance, paintability, chemical resistance, and weather resistance obtained by compounding rubber-reinforced resin obtained by graft copolymerization of body components with polyolefin and specific elastomer as main components Composition.

[Conventional technology]

In recent years, the use of polypropylene (PP) -based resin materials for automobile exterior parts such as bumpers has been increasing, and Japanese Patent Application Laid-Open Nos. As can be seen in JP-A-43650, improvements in paintability and rigidity have also been made.

However, such a PP-based resin material has a low polarity and has a low surface energy among plastics, so it can be said that it is a representative example of a material having poor paint adhesion. Therefore, as a measure for improving the adhesion of the paint, etching with a solvent such as 1,1,1-trichloroethane or trichlorotrifluoroethane, and an undercoating step of an adhesive primer are required. However, due to the recent problem of environmental pollution and the demand for simplification of the process, such measures for improving the adhesion cannot be sufficiently solved.

[Problems to be solved by the invention]

The present invention has been made in view of the problems of the prior art, and has as its object to provide a thermoplastic resin composition having good paintability, impact resistance, chemical resistance, and weather resistance.

[Means for solving the problem]

The present invention relates to a hydrogenated diene-based polymer obtained by hydrogenating a diene-based polymer (hereinafter, referred to as a "diene-based polymer") comprising (a) 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene. Combination (I) (hereinafter referred to as "hydrogenated diene polymer (I)") in the presence of 5 to 60 parts by weight of (meth) acrylate (a) and / or aromatic vinyl compound (b) 30 to 100% by weight of a monomer, 70 to 0% by weight of another copolymerizable vinyl monomer (c) [however,
(A) + (b) + (c) = 100% by weight] (hereinafter referred to as “monomer component (II)”).
1 to 98 parts by weight of a rubber reinforced resin (hereinafter referred to as “(A) rubber reinforced resin” or “(A) component”) obtained by graft copolymerization of parts by weight, and (B) a polyolefin (hereinafter referred to as “(B) component”) (C) the hydrogenated diene polymer (I), ethylene-α-
1 to 60 parts by weight of at least one elastomer selected from an olefin rubber and an aromatic vinyl compound-conjugated diene copolymer (hereinafter referred to as "(c) elastomer" or "(c) component"); + (B) + (c)
= 100 parts by weight) (hereinafter referred to as “first composition”).

Further, the present invention relates to 100 parts by weight of the first composition,
(D) Epoxy group-containing monomer (d), carboxyl group-containing monomer (e), amino group-containing monomer (f), hydroxyl group-containing monomer (g) and dicarboxylic anhydride group-containing monomer Compatibilizer obtained by copolymerizing at least one functional group-containing monomer component (III) selected from the group of the monomer (h) (hereinafter referred to as “functional group-containing monomer component (III)”) "(D) Compatibilizer" or "(d) component")
A thermoplastic resin composition comprising 5 to 20 parts by weight (hereinafter referred to as "second composition", and the first and second compositions are collectively referred to as "thermoplastic resin composition") To provide.

First, the first composition of the present invention will be described. This first composition contains (a) a rubber-reinforced resin, (b) a polyolefin, and (c) an elastomer as main components.

The hydrogenated diene-based polymer (I) constituting the component (a) of the first composition is defined as a diene-based polymer comprising 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene. It is added.

Here, the aromatic vinyl compound used for the hydrogenated diene polymer (I) includes styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, Bromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like. And styrene and α-methylstyrene are particularly preferred.

As the conjugated diene, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4 , 5-Diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, etc., which can be used industrially to obtain a hydrogenated diene polymer (I) having excellent physical properties. Is preferably 1,3-butadiene, isoprene and 1,3-pentadiene, more preferably 1,3-butadiene.

Specifically, the diene polymer used in the present invention is a copolymer comprising at least one of the following blocks A or C and at least one of the following blocks B or A / B. It is a diene-based polymer formed by merging or a block B or A / B. The specific constitution is as follows: A; vinyl aromatic compound polymer block, B; conjugated diene polymer block, A / B; random copolymer block of vinyl aromatic compound / conjugated diene, C; conjugated diene and vinyl aromatic When each of the tapered blocks is made of a copolymer of the compound and gradually increases in the amount of the vinyl aromatic compound, the tapered block has the following structure.

A-B, A-B- A, A-B-C, A-B 1 -B 2 ( wherein the vinyl bond content of B ₁ represents preferably 20% or more, a vinyl bond content of B ₂ is less than 20% ), B, A / B, A-A / B, A-A / B-C, A-A / B-A, B 2 -B 1 -B 2 ( wherein, B _1, B ₂ in the The same), CB, CBC, CA / BC, CAB.

In addition, a copolymer having these basic skeletons repeatedly can be mentioned, and a diene-based polymer obtained by coupling them may be used.

For a structure of the A-B ₁ -B ₂ is No. Sho 63
Japanese Patent Application Laid-Open No. 63-127400 discloses the structure of the above B and A / B described in Japanese Patent Application No. 285774.

The structures of A-A / B and A-A / B-C are described in Japanese Patent Application Nos. 1-124429 and 1-124430.

The ratio of the vinyl aromatic compound / conjugated diene in the diene polymer is from 0 to 60/100 to 40, preferably from 0 to 50, by weight.
/ 100 to 50, and when a vinyl aromatic compound is essential, it is preferably 10 to 50/90 to 50. Here, when the content of the vinyl aromatic compound exceeds 60% by weight, the composition becomes resinous, and the impact resistance of the obtained composition decreases.

Further, the vinyl bond content of the conjugated diene portion in the diene polymer is preferably 10% by weight or more, more preferably 20 to 80% by weight, particularly preferably 30 to 60% by weight,
If it is less than 10% by weight, the structure after hydrogenation becomes close to that of polyethylene, and the impact strength will be reduced when a resin composition is used. On the other hand, if it exceeds 60% by weight, it will lose its rubber-like properties after hydrogenation. The impact strength is undesirably reduced.

The diene-based polymer is preferably the following (I), (II), and when this hydrogenated diene-based polymer is used, a more excellent molded appearance such as the effect and coloring property aimed at by the present invention, The resin composition of the present invention having excellent low-temperature characteristics and fatigue characteristics can be obtained.

 A more preferred diene polymer is [I].

[I] A-A / B block copolymer consisting of a vinyl aromatic compound polymer block A, a random copolymer block A / B of a vinyl aromatic compound and a conjugated diene, or vinyl An A-A / B-C block copolymer in which a polymer block C mainly composed of an aromatic compound is bonded to the A-A / B block copolymer, wherein (I) a vinyl aromatic compound / conjugated diene (II) The total amount of the vinyl aromatic compounds of the block A and the block C is 3 to 40% by weight in the whole copolymer, and (III) the block A / The block copolymer wherein the conjugated diene moiety of B has a vinyl bond content of 15 to 80% by weight.

[II] In the molecule shown above, polymer blocks A and B ₁
And B ₂ (where A is 90% by weight of vinyl aromatic compound)
Polymer block composed mainly of the above vinyl aromatic compound, B ₁ is 1,2-vinyl bond content of 30% to 70% of the polybutadiene polymer block, B ₂ is a 1,2-vinyl bond content of 30%
A block copolymer having a polybutadiene polymer block is) one or more, respectively less than, the content of the polymer block A in the block copolymer is 10 to 50 wt%, the content of the polymer B ₁ 30-80 wt%, the polymer block B ₂
Said polymer block A block copolymer content of 5 to 30% by weight or the block copolymer units, via a coupling agent residue, at least one of B ₁ and B ₂
It is a block copolymer combined with two polymer blocks.

The hydrogenated diene polymer (I) used in the present invention
It is necessary that at least 70%, preferably 90% or more, more preferably 95% or more of the double bond of the conjugated diene portion be hydrogenated and saturated, and if it is less than 70%, heat resistance and weather resistance Is undesirably reduced.

Further, the hydrogenated diene polymer (I) of the present invention has a number average molecular weight of preferably 5,000 to 1,000,000, more preferably 30,000 to 300,000, and if it is less than 5,000, the polymer does not become rubbery and becomes liquid, On the other hand, if it exceeds 1,000,000, workability tends to decrease, which is not preferable.

Further, the ratio of the weight average molecular weight to the number average molecular weight (Mw / M
n) is preferably 10 or less.

The hydrogenated diene polymer (I) used in the present invention is obtained by subjecting block A, block B, block A / B or taper block C to living anionic polymerization in an organic solvent using an organic alkali metal compound as an initiator. , A block copolymer or a random copolymer is obtained, and then the block copolymer and / or the random copolymer are subjected to hydrogenation.

As the organic solvent, a hydrocarbon solvent such as pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, and xylene is used.

As the organic alkali metal compound as a polymerization initiator,
Organolithium compounds are preferred.

As the organic lithium compound, an organic monolithium compound, an organic dilithium compound, and an organic polylithium compound are used. Specific examples of these include ethyl lithium, n-propyl lithium, isopropyl lithium,
n-butyllithium, sec-butyllithium, t-butyllithium, hexamethylenedilithium, butadienyllithium, isoprenyldilithium, and the like, and used in an amount of 0.02 to 0.2 parts by weight per 100 parts by weight of the monomer. Can be

At this time, Lewis bases such as ethers and amines, such as diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ether, and ethylene glycol Ether derivatives of polyethylene glycol such as butyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine; and these are used together with the organic solvent.

Further, the polymerization reaction is usually carried out at -30C to 150C.

Further, the polymerization may be carried out while controlling at a constant temperature, or may be carried out at an elevated temperature without removing heat.

The method of forming the block copolymer may be any method. For example, generally, the block A or the block B is first polymerized using the polymerization initiator such as the alkali metal compound in the organic solvent, and then the block B is used. Alternatively, block A is polymerized.

It does not matter which block A or block B is polymerized first. Also, the boundary between block A and block B does not necessarily need to be clearly distinguished. Further, an ABC block copolymer or ABA
In order to obtain a block copolymer, an aromatic vinyl compound is added using an organic lithium initiator in an organic solvent to polymerize the block A, and then a conjugated diene or a conjugated diene and an aromatic vinyl compound are added. Block B, and then the tapered block C or block A may be polymerized by adding a conjugated diene and an aromatic vinyl compound or an aromatic vinyl compound.

In this case, the taper block C or the block A may be polymerized first, and then the block B and the block A may be polymerized.

To obtain a random copolymer, an aromatic vinyl compound and a conjugated diene compound may be simultaneously polymerized using an organic lithium initiator in an organic solvent.

The block copolymer or random copolymer thus obtained may be a copolymer having a polymer molecular chain extended or branched by adding a coupling agent.

As the coupling agent at this time, for example, diethyl adipate, divinylbenzene, tetrachlorosilicon, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromoethane, 1,4 -Chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate and the like.

Incidentally, the bond content of the vinyl aromatic compound in the block copolymer or random copolymer is adjusted by the supply amount of the monomer at the time of polymerization in each step, the vinyl bond content of the conjugated diene, It is adjusted by varying the components.

Further, the number average molecular weight and the melt flow rate are adjusted by the addition amount of a polymerization initiator, for example, n-butyllithium.

The hydrogenated diene polymer (I) of the present invention is obtained by dissolving the diene polymer thus obtained in an inert solvent,
The reaction is carried out in the presence of a hydrogenation catalyst at 20 to 150 ° C. under 1 to 100 kg / cm ² of pressurized hydrogen.

Inert solvents used for hydrogenation include hexane,
Examples thereof include hydrocarbon solvents such as heptane, cyclohexane, benzene, toluene, and ethylbenzene, and polar solvents such as methyl ethyl ketone, ethyl acetate, ethyl ether, and tetrahydrofuran.

Examples of the hydrogenation catalyst include dicyclopentadienyl titanium halide, a nickel carboxylate, a hydrogenation catalyst composed of an organic nickel compound and an organometallic compound of Groups I to III of the periodic table, carbon, silica, and diatomaceous earth. Nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalyst, cobalt, nickel, rhodium, ruthenium complex, or lithium aluminum hydride, p-toluenesulfonyl hydrazide, and further Zr-Ti-Fe-V-Cr Alloy, Zr-Ti-Nb-
Fe-V-Cr alloy, and a hydrogen storage alloy such as LaNi ₅ alloys.

The hydrogenation rate of the double bond in the conjugated diene portion of the hydrogenated diene polymer (I) of the present invention varies depending on the amount of the hydrogenation catalyst and the hydrogenated compound, or the hydrogen pressure and the reaction time during the hydrogenation reaction. Is adjusted by

The catalyst residue is removed from the hydrogenated polymer solution, a phenolic or amine-based antioxidant is added, and the hydrogenated diene polymer (I) is easily isolated from the polymer solution. Can be. Isolation of the hydrogenated diene-based polymer (I) includes, for example, a method in which acetone or alcohol is added to the polymer solution to cause precipitation, a method in which the polymer solution is poured into boiling water with stirring, and the solvent is distilled off. Can be done with

When the (meth) acrylate (b) in the monomer component (II) to be graft-copolymerized with the hydrogenated diene polymer (I) is a polymer alone, the glass transition of the polymer is Temperature [measured by differential scanning calorimeter (DSC)] is 5
The temperature is 0 ° C. or higher, and the alkyl preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4. Among the alkyl methacrylate and the alkyl acrylate, the alkyl methacrylate is preferred.

Examples of these include methyl acrylate, ethyl acrylate, n-propyl acrylate, methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, t-butylcyclohexyl methacrylate, methacrylic acid. Butyl acrylate, hexyl methacrylate, (meth) acrylate represented by the following formula; (Wherein n is an integer of 0 to 3, R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and m is an integer of 3 to 4). One or more of these can be used. Of these, methyl methacrylate and ethyl methacrylate are preferred, and methyl methacrylate is more preferred.

The aromatic vinyl compound (b) in the monomer component (II) to be graft-copolymerized with the hydrogenated diene polymer (I) is used for producing the hydrogenated diene polymer (I). The same thing as an aromatic vinyl compound is mentioned.

Further, other vinyl monomers (c) copolymerizable with the above (a) to (b) in the monomer component (II) to be graft-copolymerized to the hydrogenated diene polymer (I) include: , Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide,
An imide compound of α, β-unsaturated dicarboxylic acid such as N-phenylmaleimide and N-cyclohexylmaleimide is exemplified.

As the vinyl monomer (c), a vinyl cyanide compound is preferable. When a vinyl cyanide compound is used, a composition having more excellent impact resistance, chemical resistance and coatability can be obtained.

The proportion of the monomer component (II) is 30 to 100% by weight, preferably 50 to 1% by weight of a monomer composed of the (meth) acrylate (a) and / or the aromatic vinyl compound (b).
00% by weight, 70 to 0% by weight of the other monomer (c), preferably
50 to 0% by weight [(a) + (b) + (c) = 100
%), And if the amount of the monomer composed of (a) and / or (b) is less than 30% by weight, a product having sufficient moldability cannot be obtained.

 Particularly preferred monomer components (II) are listed below.

Aromatic vinyl compound (b) / (meth) acrylate (a) / vinyl cyanide compound = 1-90 / 1-90 / 0-
60% by weight, aromatic vinyl compound (b) / (meth) acrylate (a) / vinyl cyanide compound = 40 to 95/0 to 55/5
60% by weight.

The content of the hydrogenated diene polymer (I) in the production of the rubber-reinforced resin (A) in the present invention can be arbitrarily selected depending on the purpose. In order to satisfy the moldability, the range is 5 to 60% by weight, preferably 10 to 60% by weight. If the amount of the hydrogenated diene polymer (I) is less than 5% by weight, only a composition having insufficient impact resistance is obtained, while if it exceeds 60% by weight, the moldability deteriorates, which is not preferable. Therefore, the content of the graft monomer component serving as the matrix resin is the remaining content.

The graft ratio of the rubber-reinforced resin (a) is preferably 20 to 90%, more preferably 25 to 85%, and particularly preferably 30 to 80%. Here, the graft ratio refers to a ratio of a copolymer component directly graft-bonded to rubber with respect to a rubber amount of the graft polymer. This graft ratio can be controlled by the amount of the polymerization initiator, the polymerization temperature, and the like. When the graft ratio of the component (a) is less than 20%, the impact strength is sufficient even if substantially no grafting is performed, as exemplified in JP-A-51-9183, but the chemical resistance is high. Is significantly reduced, and the appearance of the molded product is also deteriorated.

Furthermore, the intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone-soluble portion of the resin part of the rubber reinforced resin (a) of the present invention is 0.2 dl / g or more, preferably 0.22 to 1.5 dl / g, more preferably Is 0.24 to 1.2 dl / g.

(A) The rubber-reinforced resin is a graft copolymer or a hydrogenated diene polymer (I) obtained by polymerizing the monomer component (II) in the presence of the hydrogenated diene polymer (I). In the presence, a part of the monomer component [preferably 5 of the monomer component (II)
To 95% by weight], and a blend of a polymer obtained by separately polymerizing the graft obtained by polymerizing the remaining monomer component (II).

The rubber-reinforced resin (a) used in the present invention is produced by emulsion polymerization, solution polymerization, suspension polymerization, or the like.

In this case, as the polymerization initiator, molecular weight regulator, emulsifier, dispersant, solvent and the like used for the polymerization, those usually used in these polymerization methods can be used as they are.

(A) A preferable method for producing the rubber-reinforced resin is to use a monomer and an additional emulsifier, a monomer and a polymerization initiator in the presence of the hydrogenated diene polymer (I), 30-150 ° C, polymerization time 1-15 hours, polymerization pressure -1.0
Graft copolymerization under the condition of ~ 5.0 kg / cm ² to obtain a graft copolymer (including an ungrafted polymer), or emulsion polymerization or solution with a hydrogenated diene polymer (I) It is produced by mixing a monomer component (II) (co) polymer obtained by polymerization.

Examples of the (ii) polyolefin used in the present invention include homopolymers such as polyethylene and polypropylene, and copolymers of ethylene, propylene and other α-olefins.

Of these, polypropylene is preferred, and particularly preferred is crystalline polypropylene having a density of 0.89 to 0.93 g / cm ³ and a melt flow rate (ASTM D12).
38L) is for 0.1-70g / 10min.

As the (b) polyolefin, in addition to the propylene homopolymer as described above, a block or random mixture of propylene with 20 mol% or less of an α-olefin such as ethylene, 1-butene and 4-methyl-1-pentene can be used. It is also possible to use a composition containing a copolymer or polypropylene as a main component, and a mixture of polyethylene and the like.

Further, (c) the elastomer used in the present invention includes the hydrogenated diene-based polymer (I), ethylene-α-
At least one selected from olefin-based copolymer rubber and aromatic vinyl compound-conjugated diene-based copolymer is exemplified. Among them, ethylene-α-olefin copolymer rubbers include ethylene-propylene copolymer rubber (EPM) and ethylene-propylene-diene copolymer rubber (EPDM), and aromatic vinyl compound-conjugated diene copolymer rubber. Examples of the copolymer include the above-mentioned block copolymer or random copolymer in a stage before the hydrogenated diene polymer (I) is produced by hydrogenation. Of these (c) elastomers, preferred are the hydrogenated diene polymers (I).

In the hydrogenated diene polymer (I), particularly preferably, it is the same as the hydrogenated diene polymer (I) in the rubber reinforced resin (1).

The first composition of the present invention comprises: (a) a rubber-reinforced resin,
(B) Polyolefins and (C) elastomers are the main components, and the mixing ratio of the components (A) to (C) is (A)
Component is 1 to 98 parts by weight, preferably 2 to 95 parts by weight, more preferably 5 to 90 parts by weight, (b) component is 1 to 98 parts by weight,
Preferably 2 to 95 parts by weight, more preferably 5 to 90 parts by weight, component (c) 1 to 60 parts by weight, preferably 2 to 40 parts by weight, more preferably 5 to 40 parts by weight [however, (a) +
(B) + (c) = 100 parts by weight].

Here, when the component (a) is less than 1 part by weight, the resulting composition has poor impact resistance and coatability, while the chemical resistance and weather resistance exceeding 98 parts by weight deteriorate.

If the component (b) is less than 1 part by weight, the chemical resistance and weather resistance are poor, while if it exceeds 98 parts by weight, the impact resistance and paintability are reduced.

Further, when the component (c) is less than 1 part by weight, the impact resistance of the obtained composition is low, while when it exceeds 60 parts by weight, the obtained composition becomes soft, and as a result, the molded article is easily deformed, Moreover, it is not preferable because it is easily damaged.

The first composition of the present invention comprises: (a) a rubber-reinforced resin,
It is obtained by mixing (b) a polyolefin and (c) an elastomer using a usual mixing method.

For example, after mixing each component with a mixer, the mixture is melt-kneaded at 180 to 300 ° C. with an extruder and granulated.

Furthermore, each component can be simply melt-kneaded and molded in a molding machine.

Next, the second composition of the present invention comprises the first composition (A) to (A).
In addition to the component (c), (d) a compatibilizer is blended.

Here, (d) the compatibilizer used in the second composition is:
The purpose is to improve the impact resistance by playing a role of compatibilizing the rubber reinforced resin (A) with the polyolefin and the elastomer (B), which are general-purpose engineering plastics, and to improve the chemical resistance.

The (d) compatibilizer includes an epoxy group-containing monomer (d), a carboxyl group-containing monomer (e), an amino group-containing monomer (f), a hydroxyl group-containing monomer (g), and a dicarboxylic acid. Modified vinyl polymer and / or rubbery modified vinyl polymer obtained by copolymerizing at least one functional group-containing monomer component (III) selected from the group of acid anhydride group-containing monomers (h) It is a polymer.

Here, the epoxy group-containing monomer (d) is a compound having an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound and an epoxy group in the molecule. Examples of the epoxy group-containing monomer (d) include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, butene carboxylate, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, , 4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene , Vinylcyclohexene monoxide, p-glycidyl styrene and the like. These epoxy group-containing monomers may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer (e) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid, and preferably acrylic acid and methacrylic acid.

These monomers can be used alone or in combination of two or more.

Further, as the amino group-containing monomer (f), the following general formula: (Wherein, R ¹ is a hydrogen atom, a methyl group or an ethyl group, R ² is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkanoyl group having 2 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, Number 6
At least one of an amino group or a substituted amino group represented by the formula:
It is a vinyl monomer having a seed.

As specific examples of the amino group-containing monomer (f), allylamine, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene and the like are particularly preferably used because they are economically available on an industrial scale. These monomers can be used alone or in combination of two or more.

Further, as the hydroxyl group-containing monomer (g),
It is a compound having at least one unsaturated bond (double bond, triple bond) and containing a hydroxyl group. Typical examples thereof include alcohols having a double bond, alcohols having a triple bond, esters of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol,
Esters of the unsaturated carboxylic acid with an unsubstituted trihydric alcohol, esters with an unsubstituted tetrahydric alcohol, and esters with an unsubstituted pentahydric or higher alcohol.

As a specific example of these hydroxyl group-containing monomers (g), it is preferable to use 2-hydroxyethyl methacrylate. These unsaturated compounds having a hydroxyl group can be used alone or in combination of two or more.

Further, as the dicarboxylic anhydride group-containing monomer (h), maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenyl succinic anhydride,
Examples thereof include tetrahydrophthalic anhydride and the like, and preferred is maleic anhydride.

These monomers can be used alone or in combination of two or more.

(D) Examples of the base material for producing the compatibilizer include a rubbery polymer, a graft layer of a graft copolymer, and a non-grafted vinyl polymer, and among them, preferred is. .

If the component (d) thus obtained is specifically shown, conventional acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylene-propylene-styrene resin (AES resin), methyl methacrylate-butadiene-styrene resin Resin (MBS resin), acrylonitrile-butadiene-methyl methacrylate-styrene resin, acrylonitrile-n-butyl acrylate-styrene resin (AAS resin), rubber-modified polystyrene (high impact polystyrene; HIPS), acrylonitrile-styrene resin (AS resin) , Methyl methacrylate-styrene resin (MS resin), methyl methacrylate-styrene-
When producing a copolymer resin such as an acrylonitrile resin, a part of the monomer in the copolymer resin or in the vinyl-based polymer to be mixed with the copolymer resin is converted into the functional group-containing monomer component. It is obtained by polymerizing instead of (III).

At this time, the functional group-containing monomer component (II) in the component (d)
The content of I) is preferably 0.01 to 80% by weight, more preferably 0.1 to 50% by weight.

The component (d) used in the present invention is produced by emulsion polymerization, solution polymerization, suspension polymerization or the like.

In this case, as the polymerization initiator, molecular weight regulator, emulsifier, dispersant, solvent and the like used for the polymerization, those usually used in these polymerization methods can be used as they are.

(D) As a preferred method for producing the component, the monomer component (III) is used in the presence of a rubbery polymer obtained by emulsion polymerization. Using an emulsifier and a polymerization initiator, generally a polymerization temperature of 30 to 150 ° C., a polymerization time of 1 to 15 hours, and a polymerization pressure of −1.0 to 5.
Emulsion polymerization or solution of the graft copolymer (including ungrafted vinyl polymer), rubbery polymer and monomer component (III) obtained by graft copolymerization under the condition of 0 kg / cm ² It is produced by mixing with a vinyl polymer obtained by polymerization or by subjecting a mixture of monomer components (III) to emulsion polymerization or solution polymerization.

(D) A composition having more excellent impact resistance and chemical resistance by adding 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight, with respect to 100 parts by weight of the first composition. Things are obtained.

If the amount of the component (d) is less than 0.5 parts by weight or more than 20 parts by weight, the impact resistance is poor, which is not preferable.

The thermoplastic resin composition of the present invention includes the above (a) to (c).
Components, or (a) to (d) as the main components,
Other thermoplastic polymers such as vinyl chloride resin,
Various general synthetic resins such as polyamide resin, polyester resin, polycarbonate, polyphenylene ether and polyglutarimide, or other elastomers
The content can be about 50% by weight or less.

Further, various kinds of compounding agents can be added to the composition of the present invention.

These compounding agents include, for example, 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-
Bis- (4-ethyl-6-t-butylphenol), 4,
Antioxidants such as 4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, wax; pt-butylphenyl salicylate; 2,2'-
Dihydroxy-4-methoxybenzophenone, 2-
(2'-hydroxy-4'-n-octoxyphenyl)
UV absorbers such as benzotriazole; lubricants such as paraffin wax, stearic acid, hardened oil, stearamide, methylenebisstearamide, n-butylstearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride; antimony oxide , Ammonium hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A and other flame retardants; stearoamidopropyldimethyl-β- Antistatic agents such as hydroxyethylammonium nitrate; coloring agents such as titanium oxide and carbon black; calcium carbon, clay, silica, glass fiber,
Fillers such as glass spheres and carbon fibers; and pigments.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, parts and% are by weight unless otherwise specified.

The analysis of the polymer and the various physical property test methods in the examples were measured according to the following procedures.

That is, the analysis of the polymer was measured as follows.

The bound styrene content was determined from a calibration curve by an infrared method based on the absorption of a phenyl group at 699 cm ^-1 .

The vinyl bond content was determined by an infrared method (Morello method).

The molecular weight was determined by gel permeation chromatography (GPC).

Hydrogenation ratio was calculated from the four reference ethylene chloride Keep in solvent, the spectrum reduction in踏飽sum coupling portion of ¹ H-NMR spectrum of 100Hz was measured at 15% strength.

On the other hand, the thermoplastic resin compositions of Examples and Comparative Examples were kneaded at 220 ° C. to produce pellets, and an injection molding machine (Toshiba Corporation)
Manufactured at 220 ° C using IS-80A)
Physical properties were evaluated.

Among them, the Izod impact strength is ASTM D256 (cross section
1/4 x 1/2 inch, with notch).

The weather resistance was measured by measuring the Izod impact strength by exposing to a sunshine weather meter using a carbon arc as a light source for 1,000 hours. The black panel temperature was 63 ± 3 ° C. and the water showering was for 18 minutes every 2 hours.

For chemical resistance, a test piece (1/8 "x 5") is given a constant strain of 1% strain rate, dioctyl phthalate (DOP) or brake fluid is applied to the bent part and left at 23 ℃ to break (Time until solvent cracking) was measured and used as an index of chemical resistance. In addition, those that withstand 100 hours or more were evaluated as ◎, and those that withstand 50 hours or more were evaluated with ○.

The paintability is as follows: After cleaning the injection molded product (83 x 60 x 3 mm) with ethyl alcohol, apply a two-part curable urethane paint (Nippon Oil & Fats Co., Ltd., High Urethane No. 5000) with a film thickness of 25μ.
m, and dried at 80 ° C. for 30 minutes, and then left at room temperature for 24 hours to obtain a coatability test piece.

On the coating film of this test piece, 100 squares of 1 mm long and 1 mm wide were cut with a cutter and 100 g of cellophane tape was adhered. And the adhesion of the coating film was evaluated.

Reference Example Production of hydrogenated diene-based random copolymers R-1 to R-3 [R-1] An autoclave having an internal volume of 5 was charged with 2,500 g of degassed and dehydrated cyclohexane and 100 g of styrene, and then 9.8 g of tetrahydrofuran and n 0.2 g of -butyllithium was added to carry out isothermal polymerization at a polymerization temperature of 50 ° C.

After the polymerization conversion reached almost 100%, the 1,3-
Polymerization was carried out at a temperature of 70 ° C. while continuously adding a mixture of 437.5 g of butadiene and 62.5 g of styrene at a rate of 75 g per 10 minutes.

Sampling was performed every 5 minutes during the polymerization, and the styrene content and the microstructure of 1,3-butadiene in the polymer generated as needed were measured.

After the polymerization conversion reaches almost 100%, the reaction solution is heated to 70 ° C.
0.6 g of n-butyllithium, 0.6 g of 2,6-t-butyl-p-cresol, bis (cyclopentadienyl)
Add 1.1 g of titanium dichloride and 10 kg / c with hydrogen gas
The reaction was carried out for 1 hour while maintaining the pressure at m ² .

The reaction solution was cooled to room temperature, desolvated by steam stripping, and dried with a roll at 120 ° C. to obtain a hydrogenated diene polymer R-1.

The molecular characteristics of the obtained hydrogenated diene polymer R-1 were determined as follows:
It is shown in the table.

[R-2] A hydrogenated diene polymer R-2 shown in Table 1 was obtained by appropriately changing the monomer composition, the polymerization aid, and the polymerization conditions so as to obtain the polymer structural characteristics shown in Table 1. . Table 1 shows the molecular characteristics.

[R-3] An autoclave having an internal volume of 5 was charged with 2,500 g of degassed and dehydrated cyclohexane and 350 g of 1,3-butadiene, and 0.50 g of n-butyllithium was added.
C. Isothermal polymerization was performed. After the polymerization conversion reached 31%, 12.5 g of tetrahydrofuran was added, and 50 ° C to 80 ° C.
Was heated.

After the polymerization conversion rate has reached almost 100%, 150 g of styrene
Was added and polymerization was carried out for 15 minutes to obtain a block copolymer.

Next, hydrogenation is performed in the same manner as in R-1.
A hydrogenated diene polymer R-3 was obtained. Table 1 shows the molecular characteristics.

(A) Production of rubber-reinforced resins A-1 to 10 [Production example A-1] A refractive index of 1.50 previously prepared as a uniform solution in a stainless steel autoclave having an internal volume of 10 equipped with a paddle-type stirrer.
7 hydrogenated diene block copolymer KRATON G-1650
(Shell Chemical Co., SEBS) 10 parts, styrene 10.8 parts,
100 parts of toluene and 0.1 part of t-dodecyl mercaptan were charged, the temperature was raised while stirring, and 79.2 parts of methyl methacrylate and 0.5 part of t-butylperoxyisopropyl carbonate were added at 50 ° C. After the system was replaced with nitrogen, the temperature was further raised to 90 ° C.
The polymerization was continued under stirring until the concentration reached 74%.

When the polymerization conversion reached 74%, the polymerization was stopped, and an antioxidant was added. After that, it was taken out of the autoclave and unreacted monomers and solvent were distilled off by steam distillation.
After pulverizing finely, the extruder with a 40mmφ vent (22
At 0 ° C. and 700 mmHg vacuum), volatile components were substantially distilled off, and the polymer was pelletized to obtain a rubber-reinforced resin A-1 of the present invention.

[Production Example A-2] Hydrogenated diene-based block copolymer KRATON having a refractive index of 1.5105
1701X (Shell Chemical, SEP) 15 parts, Styrene 1
Using 2.8 parts of methyl methacrylate and 72.2 parts of methyl methacrylate, a polymerization reaction was carried out in the same manner as in rubber-reinforced resin A-1.

After the polymerization conversion reached 70%, the polymerization was stopped, and post-treatment was carried out in the same manner as in I-1 to obtain a rubber reinforced resin A-2 as a graft copolymer.

The rubber content of the obtained rubber-reinforced resin A-2 was 20%, and the refractive index of the copolymer resin composed of only the monomer mixture was 1.
5113.

[Production Example I-3] Polymerization was carried out under the conditions shown in Table 2 using a polymerization reaction apparatus equipped with two stainless steel autoclaves each having a capacity of 30 and equipped with a paddle type stirring device.

The rubber content in the obtained rubber-reinforced resin was 24.8%, and the refractive index of the copolymer consisting of only the monomer mixture was 1.50.
66.

[Production Example I-4 (Control)] Production of rubbery polymer; 0.2 parts of potassium stearate, 1.5 parts of potassium laurate, and sodium alkylnaphthalenesulfonate in a 100-volume stainless steel autoclave equipped with a paddle-type stirring blade 0.1 parts, potassium hydroxide 0.1 g, potassium chloride 1.5
Parts of ion-exchanged water containing 90 parts of acrylic acid
70 parts of butyl and 30 parts of styrene were added. The temperature was raised under stirring at 90 rpm under a nitrogen atmosphere, and when the temperature reached 45 ° C, potassium persulfate was added. Thereafter, the polymerization reaction was performed while controlling the temperature to be kept constant at 45 ° C, and the polymerization rate was 90%. Upon reaching 0.1, the reaction was stopped by adding 0.1 parts of diethylhydroxylamine, and the unreacted monomers were substantially removed by steam distillation to obtain a rubbery polymer latex.

The polymer latex was precipitated with alcohol, purified, and dried to obtain a rubbery polymer.

Production of rubber-reinforced resin; except that instead of the hydrogenated diene-based block copolymer, n-butyl acrylate-styrene copolymer elastic material (n-BA-ST) having a refractive index of 1.507 obtained by the above method was used. Polymerization, post-treatment, and evaluation were performed in the same manner as in Examples A and B-1.

[Production Example A-5 (Control)] Polybutadiene (PBD) was used as a base rubber, and polymerization and post-treatment were carried out in the same manner as in A-1, and evaluated.

[Production Example A-6 (Comparative Example)] An ethylene-propylene copolymer rubber having a refractive index of 1.4855 (JSR EP01P manufactured by Nippon Synthetic Rubber Co., Ltd.) (EP
R) Polymerization, post-treatment and evaluation were conducted in the same manner as in I-1, except that 10 parts, 81 parts of methyl methacrylate and 9 parts of methyl acrylate were used.

[Production Example A-7] Using a hydrogenated diene-based random copolymer (R-1), polymerization was carried out in the same manner as in A-1, followed by post-treatment and evaluation.

[Production Example A-8] Using a hydrogenated diene-based random copolymer (R-2), polymerization and post-treatment were carried out in the same manner as in A-1, followed by evaluation.

[Production Example A-9] Using a hydrogenated diene-based random copolymer (R-3), polymerization was carried out in the same manner as in A-1, followed by post-treatment and evaluation.

[Production Example A-10 (Control)] Using an unhydrogenated SBS block copolymer TR2000 (manufactured by Nippon Synthetic Rubber Co., Ltd.), polymerization was performed in the same manner as in Production Example A-1.
After-treatment and evaluation.

The polymers obtained in Production Examples A-1 to A-10 are collectively shown in Table 3.

(B) Polyolefin resin Table 4 shows the polyolefin used in this example.

(C) Elastomer The elastomer (C) used in this example is shown in Table 5.

(D) Compatibilizer As a (d) compatibilizer used in the present example, MODIPER A4401 manufactured by NOF Corporation was used.

Examples 1 to 25 and Comparative Examples 1 to 13 Using a 50 mmφ extruder, the above components (a) to (c) or components (a) to (d) were mixed at 220 ° C. according to the formulation shown in Table 6. A pellet was prepared by kneading, a test piece was prepared at 220 ° C. using an injection molding machine (IS-80A, manufactured by Toshiba Corporation), and the physical properties were evaluated.

 The results are shown in Table 6.

As is clear from Table 6, the compositions of Examples 1 to 25 of the present invention are excellent in all of impact resistance, weather resistance, chemical resistance, paintability and moldability.

On the other hand, the compositions of Comparative Examples 1 to 4 consist only of (a) a rubber-reinforced resin and (b) a polyolefin, and are inferior in impact resistance.

Further, the compositions of Comparative Examples 5 to 7 contain (c) an elastomer beyond the scope of the present invention, and are inferior in moldability.

Further, the compositions of Comparative Examples 8 to 13 contain components other than the component (a) or the component (c) of the present invention, and are inferior in impact resistance, weather resistance and chemical resistance.

(Effect of the Invention) The thermoplastic resin composition of the present invention has impact resistance, weather resistance,
Excellent in chemical resistance, paintability and molding processability, various automotive parts such as bumpers and molds, home appliances,
Useful as household goods and other industrial materials.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-56-38338 (JP, A) JP-A-63-182361 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 51/04-51/06 C08L 23/02-23/24 C08L 21/00 C08L 9/06

Claims (2)

(57) [Claims] 1. A hydrogenated diene polymer (I) obtained by hydrogenating a diene polymer consisting of 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene (I): 5 to 60 parts by weight. In the presence of (meth) acrylate (a) and / or
Or 30 to 10 monomers composed of an aromatic vinyl compound (b)
0% by weight, other copolymerizable vinyl monomer (c) 70 to
1 to 98 parts by weight of a rubber reinforced resin obtained by graft copolymerizing 95 to 40 parts by weight of a monomer component (II) consisting of 0% by weight (provided that (I) + (II) = 100 parts by weight); 1 to 98 parts by weight of polyolefin, and (c) at least one elastomer 1 selected from the group consisting of the hydrogenated diene polymer (I), ethylene-α-olefin rubber and aromatic vinyl compound-conjugated diene copolymer ~ 60 parts by weight (However, (A)
+ (B) + (c) = 100 parts by weight). 2. An epoxy group-containing monomer (d), a carboxyl group-containing monomer (e), and an amino group-containing monomer per 100 parts by weight of the thermoplastic resin composition according to claim 1. (F), at least one functional group-containing monomer component (III) selected from the group consisting of a hydroxyl group-containing monomer (g) and a dicarboxylic anhydride group-containing monomer (h) A thermoplastic resin composition comprising 0.5 to 20 parts by weight of the obtained compatibilizer.