JP2730182B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a heat resistant material having excellent mechanical strength represented by permanent antistatic properties and impact resistance, heat resistance, molding processability, weather resistance and surface appearance. The present invention relates to a plastic resin composition.

[Conventional technology]

2. Description of the Related Art Conventionally, thermoplastic resins are lightweight and excellent in moldability, and are used in various fields such as automobile parts and electric appliances. Further, the thermoplastic resin is an electric insulator because its structure is based on an organic compound, and is effective as an insulating material.On the other hand, the thermoplastic resin cannot leak charged electricity, and dust is generated on the surface. There is a drawback that charged electricity causes interference in electronic devices.

Therefore, as a means for preventing such charging, a method of kneading an antistatic agent, carbon black, and metal powder is generally known.

The method of kneading an antistatic agent into a thermoplastic resin is effective as a method for imparting antistatic performance without impairing the appearance and workability of the resin, but the performance is not sufficient, for example, the lower limit of the surface specific resistance value Is about 10 ¹¹ to 10 ¹² Ω.
In addition, this method has a drawback that the antistatic effect is not maintained and the surface resistivity increases with the passage of time.

On the other hand, the method of kneading carbon black or metal powder imparts sufficient antistatic performance and can easily make the surface specific resistance value 10 ⁵ Ω or less. However, when carbon black is used, the resin is colored black, which greatly impairs the characteristic of the thermoplastic resin that it can be colored any color. Also, when metal powder is kneaded, there is a disadvantage that the moldability is reduced, the appearance of the molded resin surface is impaired, and the physical properties such as impact resistance are reduced.

On the other hand, an aromatic vinyl compound and other monomers copolymerizable therewith are grafted onto a hydrogenated diene-based polymer obtained by hydrogenating a block and / or random copolymer comprising an aromatic vinyl compound and a conjugated diene. The copolymerized rubber reinforced resin is conventionally used widely as a rubber reinforced resin such as ABS resin (acrylonitrile-butadiene-styrene resin), HIPS (high impact polystyrene), AES resin (acrylonitrile-ethylene-propylene-styrene resin) or It has better weather resistance and surface appearance than AAS resin (acrylonitrile-n-butyl acrylate-styrene resin), and is being developed for applications requiring weather resistance and good surface appearance. However, this graft copolymer also has a disadvantage that it is easily charged, which is a characteristic of the thermoplastic resin as described above, and the surface appearance, which should be originally excellent, is deteriorated due to adhesion of dust and the like. There is a tendency.

[Problems to be solved by the invention]

The present invention has been made in view of the problems of the prior art, and provides a thermoplastic resin composition having excellent permanent antistatic properties, mechanical properties, heat resistance, moldability, weatherability, and surface appearance. With the goal.

[Means for solving the problem]

The present invention relates to (a) a polyamide elastomer (hereinafter sometimes referred to as “component (i)”) in an amount of 1 to 90% by weight, Polymer) and / or a hydrogenated diene polymer obtained by hydrogenating a random copolymer comprising an aromatic vinyl compound and a conjugated diene (hereinafter referred to as “random copolymer”) In the presence of 5 to 60% by weight of the polymer (I), 5 to 100% by weight of the aromatic vinyl compound (a) and 95 to 0% by weight of another monomer (b) copolymerizable therewith [provided that
(A) + (b) = 100% by weight], a rubber-reinforced resin (hereinafter sometimes referred to as “(b) component”) obtained by graft copolymerizing a total amount of 95 to 40% by weight; C)
Modified vinyl polymer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, an epoxy group and a hydroxyl group, based on 100 parts by weight of the components (a) and (b). And / or a rubber-modified vinyl polymer (hereinafter sometimes referred to as “component (C)”) in an amount of 0 to 100 parts by weight.

The polyamide-based elastomer (A) used in the present invention includes aminocarboxylic acids or lactams as hard segments, or nylon mn salts (X) having m + n or more of 12 as a hard segment, and polyols as soft segments. Are those composed of poly (alkylene oxide) glycol (Y) and having a proportion of X component in the elastomer of 10 to 95% by weight, preferably 20 to 90% by weight, more preferably 80 to 90% by weight. Can be mentioned.

(A) If the proportion of the X component in the polyamide elastomer is less than 10% by weight, the compatibility with the (A) component is inferior. On the other hand, if it exceeds 95% by weight, the antistatic property is inferior.

As the aminocarboxylic acid or lactam having 6 or more carbon atoms or the nylon mn salt (X) having m + n ≧ 12,
Aminocarboxylic acids such as aminocaproic acid, ω-aminoenanoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; lactams such as caprolactam and laurolactam Kinds; nylon 6,6, nylon 6,10,
Nylon 6,12, Nylon 11,6, Nylon 11,10, Nylon 12,6, Nylon 11,12, Nylon 12,6, Nylon 12,1
And nylon salts such as 0, nylon 12,12.

Also, poly (alkylene oxide) glycol (Y)
As polyethylene glycol, poly (1,2 and
1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, block or random copolymer of ethylene oxide and propylene oxide, block or random copolymer of ethylene oxide and tetrahydrofuran, etc. Is mentioned.

The number average molecular weight of these glycols (Y) is from 200 to
It is 6,000, preferably 250-4,000. Among these glycols (Y), in that they have excellent antistatic properties,
Particularly, polyethylene glycol is preferably used.

In the present invention, both ends of the poly (alkylene oxide) glycol (Y) may be aminated or carboxylated.

The bond between the component (X) and the component (Y) may be an ester bond or an amide bond corresponding to the terminal group of the polyamide elastomer (a).

At the time of this bonding, a third component such as dicarboxylic acid or diamine is used.
Components can be used.

The dicarboxylic acid has 4 to 20 carbon atoms. In particular, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid are preferable in terms of polymerizability, color tone and physical properties. Is preferably used.

As the diamine, an aromatic, alicyclic or aliphatic diamine is used. Specifically, examples of the aliphatic diamine include hexamethylene diamine.

(A) The method for synthesizing the polyamide elastomer is not particularly limited, and examples thereof include JP-B-56-45419 and JP-A-55-1.
The method disclosed in, for example, JP-A-33424 can be employed.

Next, the hydrogenated diene-based polymer (I) constituting the component (b) of the present invention refers to a hydrogenated block copolymer composed of an aromatic vinyl compound and a conjugated diene and / or an aromatic copolymer. It is obtained by hydrogenating a random copolymer comprising a vinyl compound and a conjugated diene.

Here, as the aromatic vinyl compound used for the hydrogenated diene polymer, styrene, t-butylstyrene, α
-Methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p
-T-butylstyrene, ethylstyrene, vinylnaphthalene, divinylbenzene, 1,1-diphenylstyrene,
N, N-diethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene, vinylpyridine and the like can be mentioned, 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, and the like, which can be used industrially and obtain a hydrogenated diene polymer having excellent physical properties. 1,3-butadiene, isoprene and 1,3-pentadiene are preferred, more preferably 1,3
-Butadiene.

The block copolymer or random copolymer used in the present invention includes, for example, A; vinyl aromatic polymer block B; conjugated diene polymer block A / B; random copolymer of vinyl aromatic compound / conjugated diene. Coalescing block C; a taper block comprising a copolymer of a conjugated diene and a vinyl aromatic compound and gradually increasing the vinyl aromatic compound is defined as follows.

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 wherein the same) C-B C-B- CCA / BCCAB In these block copolymers or random copolymers, the ratio of vinyl aromatic compound / conjugated diene in all monomers is preferably 5 to 40/95 by weight. ~ 60. Here, when the content of the vinyl aromatic compound is less than 5% by weight,
If the surface appearance deteriorates, on the other hand, if the content of the vinyl aromatic compound exceeds 40% by weight, it becomes resinous and the impact strength deteriorates.

Further, the bond content of the vinyl aromatic compound in the block A and the taper block C in all monomers is preferably 3 to 25.
%, More preferably 5 to 20% by weight, and if it is less than 3% by weight, the surface appearance deteriorates, while if it exceeds 25% by weight, it becomes resinous and impact strength deteriorates.

Further, the vinyl bond content of the conjugated diene portion in the block copolymer or the random copolymer is preferably 15
% Or more, more preferably 30 to 80% by weight,
When the amount is less than the weight percentage, the impact strength at low temperature is deteriorated.

As the block copolymer or the random copolymer, the use of the above-mentioned compounds, and more preferably the use of the above-mentioned compounds, results in a composition having excellent low-temperature properties and fatigue properties.

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

Further, the hydrogenated diene polymer (I) of the present invention has a number average molecular weight of 50,000 to 600,000, preferably 100,000 to 400,000, and if the number average molecular weight is out of this range, in a composition blended with another resin, A sufficient reforming effect cannot be obtained. For example, when the number average molecular weight is less than 50,000, the impact resistance of the obtained composition is reduced. On the other hand, when it exceeds 600,000, the fluidity and processability are reduced, and the surface appearance is reduced.

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 anion 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

Also, at this time, as a regulator of the microstructure, that is, a Lewis base such as an ether or an amine, specifically, diethyl ether, tedrahydrofuran, propyl ether, butyl ether, a higher ether, or the like, as a regulator of the vinyl bond content of the conjugated diene portion, or Ether derivatives of polyethylene glycol such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, and triethylene glycol dimethyl ether; examples of amines include tertiary amines such as tetramethylethylenediamine, pyridine, and tributylamine; Used.

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, in order to obtain an ABC block copolymer or an ABA block copolymer, an aromatic vinyl compound is added in an organic solvent using an organic lithium initiator to polymerize the block A. Then, a conjugated diene or a conjugated diene and an aromatic vinyl compound are added to form a block B, and a taper block C or block A is polymerized by further adding a conjugated diene and an aromatic vinyl compound or an aromatic vinyl compound. I just need. 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.

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-based polymer (I) of the present invention is obtained by dissolving the block copolymer or random copolymer thus obtained in an inert solvent, at 20 to 150 ° C and 1 to 100 kg / cm ^2.
In the presence of a hydrogenation catalyst under hydrogen pressure.

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 organic carboxylate, a hydrogenation catalyst comprising a nickel organic carboxylate and an organic metal compound of Group I to III of the periodic table, carbon, silica, diatomaceous earth, and the like. Supported on nickel, platinum, palladium, ruthenium, rhenium, rhodium metal catalyst, cobalt, nickel, rhodium, ruthenium complex, or lithium aluminum hydride, p-toluenesulfonyl hydrazide, and also a 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

Examples of the aromatic vinyl compound (a) to be graft-copolymerized with the hydrogenated diene polymer (I) include the same aromatic vinyl compounds as used in the production of the hydrogenated diene polymer (I). Can be

Examples of the monomer (b) copolymerizable with the aromatic vinyl compound (a) include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.
Used in species or two or more.

 In particular, acrylonitrile is preferred.

Further, other monomers (b) include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, and phenyl acrylate Alkyl acrylates such as benzyl acrylate; methyl methacrylate, ethyl ethacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, Be Alkyl methacrylates such as zyl methacrylate; unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; acrylic acid, methacrylic acid and the like; and maleimide, N-methylmaleimide, N-butylmaleimide, N- (P-methylphenyl) maleimide, N-phenylmaleimide, N
Imide compounds of α, β-unsaturated dicarboxylic acids such as -cyclohexylmaleimide.

As the other monomer (b), a vinyl cyanide compound and / or an alkyl (meth) acrylate are preferable, and a further excellent effect intended by the present invention can be obtained. When a vinyl cyanide compound is used, a composition having more excellent impact resistance, chemical resistance, and coatability is obtained. When an alkyl (meth) acrylate is used, a composition having further excellent weather resistance is obtained. It is preferable to use a large amount of (meth) acrylic acid alkyl ester since a composition having excellent transparency can be obtained.

When the preferred alkyl (meth) acrylate is a polymer alone, the glass transition temperature (measured by a differential scanning calorimeter (DSC)) of the polymer 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 are methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, t-butyl cyclohexyl methacrylate, butyl methacrylate, hexyl methacrylate, represented by the following formula ( (Meth) acrylates; (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.

In the present invention, the (co) polymer formed from the hydrogenated diene polymer (I) and the aromatic vinyl compound (a) [and the other monomer (b)] grafted thereto is used. When the difference in the refractive index is 0.02 or less, a thermoplastic resin composition having excellent transparency can be obtained.

The weight ratio of the aromatic vinyl compound (a) to the other monomer (b) is 5 to 100/95 to 0, preferably 10 to 95/9.
0 to 5. If the amount of the aromatic vinyl compound (a) is less than 5% by weight, moldability is poor.

When a monomer having an aromatic vinyl compound (a) and a vinyl cyanide compound (b) as main components is used as the graft monomer, the obtained rubber-reinforced resin is a vinyl cyanide compound (b) It has excellent chemical resistance compared to those obtained without using, and it has excellent properties that it does not easily cause coating phenomena such as uneven coating, cracks and adhesion when coating molded products. Thus, a more excellent effect aimed at by the present invention can be obtained.

When the aromatic vinyl compound (a) and the vinyl cyanide compound (b) are used as the graft monomer component, the preferred weight ratio is aromatic vinyl compound (a) / vinyl cyanide compound (b) = 30 to 95. / 70-5, more preferably 60-95 / 40-5.

As the graft monomer component, especially when the cyan vinyl compound (b) is in the range of 15 to 70% by weight, a composition having an excellent balance of physical properties such as moldability, thermal stability, thermal discoloration and chemical resistance can be obtained. Can be

Preferred specific combinations of the aromatic vinyl compound (a) and the other monomer (b) in the present invention include the following.

Styrene-acrylonitrile styrene-methyl methacrylate Styrene-acrylonitrile-methyl methacrylate In addition, by replacing a part or all of the above-mentioned styrene with α-methylstyrene, heat resistance can be imparted. Further, by replacing part or all of styrene with halogenated styrene, flame retardancy can be imparted.

Further, in the above combination, when methyl methacrylate is used in combination, the transparency of the rubber-reinforced resin is improved, and further excellent coloring properties are obtained.

The content of the hydrogenated diene polymer (I) in producing the rubber reinforced resin of the present invention can be arbitrarily selected depending on the purpose, but the impact resistance and moldability of the obtained composition are satisfied. The range is 5 to 60% by weight, preferably 10 to 60% by weight.
% By weight.

Further, the total amount of the aromatic vinyl compound (a) and the other monomer (b) is 95 to 40% by weight, preferably 90 to 40% by weight.

If this hydrogenated diene polymer (I) is less than 5% by weight,
Only a composition with insufficient impact resistance was obtained, while 60% by weight
Exceeding the range is not preferred because the moldability decreases. Therefore, the graph monomer component to be the matrix resin has the remaining content.

The rubber-reinforced resin (b) 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.

(B) 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 copolymer obtained by graft copolymerization under the condition of ~ 5.0 kg / cm ² (including non-grafted polymer)
And a polymer of the aromatic vinyl compound (a) obtained by emulsion polymerization or solution polymerization [and another monomer (b) used as necessary].

Next, the component (c) used in the present invention is a modified vinyl polymer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, an epoxy group and a hydroxyl group. And / or a rubber-modified vinyl polymer, which plays a role of a compatibilizer for the components (A) and (B) in the present invention.

Here, as the carboxyl group-containing unsaturated compound,
Acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid and the like can be mentioned, and acrylic acid and methacrylic acid are preferable.

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

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, tetrahydrophthalic anhydride and the like. is there. These compounds can be used alone or in combination of two or more.

Further, as the amino group-containing unsaturated compound, 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).

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

The epoxy group-containing unsaturated compound 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 unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, butene carboxylate, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether,
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 unsaturated compounds containing an epoxy group may be used alone or in combination of two or more.

The hydroxyl group-containing unsaturated compound is a compound having at least one unsaturated bond (double bond, triple bond) and 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.

Specific examples of these hydroxyl group-containing unsaturated compounds include 3-hydroxy-1-propane, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene,
Trans-4-hydroxy-2-butene, 3-hydroxy-2-methyl-1-propane, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, cis-1,4-dihydroxy- 2-butene, trans-1,4-dihydroxy-2-butene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl crotonate, 2,3 , 4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-tetrahydroxy Pentyl methacrylate and the like. Of these, 2
It is preferred to use -hydroxyethyl methacrylate. These unsaturated compounds having a hydroxyl group can be used alone or in combination of two or more.

Examples of the base material for producing the component (c) include a rubbery polymer, a graft layer of a graft copolymer, and a non-grafted vinyl polymer. Of these, the preferable one is.

The component (C) obtained in this manner can be specifically described as follows: 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-styrene-
When producing a copolymer resin such as an acrylonitrile resin, a part of the monomer in the copolymer resin or in the vinyl polymer to be mixed with the copolymer resin is replaced with the functional group unsaturated compound. And polymerized to contain a functional group-containing unsaturated compound.

At this time, the content of the functional group-containing unsaturated compound in the component (c) is preferably 0.01 to 80% by weight, more preferably
0.1 to 50% by weight.

The component (c) 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.

(C) As a preferred method for producing the component, a monomer and an additional emulsifier, a monomer, and a polymerization initiator are used in the presence of a rubbery polymer obtained by emulsion polymerization, and the polymerization temperature is generally 30 to 40. 150 ° C, polymerization time 1 to 15 hours, polymerization pressure-
A graft copolymer obtained by graft copolymerization under a condition of 1.0 to 5.0 kg / cm ² (including a non-grafted vinyl polymer), and a vinyl polymer obtained by emulsion polymerization or solution polymerization. Is produced by mixing

The thermoplastic resin composition of the present invention contains the above-mentioned (a) a polyamide elastomer, (b) a rubber-reinforced resin, and (c) a modified vinyl polymer and / or a rubber modified vinyl polymer as main components. First, the mixing ratio of the component (a) and the component (b) is 1 to 90% by weight, preferably 3 to 90% by weight of the component (a).
75% by weight, more preferably 5 to 60% by weight, (b) component
It is 99 to 10% by weight, preferably 97 to 25% by weight, more preferably 95 to 40% by weight [however, (a) + (b) = 100% by weight].

Here, if the amount of the component (a) is less than 1% by weight, the obtained composition has insufficient antistatic properties, whereas if it exceeds 90% by weight, the composition becomes soft and has poor mechanical properties.

Component (C) is added in an amount of 0 to 100 parts by weight, preferably 1 to 100 parts by weight of component (A) + component (B).
50 parts by weight.

The composition obtained by blending only the component (a) and the component (b) without blending the component (c) has excellent mechanical strength represented by impact resistance. By blending the component (1), more excellent mechanical strength and antistatic performance can be obtained. On the other hand, if the compounding amount of the component (c) exceeds 100 parts by weight with respect to 100 parts by weight of the components (a) and (b), the surface appearance deteriorates, which is not preferable.

The thermoplastic resin composition of the present invention comprises: (a) a polyamide elastomer, (b) a rubber-reinforced resin, and (c) a functional group-containing modified vinyl polymer and / or a rubbery modified vinyl polymer. It is obtained by mixing using a mixing method.

For example, after mixing each component with a mixer, the mixture is melt-kneaded at 200 to 280 ° C. with an extruder and granulated.

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

The composition of the present invention contains the above-mentioned components (a) to (c) as main components. In addition to the resin composition of the present invention, other thermoplastic polymers such as a vinyl chloride resin and a polyolefin resin are used. , Polyamide, polybutylene terephthalate, polyethylene terephthalate, polycarbonate, polyphenylene ether, polyglutarimide, styrene-butadiene block copolymer, and other general synthetic resins, or elastomers, in an amount of 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 carbonate, 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.

Reference Example 1 (Preparation of each component) (A) Preparation of polyamide elastomer a-1; PEBAX 4011MAOO (manufactured by Atochem) was used.

B-2: PEBAX 5533SAOO (manufactured by Atochem) was used.

(B) Preparation of rubber-reinforced resin (1) Production of hydrogenated diene polymer (I) KRATON G1650 (manufactured by Shell Chemical Company) and the following R-1 and R-2 were used as hydrogenated diene (I). .

R-1; degassed and dehydrated in an autoclave having an internal volume of 5 and charged with 2,500 g of cyclohexane, 150 g of styrene and 350 g of 1,3-butadiene, and then polymerized by adding 2.5 g of tetrahydrofuran and 0.34 g of n-butyllithium. . The temperature was raised from 30 ° C to 80 ° C.

After the polymerization conversion reaches almost 100%, silicon tetrachloride
0.14 g was added. Thereafter, 2,6-di-t-butylcatechol was added, and the solvent was removed by a steam stripping method.
The polymer was dried with a hot roll at 0 ° C. to obtain a polymer.

The styrene-butadiene copolymer thus obtained has a vinyl bond content of 30%, a bound styrene content of 30%,
5 branched polymers with 3 or more branches (coupling efficiency, C / E)
6%.

Further, the number average molecular weight by GPC analysis was about 200,000, and Mw / Mn was 1.5.

The conjugated diene-based polymer polymerized in the
Was charged in an autoclave to obtain a 15% cyclohexane solution. After purging the system with nitrogen, the catalyst solution of nickel naphthenate: n-butyllithium: tetrahydrofuran = 1: 8: 20 (molar ratio) prepared in a separate container in advance was used in an amount of 1 mol as nickel with respect to 2,000 mol of the olefin portion. It was charged to become. Then, hydrogen was introduced into the reaction system, and 70
A hydrogenation reaction was performed at ℃.

After adjusting the hydrogenation rate according to the amount of hydrogen absorbed and consumed, the hydrogen in the system is replaced with nitrogen, and the antioxidant 2,6-di-
t-Butyl-p-cresol was added for 1 Phr. Decatalysis,
After repeating the coagulation, roll drying is performed in the usual way,
A hydrogenated diene polymer (R-1) having a hydrogenation rate of 95% was obtained.

 Table 1 shows the analysis results of the hydrogenated diene system R-1.

In Table 1, various analyzes were 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 number average molecular weight, molecular weight distribution (Mw / Mn) and coupling efficiency (C / E) were determined by 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.

R-2: After degassing and dehydrating the autoclave of the inner solution 5 and charging 2,500 g of cyclohexane and 25 g of styrene, 9.8 g of tetrahydrofuran and 0.2 g of n-butyllithium were added, and isothermal polymerization was performed at a polymerization temperature of 50 ° C. ( First stage polymerization).

After the polymerization conversion reached almost 100%, a mixture of 300 g of 1,3-butadiene and 75 g of styrene was added for 7 minutes per 10 minutes.
Polymerization was carried out at a temperature of 70 ° C. while continuously adding at a rate of 5 g (second stage polymerization).

After the polymerization conversion reached almost 100%, a mixture of 50 g of 1,3-butadiene and 50 g of styrene was added all at once, and adiabatic polymerization was performed (third stage polymerization).

During the polymerization, sampling was performed every 5 minutes, and the bound styrene content and the microstructure of 1,3-butadiene in the polymer produced 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)
0.28 g of titanium dichloride and 1.1 g of diethylaluminum chloride were added, and the mixture was reacted with hydrogen gas for 1 hour while maintaining the pressure at 10 kg / cm ² .

The reaction solution was cooled to room temperature, desolvated by a steam stripping method, and dried with a hot roll at 120 ° C. to obtain a hydrogenated diene polymer R-2.

The properties of the diene polymer before hydrogenation are as follows.

Structure of diene copolymer Styrene polymer block (A block) -styrene /
Butadiene random copolymer block (B block)
Styrene / butadiene copolymer block (C block) in which the bound styrene content increases gradually Bound styrene content in diene polymer = 30% Total bound styrene content of A block and C block in diene polymer = 15% Diene Bound Styrene Content of A Block in System Polymer =
5% Vinyl bond content of butadiene portion in B block = 40
% Molecular weight of diene-based polymer = 160,000 Hydrogenation rate of diene-based polymer = 98% (2) Production of rubber-reinforced resin [(b) component] Next, rubber-reinforced resins B-1 to B-5 were produced.

B-1; In a stainless steel autoclave having an internal volume of 10 equipped with a paddle-type stirrer, a refractive index of 1.
507 hydrogenated block copolymer KRATON G1650 (Shell Chemical Co., Ltd.) 15 parts, styrene 59.5 parts, toluene 100 parts, t
-0.1 part of dodecyl mercaptan was charged, the temperature was elevated while stirring, and 25.5 parts of acrylonitrile and 0.5 part of t-butylperoxyisopropyl carbonate were added at 50 ° C. After the inside of the system was replaced with nitrogen, the temperature was further raised to 100 ° C., and when the polymerization conversion reached 95% or more at this temperature, the polymerization was stopped, and 2,2′-methyl-bis ( 0.2 parts of 4-methyl-6-t-butylphenol) was added. Thereafter, the reaction product liquid was taken out of the autoclave, and the unreacted monomer and the solvent were removed by a steam stripping method.

The obtained polymer was finely ground and dried, and then pelletized by an extruder equipped with a 40 mm vent.

B-2. A polymerization reaction was carried out in the same manner as in Production Example 1 using 25 parts of hydrogenated diene polymer R-2 having a refractive index of 1.507, 9 parts of styrene, and 4 parts of acrylonitrile. When the polymerization conversion rate reaches 95% or more, the polymerization is stopped.
Post-treatment was conducted in the same manner as in Production Example 1 to obtain a rubber reinforced resin as a graft copolymer.

B-3; Production example of B-1 using 25 parts of hydrogenated diene polymer KRATON G1650 (SEBS, manufactured by Shell Chemical Co., Ltd.) having a refractive index of 1.507, 9 parts of styrene, 4 parts of acrylonitrile, and 62 parts of methyl methacrylate A polymerization reaction was carried out in the same manner as described above. When the polymerization conversion reached 95% or more, the polymerization was stopped, and post-treatment was performed in the same manner as in Production Example 1 to obtain a rubber-reinforced resin as a graft copolymer.

B-4 Using the hydrogenated diene polymer R-1, polymerization and post-treatment were carried out in the same manner as in the production example of B-1 to obtain a rubber reinforced resin as a graft copolymer.

B-5.Production of rubber-like polymer In a stainless steel autoclave having an internal volume of 100 equipped with a paddle-type stirrer, 0.2 part of potassium stearate, 1.5 parts of potassium laurate, 0.1 part of sodium alkylnaphthalenesulfonate, 0.1 part of potassium hydroxide 0.1 , 90 parts of ion-exchanged water containing 1.5 parts of potassium chloride, and then 70 parts of n-butyl acrylate 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. At that time, 0.1 parts of diethylhydroxylamine was added to stop the reaction, and the unreacted monomer was substantially removed by a steam stripping method to obtain a rubbery polymer latex.

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

Production of graft copolymer Instead of hydrogenated diene polymer, the refractive index obtained by the above method 1.
Except for using the n-butyl acrylate-styrene copolymer elastic material (n-BA-ST) of 507, polymerization and post-treatment were conducted in the same manner as in Production Example B-2 to obtain a graft copolymer. Was.

B-6. Using polybutadiene (PBD) as the base rubber,
Polymerization and post-treatment were carried out in the same manner as in Production Example 1 to obtain a graft copolymer.

Table 2 summarizes the compositions of the copolymers obtained from the above B-1 to B-6.

In Table 2, ST is styrene, AN is acrylonitrile, MMA
Represents methyl methacrylate.

(C) Preparation of a functional unit-containing modified vinyl polymer c-1; 80 parts of methyl methacrylate was prepared by a usual emulsion polymerization method.
A copolymer comprising 11 parts of styrene, 4 parts of acrylonitrile, and 5 parts of 2-hydroxyethyl methacrylate was obtained.

C-2; styrene in the presence of 40 parts of polybutadiene latex
A monomer mixture consisting of 40.5 parts, 13.5 parts of acrylonitrile and 6 parts of methacrylic acid was subjected to emulsion graft polymerization to obtain a rubber-modified vinyl polymer.

C-3 A copolymer comprising 74 parts of styrene, 24 parts of acrylonitrile and 2 parts of maleic anhydride was obtained by a usual emulsion polymerization method.

Examples 1 to 8 and Comparative Examples 1 to 5 The components were mixed at the mixing ratios shown in Table 3 using a Henschel mixer.

The mixture was melt-kneaded at a temperature of 230 ° C. using an extruder having a diameter of 50 mm and a twin-screw vent to produce pellets.
Using these pellets, the melt flow rate (measurement conditions; 220 ° C., 10 kg) was measured in accordance with JIS K7210.

Further, using the pellets, injection molding at a molding temperature of 230 ° C. using an injection molding machine IS-80A manufactured by Toshiba Machine Co., Ltd.
Test specimens were prepared and tested for Izod impact strength (ASTM D256, 1 /
4 "notched, 23 ° C), heat distortion temperature (ASTM D648, 18.
6 kg / cm ² , 1/2 ″), flexural modulus (ASTM D790), tensile strength (ASTM D638), tensile speed 15 mm / min).

Further, using the above-mentioned pellets, using a Toshiba Machine Co., Ltd., injection molding machine IS-25EP, molding temperature 230 ° C., diameter 100 mm,
Make a 2mm thick disc, relative humidity 50%, ambient temperature 23 ℃
After conditioning for 24 hours after molding, after leaving it for one month, it was washed with a detergent, and the surface specific resistance of the test piece was measured using a 4329A super insulation resistance meter manufactured by Yokogawa-Hewlett-Packard Company. .

The weather resistance was evaluated by exposing to a sunshine weather meter using a carbon arc light source for 1,000 hours, and measuring the Izod impact strength. The black panel temperature at this time was 63 ± 3 ° C.

Further, using the test piece measured the surface specific resistance value,
The surface appearance was visually determined. The evaluation criteria indicate that ○ is good, Δ is slightly bad, and × is very bad.

Furthermore, using this test piece, the total light transmittance (ASTM D6
48) and haze value (ASTM D1003).

 Table 3 shows the evaluation results of the physical properties.

As is clear from Table 3, Examples 1 to 8 are the thermoplastic resin compositions of the present invention, all of which have excellent fluidity, heat resistance, mechanical strength, weather resistance, surface appearance, and low surface. It has specific resistance, maintains a low surface specific resistance value even with aging and surface cleaning, and has excellent permanent antistatic properties.

In Examples 2, 3, and 6, the difference in refractive index between the components was 0.02.
The following thermoplastic resin composition of the present invention has excellent transparency.

On the other hand, as shown in Comparative Examples 1 and 2, when an acrylic polymer or polybutadiene is used as the rubber component of the rubber-reinforced resin, the weather resistance is poor.

In addition, as shown in Comparative Example 3, when (a) the polyamide elastomer was less than 1 part, the surface specific resistance was high, the sample did not have antistatic performance, and as shown in Comparative Example 4, (A) If the amount of the polyamide elastomer exceeds 90 parts, the flexural modulus and the tensile strength are extremely low, and the mechanical strength is poor.

Further, as shown in Comparative Example 5, (c) the functional group-containing vinyl polymer was added in an amount of 1% based on 100 parts by weight of the components (a) and (b).
If it exceeds 00 parts by weight, the surface appearance becomes matte and deteriorates.

[Effects of the Invention] The thermoplastic resin composition of the present invention has permanent antistatic properties, is excellent in mechanical strength, heat resistance, moldability, weatherability, surface appearance, and has a problem of electrostatic damage conventionally. Had been
OA equipment housings, chassis, optical and magnetic media housings, storage cases, trays during the electronic component manufacturing process,
It is useful for applications such as containers and exterior parts of home electric appliances, whose appearance may be deteriorated due to adhesion of dust and dust.

Claims (1)

(57) [Claims] 1. A hydrogenated diene-based polymer and / or an aromatic vinyl compound obtained by hydrogenating a block copolymer comprising (a) 1 to 90% by weight of a polyamide elastomer and (b) an aromatic vinyl compound and a conjugated diene. 5-100% by weight of an aromatic vinyl compound (a) and its copolymerization in the presence of 5-60% by weight of a hydrogenated diene-based polymer (I) obtained by hydrogenating a random copolymer consisting of 95 to 0% by weight of another possible monomer (b) [provided that (a) + (b) = 10
0% by weight] of a rubber-reinforced resin obtained by graft copolymerization of a total amount of 95 to 40% by weight, and (C) 100 parts by weight of the component (A) and the component (B).
0-100 parts by weight of a modified vinyl polymer and / or rubbery modified vinyl polymer having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group and an epoxy group The thermoplastic resin composition which mix | blends.