JP2979615B2 - Thermoplastic resin composition for coating - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hydrogenated diene polymer comprising a diene polymer comprising 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene. For coatings with excellent impact resistance, paintability, chemical resistance, and weather resistance obtained by blending a polyolefin as the main component with a gum reinforced resin obtained by graft copolymerizing a specific monomer component in the presence The present invention relates to a thermoplastic resin composition.

[Related Art] In recent years, the use of polypropylene (PP) -based resin materials for exterior parts and interior parts for automobiles, electric products, and the like has been increasing, and Japanese Patent Application Laid-Open No. 58-213043 and 60
As disclosed in JP-188453 and JP-A-61-43650, 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 typical example of a material having poor paint adhesion. Therefore,
As a measure for improving the adhesion of the paint, it is necessary to perform etching with a solvent such as 1,1,1-trichloroethane or trichlorotrifluoroethane, and a primer coating step for an adhesive primer. 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 described above, and is a thermoplastic resin composition for coating excellent in all of paintability, impact resistance, chemical resistance and weather resistance. The purpose is to provide.

[Means for Solving the Problems] The present invention relates to (1) (a) hydrogen comprising a polymer obtained by hydrogenating a polymer comprising 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene compound; Added diene polymer (I) 5 to 60
(Meth) acrylic acid ester (a) in the presence of
And / or an aromatic vinyl compound (b), or a monomer (II) composed of these monomers and a copolymerizable vinyl monomer (c) other than (a) and (b) (95 to 40% by weight) % Of a rubber-reinforced resin having a graft ratio of 20 to 90%, an intrinsic viscosity [η] of 0.2 dl / g or more obtained by graft copolymerization of 1 to 99% by weight, and (b) polyolefin 99.
(1) 100% by weight of the thermoplastic resin composition for coating according to (1), wherein the thermoplastic resin composition for coating comprises 1 to 1% by weight. In contrast, (c) a copolymer (c-1) obtained by copolymerizing a functional group-containing monomer component (III) and a vinyl monomer, and a copolymer of a vinyl monomer and an α-monoolefin. At least one copolymer 0.5 selected from polymers (c-2)
The present invention provides a thermoplastic resin composition for coating (hereinafter, also referred to as a "second composition") containing up to 20 parts by weight.

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

The hydrogenated diene polymer (I) constituting the component (a) of the first composition is a diene polymer comprising 0 to 600% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene compound. It is obtained by hydrogenation.

Here, the aromatic vinyl compound used for the hydrogenated diene polymer (I) includes styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, and dichlorostyrene. , Monobromostyrene, dibromostyrene, fluorostyrene, pt-butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, 1,1-diphenylstyrene, vinylpyridine and the like.
α-Methylstyrene is 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, 1,3-pentadie, and 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 copolymer by coalescence or 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; copolymer of conjugated diene and vinyl aromatic compound When each is defined as a taper block composed of a polymer and having a vinyl aromatic compound gradually increasing, one having the following structure is exemplified.

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,
B the vinyl bond content is less than 20% of the _{2) 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 is the same as described above) C-B-C-B-C-C-A / B-C-C-A-B-C Also, copolymers having these basic skeletons repeatedly can be mentioned. It may be a diene polymer obtained by the above method.

No. Sho for a structure of the A-B ₁ -B ₂ 63-
The structure having the A / B structure of B and B described in Japanese Patent No. 285774 is described in JP-A-63-127400.

The structures of A-A / B and A-A / B-C described above are described in Japanese Patent Application No. 1-124429 and Japanese Patent Application No.
-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 the content 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 the content exceeds 60% by weight, the rubbery properties will be lost after hydrogenation. Also, the impact strength is undesirably reduced.

The following diene polymer is preferably (i):
(Ii) When the hydrogenated diene polymer is used, the resin composition of the present invention, which is more excellent in the effects of the present invention and has excellent molding appearance such as coloring, low-temperature properties, and fatigue properties, is obtained. can get. Further, a more preferred diene polymer is (i).

(I) A-A / B block copolymer comprising 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 (1) a vinyl aromatic compound / conjugated diene (2) The total amount of the vinyl aromatic compounds in block A and block C is 3 to 40% by weight in the total copolymer. (3) Conjugation of block A / B A block copolymer having a vinyl bond content of a diene portion of 15 to 80% by weight.

(Ii) polymer blocks A and B ₁ in the molecule shown above;
And B ₂ (where A is 90% by weight of vinyl aromatic compound)
Polymer block, B ₁ is 1,2-vinyl bond content of 20% to 70% of the polybutadiene polymer blocks mainly more vinyl aromatic compounds, B ₂ is a 1,2-vinyl bond content of 20%
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, when it exceeds 1,000,000, the 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 using an organic alkali metal compound as an initiator in an organic solvent, and forming a block. After obtaining a copolymer or a random copolymer, the block copolymer and / or the random copolymer are further subjected to hydrogenation.

When the (meth) acrylate (a) 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 as follows. Temperature [measured by differential scanning calorimeter (DSC)] is 5
0 ° C. or higher, having 1 to 10 carbon atoms as an alkyl group
Is more preferable, more preferably 1 to 6, 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. Examples thereof include butyl acrylate, hexyl methacrylate, and (meth) acrylate having a norbornene ring, and 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, the other vanyl-based monomer (c) copolymerizable with the above (a) to (b) in the monomer component (II) to be graft-copolymerized to the hydrogenated diene-based polymer (I) includes: , Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide,
Examples include α, β-unsaturated dicarboxylic acid imide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide. In this vinyl monomer (c),
Vinyl cyanide compounds are preferred. 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 = 1-99 / 1-99 / 0
To 60% by weight aromatic vinyl compound (b) / (meth) acrylate (a) / vinyl cyanide compound = 40 to 95/0 to 55/5
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. The range is 5 to 60% by weight, preferably 10 to 60% by weight in order to satisfy impact resistance and moldability. If the hydrogenated diene polymer (I) is less than 5% by weight, only a composition having insufficient impact resistance can be obtained. On the other hand, 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.

In addition, (a) the graft ratio of the rubber-reinforced resin is 20 to 90%,
It is preferably 25-85%, more preferably 30-80%. 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. If the graft ratio of the component (a) is less than 20%, the coatability is deteriorated, and the appearance of the molded product is unfavorably 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 obtained by polymerizing the monomer component (II) in the presence of the hydrogenated diene polymer (I) or a hydrogenated diene polymer (I). 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 amount of the hydrogenated diene-based polymer (I) in the rubber-reinforced resin of the present invention is from 5 to 60 based on the balance between moldability and impact resistance.
% By weight.

The average dispersed particle size of the hydrogenated diene polymer in the rubber reinforced resin is 0.05 μm or more from the balance between impact resistance and paintability.
Particularly preferred is 1.5 μm.

The rubber-reinforced resin (A) used in the present invention is produced by emulsion polymerization, solution polymerization, bulk polymerization, or the like. In this case, a polymerization initiator used for polymerization, a molecular weight regulator,
As the emulsifier, dispersant, solvent and the like, those usually used in these polymerization methods can be used as they are.

(A) Preferred methods for producing the rubber-reinforced resin include bulk polymerization, solution polymerization, and suspension 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. Among these, polypropylene is preferred, and particularly preferred is crystalline polypropylene, which has a density of 0.89 to 0.93 g / cm ³ and a melt flow rate (ASTM D1238L) of 0.1 to 70 g / 10 minutes.

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, as the polyolefin of the present invention, those modified with an acid anhydride group, an epoxy group, a carboxyl group, a hydroxyl group, an amino group, an oxazoline group or the like can be used.

Examples of the modification method include a method of copolymerizing an unsaturated compound having the above functional group, and a method of adding an unsaturated compound to a polyolefin.

The polyolefin of the present invention is used alone or in combination of two or more.

The first composition of the present invention contains the above-mentioned (a) a rubber-reinforced resin and (b) a polyolefin as main components.
The mixing ratio of the component (b) is such that the component (a) is 1 to 99% by weight,
Preferably it is 5-95% by weight, more preferably 10-90% by weight. The component (b) is 1 to 99% by weight, preferably 5 to 95% by weight, and more preferably 10 to 90% by weight.

If the component (a) is less than 1% by weight (the component (b) exceeds 99% by weight), the impact resistance, coating adhesion and weather resistance are poor, while the component (A) exceeds 99% by weight [ (A) component is less than 1% by weight], the chemical resistance is poor.

The first composition of the present invention is obtained by mixing the rubber reinforced resin (a) and the polyolefin (b) 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 (a) the first composition,
(B) In addition to the component (c) Specific copolymer (compatibilizer)
Is blended.

Here, (c) the compatibilizer used in the second composition is:
It serves to compatibilize the rubber-reinforced resin (A) with the polyolefin (B), which is a general-purpose engineering plastic, to improve impact resistance and improve paintability.

The copolymer (c-1) in the compatibilizer (c) includes an epoxy group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, an oxazoline group-containing monomer, and a hydroxyl group-containing monomer. A modified vinyl polymer obtained by copolymerizing at least one functional group-containing monomer component (III) selected from the group consisting of a monomer and a dicarboxylic anhydride group-containing monomer; It is a modified vinyl polymer.

Here, the epoxy group-containing monomer is a compound having an epoxy group and an unsaturated group copolymerizable with an olefin and an ethylenically unsaturated compound in the molecule.

Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, butene carboxylate, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, and 3,4- 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-glycidylstyrene 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 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, 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
To 12-cycloalkyl groups or derivatives thereof) are vinyl monomers having at least one amino group or substituted amino group represented by the formula:

As specific examples of the amino group-containing monomer, 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, the hydroxyl group-containing monomer has at least one unsaturated bond (double bond, triple bond),
And a compound containing a hydroxyl group. Typical examples thereof include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monohydric or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and an unsubstituted tricarboxylic acid of the unsaturated carboxylic acid. Esters with a hydric 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, it is preferable to use 2-hydroxyethyl methacrylate. The unsaturated compound containing a hydroxyl group is 1
Species 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. Examples of the oxazoline group-containing monomer include vinyl oxazoline. These monomers can be used alone or in combination of two or more.

(C) Examples of the base material for producing the copolymer (C-1) in the compatibilizer include a rubbery polymer, a graft layer of a graft copolymer, and a non-grafted vinyl polymer. However, among these, is preferred.

The copolymer (C-1) thus obtained can be specifically described as a conventional acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-ethylene-
Propylene-styrene resin (AES resin), methyl methacrylate-butadiene-styrene 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-
When producing a copolymer resin such as a styrene-acrylonitrile resin or the rubber-reinforced resin (a), one of the monomers in the copolymer resin or the vinyl-based polymer mixed with the copolymer resin is used. Part is obtained by polymerization instead of the functional group-containing monomer component (III).

At this time, the content of the functional group-containing monomer component (III) in the copolymers (c-1) and (d) is preferably 0.01 to 80% by weight, more preferably 0.1 to 50% by weight. .

The copolymer (c-1) used in the present invention is produced by emulsion polymerization, solution polymerization, suspension polymerization or the like. In this case, a polymerization initiator used for polymerization, a molecular weight regulator,
As the emulsifier, dispersant, solvent and the like, those usually used in these polymerization methods can be used as they are.

(C) The vinyl monomer-α-monoolefin copolymer (C-2) in the compatibilizer is a copolymer of a vinyl monomer and an α-monoolefin. It is a polymer obtained by polymerizing one monomer as a main component with another monomer, and more preferably, a (co) polymer of a vinyl monomer is copolymerized with an α-monoolefin (co) polymer. And one obtained by graft polymerization and one obtained by block copolymerization. One or more of the above-mentioned vinyl monomers are used here. Also,
As the α-monoolefin, all those described above are used. Preference is given to homopolymers of ethylene and propylene and their block or random copolymers.

(C) The copolymer (compatibilizer) is the first composition 100
By blending 0.5 to 20 parts by weight, preferably 1 to 6 parts by weight with respect to parts by weight, a composition having more excellent impact resistance and chemical resistance can be obtained.

If the compounding amount of the component (c) is less than 0.5 parts by weight or more than 20 parts by weight, the impact resistance is inferior.

In kneading with an extruder, after kneading a part or the whole amount of any component, the remaining components may be added and kneaded to obtain a composition, or the whole amount may be kneaded all at once to obtain a composition. Good.

The composition of the present invention has excellent impact resistance, paintability, chemical resistance, and weather resistance, as well as adhesiveness, secondary workability (plating property, etc.), dimensional stability (dimensional accuracy during molding), and molding. It has excellent characteristics of mold transferability.

For this reason, it can be used for automotive parts applications, such as bumpers, instrument panels, front grills, pillar air spoilers, and the like.

The thermoplastic resin composition of the present invention contains the above-mentioned components (A) and (B) or components (A) to (C) as main components, and other thermoplastic polymers such as vinyl chloride resin and polyamide. Resin, polyester resin, polycarbonate, polyphenylene ether, polyglutarimide, polyamide elastomer, polyester elastomer, hydrogenated product of fluoropolymer or conjugated diene polymer, acrylic rubber, ethylene-α-olefin copolymer rubber, etc. About 50% by weight or less of the rubbery polymer.

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, methone 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 carbonate, clay, silica, glass fiber,
Fillers such as glass spheres and carbon fibers; and pigments.

EXAMPLES 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 methods for testing various physical properties 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 from gel permeation chromatography (GPC).

The degree of hydrogenation was calculated from the decrease in the unsaturated bond portion of the ¹ H-NMR spectrum at 100 Hz measured at a concentration of 15% using ethylene tetrachloride as a solvent.

On the other hand, the thermoplastic resin compositions of Examples and Comparative Examples were heated at 220 ° C.
A test piece was prepared at 220 ° C. using an injection molding machine (manufactured by Toshiba Corporation, IS-80A), and the physical properties were evaluated.

 The impact strength was measured by DuPont impact strength.

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

The chemical resistance is 1% for the test piece (1 x 8 "x 5").
, A brake fluid was applied to the bent portion, and the surface appearance after 23 hours at 23 ° C. was visually evaluated, and evaluated according to the following criteria.

；: No cracks ；: microcracks occurred ×: rupture Paintability was determined by washing an injection-molded product (83 × 60 × 3 mm) with ethyl alcohol and then applying an acrylic paint to a 25 μm thick chemical.
And dried at 80 ° C. for 30 minutes, and then left at room temperature for 24 hours to obtain a coatable test piece. On the coating film of this test piece, a 1 mm long and 1 mm wide cross-cut
After 100 pieces were cut and the cellophane tape was adhered, the cellophane tape was rapidly peeled off, and the percentage of the cross-section of the remaining coating film was determined in%, thereby evaluating the coating film adhesion.

Reference Example Production of hydrogenated diene-based random copolymer R-1 to 3 [R-1] A degassed and dehydrated cyclohexane of 2,500 g and 100 g of styrene were charged into an autoclave having an internal volume of 5, and then 9.8 g of tetrahydrofuran was added. Polymerization was carried out by adding 0.2 g of n-butyllithium, followed by isothermal polymerization at a temperature of 50 ° C.

After the polymerization conversion reached almost 100%, polymerization was carried out at a temperature of 70 ° C. while continuously adding a mixture of 437.5 g of 1,3-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 1,3-butadiene in the polymer generated as needed were measured for the microstructure.

After the polymerization conversion reached almost 100%, the reaction solution was cooled to 70 ° C., and 0.6 g of n-butyllithium, 2,6-t-butyl-
0.6 g of p-cresol and 1.1 g of bis (cyclopentadienyl) titanium dichloride were added, and 10 kg / cm ^{2 of} hydrogen gas was added.
The reaction was carried out for 1 hour while maintaining the pressure.

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. Table 1 shows the molecular characteristics of the obtained hydrogenated diene polymer R-1.

[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] 2,500 g of degassed and dehydrated cyclohexane and 350 g of 1,3-butadiene were charged into an autoclave having an internal volume of 5, and 0.50 g of n-butyllithium was added.
C. isothermal polymerization was carried out. After the polymerization conversion reached 31%, 12.5 g of tetrahydrofuran was added, and the temperature was changed from 50 ° C to 80 ° C.
Was heated.

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

Next, hydrogenation was performed in the same manner as in R-1 to obtain a hydrogenated diene polymer R-3. Table of molecular properties
It is shown in FIG.

(A) Production of Rubber-Reinforced Resins A-1 to 5 [Production Example A-1] In a stainless steel autoclave with an internal volume of 10 equipped with a paddle-type stirrer, a refractive index of 1.
507 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-dodecylmercaptan were charged, the temperature was increased while stirring, and 79.2 parts of methyl methacrylate and 0.5 part of t-butylperoxyisopropyl carbonate were added at 50 ° C. After replacing the system with nitrogen,
The temperature was further raised to 90 ° C, at which point the polymerization conversion rate was 74%.
The polymerization was continued under stirring until the mixture became.

When the polymerization conversion reached 74%, the polymerization was stopped, and an antioxidant was added. Thereafter, the product was taken out of the autoclave, and the unreacted monomer and solvent were distilled off by steam distillation.
After pulverizing finely, an extruder with a 40 mmφ vent (220 ° C, 7
(00 mmHg vacuum) to substantially remove volatile components,
The polymer was pelletized to obtain a rubber-reinforced resin A-1 of the present invention.

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

[Production Example A-3] Using a hydrogenated diene-based random copolymer (R-2), polymerization was performed in the same manner as in A-1, followed by post-treatment, and evaluated.

[Production Example A-4] Using a hydrogenated diene-based random copolymer (R-3), polymerization was performed in the same manner as in A-1, followed by post-treatment and evaluation.

[Production Example A-5 (Control)] Unhydrogenated SBS block copolymer (Nippon Synthetic Rubber Co., Ltd.)
And TR2000) in the same manner as in Production Example A-1.

Table 2 summarizes the polymers obtained in Production Examples A-1 to 5 described above.

(B) Polyolefin resin Table 3 shows the polyolefin used in this example.

(Iii) Compatibilizer A modified vinyl polymer obtained by copolymerizing maleic anhydride with an acrylonitrile-styrene resin in a composition shown in Table 4 was used as (iii-1) a compatibilizer used in this example.

As the compatibilizer (c-2) used in this example, MODIPER A3 manufactured by NOF CORPORATION produced by copolymerizing styrene-acrylonitrile resin with polypropylene in the composition shown in Table-4.
411 was used.

(C-3) and (C-4) were obtained by the same formulation as (C-2), and (C-3) was obtained when the acrylonitrile-styrene copolymer (C-2) was produced. Maleic anhydride was copolymerized, while (C-4) was (C-4)
Propylene-maleic anhydride copolymer (maleic anhydride content 10% by weight) in place of polypropylene used in 2)
Is used.

[Examples 1 to 13 and Comparative Examples 1 to 3] Using a 50 mmφ extruder, the above components (a) to (b) or components (a) to (c) were prepared according to the formulation shown in Table-5.
Pellets were prepared by kneading at 0 ° C, and test pieces were prepared at 220 ° C using an injection molding machine (IS-80A, manufactured by Toshiba Corporation) to evaluate physical properties. The results are shown in Table-5.

As is clear from Table 5, the compositions of Examples 1 to 13 of the present invention are excellent in all of impact resistance, weather resistance, chemical resistance, and paintability.

[Effect of the Invention] The thermoplastic resin composition of the present invention has impact resistance, weather resistance,
Excellent paintability and moldability, various automotive parts such as bumpers and molds, home appliances, household goods,
In addition, it is useful as various industrial materials.

Continuation of the front page (72) Inventor Takeki Furuyama 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-63-39951 (JP, A) JP-A-2-180950 (JP, A) JP-A-1-240542 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 51/04-51/06 C08L 23/00-23/36

Claims (2)

(57) [Claims] 1. A hydrogenated diene polymer (I) comprising a polymer obtained by hydrogenating a polymer comprising 0 to 60% by weight of an aromatic vinyl compound and 100 to 40% by weight of a conjugated diene compound.
In the presence of 5 to 60% by weight, a (meth) acrylic acid ester (a) and / or an aromatic vinyl compound (b), or a copolymerizable with these monomers other than (a) and (b) Graft ratio of 20 to 90 obtained by graft copolymerization of 95 to 40% by weight of monomer (II) composed of vinyl monomer (c).
%, Methyl ethyl ketone soluble matter intrinsic viscosity [η] 0.2dl /
A thermoplastic resin composition for coating, comprising 1 to 99% by weight of a rubber reinforced resin of at least g and (2) 99 to 1% by weight of a polyolefin. 2. The thermoplastic resin composition for coating according to claim 1.
(C) Functional group-containing monomer component (II
Copolymer (I) and a vinyl monomer (C)
1) and a thermoplastic resin composition for coating comprising 0.5 to 20 parts by weight of at least one copolymer selected from copolymers of vinyl monomers and α-monoolefins (c-2) Stuff.