JP3453891B2 - Thermoplastic resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to conductivity, antistatic property,
The present invention relates to a thermoplastic resin composition having excellent impact resistance, heat resistance, solvent resistance and moldability. This molded product is used in a wide variety of fields such as antistatic packaging sheets, automobile parts, electric and electric equipment parts such as switches, housings, surface heating elements, semiconductor device containers, trays and hollow containers.

[0002]

2. Description of the Related Art It is known to obtain a conductive resin by blending a thermoplastic resin with a conductive substance such as carbon black, carbon fiber or metal fiber. Saturated polyester, which has excellent melt flowability, solvent resistance, heat resistance, etc., absorbs water and undergoes hydrolysis during molding and during use under high temperature and high humidity conditions.
Since it has a drawback that mechanical properties are easily changed,
It has been proposed to blend a crystalline olefin resin such as polypropylene or polyethylene, which is excellent in molding processability, water absorption resistance and solvent resistance, and is inexpensive. further,
It has been proposed to add an elastomer component to ameliorate the drop in impact strength due to its poor compatibility.

These resin compositions having a remarkably large electric resistance are used for surface heating elements which require conductivity, and for applications such as containers and trays for semiconductors which are required to prevent electrostatic charge from being electrically conductive or charged. It is necessary to impart preventive property. Therefore, if the above-mentioned conductive substance is added, conductivity and antistatic property can be imparted, but there is a drawback that impact strength is greatly reduced. In order to improve impact strength, a method of blending an elastomer is known. Specifically, a method of adding a styrene-butadiene block copolymer or a hydrogenated product thereof (JP-A-53-124559) is disclosed, which shows an impact strength improving effect. The resin composition to which 2 to 80% by weight of the inorganic filler is added has a low compatibility and is liable to cause delamination, has a low impact strength, and has a high compatibility to improve the performance. Needs to be improved.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition having excellent conductivity, antistatic property, impact resistance, heat resistance, solvent resistance and moldability.

[0005]

The inventors of the present invention have conducted extensive studies for this reason and as a result, as an elastomer having an affinity for both the crystalline olefin resin and the saturated polyester, an elastomer having a specific amount of hydroxyl groups has been obtained. A saturated compound or a hydrogenated product of an aromatic vinyl compound-conjugated diene block copolymer graft-modified with a specific amount of an aromatic vinyl compound and a conductive substance is used as a resin composition comprising a crystalline olefin resin and a saturated polyester. It was found that a resin composition which is excellent not only in conductivity but also in impact strength, tensile elongation, appearance, and molding processability can be obtained by blending it with a resin, and has arrived at the present invention.

That is, the present invention provides the following component (A),
A thermoplastic resin composition containing (B), (C) and (D) in the following compounding ratio. (A) Crystalline olefin resin 20 to 70 parts by weight (B) Saturated polyester 80 to 30 parts by weight (C) Hydrogenated product of aromatic vinyl compound-conjugated diene block copolymer A modified resin obtained by subjecting a saturated compound (0.05 to 50 parts by weight) and an aromatic vinyl compound (0 to 50 parts by weight) to a graft polymerization step, and a total of 100 parts by weight of the component (A) and the component (B), 2 to 40 parts by weight (D) 100 parts by weight of the total of the conductive substance, the component (A), the component (B) and the component (C), 2 to 100 parts by weight, especially the residual hydroxyl group of the modified resin (measurement method described later ) Is 0.3-
The above-mentioned thermoplastic resin composition is 1.0.

The hydroxyl group of the modified resin of the component (C), which is compatible with the crystalline olefin resin of the component (A) used in the present invention, reacts with the ester group, carboxy group or hydroxyl group of the saturated polyester of the component (B). As a result, a block copolymer and / or a graft copolymer of the modified resin and the saturated polyester is produced, and this serves as a compatibilizer, and the modified resin of the component (C) forms a fine and stable dispersion structure, Further, it is presumed that the conductive substance is efficiently dispersed in the dispersed structure formed by these resin components so that not only the conductivity is excellent, but also the mechanical strength, the appearance and the moldability are improved. The present invention will be described in detail below.

<Constituents> (1) Crystalline olefin resin (A) The crystalline olefin resin (A) is an α-carbon resin having 2 to 10 carbon atoms.
A polymer or copolymer comprising at least one olefin and having a crystallinity of 1 at room temperature by X-ray diffraction
It is preferably 5% or more, more preferably 30 to 70%, and has a melting point of 85 to 250 ° C, preferably 110 to 200.
And the bending elastic modulus at 23 ° C is 500 to 4000M.
Pa. The decrease in crystallinity decreases the elastic modulus of the final composition. Further, this olefin resin needs to have a sufficient molecular weight as a molding resin at room temperature. For example, when propylene is the main component, JIS
Melt flow rate (2
30 ° C., 2.16 kg load, hereinafter referred to as “MFR”) is 0.01 to 100 g / 10 minutes, preferably 0.1 to 50.
It has a molecular weight corresponding to g / 10 minutes.

Examples of the above α-olefin which is a constituent of the crystalline olefin resin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1. , 3,3-dimethylpentene-1,3-methylhexene-1,4-methylhexene-1,4,4-dimethylhexene-1,5
-Methylhexene-1, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexylbutene-1, vinylcyclopentane, vinylcyclohexane, 2-vinyl-bicyclo (2,2,1) heptane,
Heptene-1, octene-1, etc. are mentioned.

Among the above, preferred examples of α-olefins are ethylene, propylene, butene-1, pentene-1, hexene-1,3-methylbutene-1,4-methylpentene-1,3-methylhexene-1. Can be raised. In particular, ethylene, propylene, butene-1,
4-methylpentene-1 is preferred. Further, as another component, a non-conjugated diene such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene is a polymer component. May be used as a part of.

Specific examples of the crystalline olefin resin include propylene homopolymer, propylene-ethylene copolymer, propylene-ethylene-butene-1 copolymer, propylene-butene-1 copolymer and propylene-4-. Methylpentene-1 copolymer, poly (4-methylpentene-
1), a propylene-3-methylpentene-1 copolymer,
Examples include high-density polyethylene, linear medium-density polyethylene, linear low-density polyethylene, propylene-1,9-decadiene copolymer and the like.

Of these, isotactic polypropylene and propylene-ethylene block copolymers are preferable from the viewpoint of providing a high level of moldability and a balance of mechanical strength. Higher stereotacticity (tacticity) of isotactic polypropylene and propylene-ethylene block copolymer is preferable because it gives a molded article having higher rigidity.

These crystalline olefin resins can be modified and used in the presence or absence of a radical initiator. The modification method can be carried out by a general method as exemplified in the section of the modified resin of the component (C). The modifier used for modification is a compound having a functional group and an unsaturated bond, and examples thereof include α, β-unsaturated carboxylic acids and their derivatives, and vinyl monomers. Specific examples of the α, β-unsaturated carboxylic acid and its derivative include maleic anhydride, 2-hydroxyethyl methacrylate, glycidyl methacrylate and the like, and specific examples of the vinyl monomer include:
Examples thereof include styrene, methylstyrene, vinyl acetate and the like.

(2) Saturated Polyester (B) As the saturated polyester (B) used in the present invention, various saturated polyesters can be used. For example, a thermoplastic saturated polyester produced by polycondensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative and a glycol according to a usual method can be mentioned.

Specific examples of the aromatic or aliphatic dicarboxylic acid suitable for producing the saturated polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid and terephthalic acid. ,
Isophthalic acid, p, p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxyvaleric acid, 2,6-naphthalene dicarboxylic acid,
2,7-naphthalene dicarboxylic acid or a mixture of these carboxylic acids may be mentioned.

Specific examples of glycols have 2 to 2 carbon atoms.
12 straight chain alkylene glycols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc .; As aromatic glycols, for example, pyrocatechol, resonosinol, hydroquinone, bisphenol-A, etc. Alicyclic glycols such as cyclohexanedimethanol;
Alternatively, alkyl-substituted derivatives of these compounds can be mentioned.

Suitable saturated polyesters include polyethylene terephthalate, polybutylene terephthalate,
Examples thereof include polyethylene naphthalate and poly (1,4-cyclohexanedimethylene terephthalate). Liquid crystalline polyester, such as Eastman Kodak X7
Those commercially available under the trade names of G, Vectra by Hoechst Celanese, and Econol by Sumitomo Chemical Co., Ltd. are also preferable. These can be used alone or in combination of two or more. The saturated polyester as the component (B) contributes to improvement in fluidity during molding of the final resin composition, heat resistance of a molded product, rigidity and the like.

(3) Modified Resin (C) The modified resin of the component (C) is an unsaturated compound having a hydroxyl group of 0.05 to 100 parts by weight of the hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer. It is an elastomer-type modified resin obtained by graft-modifying 50 parts by weight of an aromatic vinyl compound with 0 to 50 parts by weight.

I) Hydrogenated product of aromatic vinyl compound-conjugated diene block copolymer The hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer used in the present invention is specifically at least 1
At least 80% of the aliphatic double bonds based on the conjugated diene of a block copolymer composed of a polymer block mainly containing one aromatic vinyl compound and at least one polymer block mainly containing a conjugated diene It is a hydrogenated product of a block copolymer obtained by addition.

As the aromatic vinyl compound, for example, styrene, α-methylstyrene, α-methoxystyrene,
Methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene,
Examples thereof include bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene, and the like, with styrene being preferred. These can be used alone or in combination of two or more.

As the conjugated diene, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,
One or more selected from 3-butadiene,
Of these, butadiene, isoprene or a combination thereof is preferable. As a method for producing these block copolymers, for example, the method described in JP-A-40-23798 can be used to synthesize the block copolymer in an inert solvent using a lithium catalyst.

In the polymer block mainly composed of the conjugated diene, the microstructure in the block can be arbitrarily selected. For example, in the polybutadiene block,
1,2-vinyl bond structure is 5 to 65%, preferably 10
~ 50%. The molecular structure of the block copolymer may be linear, branched, radial, radial teleblock, or any combination thereof.

The preferred block copolymer is styrene-
Butadiene block copolymer, styrene-butadiene-
They are a styrene block copolymer, a butadiene-styrene-butadiene block copolymer, a styrene-isoprene block copolymer, a styrene-isoprene-styrene block copolymer, and an isoprene-styrene-isoprene block copolymer.

As a method for producing a hydrogenated product of a block copolymer, for example, Japanese Patent Publication Nos. 42-8704 and 43-43 can be used.
It can be obtained by the method described in each publication of 6636. In particular, the heat resistance of the hydrogenated product of the obtained block copolymer, the hydrogenated product of the block copolymer synthesized by using a titanium-based hydrogenation catalyst exhibiting excellent performance in heat deterioration resistance is most preferable, for example, JP-A-59-13320
The block copolymer having the above structure can be obtained by hydrogenating in the presence of a titanium-based hydrogenation catalyst in an inert solvent according to the method described in JP-A No. 3 and 60-79005. At that time, at least 80% of the aliphatic double bond based on the conjugated diene of the aromatic vinyl compound-conjugated diene block copolymer is hydrogenated, and the polymer block mainly composed of the conjugated diene is morphologically changed to the olefin compound weight. Need to be converted to coalesce. The amount of non-hydrogenated aliphatic double bonds contained in the hydrogenated product of this block copolymer can be easily known by infrared spectroscopy, nuclear magnetic resonance method or the like. The content of the aromatic vinyl compound block is 10 to 50% by weight, preferably 20 to 40%.
% By weight.

The molecular weight of the hydrogenated product of the block copolymer is 10,000 to 200,000, preferably 20,000 to 1 in terms of number average molecular weight.
It is 50,000, more preferably 30,000 to 100,000. The hydrogenated product of the block copolymer can be obtained from Shell Chemical Co., Ltd. under the grade names such as Kraton G1652 and Kraton G1701, and from Kuraray Co., Ltd. under the grade names such as Septon 2007.

Ii) Unsaturated Compound Having Hydroxyl Group The unsaturated compound having a hydroxyl group used for modifying the hydrogenated product of the block copolymer includes a hydroxyl group and an unsaturated group, that is, a hydrogenated product of the block copolymer. It is a compound having a carbon-carbon double bond capable of graft polymerization in the same molecule.

Examples of the unsaturated compound having a hydroxyl group include α, β-unsaturated carboxylic acid esters, specifically 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2,3-dihydroxy. Propyl (meth) acrylate, 2-hydroxymethyl-3-hydroxypropyl (meth) acrylate, 2,2-bishydroxymethyl-3-hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, C4-40. And ethylene glycol oligomer (meth) acrylic acid ester. Here, (meth) acrylate means acrylate and methacrylate. Furthermore, N-methylol acrylamide, N-methylol methacrylamide,
Bis (2-hydroxyethyl) malate, bis (2-hydroxypropyl) malate, bis (2,3-dihydroxypropyl) malate, bis (2-hydroxymethyl-)
2-Hydroxypropyl) malate, bis (2,2-bishydroxymethyl-3-hydroxypropyl) malate, etc., and their isomers, fumarate, and maleic acid, which is an oligomer of ethylene glycol or propylene glycol having 4 to 40 carbon atoms. Alternatively, the fumaric acid ester can be exemplified as a compound in which both carboxylic acids are not esters of hydroxyalkyl groups as described above and one of them is similarly effective.

Further, allyl alcohol, crotyl alcohol, 4- (2-hydroxyethyl) styrene, 3-
(2-hydroxyethyl) styrene, 4- (hydroxymethyl) styrene, 3- (hydroxymethyl) styrene, 4-hydroxystyrene, 3-hydroxystyrene and the like can be mentioned. The above unsaturated compounds having a hydroxyl group can be used alone or in combination of two or more kinds.
Among these, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable from the viewpoint of obtaining a molded product having a higher level of mechanical properties.

The amount of the unsaturated compound having a hydroxyl group grafted onto the hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer is 0.05 to 10% by weight, preferably 0.2 to 5% by weight. It is preferably 0.5 to 3% by weight. If it is less than 0.05% by weight, the effect of improving the impact strength and appearance of the molded product is small, and if it exceeds 10% by weight, problems such as deterioration of mechanical properties due to molecular cleavage of polyester are likely to occur.

The residual hydroxyl group ratio of the unsaturated compound having a hydroxyl group graft-polymerized to the hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer (described later in the measuring method) is in the range of 0.3 to 1.0. Preferably, more preferably 0.
It is in the range of 5 to 1.0, particularly preferably 0.7 to 1.0. When the residual ratio of hydroxyl groups is 0.3 or more, the above-mentioned improving effect tends to be greater.

The amount of the unsaturated compound having a hydroxyl group used in the graft polymerization step is 0.05 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the hydrogenated product of the block copolymer. is there. If the amount is less than 0.05 parts by weight, the required amount of graft cannot be obtained, so that the impact strength and appearance of the molded product are not improved, and if it exceeds 50 parts by weight, excessive molecular cleavage or crosslinking of the polyester is promoted, resulting in a molding process. However, this may cause problems with the properties and may reduce the mechanical properties of the molded product.

Iii) Aromatic vinyl compound For the purpose of improving the graft amount of the block copolymer of the unsaturated compound having a hydroxyl group to the hydrogenated product, the aromatic vinyl compound is used in the graft polymerization step, particularly in the graft polymerization step by the melt kneading method. It is effective to use a group vinyl compound in combination.
Specific examples of the aromatic vinyl compound include styrene and α-
Methylstyrene, α-methoxystyrene, methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, nitrostyrene, chloromethylstyrene, cyanostyrene, t-butylstyrene, vinylnaphthalene, etc. Among them, styrene, α-methylstyrene,
Methylstyrene is preferred. These can be used alone or in combination of two or more.

The amount of the aromatic vinyl compound added to 100 parts by weight of the hydrogenated product of the block copolymer is 0 to 50 parts by weight, preferably 0.05 to 50 parts by weight, particularly preferably 1 to 20 parts by weight. is there. The addition of the aromatic vinyl compound enhances the effect of improving the graft amount of the unsaturated compound having a hydroxyl group on the hydrogenated product of the block copolymer. On the other hand, if it exceeds 50 parts by weight, the impact strength of the obtained molded article is lowered.

Iv) Radical Initiator As the radical initiator, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, t-butylperoxybenzoate, benzoylperoxide. Organic and inorganic peroxides such as oxides, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxide, methyl ethyl ketone peroxide, potassium peroxide and hydrogen peroxide, 2,2 ' -Azobisisobutyronitrile, 2,2'-azobis (isobutyramide) dihalide, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide],
Azo compounds such as azodi-t-butane and carbon radical generators such as dicumyl can also be used. These radical initiators can be appropriately selected in relation to the modifier and the reaction conditions, and two or more kinds can be used in combination. The amount of the radical initiator used is in the range of 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the hydrogenated product of the block copolymer. Especially when the graft polymerization is carried out by melt-kneading, it is preferably in the range of 0.05 to 3 parts by weight.

V) Graft modification method The graft modification of the unsaturated compound having a hydroxyl group or the aromatic vinyl compound with the hydrogenated product of the block copolymer is carried out by swelling, dissolving, melting or solid state block copolymer. It is carried out by heating the hydrogenated product of (1) above with an unsaturated compound having a hydroxyl group or an aromatic vinyl compound and a radical initiator impregnated therewith, and a reaction in dissolution or melting is particularly preferable.

The solvent used in the reaction in the dissolved state is appropriately selected depending on the type of reaction, and examples thereof include aliphatic, alicyclic and aromatic hydrocarbons and their halides.
Often selected from esters, ketones, ethers having 6 or more carbon atoms, carbon disulfide and the like. Further, these may be used as a mixed solvent of two or more kinds. The melting reaction does not require the use of a solvent or uses only a small amount, so that it has advantages such as saving the manufacturing cost and avoiding the release of the solvent vapor to the environment.

The radical graft modification method by melt-kneading will be specifically described below. For the reaction in the molten state, an ordinary melt-kneading device such as an extruder or a stirrer can be used. Specifically, Labo Plastomill,
A single-screw or twin-screw kneader, a horizontal-screw twin-screw multi-disk device, a horizontal twin-screw surface renewal machine, and a double helical ribbon stirrer. The kneading temperature at this time may be any temperature as long as the hydrogenated product of the aromatic vinyl compound-conjugated diene block copolymer is in a molten state, but the kneading temperature may be 150 to 150 in terms of deterioration prevention and the like. 250 ° C is desirable. The kneading time is 0.
It is between 01 and 10 minutes, preferably between 0.1 and 5 minutes. Further, in order to remove unreacted unsaturated compounds having a hydroxyl group and prevent deterioration of the obtained modified resin, it is desirable to carry out melt kneading and granulation under reduced pressure.

The unsaturated compound having a hydroxyl group or the aromatic vinyl compound and the graft modifier are added by the following method.
Examples thereof include a method of dry-blending with a hydrogenated product of the block copolymer and kneading at once, and a method of adding a modifier and a radical initiator to the hydrogenated product of the block copolymer in a molten state. At this time, a small amount of an organic solvent may be added to improve the reaction efficiency.

(4) Conductive substance (D) The conductive substance used in the present invention is a powdery, hollow spherical or fiber-like substance having conductivity, and specifically, carbon black, graphite, Examples thereof include carbon fiber, carbon hollow sphere, metal powder and metal fiber. From the viewpoint of obtaining a lightweight molded product, a carbonaceous product is preferable. Further, particulate carbon black that is easily dispersed in the resin component is preferable. As the carbon black, channel black, furnace black, thermal black, lamp black, ketjen black, acetylene black and the like can be used, and of these, furnace black, ketjen black and acetylene black are preferable.

Among the carbon blacks, those having a large specific surface area are preferable, and specifically, 20 m ² / g.
Above, more preferably 40 m ² / g or more.
Superconducting furnace (Super)
r Conductive Furnace: SC
F), Extra Conductive Furnace (Extr
a Conductive Furnace: EC
F), acetylene black and the like are also preferable, and the use of these gives a resin composition which gives a molded article having a higher level of conductivity.

These carbon blacks can be appropriately selected and used from commercial products, and specific examples include Furnace Black # 3050 and Furnace Black # 315 manufactured by Mitsubishi Chemical Corporation.
0, # 3250, # 3750, # 3950, etc., S
Cabot Vulcan SC and Vulcan P as CF,
As ECF, Ketjen Black EC manufactured by Ketjen Black International, Vulcan X manufactured by Cabot
C-72, CXS-99 and the like, and examples of acetylene black include those with trade names such as Denka Black manufactured by Denki Kagaku. Two or more kinds of these conductive materials can be used in combination.

(5) Additional component The thermoplastic resin composition of the present invention comprises the above component (A),
Other components other than (B), (C) and (D) can be contained. For example, a part of the modified resin of the component (C) is an unmodified styrene-butadiene block copolymer hydrogenated product, styrene-isoprene block copolymer hydrogenated product, styrene-butadiene random copolymer hydrogenated product, ethylene. -It may be replaced with an elastomer such as a propylene copolymer.

A resin composition such as polyphenylene ether, polyamide, polycarbonate, ABS, AES, acrylic rubber, acrylic-styrene core-shell rubber or a mixture thereof may be contained. Furthermore, the addition of organic / inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc., is effective in improving rigidity and heat resistance. For practical use, various colorants and their dispersants can also be used.

If desired, non-resinous additives may be added to improve the chemical and physical properties. For example, hindered phenol antioxidants, phosphite antioxidants, amine antioxidants, benzotriazole UV absorbers, benzophenone UV absorbers, aliphatic carboxylic ester lubricants, paraffin lubricants, difficult Examples include a flame retardant, a release agent, an antistatic agent, and a coloring agent.

Specific examples of the above hindered phenolic antioxidant include 2,6-di-t-butyl-p-cresol, Irganox 1076 (trade name of Ciba Geigy), Sumilizer GM (trade name of Sumitomo Chemical Co., Ltd.). And so on. Further, as the phosphorus-based antioxidant, Sumilizer TNP (trade name of Sumitomo Chemical Co., Ltd.), Mark PEP36
(Adeka Ardes Co., Ltd. product name), Irgafoss 168 (Ciba Geigy company product name), and the like.

(6) Composition Ratio of Constituents In the thermoplastic resin composition of the present invention, the composition ratio of the crystalline olefin resin as the component (A) and the saturated polyester as the component (B) is 100 parts by weight in total. On the other hand, the component (A) is 20 to 70 parts by weight, preferably 30 to 55 parts by weight, and the component (B) is 80 to 30 parts by weight, preferably 70 to 45 parts by weight. When the amount of the component (A) exceeds 70 parts by weight, heat resistance and impact strength at low temperature are low, and when it is less than 20 parts by weight, there is little effect of physical property change due to hydrolysis and improvement of molding processability. If the component (B) exceeds 80 parts by weight,
The effect of improving the moldability and water absorption resistance is small, and if it is less than 30 parts by weight, the impact strength of the molded product is low.

The amount of the modified resin as the component (C) is 2 to 100 parts by weight of the total of the components (A) and (B).
40 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 25 parts by weight. The amount of component (C) is 2
If it is less than 40 parts by weight, the effect of improving the impact strength is small, and if it exceeds 40 parts by weight, the elastic modulus of the molded product is largely lowered. The content of the conductive carbon as the component (D) is 100 parts by weight of the total of the components (A), (B) and (C).
2 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 8 to 30 parts by weight. If the compounding amount of the component (D) is less than 2 parts by weight, the effect of improving the conductivity, antistatic property and elastic modulus is small, and if it exceeds 100 parts by weight, the impact resistance is largely decreased.

(7) Composition Preparation Method and Molding Method The method for obtaining the thermoplastic resin composition of the present invention is not particularly limited, such as a melting method, a solution method and a suspension method, but in practice, melt kneading is performed. Method is preferred. As a method of melt-kneading, a method generally used for thermoplastic resins can be applied. For example, if necessary, the powdery or granular components are uniformly mixed with the above-mentioned additional components by a Henschel mixer, a ribbon blender, a V-type blender, etc., and then a uniaxial or multiaxial kneading extruder, rolls, Banbury mixer, etc. Can be kneaded. The temperature of the melt-kneading of each component is in the range of 180 to 350 ° C., preferably 22.
It is in the range of 0 to 300 ° C. The kneading order and method of each component are not particularly limited, and for example, a method of kneading each component at once, or after kneading a part or all of the modified resin and the saturated polyester, the remaining components are kneaded. Method,
Any method such as kneading under reduced pressure may be used. Furthermore, during melt-kneading, organic solvents such as chlorobenzene, trichlorobenzene, xylene, and tetrakis (2-
It is also possible to add a catalyst such as ethylhexoxy) titanium or dibutyltin oxide. Molding method of the thermoplastic resin composition of the present invention is not particularly limited,
For the thermoplastic resin, general molding methods, that is, various molding methods such as injection molding, extrusion molding, blow molding, thermoforming, and press molding can be applied.

[0049]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

Reference Example 1: Production of Modified Resin-1 Hydrogenated substance of styrene-butadiene triblock copolymer (Clayton G1701 manufactured by Shell Chemical Co., hereinafter abbreviated as "G1701") 6 kg, 2-hydroxyethyl Methacrylate (hereinafter abbreviated as "HEMA") 60
0 g, styrene monomer (hereinafter abbreviated as "SM") 30
After dry blending 0 g and 30 g of 1,3-bis (t-butylperoxyisopropyl) benzene (manufactured by Kayaku Akzo Co., Ltd., trade name Percadox 14, hereinafter abbreviated as “P14”), a twin-screw extruder (Nippon Steel) Product name TEX
-30 type), cylinder temperature 160 ° C., screw rotation speed 200 rpm, discharge rate 2 kg / hr, vent pressure 50 mmHg, and kneading under reduced pressure to obtain modified resin.
Got 1. 0.3 g of the obtained modified resin was added to chloroform 5
It was dissolved in 0 ml at room temperature and poured into 300 ml of methanol to cause precipitation. The precipitate was filtered off and dried under reduced pressure (normal temperature) to obtain a purified resin. The HEMA content of this purified resin was determined by the following method.

HEMA quantification method Infrared spectroscopy (hereinafter referred to as "IR method"): The obtained purified resin was press-molded into a film, and the IR spectrum was measured. The quantification was performed by a calibration curve using the characteristic absorption of the carbonyl group at 1724 cm ^-1 . Proton nuclear magnetic resonance spectroscopy (hereinafter referred to as "H-NMR method"): Purified resin 30 to 5
0 mg was dissolved in about 1 ml of o-dichlorobenzene at 130 ° C., a small amount of deuterated benzene was added to prepare a sample, and the H-NMR spectrum was measured. Quantitative determination was carried out with methylene bonded to hydroxyl group (chemical shift: 3.9 ppm) and methylene bonded to ester group (chemical shift: 4.2 pp.
m) was absorbed.

The value obtained by the IR method shows the graft addition amount of HEMA, and the value obtained by the H-NMR method shows the amount of HEMA having a hydroxyl group. Therefore, the residual rate of hydroxyl groups can be defined by the following equation.

[0053]

[Equation 1]

The results are shown in Table 1. Reference Example 2: Production of Modified Resin-2 A modified resin-2 was obtained in the same manner as in Reference Example 1 except that HEMA was changed from 600 g to 300 g. The results are shown in Table 1.

Reference Example 3: Production of Modified Resin-3 In Reference Example 1, G1701 was a hydrogenated product of a styrene-isoprene diene block copolymer (trade name: Clayton G1652, manufactured by Shell Chemical Co., hereinafter abbreviated as "G1652"). Modified resin-3 was obtained in the same manner as in Reference Example 1 except that The results are shown in Table 1.

Reference Example 4: Production of modified resin-4: 10 g of chlorobenzene, 600 g of hydrogenated styrene-butadiene triblock copolymer (trade name: Clayton G1650 manufactured by Shell Chemical Co., hereinafter abbreviated as "G1650"), 250 g of HEMA. Was dissolved. While stirring at 110 ° C under a nitrogen atmosphere, 80 g of benzoyl peroxide (water content 25% by weight) dissolved in 0.6 liter of chlorobenzene was added dropwise to this solution over 2 hours, and stirring was continued for 3 hours. It was After allowing to cool to room temperature, it was poured into a large amount of methanol to precipitate a polymer component, which was separated by filtration, washed with methanol, and then dried under reduced pressure to obtain a modified resin-4. The results are shown in Table 1.

[0057]

[Table 1]

Reference Example 5 Production of Modified PP 4 kg of polypropylene (pulverized product of Mitsubishi Chemical Co., Ltd., trade name MA8), 200 g of HEMA, 200 g of SM, and 40 g of t-butyl peroxybenzoate (Perbutyl Z, trade name of NOF Corporation) are dry blended. After that, using a twin-screw kneader (trade name: TEX30, manufactured by Japan Steel Works, Ltd.), the cylinder temperature is 180 ° C. and the screw rotation speed is 250.
A modified PP was obtained by kneading under reduced pressure under the conditions of rpm, discharge rate of 5 kg / h and vent pressure of 50 mmHg. HE of modified PP
The amount of MA graft was measured by the following method. 0.3 g of the obtained modified PP was added to 50 ml of xylene,
After being dissolved at 0 ° C., it was poured into 300 ml of methanol to cause precipitation. The precipitate was filtered off and dried under reduced pressure at room temperature to obtain a purified resin. Modified resin-1 H-NM
H of this purified resin measured by the same method as R method
The amount of EMA graft was 2% by weight.

Examples 1-14, Comparative Examples 1-7 Modified resins obtained in Reference Examples 1-4, G1652, G17
01, polypropylene (trade name MA3 manufactured by Mitsubishi Chemical Corporation
Bending elastic modulus at MFR 10g / 10min, 23 ° C 14
00 MPa, abbreviated as "PP1", product name MA8 manufactured by the same company
MFR 0.8 g / 10 min, bending elastic modulus at 23 ° C. 1350 MPa, abbreviated as “PP2”, propylene-ethylene block copolymer (abbreviated as “PP3”, Mitsubishi Chemical Co., trade name BC5D MFR 4 g / 10 min, bending at 23 ° C. Elastic modulus 883 MPa), modified PP obtained in Reference Row 5 above, polybutylene terephthalate (trade name Novador 5010 manufactured by Mitsubishi Chemical Co., hereinafter abbreviated as “PBT”), polyethylene terephthalate (manufactured by Kanebo Corporation).
Product name PBK-1, abbreviated as "PET" below. ), Conductive carbon black (CB-1: Mitsubishi Chemical Co., Ltd., trade name Furnace Black 3050B, specific surface area 50 m ² / g,
CB-2: Ketjen Black International, trade name Ketjen Black EC, specific surface area 1000 m
² / g) according to the composition ratios shown in Table 2, each component was mixed with a twin-screw extruder (trade name: TEX-30, manufactured by Japan Steel Works, Ltd.) at a cylinder temperature of 250 ° C. and a screw rotation speed of 250.
Pellets were obtained by kneading under reduced pressure under the conditions of rpm and a treatment amount of 9.5 kg per hour. When melt-kneading these resin components, 0.2 part by weight of 4-methyl-2,6-di-t-butylphenol and 0.2 part by weight of Irganox are used with respect to 100 parts by weight of these resin components in total. 1010
(Manufactured by Ciba Geigy) was added.

The characteristics of the obtained resin composition were measured by the following methods. (1) Melt flow rate (MFR): Examples 1 to 1
3, and the MFR of the resin compositions shown in Comparative Examples 1 to 7,
Using a melt flow rate measuring device manufactured by Toyo Seiki Seisakusho,
According to the operation described in JIS K7210 and ISO R1133, the measurement was performed under the conditions of a temperature of 250 ° C. and a load of 2.16 kg. Before measurement, the pellet sample was dried at 80 ° C. for 15 hours. Regarding the resin composition shown in Example 14, the MFR was measured under the same conditions as the other resin compositions except that the temperature was 280 ° C.

In order to measure the flexural modulus and the Izod impact strength, an injection molding machine (IS-55 manufactured by Toshiba Machine Co., Ltd.) was used.
A mold was used to prepare a test piece. For Examples 1 to 13 and Comparative Examples 1 to 7, the cylinder temperature was 250 ° C and the mold cooling temperature was 60 ° C, and for Example 14, the cylinder temperature was 280 ° C and the mold cooling temperature was 80 ° C. The flexural modulus and Izod impact strength of these molded products were measured and evaluated by the following methods. Before molding, it was dried at 80 ° C. for 15 hours.

(2) Izod impact strength: JIS K7
According to 110, Izod impact strength with notch at 23 ° C. was measured. (3) Flexural modulus: Measured according to JIS K7203. (4) Conductivity

(Production of molded sheet for measurement by compression molding) Using a hydraulic compression molding machine manufactured by Toyo Seiki Seisakusho, temperature 2
Preheating at 5 ° C for 3 minutes, 250 ° C at 19.6 MPa for 3 minutes, followed by pressure molding at 25 ° C and 22.1 MPa for 5 minutes under pressure and cooling to evaluate conductivity and antistatic properties. Forming a sheet of 100 mm each and a thickness of 2 mm, 23 ± 2
Conditioning was performed for 2 days in an atmosphere of ℃ and humidity of 50 ± 5%.
In addition, in Example 14, molding was performed while changing the temperature during preheating and pressurization to 280 ° C.

(Surface resistivity measurement) 23 ± 2 ° C., humidity 5
IEC-93 for compression molded sheets of samples containing no carbon black in an atmosphere of 0 ± 5%.
-1958 and JEC-147-1976,
Advantest Super Insulation Resistance Tester (Brand name R8340)
And a chamber for measuring resistance (trade name R12702A), and for a sample containing carbon black,
Surface resistivity was measured using a Mitsubishi Chemical Corporation Lorester AP. The above measurement results are shown in Tables 2 to 4.

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention gives a molded article excellent in conductivity, antistatic property, impact resistance, rigidity and moldability.

Claims (2)

(57) [Claims] 1. A thermoplastic resin composition containing the following components (A), (B), (C) and (D) in the following compounding ratio. (A) Crystalline olefin resin 20 to 70 parts by weight (B) Saturated polyester 80 to 30 parts by weight (C) Hydrogenated product of aromatic vinyl compound-conjugated diene block copolymer A modified resin obtained by subjecting a saturated compound (0.05 to 50 parts by weight) and an aromatic vinyl compound (0 to 50 parts by weight) to a graft polymerization step, and a total of 100 parts by weight of the component (A) and the component (B), 2 to 40 parts by weight (D) 2 to 100 parts by weight per 100 parts by weight of the conductive substance, component (A), component (B) and component (C) in total 2. The hydroxyl group residual ratio of the modified resin is 0.3 to 1.
The thermoplastic resin composition according to claim 1, which is 0.