JP2006008815A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which gives a molded article excellent in impact resistance, chemical resistance and antistatic property in a low humidity atmosphere. <P>SOLUTION: The thermoplastic resin composition comprises 5-100 mass% of a component (A) and 0-95 mass% of a component (B) (provided that the total of the component (A) and the component (B) is 100 mass%), and further contains 0.5-100 pts. mass of a component (C) and 1-50 pts. mass of a component (D), each based on 100 pts. mass of the total of the component (A) and the component (B). The component (A) is a styrene resin obtained by (co)polymerizing an aromatic vinyl compound or the aromatic vinyl compound with other vinyl monomers copolymerizable with the aromatic vinyl compound in the presence or absence of a rubbery polymer. The component (B) is an olefin resin. The component (C) is a block polymer having a structure where an olefin block (C-1) and a hydrophilic polymer block (C-2) are repeatedly alternately bonded. The component (D) is a low-molecular weight polyolefin modified with an unsaturated acid and/or an unsaturated acid anhydride. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition excellent in impact resistance, chemical resistance, and antistatic performance under low humidity, and a molded article made of this thermoplastic resin composition.

  Rubber reinforced styrene resin such as ABS resin has excellent mechanical strength such as impact resistance, moldability, rigidity, etc., and also has a good appearance on the surface of the molded product. Therefore, electrical / electronic field, OA / home appliance field, vehicle field, sanitary Although widely used in fields, etc., chemical resistance is not sufficient depending on the intended use, and further improvement in chemical resistance has been demanded.

  On the other hand, polyolefin resins such as polypropylene are excellent in chemical resistance, heat resistance, fluidity, etc., so they are widely used in the electrical / electronic field, OA / home appliance field, vehicle field, sanitary field, etc. as well as the styrene resin. However, there are problems such as low impact resistance and the tendency for warpage and sink marks to occur in molded products. Another problem is that the change over time in the physical properties and dimensions after molding is large.

For the purpose of improving the above problems, it is conceivable to blend ABS resin and polypropylene. However, both materials have poor compatibility, and only a very brittle material can be obtained simply by melt mixing. Patent Document 1 proposes the presence of a styrene-butadiene-block copolymer rubber when blending a polystyrene resin and a polypropylene resin. Description of an example of blending ABS resin, AS resin, etc. with polypropylene. There is no. Patent Document 2 proposes blending a hydrogenated styrene-butadiene block copolymer when blending a polyolefin resin and a polystyrene resin. However, ABS resin, AS resin, etc. and a polyolefin resin are proposed. The example which mix | blended with is not described. Patent Document 3 proposes a composition comprising a polyolefin resin, a low molecular weight polystyrene, and a styrene-butadiene block copolymer, but does not describe an example in which an ABS resin, an AS resin, or the like is blended.
Further, Patent Document 4 proposes to use an epoxy-modified polypropylene and a styrene resin modified with an unsaturated carboxylic acid or anhydride as a compatibilizing agent, and Patent Document 5 discloses a polypropylene modified with an epoxy group. It has been proposed to use a styrene-butadiene-styrene block copolymer modified with a base resin and an unsaturated carboxylic acid or an anhydride thereof, but the impact resistance is insufficient. Moreover, the molded product is easily charged, and it is difficult to use the molded product in applications that cause static electricity damage.
The antistatic performance of a molded product is generally expressed by surface specific resistance, but the surface specific resistance is easily affected by humidity, and the surface specific resistance is low under high humidity. On the other hand, in an environment with low humidity, the surface resistivity tends to be high, which may cause an undesirable electrostatic failure.
For these reasons, materials having a low surface resistivity that are stable even in a low-humidity environment are desired for various molded articles in the field of electronic materials that require a particularly high level of antistatic performance.

Japanese Patent Publication No.52-17055 Japanese Patent Laid-Open No. 56-38338 JP 56-104978 A JP-A-1-174550 JP-A-4-266953

  An object of the present invention is to provide a thermoplastic resin composition and a molded product excellent in impact resistance, chemical resistance, molded product surface appearance, and antistatic property under low humidity.

As a result of intensive studies to achieve the above object, the present inventors have found that when mixing a styrene resin such as an ABS resin and a polypropylene resin, a block polymer in which a polyolefin block and a polyether block are bonded alternately and repeatedly, and In addition, it has been found that by blending a low molecular weight polyolefin modified with maleic anhydride or the like, a molded article excellent in impact resistance, chemical resistance and antistatic property under low humidity can be obtained. Furthermore, the inventors have found that the impact resistance and antistatic property are remarkably improved by blending a polymer having a specific block structure, and the present invention has been completed.
That is, according to the present invention, it contains 5 to 100% by mass of the following (A) component and 0 to 95% by mass of the following (B) component (however, the sum of the (A) component and the (B) component is 100% by mass),
Furthermore, 0.5-100 mass parts of the following (C) component and 1-50 mass parts of the following (D) component with respect to 100 mass parts in total of this (A) component and this (B) component. The thermoplastic resin composition characterized by containing is provided.
(A) Styrenic polymer obtained by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence or absence of a rubbery polymer resin,
(B) an olefin resin,
(C) a block copolymer having a structure in which an olefin block (C-1) and a hydrophilic polymer block (C-2) are repeatedly and alternately bonded;
(D) Low molecular weight polyolefin modified with unsaturated acid and / or unsaturated acid anhydride.
Moreover, according to this invention, in addition to said (A)-(D) component, Furthermore, with respect to a total of 100 mass parts of said (A) component and said (B) component, following (E) component, ( A thermoplastic resin composition containing 1 to 200 parts by mass of at least one selected from the group consisting of component (F) and component (G) is provided.
(E) a block copolymer having a polymer block (E-1) mainly composed of an aromatic vinyl compound and a polymer block (E-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof,
(F) A graft polymer obtained by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the component (E),
(G) An aromatic polycarbonate block copolymer comprising a polymer block comprising the component (E) and an aromatic carbonate polymer block (G-1).
Moreover, according to this invention, the molded article using the said thermoplastic resin composition is provided.

  The thermoplastic resin composition of the present invention comprises (A) a styrene resin, (B) an olefin resin, (C) a block copolymer comprising a polyolefin block and a hydrophilic polymer block, (D) an unsaturated acid, and / or Alternatively, it is made of a low molecular weight polyolefin modified with an unsaturated acid anhydride, and a molded product having particularly excellent impact resistance, chemical resistance and antistatic performance can be obtained.

The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and / or copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” "Means acrylate and / or methacrylate.
The styrenic resin (A) according to the present invention is an aromatic vinyl compound in the presence or absence of the rubbery polymer (a), or other vinyl copolymerizable with the aromatic vinyl compound and the aromatic vinyl compound. This is a polymer obtained by (co) polymerizing a vinyl monomer (b) containing a monomer, and is a polymer obtained by graft (co) polymerization in the presence of a rubbery polymer (a) in terms of impact resistance. Those containing at least one coalescence are preferred. The content of the rubber-like polymer (a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, particularly preferably 10 to 60% by mass, with the styrene resin (A) being 100% by mass. is there.

The rubbery polymer (a) is not particularly limited, but polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, Examples include ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, acrylic rubber, silicone rubber, and silicone / acrylic IPN rubber. These may be used alone or in combination of two or more. Can be used in combination.
Of these, polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer, acrylic rubber, and silicone rubber are preferable. As the butadiene / styrene copolymer used here, a copolymer other than a block copolymer, particularly a random copolymer is used.

The gel content of the rubbery polymer is not particularly limited, but when the component (a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, more preferably 40 to 98% by mass. is there. Within this range, it is possible to obtain a thermoplastic resin composition that gives a molded article particularly excellent in impact resistance.
In addition, the said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was put into 100 ml of toluene and allowed to stand at room temperature for 48 hours, and then the toluene-insoluble matter and the wire mesh filtered through a 100-mesh wire mesh (with a mass of W ₁ gram) were heated at 80 ° C for 6 hours. It vacuum-drys, weighs (it is set as mass W ₂ grams), and calculates by following formula (1).

Gel content (% by mass) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100 (1)
The gel content is adjusted by appropriately setting the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature, the polymerization conversion rate and the like during the production of the rubbery polymer.

  Examples of the aromatic vinyl compound constituting the vinyl monomer (b) include styrene, α-methylstyrene, hydroxystyrene, and the like. These may be used alone or in combination of two or more. it can. Of these, styrene and α-methylstyrene are preferred.

  Examples of other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and other various functional group-containing unsaturated compounds. Preferably, the vinyl monomer (b) comprises an aromatic vinyl compound as an essential monomer component, and, if necessary, a group consisting of a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound. One or more selected from the above are used in combination as a monomer component, and if necessary, at least one of other various functional group-containing unsaturated compounds is used in combination as a monomer component. As other various functional group-containing unsaturated compounds, unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, substituted or unsubstituted And amino group-containing unsaturated compounds. The other various functional group-containing unsaturated compounds can be used alone or in combination of two or more.

Examples of the vinyl cyanide compound used here include acrylonitrile and methacrylonitrile, and these can be used alone or in combination of two or more. When a vinyl cyanide compound is used, chemical resistance is imparted. When using a vinyl cyanide compound, the usage-amount is (1) in component (b), Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.
Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. Can be used in combination. Use of a (meth) acrylic acid ester compound is preferable because surface hardness is improved. When the (meth) acrylic acid ester compound is used, the amount used is preferably 1 to 80% by mass, more preferably 5 to 80% by mass in the component (b).
Examples of maleimide compounds include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. These can be used alone or in combination of two or more. In order to introduce a maleimide unit, maleic anhydride may be copolymerized and post-imidized. When a maleimide compound is used, heat resistance is imparted. When a maleimide compound is used, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (b).

Examples of unsaturated acid compounds include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like. These may be used alone or in combination of two or more. Can be used.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more.

Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2- Examples thereof include methyl-1-propene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide, and these may be used alone or in combination of two or more. it can.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used singly or in combination of two or more.
Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more.
Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, and acrylamine , Methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene, etc., and these can be used alone or in combination of two or more.
When the above-mentioned various other functional group-containing unsaturated compounds are used, when the styrenic resin and another polymer are blended, the compatibility between them can be improved. Preferred monomers for achieving such effects are epoxy group-containing unsaturated compounds, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing unsaturated compounds, more preferably hydroxyl group-containing unsaturated compounds, particularly preferably. 2-hydroxylethyl (meth) acrylate.
The amount of the other functional group-containing unsaturated compound used is the total amount of the functional group-containing unsaturated compound used in the styrenic resin, and is 0.1 to 20% by mass with respect to the entire styrenic resin. Preferably, 0.1-10 mass% is more preferable.

  The amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (b) is preferably 80% by mass or less, more preferably 100% by mass when the total of the vinyl monomers (b) is 100% by mass. 60% by mass or less, particularly preferably 40% by mass or less. More preferable combinations of monomers constituting the vinyl monomer (b) are styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate, styrene / acrylonitrile / 2- Monomers that are polymerized in the presence of rubbery polymer (a), such as hydroxyethyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N-phenylmaleimide, styrene / methyl methacrylate / cyclohexylmaleimide Particularly preferred combinations of styrene / acrylonitrile = 65/45 to 90/10 (mass ratio), styrene / methyl methacrylate = 80/20 to 20/80 (mass ratio), styrene / acrylonitrile / methacrylic Acid methyl styrene content of 20 to 80 wt%, the sum of acrylonitrile and methyl methacrylate is any in the range of 20 to 80 wt%.

  The component (A) of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Among these, preferred polymerization methods for the polymer obtained by (co) polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a) are emulsion polymerization and solution polymerization. On the other hand, preferred polymerization methods for the polymer obtained by (co) polymerizing the vinyl monomer (b) in the absence of the rubbery polymer (a) include bulk polymerization, solution polymerization, suspension polymerization, and Emulsion polymerization.

In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used, and any known one can be used.
As polymerization initiators, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, azobisisobutyronitrile, etc. Can be mentioned.
Moreover, it is preferable to use redox systems such as various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, etc., as polymerization initiation assistants.
Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, terpinolene and the like.
Emulsifiers include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher fatty acid salts such as potassium laurate, potassium stearate, potassium oleate, and potassium palmitate, rosin acid A rosin acid salt such as potassium can be used.

  In the emulsion polymerization, the rubber polymer (a) and the vinyl monomer (b) are used by adding the vinyl monomer (b) in the presence of the total amount of the rubber polymer (a). You may superpose | polymerize or may superpose | polymerize by dividing | segmenting or adding continuously. Moreover, you may add a part of rubber-like polymer (a) in the middle of superposition | polymerization.

  After the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the component (A) powder of the present invention. At this time, two or more kinds of latexes of component (A) obtained by emulsion polymerization may be appropriately blended and then coagulated. As the coagulant used here, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, citric acid and malic acid can be used.

Solvents that can be used when the component (A) is produced by solution polymerization are inert polymerization solvents used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, acetone, and the like. Ketones, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like.
The polymerization temperature is preferably in the range of 80 to 140 ° C, more preferably 85 to 120 ° C.
In the polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. As the polymerization initiator, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, and the like are preferably used.
When a chain transfer agent is used, for example, mercaptans, terpinolenes, α-methylstyrene dimer, etc. can be used.
Moreover, when manufacturing by block polymerization and suspension polymerization, the polymerization initiator, chain transfer agent, etc. which were demonstrated in solution polymerization can be used.
The amount of monomer remaining in the component (A) obtained by the above polymerization methods is preferably 10,000 ppm or less, more preferably 5,000 ppm or less.

In addition, in the polymer component obtained by polymerizing the vinyl monomer (b) in the presence of the rubber polymer (a), the vinyl monomer (b) is usually the rubber polymer (a). And a non-grafted component [(co) polymer of the above vinyl monomers (b)] not grafted to the rubber polymer.
The graft ratio of the component (A) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, particularly preferably 40 to 120% by mass, and the graft rate is determined by the following formula (2). Can do.

Graft ratio (mass%) = {(TS) / S} × 100 (2)
In the above formula (2), T is a mixture of 1 g of component (A) into 20 ml of acetone (but acetonitrile when the rubbery polymer (a) uses acrylic rubber). This is the mass (g) of the insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) after shaking for a while and separating the insoluble matter and the soluble matter, and S is ( A) Mass (g) of the rubbery polymer contained in 1 g of the component.

In addition, the limiting viscosity [η] (soluble in methyl ethyl ketone as a solvent) of acetone (in the case where the rubbery polymer (a) uses acrylic rubber, acetonitrile) as the component (A) related to the present invention. Used and measured at 30 ° C.) is preferably 0.2 to 1.2 dl / g, more preferably 0.2 to 1.0 dl / g, particularly preferably 0.3 to 0.8 dl / g.
The average particle size of the grafted rubber polymer particles dispersed in the component (A) according to the present invention is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1, It is in the range of 500 to 8,000cm. The average particle diameter can be measured by a known method using an electron microscope.

  The used amount of the component (A) constituting the thermoplastic resin composition of the present invention is 5 to 100% by mass, preferably 5 to 100% by mass in the total 100% by mass of the (A) component and the (B) component of the present invention. 98 mass%, More preferably, it is 10-98 mass%, Most preferably, it is 15-95 mass%, and if it is less than 5 mass%, it exists in the tendency for impact resistance to be inferior and for antistatic property to fall.

The olefin resin (B) according to the present invention is a polymer containing at least one α-olefin having 2 to 10 carbon atoms as a constituent monomer unit. As this olefin resin, those showing a crystallinity at room temperature by X-ray diffraction are preferred, more preferably those having a crystallinity of 20% or more and a melting point of 40 ° C. or more. In addition, this olefin resin must have a sufficient molecular weight as a molding resin at room temperature.
For example, when propylene is the main component, the melt flow rate measured according to JIS K-6758 is preferably 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min. Of molecular weight.

  Examples of α-olefins that are monomers of the olefin resins include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methyl. Hexene-1 and the like, preferably ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1. In addition, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, and 1,9-decadiene are used as one of the polymer components. Can be used as a part.

  The use amount of the component (B) constituting the thermoplastic resin composition of the present invention is 0 to 95% by mass in a total of 100% by mass of the component (A) and the component (B) of the present invention, preferably It is 2-95 mass%, More preferably, it is 2-90 mass%, Most preferably, it is 5-85 mass%, and when it exceeds 95 mass%, there exists a tendency for impact resistance to be inferior and for antistatic property to fall.

  The component (C) of the present invention is a block copolymer having a structure in which olefin blocks (C-1) and hydrophilic polymer blocks (C-2) are repeatedly and alternately bonded. The polyolefin block (C-1) is a (co) polymer of the α-olefin described above. The polystyrene block number average molecular weight of the polyolefin block (C-1) by gel permeation chromatography (GPC) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1, 200 to 6,000.

The block (C-1) is chemically bonded to the block (C-2), and the bond is at least one selected from an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, and the like. It is a bond of species, and has a structure in which these bonds are repeatedly and alternately bonded through these bonds.
For this reason, both molecular ends of the block (C-1) need to be modified with functional groups having reactivity with the molecular end functional groups of the block (C-2). Examples of these functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, and epoxy groups.
A preferred method for imparting these functional groups is a (C-1) component having a carbon-carbon double bond at the molecular end obtained by a thermal degradation method, and a carbon-carbon unsaturated compound having the functional group described above. It is a method of adding.

Examples of the hydrophilic polymer of the block (C-2) include polyether (C-2-a), polyether-containing hydrophilic polymer (C-2-b), and anionic polymer (C-2-c). Can be mentioned.
Examples of the polyether (C-2-a) include polyether diol, polyether diamine, and modified products thereof.
The polyether-containing hydrophilic polymer (C-2-b) includes polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, and polyether ester having a polyether diol segment. , Polyether amides having polyether diamine segments, and polyether urethanes having polyether diol or polyether diamine segments.
As the anionic polymer (C-2-c), a dicarboxylic acid having a sulfonyl group and a polyether (C-2-a) are essential structural units, and preferably 2 to 80 per molecule. More preferred are anionic polymers having 3 to 60 sulfonyl groups.
These may be linear or branched.
Particularly preferred block (C-2) is polyether (C-2-a).

As the polyether diol in the polyether (C-2-a), the general formula (I):
H- (OA ¹ ) _n —O—E ¹ —O— (A ¹ O) _{n ′} —H, and general formula (II):
H- (OA ² ) _m —O—E ² —O— (A ² O) _{m ′} —H are exemplified.
In general formula (I), E ¹ is a residue obtained by removing a hydroxyl group from a divalent hydroxyl group-containing compound, A ¹ is an alkylene group having 2 to 4 carbon atoms, and n and n ′ are hydroxyl groups of the divalent hydroxyl group-containing compound. This represents the number of alkylene oxide additions per unit. n (OA ¹ ) and n ′ (A ¹ O) may be the same or different, and the bond form in the case where these are composed of two or more oxyalkylene groups May be either block or random or a combination thereof. n and n ′ are usually 1 to 300, preferably 2 to 250, particularly preferably 10 to 100. N and n ′ may be the same or different.

Examples of the divalent hydroxyl group-containing compound include compounds containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, dihydroxy compounds. Specifically, divalent alcohols (for example, having 2 to 12 carbon atoms) Aliphatic, alicyclic, or aromatic dihydric alcohols), C6-C18 dihydric phenols, tertiary amino group-containing diols, and the like.
Examples of the aliphatic dihydric alcohol include alkylene glycols such as ethylene glycol and propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,12-dodecanediol, and the like.
Examples of the alicyclic dihydric alcohol include 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Examples of the aromatic dihydric alcohol include xylene diol.
Dihydric phenols include monocyclic dihydric phenols such as hydroquinone, catechol, resorcin, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, dihydroxydiphenyl ether And condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

In the general formula (II), E ² is a residue obtained by removing the hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (I), and A ² is at least partly the general formula (III): —CHR— CHR ′ — [wherein one of R and R ′ is a group represented by general formula (IV): —CH ₂ O (A ³ O) _X R ″, and the other is H. General formula (IV) Wherein x is an integer of 1 to 10, R ″ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an acyl group, and A ³ is an alkylene group having 2 to 4 carbon atoms. is there. The remaining alkylene group may be an alkylene group having 2 to 4 carbon atoms. m (OA ² ) and m ′ (A ² O) may be the same or different. m and m ′ are preferably 1 to 300, more preferably 2 to 250, and particularly preferably 10 to 100. M and m ′ may be the same or different.

  The polyether diol represented by the general formula (I) can be produced by subjecting a divalent hydroxyl group-containing compound to an addition reaction of alkylene oxide. Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, and 1,3-butylene oxide. Two or more combined systems are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. Preferable alkylene oxides are ethylene oxide alone and block and / or random addition using ethylene oxide in combination with other alkylene oxides. The number of alkylene oxides added is preferably 1 to 300, more preferably 2 to 250, and particularly preferably 10 to 100, per hydroxyl group of the divalent hydroxyl group-containing compound.

  Preferred methods for producing the polyether diol represented by the general formula (II) include the following methods (a) and (b).

［一般式（V）中のＡ^４は炭素数２〜４のアルキレン基、ｐは１〜１０の整数、Ｒ^１はＨまたは炭素数１〜１０のアルキル基、アリール基、アルキルアリール基、アリールアルキル基またはアシル基である。］
で表されるグリシジルエーテルを重合、または炭素数２〜４のアルキレンオキサイドと共重合する方法。 (A) Starting from the above-mentioned divalent hydroxyl group-containing compound, the general formula (V):

^{[A 4} in the general formula (V) is an alkylene group having 2 to 4 carbon atoms, p is an integer of from 1 to 10, ^{R 1} is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an aryl An alkyl group or an acyl group; ]
The method of superposing | polymerizing the glycidyl ether represented by these, or copolymerizing with C2-C4 alkylene oxide.

(A) A method of using a divalent hydroxyl group-containing compound as a starting material and passing through a polyether having a chloromethyl group in the side chain. More specifically, epichlorohydrin or epichlorohydrin and alkylene oxide are added and copolymerized to obtain a polyether having a chloromethyl group in the side chain, and then the polyether, a polyalkylene glycol having 2 to 4 carbon atoms and R ^1. X (R ¹ is as described above, X is Cl, Br or I) is reacted in the presence of an alkali, or the polyether is reacted with a polyalkylene glycol monocarbyl ether having 2 to 4 carbon atoms in the presence of an alkali. Is the method.

As the alkylene oxide having 2 to 4 carbon atoms used here, all of those described above can be used.
In addition, the component (C) of the present invention can be obtained by polymerizing the polyolefin block (C-1) and the hydrophilic polymer block (C-2) by a known method. For example, the block (C-1) and the block (C-2) can be produced by performing a polymerization reaction at 200 to 250 ° C. under reduced pressure. A known polymerization catalyst can be used in the polymerization reaction.

  In addition, known polymerization catalysts can be used in the polymerization reaction, but preferred are tin-based catalysts such as monobutyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, and titanium-based catalysts such as tetrabutyl titanate. , Zirconium hydroxide, zirconium oxide, zirconium acetate such as zirconyl acetate, or a combination of two or more selected from group IIB organic acid salt catalysts.

For the purpose of further improving the antistatic property, which is the object of the present invention, an alkali metal and / or alkaline earth metal salt (H) can be contained. These components can be contained at the time of polymerization of the component (C), can be contained after the polymerization of the component (C), or can be blended when producing the thermoplastic resin composition of the present invention. Moreover, it can also contain by the method of combining these.
Examples of the component (H) include organic acids, sulfonic acids, inorganic acid salts, halides, and the like of alkali metals such as lithium, sodium and potassium and / or alkaline earth metals such as magnesium and calcium.

  Specific preferred examples of the component (H) include halides of alkali metals such as lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide; lithium perchlorate, sodium perchlorate, Inorganic acid salts of alkali metals such as potassium perchlorate, organic acid salts of alkali metals such as potassium acetate and lithium stearate; lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, lithium methanesulfonate , Alkali metal sulfonates such as sodium methanesulfonate and potassium methanesulfonate, and the like. These are preferably 0.001 to 3% by mass, more preferably based on the component (C) of the present invention. It can be used in the range of 0.01 to 2% by mass.

The preferred ratio (mass ratio) of the block (C-1) / block (C-2) in the component (C) of the present invention is in the range of 10 to 90/10 to 90, more preferably 20 to 80/20. -80, particularly preferably in the range of 30-70 / 30-70.
Such a block copolymer (C) can be produced by, for example, the methods described in JP-A Nos. 2001-278985 and 2003-48990, and the component (C) of the present invention. Can be obtained as 300, 303, 230 (trade name), etc. of Pelestat 300 series manufactured by Sanyo Chemical Industries.

  The component (C) of the present invention is 0.5 to 100 parts by mass, preferably 0.5 to 80 parts by mass, more preferably 100 parts by mass in total of the components (A) and (B). It can be used in the range of 1 to 60 parts by mass, particularly preferably 2 to 50 parts by mass. When the amount used is less than 0.5 parts by mass, the antistatic effect cannot be obtained, the chemical resistance effect is not sufficient, and the impact resistance is inferior. When it exceeds 100 parts by mass, the impact resistance is inferior.

  The component (D) of the present invention is a low molecular weight polyolefin modified with an unsaturated acid and / or an unsaturated acid anhydride. The low molecular weight polyolefin used here is a low molecular weight body of the component (B) of the present invention, and among these, preferred are low molecular weight polypropylene or low molecular weight polyethylene.

  The weight average molecular weight of the low molecular weight polyolefin is preferably 1,000 to 100,000, more preferably 5,000 to 60,000, and particularly preferably 8,000 to 50,000. The low molecular weight polyolefin can be obtained by a polymerization method or a thermal degradation method of a high molecular weight polyolefin. A thing preferable by the thermal degradation method is preferable from the ease of modification | denaturation with an unsaturated acid and / or an unsaturated acid anhydride. The low molecular weight polyolefin by the thermal degradation method is, for example, a method in which a high molecular weight polyolefin is thermally degraded in an inert gas, usually at 300 ° C. to 450 ° C. for 0.5 hours to 10 hours (for example, described in JP-A-3-62804). Or the like.

  Examples of the unsaturated acid used here include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid and the like. These may be used alone or in combination of two or more. it can. In addition, examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, chloroitaconic anhydride, chloromaleic anhydride, and citraconic anhydride. These may be used alone or in combination of two or more. Can be used. Preferred is maleic anhydride.

  The component (D) of the present invention is preferably 0.5 to 25% by mass, more preferably 1 to 20% by mass, particularly preferably 3 to 15% by mass of the unsaturated acid, based on the mass of the low molecular weight polyolefin as 100%. And / or modified with an unsaturated acid anhydride, for example, a method such as a solution method or a melting method in a low molecular weight polyolefin in the presence of an unsaturated acid and / or an unsaturated acid anhydride if necessary in the presence of an organic peroxide Can be obtained by modification with Moreover, the material applicable to (D) component of this invention can be obtained in the market as Sanyo Chemical Industries UMEX 1001,1003,1010,100TS, 110TS, 2000, CA60 (brand name) etc., for example.

(D) component of this invention is 1-50 mass parts with respect to a total of 100 mass parts of (A) component of this invention, and (B) component, Preferably it is 1-45 mass parts, More preferably, it is 2-40. It can be used in the range of parts by mass, and if it is less than 1 part by mass, the antistatic property is inferior.
The component (E) of the present invention includes a block copolymer having a polymer block (E-1) mainly composed of an aromatic vinyl compound and a polymer block (E-2) mainly composed of a conjugated diene compound and / or hydrogen thereof. The hydrogenated product is an additive in which at least a part of the carbon-carbon double bond of the conjugated diene compound of the block (E-2) is mainly hydrogenated.

As the aromatic vinyl compound used here, all of the above-mentioned compounds can be used, but styrene and α-methylstyrene are preferable, and styrene is particularly preferable.
Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably butadiene and isoprene. These can be used individually by 1 type or in combination of 2 or more types. Further, the block (E-2) may be a block in which two or more kinds of conjugated diene compounds are used and bonded in any form of a random shape, a block shape, and a tapered block shape. Moreover, the block (E-2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and contains a vinyl bond derived from the conjugated diene compound of the block (E-2). Polymer blocks having different amounts may be appropriately copolymerized.

A preferred structure of the component (E) of the present invention is a polymer represented by the following formulas (VI) to (VIII) or a hydrogenated product thereof.
(AB) _Y ... (VI)
(AB) _Y- X (VII)
A- (B-A) _Z (VIII)
(In the structural formulas (VI) to (VIII), A is a polymer block mainly composed of an aromatic vinyl compound. If the polymer block is substantially composed of an aromatic vinyl compound, a part of the conjugated diene compound is included. Preferably, it is a polymer block containing 90% by mass or more, more preferably 99% by mass or more of an aromatic vinyl compound, B is a homopolymer of a conjugated diene compound or an aromatic vinyl compound, etc. And X is a residue of the coupling agent, Y is an integer of 1 to 5, and Z is an integer of 1 to 5.)

  The use ratio of the aromatic vinyl compound and the conjugated diene compound in the component (E) of the present invention is preferably within the range of aromatic vinyl compound / conjugated diene compound = 10 to 70/30 to 90% by mass, more preferably 15 to It is 65 / 35-85 mass%, Most preferably, it is the range of 20-60 / 40-80 mass%.

  The block copolymer composed of an aromatic vinyl compound and a conjugated diene compound is known in the technical field of anionic polymerization, for example, Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423. And the Japanese Patent Publication No. 48-20038. A method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217.

  The vinyl bond content (1,2- and 3,4-bond) content derived from the conjugated diene compound of the component (E) of the present invention is preferably in the range of 5 to 80%. The number average molecular weight of the component is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000. Among these, the number average molecular weight of the A part represented by the above formulas (VI) to (VIII) is 3,000 to 150,000, and the number average molecular weight of the B part is in the range of 5,000 to 200,000. preferable.

Adjustment of the vinyl bond amount of the conjugated diene compound is carried out by using amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octane, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diester. It can be carried out using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.
A polymer in which a polymer molecular chain is extended or branched through a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferably included in the component (E) of the present invention. Coupling agents used here include diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.

  Among the above block copolymers, preferred from the viewpoint of impact resistance is a polymer having in the range of 1 to 10 tapered blocks in which the aromatic vinyl compound gradually increases in the block (E-2), and / or It is a radial block type that has been coupled.

  Further, as the component (E), one obtained by partially or completely hydrogenating the carbon-carbon double bond of the conjugated diene portion of the block copolymer can be used. The component (E) preferably has a hydrogenation rate of 10 to 100%, more preferably 50 to 100%. From the viewpoint of the weather resistance (light) of the obtained composition, it is preferable to use a composition hydrogenated by 90% or more. From the viewpoint of impact at low temperatures, it is preferable to use a hydrogenation rate of 50% or more and less than 90%.

  The hydrogenation reaction of the polymer comprising a polymer block mainly comprising an aromatic vinyl compound unit obtained by the above method and a polymer block mainly comprising a conjugated diene compound can be carried out by a known method, The target polymer can be obtained by adjusting the hydrogenation rate by this method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 There is a method disclosed in Japanese Patent No. 297413.

  The component (E) of the present invention is preferably 1 to 200 parts by weight, more preferably 5 to 150 parts by weight, particularly preferably 10 to 10 parts by weight with respect to a total of 100 parts by weight of the components (A) and (B). By using it in the range of 100 parts by mass, it is possible to obtain a molded product particularly excellent in impact resistance and chemical resistance.

  The component (F) of the present invention (co) polymerizes an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the component (E). The aromatic vinyl compound used here and the other vinyl monomer copolymerizable with the aromatic vinyl compound are the vinyl monomer (b) of component (A). ) Can be used, and particularly preferred monomer combinations are styrene / acrylonitrile and styrene / acrylonitrile / methyl methacrylate.

  In addition, as the component (E) used here, all of those described above can be used, but preferably, the carbon-carbon double bond of the conjugated diene compound is hydrogenated, more preferably the carbon of the conjugated diene compound. -Hydrogenated 90% or more of carbon double bonds, particularly preferably 95% or more hydrogenated.

  The component (F) of the present invention is obtained by graft polymerization of the monomer component in the presence of the component (E). The amount of the component (E) in the component (F) is 10 to 60% by mass. The graft ratio is preferably in the range of 20 to 80% by mass. Such a polymer can be produced by the solution polymerization, bulk polymerization, suspension polymerization described above for the component (A), and a polymerization method combining these. The graft polymer thus obtained usually contains a copolymer in which the monomer component is graft-copolymerized with the component (E), and an ungrafted component that is not grafted on the rubbery polymer [monomer components (Co) polymer].

  The component (F) of the present invention is preferably 1 to 200 parts by mass, more preferably 10 to 170 parts by mass, particularly preferably 20 to 100 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). It is used in the range of 150 parts by mass. By using in this range, it is possible to obtain a molded product particularly excellent in impact resistance.

  (G) component of this invention is an aromatic polycarbonate block copolymer which consists of a polymer block which consists of (E) component, and an aromatic carbonate polymer block. Here, the molecular terminal of the component (E) preferably has a functional group reactive with the aromatic polycarbonate, and these functional groups include a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, etc. Is a hydroxyl group or a carboxyl group, more preferably a hydroxyl group. These functional groups are preferably those added to the molecular ends of the aromatic vinyl compound block (E-1). Such a functional group has both a case where it is present at both ends of the component (E) and a case where it is present at one end. The one end is preferred from the viewpoint of impact resistance. Furthermore, it is not necessary for all the molecules to have functional groups, and the average number is preferably 0.5 or more per molecule, and more preferably in the range of 0.7 to 2.

The method of introducing a functional group at the molecular end can be performed by a known method. For example, a method of polymerizing an aromatic vinyl compound and a conjugated diene compound in the presence of an organic alkali metal compound, and reacting the compound containing the functional group with an active point of the obtained polymer; ethylene oxide and propylene oxide; A method of adding an active hydrogen compound such as alcohols, carboxylic acids, water, etc. after addition to the end of the block copolymer to stop anionic polymerization and introducing a hydroxyl group at the end; blowing carbon dioxide gas at a low temperature and anionic polymerization And a method of introducing a carboxylic acid group at the terminal is exemplified.
The component (E) having a functional group at the molecular end is preferably hydrogenated to the carbon-carbon double bond of the conjugated diene compound by a known method, and the hydrogenation is known as described above for the component (E). It can be done by the method.

The block (G-1) is an aromatic polycarbonate, which is obtained by interfacial polycondensation between various hydroxyaryl compounds and phosgene, or transesterification (dilution polycondensation) between a dihydroxyaryl compound and a carbonate compound such as diphenyl carbonate. Any of those obtained by a known polymerization method can be used.
Examples of the dihydroxyaryl compound used as a raw material for the aromatic polycarbonate include bisphenol A, hydroquinone, 2,2-bis (4-hydroxyphenyl) pentane, 2,4-dihydroxydiphenylmethane, bis (2-hydroxyphenyl) methane, and bis (4 -Hydroxyphenyl) methane and the like, particularly preferably bisphenol A.
The viscosity average molecular weight of the aromatic polycarbonate used in the present invention is preferably 8,000 to 50,000, more preferably 12,000 to 30,000, and particularly preferably 15,000 to 26,000. Those having different viscosity average molecular weights can be used in combination as appropriate.

The viscosity average molecular weight of the aromatic polycarbonate was calculated by inserting the specific viscosity (η _sp ) measured at 20 ° C. and a concentration of 0.7 g / 100 ml (methylene chloride) into the following formula (3) using methylene chloride as a solvent. can do.
Viscosity average molecular weight = ([η] × 8130) ^1.205 (3)
Here, [η] = [(η _sp × 1.12 + 1) ^1/2 −1] /0.56C (C represents the concentration)
It is.

The component (G) of the present invention comprises the component (E) having a functional group introduced at the terminal as described above (hereinafter referred to as a functional group-modified product) and the component (G-1). A method of melt-kneading the group-modified product and the component (G-1), (ii) a method of polymerizing the component (G-1) in the presence of the functional group-modified product, and (iii) polymerization of the component (G-1). In the final step, the functional group-modified product can be added and reacted, and the industrially preferred method is the method (i) above.
Moreover, it is preferable that the mass ratio of (E) component / (G-1) component in (G) component exists in the range of 95 / 5-5 / 95, More preferably, it is 80 / 20-20 / 80. And particularly preferably 70/30 to 30/70.

The components (E) and (G-1) of the present invention are not necessarily all block copolymers, and if at least 10% by mass is a block copolymer, the object of the present invention Is achieved.
Such a block copolymer mixture can be produced by, for example, the method described in JP-A-2001-220506. Furthermore, the component (G) of the present invention can be industrially obtained as TM-S4L77, TM-H4L77 (trade name) of TM polymer series manufactured by Kuraray.

  The component (G) of the present invention is preferably used in the range of 1 to 200 parts by mass, more preferably 10 to 170 parts by mass, with respect to 100 parts by mass in total of the component (A) and the component (B). Part, particularly preferably in the range of 20 to 150 parts by weight, and in this range, a molded article having particularly excellent impact resistance can be obtained.

  The components (E), (F) and (G) of the present invention improve the impact resistance of the thermoplastic resin composition comprising the components (A), (B), (C) and (D) of the present invention. It is an effective component, and can be used in combination of at least one or two or more selected from each component. Moreover, it can also be used combining 1 type (s) or 2 or more types chosen from (E), (F) and (G) component. When any two or more of (E), (F) and (G) components are used in combination, the total amount of these components is based on 100 parts by mass of the total of (A) and (B) components. It is set as the range of 1-200 mass parts, Preferably it is 5-150 mass parts, More preferably, it is 5-100 mass parts.

The thermoplastic resin composition of the present invention can be prepared by kneading each component by a method such as melt kneading using various extruders, Banbury mixers, kneaders, continuous kneaders, and the like. A preferred production method is a method using an extruder, particularly preferably a method using a multi-screw extruder, or a method combining an extruder and a Banbury mixer, a continuous kneader or the like.
Furthermore, when each component is kneaded, the components may be kneaded in a lump, or may be kneaded in multiple stages or dividedly.

The thermoplastic resin composition of the present invention can be blended with known inorganic or organic fillers. Examples of the inorganic filler used here are glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass, carbon fiber, carbon fiber milled fiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite. , Mica, kaolin, montmorillonite, hectorite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, plate alumina, plate silica, and organically treated smectite, aramid fiber, phenol resin fiber, polyester fiber, etc. Yes, these can be used alone or in combination of two or more.
In addition, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treatment agent, sizing agent, etc. can also be used. As the known coupling agent, a silane coupling agent is used. , Titanate coupling agents, aluminum coupling agents, and the like.
The said inorganic or organic filler is normally used in 1-100 mass parts with respect to 100 mass parts of thermoplastic resin compositions of this invention.

  The thermoplastic resin composition of the present invention includes known weathering (light) agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, dyes, crystal nucleating agents, antibacterial agents, fungicides, and foaming agents. In addition, flame retardants (phosphorous flame retardants, nitrogen flame retardants, halogen flame retardants, silicone flame retardants), flame retardant aids (antimony oxide compounds, PRFE, chlorinated polyethylene), and the like can be blended.

  Further, the thermoplastic resin composition of the present invention includes other known polymers such as polyamide resin, polyamide elastomer, polyester resin, polyester elastomer, PMMA, methyl methacrylate / maleimide compound copolymer, polyphenylene ether, poly Oxymethylene, polyphenylene sulfide, epoxy resin, phenol resin, EVA, EVOH, ENE, LCP, thermoplastic polyurethane, aromatic polycarbonate, urea resin, phenoxy resin, and the like can be appropriately blended.

  The thermoplastic resin composition of the present invention thus prepared is used to obtain a molded product by a known molding method such as injection molding, press molding, sheet molding, film molding, vacuum molding, profile extrusion molding, foam molding and the like. be able to. Further, a molded product having the thermoplastic resin composition of the present invention as a surface layer and a polyolefin resin or styrene resin as a back layer or an intermediate layer can be obtained by multilayer extrusion molding, or the multilayer sheet is vacuum molded. Thus, the desired molded product can be obtained. Examples of molded products obtained by these molding methods include the following.

  Various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, wafer cases, IC trays, liquid crystal trays, switches, coil bobbins, capacitors, variable capacitor cases, optical pickup parts, oscillators, various terminal boards, For transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, LCD FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, etc. Representative electrical and electronic parts. VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademark) / compact discs, lighting parts, refrigerator parts, etc. -Office electrical product parts. Office computer related parts, telephone equipment related parts, facsimile related parts, copying machine related parts, cleaning jig related parts. Sanitary-related parts such as toilet seats, tank covers, casings, kitchen parts, washstand-related parts, bathroom-related parts. Housing and housing related parts such as window frames, furniture, flooring, and wall materials. Optical equipment and precision equipment related parts such as microscopes, binoculars, cameras and watches. Various valves such as alternator terminals, alternator connectors, IC regulators, exhaust gas valves, various valves related to fuel, exhaust systems, and intake systems. Air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air Flow meter, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, wiper harness for transmission, window washer nozzle , Air conditioner panel switch board, fuel related solenoid valve co Rubobin, fuse connector, horn terminal, insulating plates for electric equipment, step motor roller, a lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case. PC, printer, display, CRT display, notebook computer, mobile phone, PHS, DVD drive, PD drive, flexible disk drive and other storage device housing, chassis, relay, switch, case member, transformer member, coil bobbin, etc. Electronic equipment parts. Automotive exterior members such as bumpers and fenders, and other various uses.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the examples, parts and% are based on mass unless otherwise specified. Various measurements in the examples and comparative examples were based on the following methods.

[1] Evaluation method (1) Gel content of rubbery polymer: According to the above method.
(2) Average particle diameter of rubbery polymer latex;
The average particle size of the rubbery polymer latex used for forming the component (A) was measured by a light scattering method. The measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mummant method was used with 70 times integration. In addition, it confirmed with the electron microscope that the particle diameter of the dispersion-grafted rubber-like polymer particle in (A) component was substantially the same as the latex particle diameter.
(3) Graft ratio of component (A): According to the method described above.
(4) The intrinsic viscosity [η] of the acetone-soluble component of component (A);
(5) Component (E) (bonded styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate of the polymer);
(5-1) Amount of bound styrene;
It was measured on the polymer before hydrogenation. It was determined from a calibration curve by an infrared method based on absorption of a phenyl group at 699 cm ⁻¹ .
(5-2) Number average molecular weight;
It was measured on the polymer before hydrogenation. It calculated | required from the gel permeation chromatography (GPC).
(5-3) Amount of vinyl bond Measured with a polymer before hydrogenation. It calculated | required by the infrared method (Morero method).
(5-4) Hydrogenation rate;
Measurements were taken on the polymer after hydrogenation. Using ethylene tetrachloride as a solvent, was calculated from the spectrum decrease of ¹ H-NMR unsaturated double bond of the spectrum of 100MHz was measured at 15% strength.

(6) Impact resistance;
A flat plate having a thickness of 2.4 mm was placed on a tray diameter of 38 mm, and the fracture energy (kgf · cm) when the flat plate was punched at a striking rod diameter of 16 mm and a speed of 2.4 m / sec was measured.
(7) Chemical resistance;
A test piece having a thickness of 3.2 mm, a width of 12.7 mm, and a length of 127 mm was strained by 1%, the following chemicals were applied, and the surface condition of the molded product after being left at 23 ° C. for 48 hours was evaluated according to the following evaluation criteria. Based on the visual evaluation.
○: No change x: Crack generation or breakage (7-1) Chemical resistance-1; Ethyl alcohol (7-2) Chemical resistance-2; Brake fluid (8) Antistatic property Circle with a diameter of 100mm and a thickness of 2mm The plate was molded and conditioned at 23 ° C. × 30% relative humidity for 1 day, and then the surface resistivity was measured at an applied voltage of 500 V using an Agilent-Technologies high resistance meter 4339B type.

[2] Thermoplastic resin composition component (1) (A) component (1-1) Production example A1; ABS resin 75 parts of ion-exchanged water in a 7 L inner glass flask equipped with a stirrer in a nitrogen stream , 0.5 parts of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, 40 parts of polybutadiene latex (average particle size: 3500 kg, gel content: 85%), 15 parts of styrene, 5 parts of acrylonitrile The temperature was raised with stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. It was. Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After polymerization for 1 hour, 50 parts of ion-exchanged water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide for 3 hours. Then, the polymerization was continued for another hour, and then 0.2 part of 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain a styrene resin A1. The graft ratio of this A1 was 68%, and the intrinsic viscosity [η] of the acetone soluble component was 0.45 dl / g.

(1-2) Production Example 2: AS resin Two jacketed polymerization reaction vessels equipped with a ribbon wing having an internal volume of 30 L were connected and purged with nitrogen, and then 75 parts of styrene and 25 parts of acrylonitrile were added to the first reaction vessel. 20 parts of toluene were continuously added. Solution of 0.12 part of tert-dodecyl mercaptan and 5 parts of toluene as molecular weight regulator, and solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as polymerization initiator Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator and polymerization initiator supplied by the pump provided in the second reactor. To the reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and had an intrinsic viscosity [η] of 0.48. Styrene resin A2 was obtained.

(2) Component (B): Polypropylene resin Block type polypropylene “Novatec BC6C” (trade name) manufactured by Nippon Polychem was used.

(3) Component (C);
A polypropylene-polyether block copolymer “Pelestat 303” (trade name) manufactured by Sanyo Chemical Industries, Ltd. was used.

(4) Component (D);
The following maleic anhydride-modified polyolefin manufactured by Sanyo Chemical Industries, Ltd. was used as the component (D) of the present invention.
D1; Yumex 1001 (trade name of 5% maleic anhydride addition product)
D2: Yumex 1010 (trade name of 10% maleic anhydride addition product)

(5) (E) component;
(5-1) Production Example 3 Partially Hydrogenated Styrene-Butadiene-Styrene Block Copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene was charged. Next, n-butyllithium was added and polymerized at 70 ° C. for 1 hour, and then a cyclohexane solution containing 40 parts of butadiene was added and polymerized for 1 hour.
A part of the resulting block polymer solution was sampled, 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed by heating. The styrene content was 60%, the 1,2-vinyl bond content of the polybutadiene portion was 35%, and the number average molecular weight was 74,000. A solution obtained by reacting titanocene dichloride and triethylaluminum in cyclohexane was added to the remaining block copolymer solution, and a hydrogenation reaction was carried out at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 40 minutes. 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed to obtain a polymer E1.

(5-2) Production Example 4: Fully Hydrogenated Styrene-Butadiene Block Copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of butadiene solution were added. Next, 0.025 part of n-butyllithium was added to carry out isothermal polymerization at 50 ° C. When the conversion rate reached 100%, 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and the temperature was increased from 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed to obtain an A-B1-B2 triblock copolymer before hydrogenation. As a result of sampling and analysis in the same manner as in Production Example 3, styrene block 15% (A block), 1,2-vinyl content 35% butadiene block (B1 block), 1,2-vinyl content 10% butadiene block (B2 block) And a number average molecular weight 200,000 polymer.
In a separate container, 1 part of titanocene dichloride was dispersed in cyclohexane and reacted with 0.5 part of triethylaluminum at room temperature. The obtained homogeneous solution was added to the above polymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 2 hours to obtain a hydrogenated polymer E2 having a hydrogenation rate of approximately 100%.

(5-3) Production Example 5: Styrene-butadiene-styrene block copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and 0.08 parts of cyclohexane and tetrahydrofuran were converted in a nitrogen stream. Thereafter, the temperature was raised, and when the internal temperature reached 70 ° C., a cyclohexane solution containing 0.052 part of n-butyllithium was added, followed by addition of 15.5 parts of styrene and polymerization for 60 minutes (first stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (second stage). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (third stage). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (fourth stage) to polymerize three tapered blocks. Next, 15.5 parts of styrene was added and polymerized for 60 minutes (5th stage). The polymerization conversion rate was 100%.
During the polymerization, the internal temperature was controlled to 70 ° C. After completion of the polymerization, 2,6-di-tert-butylcatechol was added to the polymer solution, and then the solvent was removed by heating to obtain a block copolymer E3 having three tapered blocks in which the polystyrene gradually increased in the polybutadiene block portion. Obtained. This had a number average molecular weight of 128,000 and a styrene content of 40%.

(5-4) Production Example 6: Styrene-butadiene radial teleblock copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and 2.75 parts of cyclohexane and tetrahydrofuran were added in a nitrogen stream. After adding 25 parts of styrene and raising the temperature to 60 ° C., a cyclohexane solution containing 0.175 part of n-butyllithium was added, and a polymerization reaction was performed for 60 minutes (first stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added to conduct a polymerization reaction for 60 minutes (second stage), and a mixture of 3 parts of styrene and 20 parts of butadiene was added to conduct a polymerization reaction for 60 minutes (3). In the second stage), 29 parts of butadiene was further added, and polymerization was completed until the conversion reached 100%. After adding 0.1 part of silicon tetrachloride as a coupling agent, the coupling reaction was completed. After completion of the polymerization, 2,6-di-tert-butylcatechol was added to the polymer solution, and then the solvent was removed by heating to obtain a coupling type styrene-butadiene block copolymer E4 having a tapered block. This had a styrene content of 31% and a number average molecular weight of 200,000.

(6) Production Example 7; Component (F) After substituting a 10 L stainless steel autoclave having a ribbon-type wing with nitrogen, in a nitrogen stream, 30 parts of the polymer E2 previously made into a uniform solution using toluene as a solvent were used. Parts (solid content), 52.5 parts of styrene, 17.5 parts of acrylonitrile, 120 parts of toluene, and 0.1 part of tert-dodecyl mercaptan were charged and heated with stirring. When the internal temperature reaches 50 ° C., 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide are added, the temperature is further increased, and after reaching 80 ° C., the temperature is controlled at a constant 80 ° C. A polymerization reaction was performed. It took 1 hour from the 6th hour after the start of the reaction, the temperature was raised to 120 ° C., and the reaction was further completed for 2 hours. The conversion was 97%.
After cooling to 100 ° C., 0.2 part of 2,2-methylenebis-4-methyl-6-tert-butylphenol was added, the reaction mixture was extracted from the autoclave, unreacted substances and solvent were distilled off by steam distillation, The coalescence was pelletized to obtain a polymer F. The graft ratio of this product was 45%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(7) (G) component;
TM polymer manufactured by Kuraray Co., Ltd .; TM-S4L77 (SEPS—trade name of aromatic polycarbonate block copolymer) was used.

(8) Component (H) Lithium bromide was used.

Examples 1-16, Comparative Examples 1-5
All components were mixed with a Henschel mixer at the blending ratio shown in Table 1, and then melt-kneaded using a twin-screw extruder (cylinder setting temperature 200 ° C.) to form pellets. After the obtained pellets were sufficiently dried, test specimens for evaluation were produced by injection molding (cylinder setting temperature 200 ° C.).
Using this test piece, impact resistance, chemical resistance, and antistatic properties were evaluated by the above-described evaluation methods. The evaluation results are shown in Table 1.

From the results shown in Table 1, the following is clear.
The molded articles 1 to 16 of the examples of the present invention are excellent in impact resistance, chemical resistance, and antistatic properties.
On the other hand, Comparative Example 1 is an example in which the amount of the component (A) used in the present invention is small outside the scope of the invention and the amount of the component (B) used is large outside the scope of the invention. Antistatic property is inferior. Comparative Example 2 is an example in which the amount of component (C) used in the present invention is small outside the scope of the invention, and is inferior in impact resistance and antistatic properties. Comparative Example 3 is an example in which the amount of the component (C) used in the present invention is large outside the scope of the invention, and the impact resistance is poor. Comparative Example 4 is an example in which the amount of the component (D) used in the present invention is small outside the scope of the invention, and the antistatic property is inferior. Comparative Example 5 is an example in which the amount of component (D) used in the present invention is large outside the scope of the invention, and is inferior in impact resistance and antistatic properties.

The thermoplastic resin composition of the present invention has excellent impact resistance, chemical resistance, and antistatic property under low humidity, and has high performance required in the vehicle field, -It can be applied as various parts in the electronic field, OA / home appliance field, sanitary field, etc.

Claims (3)

The following (A) component 5-100 mass% and the following (B) component 0-95 mass% are contained (however, the sum total of this (A) component and this (B) component is 100 mass%),
Furthermore, 0.5-100 mass parts of the following (C) component and 1-50 mass parts of the following (D) component with respect to 100 mass parts in total of this (A) component and this (B) component. A thermoplastic resin composition containing the thermoplastic resin composition.
(A) Styrenic polymer obtained by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence or absence of a rubbery polymer resin,
(B) an olefin resin,
(C) a block copolymer having a structure in which an olefin block (C-1) and a hydrophilic polymer block (C-2) are repeatedly and alternately bonded;
(D) Low molecular weight polyolefin modified with unsaturated acid and / or unsaturated acid anhydride. Furthermore, with respect to a total of 100 parts by mass of the component (A) and the component (B), at least one selected from the group consisting of the following components (E), (F) and (G) is 1 It contains -200 mass parts, The thermoplastic resin composition of Claim 1 characterized by the above-mentioned.
(E) a block copolymer having a polymer block (E-1) mainly composed of an aromatic vinyl compound and a polymer block (E-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof,
(F) A graft polymer obtained by (co) polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the component (E),
(G) An aromatic polycarbonate block copolymer comprising a polymer block comprising the component (E) and an aromatic carbonate polymer block (G-1). A molded article comprising the thermoplastic resin composition according to claim 1 or 2.