JP2006291170A - Antistatic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition providing a molded article which is excellent in antistatic properties, chemical resistance and surface appearance. <P>SOLUTION: The antistatic resin composition is formed by adding a prescribed amount of (B) a block copolymer having (B-1) an olefin polymer block and (B-2) a hydrophilic polymer block and (C) a nonionic antistatic agent, to a resin composition which comprises (A) an olefin resin, and optionally, (D) a block copolymer having (D-1) a polymer block mainly comprising an aromatic vinyl compound and (D-2) polymer block mainly comprising a conjugated diene compound and/or a hydrogenated product thereof, and optionally further, (E) a styrene resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic resin composition excellent in antistatic property, chemical resistance and surface appearance of a molded product, and a molded product comprising the antistatic resin composition.

  Polyolefin resins such as polypropylene are widely used in the electrical / electronic field, OA / home appliance field, vehicle field, sanitary field and the like because of their excellent chemical resistance, heat resistance, fluidity and the like. However, because it has the drawback of being easily charged, it is used for various parts, sheets, films, etc. used in liquid crystal display devices, semiconductor peripherals, plasma displays, clean rooms, etc. It was difficult to do. For the purpose of improving such drawbacks, Patent Documents 1 and 2 propose that a specific antistatic agent is blended. However, the antistatic property is not long enough and the antistatic property is not sufficient. There was a problem such as. In addition, as a method for improving the antistatic durability, Patent Document 3 proposes that a specific polymer is blended with a polyolefin-based resin, but there is a problem that the antistatic property is not sufficiently exhibited. It was.

  On the other hand, rubber-reinforced styrene-based resins such as ABS resin are superior in mechanical strength such as impact resistance, moldability, rigidity, and the like, and also in the surface appearance of molded products. Therefore, electrical / electronic field, OA / home appliance field, vehicle field. Although it is widely used in the sanitary field, etc., the chemical resistance is not sufficient depending on the intended use, and further improvement in chemical resistance has been demanded. Further, these styrene resins also have the problem of static electricity damage as described above, and these improvements have been desired. Patent Document 4 proposes that a polyamide elastomer is blended with a styrene resin such as an ABS resin, but there is a problem that the antistatic property is not sufficiently exhibited.

JP-A-4-258647 JP 2000-313875 A Japanese Patent Laid-Open No. 2001-278985 Japanese Patent Laid-Open No. 60-23435

  An object of the present invention is to provide an antistatic resin composition having excellent antistatic properties, chemical resistance, and molded product surface appearance. Another object of the present invention is to provide the molded article.

As a result of intensive investigations to achieve the above object, the present inventors blended a polypropylene resin, a mixture of a polypropylene resin and a styrene resin with a polymer having a specific block structure and a nonionic antistatic agent in combination. Thus, it was found that the antistatic property is remarkably improved and the sustainability of the antistatic property is expressed, and the present invention has been completed.
That is, according to the first aspect of the present invention,
(A) 70 to 97% by mass of an olefin resin,
(B) 3-30% by mass of a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2),
(However, the total of the components (A) and (B) is 100% by weight)
(C) 0.01 to 10 parts by mass of a nonionic antistatic agent with respect to 100 parts by mass in total of the above component (A) and component (B),
An antistatic resin composition (hereinafter referred to as a first antistatic resin composition) is provided.
According to the second aspect of the present invention,
(A) 30 to 96% by mass of an olefin resin,
(B) 3-30% by mass of a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2),
(D) A block copolymer having a polymer block (D-1) mainly composed of an aromatic vinyl compound and a polymer block (D-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof of 1 to 40 masses %,
(However, the total of the components (A), (B), and (D) is 100% by weight)
(C) 0.01 to 10 parts by mass of a nonionic antistatic agent relative to a total of 100 parts by mass of the component (A), the component (B), and the component (D),
An antistatic resin composition (hereinafter referred to as a second antistatic resin composition) is provided.
According to a third aspect of the present invention,
(A) 12 to 91% by mass of an olefin resin,
(B) 3-30% by mass of a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2),
(D) A block copolymer having a polymer block (D-1) mainly composed of an aromatic vinyl compound and a polymer block (D-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof of 1 to 40 masses %,
(E) 5-40% by mass of a styrene resin,
(However, the total of the components (A), (B), (D), and (E) is 100% by weight)
(C) 0.01 to 10 parts by mass of a nonionic antistatic agent with respect to 100 parts by mass in total of the above component (A), component (B), component (D), and component (E),
An antistatic resin composition (hereinafter referred to as a third antistatic resin composition) is provided.

  The antistatic resin composition of the present invention comprises the component (A), the composition of the component (A) and the component (D), or the component (A), the component (D), and the component (E). In this composition, a specific amount of the component (B) and the component (C) are blended, and a molded product having excellent antistatic properties, chemical resistance, and molded product surface appearance is obtained.

 The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

Description of First Antistatic Resin Composition The olefin resin that is the component (A) of the present invention contains (co) heavy containing at least one olefin having 2 to 10 carbon atoms as a constituent monomer unit. A (co) polymer excluding the component (B) described later. 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, the melt flow rate measured according to JIS K-7210 is preferably a molecular weight corresponding to 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min.

Examples of olefins that are monomers of the olefin resin include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3- Α-olefins such as methylhexene-1, etc., preferably ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, more preferably propylene and ethylene Particularly preferably, propylene is the main component. That is, the olefin resin (A) is preferably a polymer mainly containing propylene units such as polypropylene and propylene / ethylene copolymers, and polyethylene, and particularly preferably propylene units such as polypropylene and propylene / ethylene copolymers. Is a polymer mainly containing These may be used alone or in combination. The propylene / ethylene copolymer is preferably a random copolymer or a block copolymer. In addition, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like are used as polymer components. Can be used as a part.
As the polyolefin resin used in the present invention, one obtained by decatalyzing a polymerization catalyst, or one modified with an acid anhydride, a carboxyl group or the like can also be used.

 The usage-amount of (A) component which comprises the 1st antistatic resin composition of this invention is 70-97 mass% in the total 100 mass% of the said (A) component and (B) component, Preferably Is 75 to 96 mass%, more preferably 77 to 96 mass%, particularly preferably 77 to 95 mass%. When the amount used is less than 70% by mass, the chemical resistance is inferior, and when it exceeds 97% by mass, the antistatic property and the molded product surface appearance are inferior.

 The component (B) of the present invention is a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2), which may be a diblock or a multiblock of a triblock or more. There may be. The olefin polymer block (B-1) is a (co) polymer of olefins. Examples of the olefins used herein include ethylene and α such as propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1. -There are olefins, etc., 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, 1,9-decadiene and the like are used as one of the polymer components. Can be used as a part. Furthermore, cyclic olefins such as norbornenes can be copolymerized. The number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) of the olefin polymer block (B-1) is preferably 800 to 20,000, more preferably 1,000 to 10,000, particularly preferably. 1,200 to 6,000.

The block (B-1) is chemically bonded to the block (B-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 (B-1) need to be modified with functional groups having reactivity with the molecular end functional groups of the block (B-2). Examples of these functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, and epoxy groups.
A preferable method for imparting these functional groups is carbon-carbon unsaturation having the above-mentioned functional group in the component (B-1) having a carbon-carbon double bond at the molecular end obtained by the thermal degradation method. This is a method of adding a compound.

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

As the polyether diol in the polyether (B-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 integers of 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, and tertiary amino group-containing diols.
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, aryl group, alkylaryl group, arylalkyl group or acyl group having 1 to 10 carbon atoms, and A ³ is an alkylene group having 2 to 4 carbon atoms. It is. 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 integers of 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 of these 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 an integer of 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 a 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.
Moreover, the preferable (B) component of this invention can be obtained by superposing | polymerizing the said olefin polymer block (B-1) and hydrophilic polymer block (B-2) by a well-known method. For example, the block (B-1) and the block (B-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, the component (B) contains at least one salt (F) selected from the group consisting of alkali metals and alkaline earth metals. it can. These components can be contained before the polymerization of the component (B), during the polymerization of the component (B), or after the polymerization of the component (B). Moreover, it can mix | blend when manufacturing the thermoplastic resin composition of this invention, and can also be made to contain by the method of combining these.
Examples of the salt of component (F) include alkali metals such as lithium, sodium and potassium, and / or alkaline earth metals such as magnesium and calcium, salts of organic acids, sulfonic acids and inorganic acids, and halides.

  Specific preferred examples of the component (F) 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; Octylsulfonic acid, dodecylsulfonic acid, tetradecylsulfonic acid, stearylsulfonic acid, tetracosylsulfonic acid An alkali metal salt of an alkyl sulfonic acid having an alkyl group having 8 to 24 carbon atoms such as 2-ethylhexyl sulfonic acid; an alkali metal salt of an aromatic sulfonic acid such as phenyl sulfonic acid or naphthyl sulfonic acid; octylphenyl sulfonic acid, Dodecylphenylsulfonic acid, dibutylphenylsulfone Alkali metal salts of alkylbenzene sulfonic acids having 6 to 18 carbon atoms in the alkyl group, such as dinonylphenyl sulfonic acid; dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfonic acid, etc. Alkali metal salts of 2-18 alkylnaphthalene sulfonic acids; alkali metal salts such as fluorinated sulfonic acids such as trifluoromethane sulfonic acid, etc. are used, and these are used alone or in combination of two or more. be able to. The component (F) is preferably used in the range of 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, relative to the component (B) of the present invention.

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

  The component (B) of the present invention is 3 to 30% by mass, preferably 4 to 25% by mass, more preferably 4 to 23% by mass, particularly 100% by mass of the component (A) and the component (B). Preferably it is used in 5-23 mass%. If it is less than 3% by mass, the antistatic property is inferior, and if it exceeds 30% by mass, the chemical resistance and the molded product surface appearance are inferior.

一般式中、Ｒ^４は炭素数８〜２２のアルキル基もしくはアルケニル基であり、Ｘは下記式Ｘ−１またはＸ−２で示される基

であり、
Ｙ及びＺはそれぞれ下記式Ｙ−１、Ｙ−２またはＹ−３で示される基

であって両者は互いに同一でも異なっていてもよい。ｍ＋ｎは２〜５の整数である。 Examples of the nonionic antistatic agent which is the component (C) of the present invention include (C-1) polyhydric alcohol esters, (C-2) nitrogen-containing compounds represented by the general formula (VI), and the like. Can be used singly or in combination of two or more.

In the general formula, R ⁴ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, and X is a group represented by the following formula X-1 or X-2.

And
Y and Z are groups represented by the following formulas Y-1, Y-2 or Y-3, respectively.

And they may be the same or different from each other. m + n is an integer of 2-5.

 As the component (C-1), glycerol monostearate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monobehenate, glycerol monooleate, diglycerol monolaurate, diglycerol monomyristate, Diglycerol monopalmitate, diglycerol monostearate, diglycerol monobehenate, diglycerol monooleate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan mono A laurate etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Particularly preferred are glycerin monostearate, diglycerin monostearate, glycerin monolaurate, diglycerin monolaurate, sorbitan monostearate and the component (C-1) containing at least 20% by mass or more thereof. .

 As the component (C-2), lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopronolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine, oleyl diisopropanol Amines, amines such as N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, or lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behenyl diethanolamide, oleyl diethanolamide, lauryl diisopropanol Amides, myristyl diisopropanolamide, palmityldi Propanol amide, stearyl diisopropanol amide, there are amides such as oleyl monoisopropanolamide. These can be used alone or in combination of two or more. The amine compound is preferred, and the (C-2) component containing at least 20% by mass of lauryl diethanolamine and stearyl diethanolamine is more preferred.

Moreover, a known additive can be blended with the above-mentioned compound for the purpose of improving the antistatic performance. Examples thereof include higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate and the like. In addition, for the purpose of improving miscibility, a master batch can be used.
The nonionic antistatic agent which is the component (C) of the present invention is commercially available as Kao Electro Stripper EA, TS-3B, TS-6B, TS-5, TS-2B (trade name) and the like.

  The component (C) of the present invention is 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, and more preferably 0. Used in the range of 1 to 5 parts by mass, particularly preferably 0.5 to 3 parts by mass. When the amount is less than 0.01 parts by mass, the antistatic property is inferior. Is inferior.

Description of Second Antistatic Resin Composition As the component (A) used here, the above-described component (A) is all used. Component (A) is used in an amount of 30 to 96 mass%, preferably 35 to 91 mass%, more preferably 42 to 100 mass% of the total of 100 mass% of component (A), component (B), and component (D). 91 mass%, particularly preferably 42 to 85 mass%. If it is less than 30 mass%, the chemical resistance is inferior. If it exceeds 96 mass%, the antistatic property and the surface appearance of the molded product are inferior.
As the component (B) used here, the above-described component (B) is all used. The amount of component (B) used is 3 to 30% by mass, preferably 4 to 25% by mass, more preferably 100% by mass in total of 100% by mass of component (A), component (B) and component (D). It is 4-23 mass%, Most preferably, it is 5-23 mass%. If it is less than 3% by mass, the antistatic property is inferior, and if it exceeds 30% by mass, the chemical resistance and the molded product surface appearance are inferior.

  The component (D) of the present invention comprises a block copolymer having a polymer block (D-1) mainly composed of aromatic vinyl compound units and a polymer block (D-2) mainly composed of conjugated diene compound units, and / or The hydrogenated product is a product obtained by hydrogenating at least part of the carbon-carbon double bond of the conjugated diene compound of the block (D-2).

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 (D-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. In addition, (D-2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and is a vinyl bond derived from the conjugated diene compound of the polymer block (D-2). Polymer blocks having different contents may be appropriately copolymerized.

A preferred structure of the component (D) of the present invention is a polymer represented by the following formulas (VII) to (IX) or a hydrogenated product thereof.
(AB) _Y ... (VII)
(AB) _Y- X (VIII)
A- (BA) _Z ... (IX)
(In the structural formulas (VII) to (IX), 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 conjugated diene compound is partially 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.)

  In the component (D) of the present invention, the use ratio of the aromatic vinyl compound and the conjugated diene compound 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 (D) 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 (VIII) to (IX) is in the range of 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 possible by adjusting amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octane, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethylene. 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 via a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferably included in the component (D) 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 1 to 10 tapered blocks in which the aromatic vinyl compound gradually increases in the block (D-2), and / or It is a radial block type that has been coupled.

 As the component (D), 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 (D) 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.

 (D) component of this invention is 1-40 mass% with respect to a total of 100 mass% of (A) component, (B) component, and (D) component, Preferably it is 5-40 mass%, More preferably, It is 5 to 35% by mass, particularly preferably 10 to 35% by mass. If it is less than 1% by mass, the effect of improving antistatic properties is inferior, and if it exceeds 40% by mass, the chemical resistance and the molded product surface appearance are inferior.

As the component (C) used here, all of the component (C) can be used, and the component (C) is a total of 100 masses of the components (A), (B), and (D) of the present invention. 0.01 to 10 parts by mass, preferably 0.05 to 8 parts by mass, more preferably 0.1 to 5 parts by mass, and particularly preferably 0.5 to 3 parts by mass with respect to parts. If it is less than 0.01 parts by mass, the antistatic property is inferior,
When it exceeds 10 parts by mass, the surface appearance of the molded product is inferior.

Description of Third Antistatic Resin Composition As the component (A) of the present invention, all of the above-mentioned components can be used, and the components (A), (B), (D), and (E) In total 100 mass%, 12-91 mass%, Preferably it is 22-85 mass%, More preferably, it is 25-84 mass%, Most preferably, it is used in 28-75 mass%. If it is less than 12% by mass, the chemical resistance is inferior, and the molded product surface appearance and antistatic property exceeding 91% by mass are inferior.
As the component (B) of the present invention, all of those described above can be used, and 3 to 30% by mass in a total of 100% by mass of the components (A), (B), (D), and (E). , Preferably 4 to 25% by mass, more preferably 4 to 23% by mass, particularly preferably 5 to 23% by mass. If it is less than 3% by mass, the antistatic property is inferior, and if it exceeds 30% by mass, the chemical resistance and the molded product surface appearance are inferior.

As the component (D) of the present invention, all of those described above can be used, and 1 to 40% by mass in a total of 100% by mass of the component (A), component (B), component (D), and component (E). The amount is preferably 5 to 40% by mass, more preferably 5 to 38% by mass, and particularly preferably 10 to 38% by mass. If it is less than 1% by mass, the impact resistance and the molded product surface appearance are inferior. If it exceeds 40% by mass, the chemical resistance and the molded product surface appearance are inferior.
The component (E) of the present invention is a styrene resin, and preferably comprises the following component (E-1) and / or the following component (E-2).
Component (E-1): A monomer component comprising an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the rubbery polymer (a). A rubber-reinforced styrenic resin obtained by polymerizing (b),
Component (E-2): Styrenic resin obtained by polymerizing the monomer component (b) in the absence of the rubbery polymer (a).
The component (E) of the present invention preferably contains at least one polymer grafted (co) polymerized in the presence of the rubbery polymer (a) from the viewpoint of impact resistance. The content of the rubbery polymer (a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass, with the component (E) being 100% by mass.

The rubber polymer (a) is not particularly limited, but polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, component (D), ethylene / propylene copolymer, ethylene / propylene / non-polymer. Conjugated diene copolymers, ethylene / butene-1 copolymers, ethylene / butene-1 / non-conjugated diene copolymers, acrylic rubbers, silicone rubbers, silicone / acrylic IPN rubbers, and the like. Or in combination of two or more.
Of these, polybutadiene, butadiene / styrene copolymer, component (D), 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 (a) 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. 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 ₂ mass of mass W), 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 component (b) include styrene, α-methylstyrene, hydroxystyrene and the like, and these are used alone or in combination of two or more. be able to. 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 component (b) comprises an aromatic vinyl compound as an essential monomer component, and optionally 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 above various other 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, methacrylonitrile and the like, 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 in the (b) component, Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.
Examples of (meth) acrylic acid ester compounds 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 using a (meth) acrylic acid ester compound, the usage-amount is in the (b) component, Preferably it is 1-80 mass%, More preferably, it is 5-80 mass%.
Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like, and 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 using a maleimide compound, the amount used thereof 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 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, unsaturated acid compounds, and hydroxyl group-containing unsaturated compounds.
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 monomer component (b) is preferably 80% by mass or less, more preferably 100% by mass when the total of the monomer components (b) is 100% by mass. 60% by mass or less, particularly preferably 40% by mass or less. More preferred combinations of monomers constituting the monomer component (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 the 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 / methacryl Methyl styrene amount is 20 to 80 wt%, the sum of acrylonitrile and methyl methacrylate is any in the range of 20 to 80 wt%.

  The component (E) 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 component (b) in the presence of the rubbery polymer (a) are emulsion polymerization and solution polymerization. On the other hand, a preferred polymerization method of the polymer obtained by (co) polymerizing the vinyl monomer component (b) in the absence of the rubbery polymer (a) is 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 component (b) are used in such a manner that the vinyl monomer component (b) is added in the presence of the total amount of the rubber polymer (a). Polymerization may be performed by adding all at once, or polymerization may be performed by dividing or continuously adding. 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 (E) powder of the present invention. At this time, the latex of two or more types of component (E) 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.

The solvent that can be used in the case of producing the component (E) by solution polymerization is an inert polymerization solvent used in normal radical polymerization, such as 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. Polymerization initiators include ketone peroxides, dialkyl peroxides, diacyl peroxides, peroxy esters, hydroperoxides, azobisisobutyronitrile, benzoyl peroxide, and other organic peroxides, 1,1′-azobis ( Cyclohexane-1-carbonitrile) 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 (E) obtained by each polymerization method is preferably 10,000 ppm or less, more preferably 5,000 ppm or less.

In addition, the polymer component obtained by polymerizing the vinyl monomer component (b) in the presence of the rubber polymer (a) usually contains the above-mentioned vinyl monomer component (b). Copolymer grafted to polymer (a) and ungrafted component not grafted to rubbery polymer [(co) polymer of vinyl monomer (b) similar to component (E-2) above ] Is included.
The graft ratio of the component (E) 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 (E) 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 ( E) Mass (g) of rubbery polymer contained in 1 g of component.

In addition, the intrinsic viscosity of the component (E) related to the present invention (however, when the rubbery polymer (a) uses an acrylic rubber, acetonitrile) the intrinsic viscosity [η] (methyl ethyl ketone as a solvent) 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 rubbery polymer particles dispersed in the component (E) 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 amount of the component (E) constituting the thermoplastic resin composition of the present invention is 100% by mass in total of the components (A), (B), (D), and (E) of the present invention. 5 to 40% by mass, preferably 6 to 38% by mass, more preferably 7 to 37% by mass, and particularly preferably 10 to 34% by mass. If it is less than 5% by mass, the antistatic property is inferior, and 40% by mass. If it exceeds 50%, the antistatic property and chemical resistance are inferior.
As the component (C) used here, all of the component (C) can be used, and the component (C) includes the components (A), (B), (D), and (E) of the present invention. 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the total components. Used in. If it is less than 0.01 parts by mass, the effect of improving antistatic properties is poor, and if it exceeds 10 parts by mass, the surface appearance of the molded product is inferior.
The antistatic resin composition of the present invention includes known weather resistance (light) agents, antioxidants, heat stabilizers, lubricants, silicone oils, plasticizers, sliding agents, colorants, dyes, foaming agents, processing aids. An agent (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), a flame retardant, a crystal nucleating agent, and the like can be appropriately blended.

Moreover, well-known inorganic and organic fillers can be mix | blended with this antistatic resin composition. As the filler used here, glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron powder or the like Fibrous material, carbon black, tin-coated titanium oxide, tin-coated silica, nickel-coated carbon fiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite, mica, kaolin, montmorillonite, hectorite, zinc oxide whisker, potassium titanate There are whisker, aluminum borate whisker, plate-like alumina, plate-like silica, and organically treated smectite, aramid fiber, phenol fiber, polyester fiber, etc., and these should be used alone or in combination of two or more. Can do.
Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treatment agent, sizing agent, etc. can be used. As the known coupling agent, a silane coupling agent, There are titanate coupling agents and aluminum coupling agents.
The inorganic / organic filler is usually used in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the antistatic resin composition of the present invention.

  Furthermore, the antistatic resin composition of the present invention includes other known polymers such as polyamide resin, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystal polyester, and other thermoplastic polyester resins, polyester elastomers, PMMA, methyl methacrylate / maleimide compound copolymer, polyphenylene ether, polyphenylene sulfide, aromatic polycarbonate, thermoplastic polyurethane, epoxy resin, phenol resin, urea resin, phenoxy resin, and the like can be appropriately blended.

The antistatic resin composition of the present invention can be obtained by melt-kneading the above-described constituent components with various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, and the like. At the time of kneading, the above-mentioned components of the present invention may be added together and kneaded, or may be added separately.
The antistatic resin composition of the present invention thus prepared includes injection molding, press molding, calender molding, T-die extrusion molding, inflation molding, lamination molding, vacuum molding, profile extrusion molding, and combinations thereof. A molded product can be obtained by a known molding method such as a molding method.

The thickness when processing the antistatic resin composition of the present invention into a sheet or film is preferably in the range of 10 μm to 10 mm.
The sheet and film may be a single layer sheet or film, may be multilayered with other materials, or may be a sheet or film laminated with an adhesive or the like. Furthermore, a known gas barrier film can be formed on the sheet or film.

When the antistatic resin composition of the present invention is used to form a multilayer sheet or film, the thermoplastic resin composition of the present invention is a two-layer sheet with another material, a film, or a three-layer having the other material as an intermediate layer. There are a sheet, a film, and the like. As other materials used here, known polymers can be used, and the (A) component and (E) component of the present invention are preferably used for them. Further, for the purpose of improving the rigidity and heat resistance, those containing the inorganic and organic fillers can be used.
In the multilayer sheet, the thickness of the antistatic resin composition of the present invention is preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 80 μm or more for the purpose of stably developing antistatic properties. As a method for obtaining such a multilayer sheet or film, a particularly preferable method is co-extrusion by T-die or co-extrusion by inflation. The sheet and film thus obtained can be formed into a molded product such as a tray by vacuum forming or the like as necessary.

When manufacturing an adhesive sheet or film, the surface of the base sheet or base film made of the antistatic resin composition of the present invention is known for the purpose of improving the adhesiveness with the adhesive or the primer layer. Various treatments such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment treatment, solvent treatment and the like can be performed. Moreover, the process which combined these can be performed as needed.
Furthermore, for the purpose of improving the adhesive force between the base sheet, film and pressure-sensitive adhesive, a primer layer can be formed directly on the base sheet or film or on the surface-treated surface. Specifically, a very thin layer having a thickness of about 0.1 μm to 10 μm is formed from a resin such as polyethyleneimine, polyurethane, or an acrylic resin. Usually, it can be formed by applying as a solvent (including water) solution and drying.

  Adhesives include emulsion types that are applied by screen method, gravure method, mesh method, bar coating method, etc., organic solvent types, and hot melt types that are formed by extrusion lamination method, dry lamination method, co-extrusion method, etc. Can be used. The thickness of the pressure-sensitive adhesive is not particularly specified, but is usually in the range of about 1 to 100 μm.

  The molded product thus obtained includes cases such as relay cases, wafer cases, reticle cases, mask cases, trays such as liquid crystal trays, chip trays, memory trays, CCD trays, IC trays, IC carriers, etc. In the fields of carriers, polarizing film protective sheets, surface protective films such as liquid crystal display devices and plasma displays, semiconductor protective films, protective films in clean rooms, and vending machine internal parts Can be used.

  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 diameter of the rubbery polymer latex used for forming the component (E) 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. It was confirmed with an electron microscope that the particle diameter of the dispersion-grafted rubber polymer particles in the component (E) was almost the same as the latex particle diameter.
(3) Graft ratio of component (E): According to the method described above.
(4) The intrinsic viscosity [η] of the acetone-soluble component of component (E);
(5) Component (D) (polymer bound styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate);
(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) Vinyl bond amount Measured with the 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) Antistatic property;
Using a sheet having a thickness of 1 mm, the surface resistivity after being left for 24 hours under conditions of 23 ° C. and 50% RH was measured with an applied voltage of 500 V using Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation.
(7) Chemical resistance;
Using a sheet having a thickness of 1 mm, 1% strain was applied to the test piece, the following chemicals were applied, and the surface state of the sheet after being left at 23 ° C. for 72 hours was visually evaluated based on the following evaluation criteria.
○: No change,
X: Large crack or breakage.
(7-1) Chemical resistance-1: methanol.
(7-2) Chemical resistance-2; methyl ethyl ketone.
(8) Molded product surface appearance;
The surface of the plate-like molded product obtained by injection molding was visually evaluated according to the following criteria.
◎; very good on a smooth surface,
○: Good appearance on a smooth surface
X: The surface is not smooth and the appearance is bad.

[2] Thermoplastic resin composition component (1) (A) component: Polypropylene resin The following polypropylene resin manufactured by Nippon Polypro Co., Ltd. was used as the component (A) of the present invention.
A1; Novatec PP FY6C (trade name), homotype,
A2: Novatec PP BC6C (trade name), block type,
A3: Novatec PP EG8 (trade name), random type,
A4: Novatec PP MA3AH (trade name), homotype.

(2) (B) component;
The following polymer manufactured by Sanyo Chemical Industries, Ltd. was used as the component (B) of the present invention.
B1; Pereztat 230 (trade name),
B2: Pereztat 303 (trade name).

(3) Component (C);
As the component (C) of the present invention, the following nonionic antistatic agent manufactured by Kao Corporation was used.
C1: Electro stripper TS-5 (trade name) glycerin ester antistatic agent,
C2: Electro stripper EA (trade name) diethanolamine antistatic agent,
C3: Electro stripper TS-3B (trade name) glycerin ester / diethanolamine composite antistatic agent.

(4) Component (4-1) Production Example 1; Partially Hydrogenated Styrene-Butadiene-Styrene Block Copolymer Stirrer and jacketed autoclave are dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene is added. did. 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 obtained 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 D1 having a butadiene portion hydrogenation rate of 69%.

(4-2) Production Example 2: Completely 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 1, 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 polymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 2 hours. 2,6-Di-tert-butylcatechol was added in the same manner as in Production Example 1, and then the solvent was removed to obtain a hydrogenated polymer D2 having a hydrogenation rate of approximately 100%.

(4-3) Production Example 3; Styrene-Butadiene-Styrene Block Copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 0.08 part of tetrahydrofuran were added 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 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 in the same manner as in Production Example 1, and then the solvent was removed to obtain a block copolymer D3 having three tapered blocks in which polystyrene gradually increases in the polybutadiene block portion. It was. This had a number average molecular weight of 128,000 and a styrene content of 40%.

(4-4) Production Example 4: 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 carried out 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 in the same manner as in Production Example 1, and then the solvent was removed to obtain a coupling type styrene-butadiene block copolymer D4 having a tapered block. This had a styrene content of 31% and a number average molecular weight of 200,000.

(5) Component (E) (5-1) Production Example 5: ABS resin In a nitrogen flow with a 7 L internal volume glass flask equipped with a stirrer, 75 parts of ion-exchanged water, 0.5 part of potassium rosinate, Tert-dodecyl mercaptan (0.1 part), polybutadiene latex (average particle size: 3500 kg, gel content: 85%), 40 parts (solid content), styrene (15 parts) and acrylonitrile (5 parts) were added, and the temperature was increased while 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 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 dried to obtain a rubber-reinforced styrene resin E1. The graft ratio of this E1 was 68%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(5-2) Production Example 6: AS resin Two jacketed polymerization reaction vessels equipped with a ribbon wing with 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 E2 was obtained.

Examples 1-26, Comparative Examples 1-7
After mixing with a Henschel mixer at the blending ratios shown in Tables 1 and 2, the mixture was melt-kneaded and pelletized using a twin-screw extruder (cylinder setting temperature 220 ° C.). After sufficiently drying the obtained pellets, a test piece for evaluating the appearance of the molded product surface was obtained by injection molding (cylinder setting degree 210 ° C.).
Using a sheet of the above-mentioned polymer A1 having a thickness of 800 μm for the core layer, a three-layer sheet in which the antistatic resin composition is laminated on the front and back surfaces with a thickness of 100 μm is prepared by coextrusion (temperature 220 ° C.) A sheet with a thickness of 1 mm was obtained. This sheet was cut to obtain antistatic evaluation test pieces and chemical resistance evaluation test pieces.
The evaluation method evaluated the antistatic property, the chemical resistance, and the molded product surface appearance.
Moreover, the said sheet | seat obtained in Example 1, 4, 6, 8, 9, 11, 13, 23 and 24 was preheated at the temperature of 200 degreeC, and vacuum forming was performed, and the tray molded product was obtained. And the surface specific resistance of the corner vicinity of a tray molded product was measured by the method similar to the said antistatic property measuring method.
The evaluation results are shown in Tables 1 and 2.

Examples 1 to 5 and Comparative Examples 1 to 3 are examples and comparative examples relating to the first antistatic resin composition of the present invention, and Examples 6 to 10 and Comparative Examples 4 and 5 are examples of the present invention. It is an Example and comparative example regarding a 2nd antistatic resin composition. Furthermore, Examples 11 to 26 and Comparative Examples 6 and 7 are examples and comparative examples relating to the third antistatic resin composition of the present invention.
From the results shown in Tables 1 and 2, the following is clear.
The molded products of Examples 1 to 26 of the present invention are excellent in antistatic property, chemical resistance, and molded product surface appearance.
Comparative Example 1 is an example in which the amount of the component (A) used in the present invention is large outside the scope of the invention, and the amount of the component (B) used is small outside the scope of the invention. Inferior. Comparative Example 2 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. Inferior. Comparative Example 3 is an example in which the amount of the component (C) of the present invention is small outside the scope of the invention, and the antistatic property is inferior. Comparative Example 4 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 chemical resistance and the molded product surface appearance are 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 the chemical resistance and the molded product surface appearance are poor. Comparative Example 6 is an example in which the amount of component (A) used in the present invention is small outside the scope of the invention, and the amount of component (E) used is large outside the scope of the invention, and the antistatic property and chemical resistance are poor. . Comparative Example 7 is an example in which the amount of the component (C) used in the present invention is small outside the scope of the invention, and the antistatic property is inferior to that of Examples 11 to 26 series.

The antistatic resin composition of the present invention is superior in antistatic properties, chemical resistance, and surface appearance of molded products, which are unprecedented, so that high performance is required, such as the vehicle field, the electric / electronic field, It can be applied as various parts in the OA / home appliance field, sanitary field, etc.

Claims (8)

(A) 70 to 97% by mass of an olefin resin,
(B) 3-30% by mass of a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2),
(However, the total of the components (A) and (B) is 100% by weight)
(C) 0.01 to 10 parts by mass of a nonionic antistatic agent with respect to 100 parts by mass in total of the above component (A) and component (B),
An antistatic resin composition comprising: (A) 30 to 96% by mass of an olefin resin,
(B) 3-30% by mass of a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2),
(D) A block copolymer having a polymer block (D-1) mainly composed of an aromatic vinyl compound and a polymer block (D-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof of 1 to 40 masses %,
(However, the total of the components (A), (B), and (D) is 100% by weight)
(C) 0.01 to 10 parts by mass of a nonionic antistatic agent relative to a total of 100 parts by mass of the component (A), the component (B), and the component (D),
An antistatic resin composition comprising: (A) 12 to 91% by mass of an olefin resin,
(B) 3-30% by mass of a block copolymer having an olefin polymer block (B-1) and a hydrophilic polymer block (B-2),
(D) A block copolymer having a polymer block (D-1) mainly composed of an aromatic vinyl compound and a polymer block (D-2) mainly composed of a conjugated diene compound and / or a hydrogenated product thereof of 1 to 40 masses %,
(E) 5-40% by mass of a styrene resin,
(However, the total of the components (A), (B), (D), and (E) is 100% by weight)
(C) 0.01 to 10 parts by mass of a nonionic antistatic agent with respect to 100 parts by mass in total of the above component (A), component (B), component (D), and component (E),
An antistatic resin composition comprising: The said (E) component consists of the following (E-1) component and / or the following (E-2) component, The composition of Claim 3.
Component (E-1): A monomer component comprising an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the rubbery polymer (a). A rubber-reinforced styrenic resin obtained by polymerizing (b),
Component (E-2): Styrenic resin obtained by polymerizing the monomer component (b) in the absence of the rubbery polymer (a). The composition according to any one of claims 1 to 4, comprising at least one salt (F) selected from the group consisting of alkali metals and alkaline earth metals. A molded article comprising the antistatic resin composition according to any one of claims 1 to 5. The molded article according to claim 6, which is a sheet or a film. The multilayer sheet or multilayer film formed by laminating the sheet or film comprising the antistatic resin composition according to any one of claims 1 to 5 on at least one surface of the sheet or film comprising the olefin resin. Molding.