JP5578751B2 - Antistatic thermoplastic resin composition - Google Patents

Description

BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition having a polar group and having excellent antistatic properties, and particularly relates to a thermoplastic resin composition having excellent antistatic properties and excellent thermal stability and physical properties during molding. .

[Prior art]
Conventionally, thermoplastic polyester elastomers and thermoplastic polyurethane elastomers have excellent wear resistance and mechanical strength, and are widely used. Conductive thermoplastic polyurethane elastomers containing a conductive filler are also widely used.
In recent years, with the rapid spread of precision equipment, a higher anti-static function is required, and the conventional antistatic level is no longer sufficient in terms of stability and durability.

For example, a composite of a thermoplastic polyester elastomer and a thermoplastic polyurethane elastomer with a conductive filler typified by carbon black is excellent in conductivity, but it causes a decrease in flexibility and workability, and a decrease in wearability. There is a problem such as instability of the conductive performance due to the dropping of the conductive material due to the above.
Further, since the conductive filler is black, the color tone of the molded product is limited to black, and there is a problem that the design is poor.

Further, antistatic compositions as materials such as IC trays used for packaging IC chips have been studied for weight reduction, thinning, and compactness, and tend to require strength and high rigidity. It is in. Furthermore, for the purpose of identifying the type of IC, there are design requirements such as the colorability of trays and carrier tapes. Carbon black, which is widely used in conductive fillers, is economical and can be obtained with a low resistance value. However, it is generally limited to black, and generally has problems with workability and material strength. Therefore, it is usually used in combination with various modifying materials.

Antistatic agents include a surface active type that bleeds on the surface and has a function, and an antistatic agent that exhibits a function by polymer-alloying a hydrophilic polymer material called a so-called polymer type antistatic agent. The polymer antistatic agent imparts permanent antistatic performance to a thermoplastic resin by polymerizing a hydrophilic polymer, and has high industrial utility value. However, the amount of antistatic resin to be alloyed needs to be relatively large, and since the antistatic resin is a hydrophilic segment and has a lot of flexibility, the rigidity of the resin is reduced and molding is performed. Deformation of the product occurs. For these resins, modification has been attempted by using an inorganic filler, glass fiber, etc. in the same manner as in the above antistatic composition, but on the surface, uneven gloss, weld marks, flash marks, Fluffing occurs and the surface smoothness of the molded product is not satisfactory. When the surface smoothness is inhibited, the surface specific resistance value varies, and the antistatic function is inhibited by affecting the contact state of the electrical / electronic product.
In any case, the surface specific resistivity, which is usually an index of the antistatic level, is 10 ¹¹ to 10 ¹³ Ω / sq. And the volume resistivity is 10 ¹¹ to 10 ¹³ Ω · cm.

In recent years, due to high performance and large capacity of ICs and LSIs, the electrical resistivity required for packaging applications such as trays has a surface resistivity of 10 ¹¹ Ω / sq. In the following, the volume resistivity is required to be 10 ¹¹ Ω · cm or less, and the level of the so-called conventional antistatic region is not sufficient. And in order to satisfy | fill this electrical property, the example which uses carbon black is overwhelmingly. However, this leads to a decrease in strength and flexural modulus, so that a relatively large amount of inorganic filler is generally added (Japanese Patent Laid-Open No. 59-96142).
However, mica and talc, which are widely used as inorganic fillers, are added in a relatively large amount. Therefore, in materials composed of conductive fillers, workability and impact strength are reduced. In addition to being promoted, there are problems such as increased conductivity variation.

On the other hand, in order to prevent the deterioration of the strength characteristics, there are examples in which chop fibers such as glass fiber and carbon fiber are used in combination, but these chop fibers are effective in imparting rigidity and strength, but uneven gloss. In terms of weld marks, flash marks, fluffing, etc., the surface smoothness of the molded product is not satisfactory. Furthermore, as the surface condition of the molded product deteriorates, the contact with the equipment becomes insufficient, which causes trouble.

In recent years, these thermoplastic elastomers have been used for new applications by adding various modifiers and mixing them with other polymers (forming polymer blends and polymer alloys) for the purpose of enhancing functionality. Corresponding attempts have been made.

On the other hand, there are various cases where the addition of these modifiers accelerates the thermal decomposition of the thermoplastic elastomer and other additional polymers. Further, if the molding process is performed for a long time, problems such as a decrease in molecular weight due to thermal decomposition of the resin, a decrease in physical properties, a deterioration in molding processability, and an aging of the molding machine may occur.

[Problems to be solved by the invention]
As a result of intensive studies to solve the above-described conventional technical problems, the present inventors have found that a thermoplastic elastomer having a polar group is a copolymer of ethylene and (meth) acrylic acid or a salt thereof and / or cyclic. By adding a metal salt composed of an imino ether compound and an alkali metal or alkaline earth metal cation and an anion capable of ion dissociation, the surface resistivity is 10 ¹¹ Ω / sq. An antistatic thermoplastic resin composition excellent in thermal stability, physical properties, etc., having a volume resistivity of not more than 10 ¹¹ Ω · cm and not causing foaming during molding. And reached the present invention.

［式中、ＸおよびＤはそれぞれ独立して２価の炭化水素基である］で表わされる環状イミノエーテル化合物 ０．０１〜１５重量部、および
（ｃ）過塩素酸リチウムＬｉＣｌＯ₄、過塩素酸ナトリウムＮａＣｌＯ₄、過塩素酸マグネシウムＭｇ（ＣｌＯ₄）₂、過塩素酸カリウムＫＣｌＯ₄、トリフルオロメタンスルホン酸リチウムＬｉ（ＣＦ₃ＳＯ₃）、ビス（トリフルオロメタンスルホニル）イミドリチウムＬｉ・Ｎ（ＣＦ₃ＳＯ₂）₂、ビス（トリフルオロメタンスルホニル）イミドカリウムＫ・Ｎ（ＣＦ₃ＳＯ₂）₂、ビス（トリフルオロメタンスルホニル）イミドナトリウムＮａ・Ｎ（ＣＦ₃ＳＯ₂）₂、トリス（トリフルオロメタンスルホニル）メタンリチウムＬｉ・Ｃ（ＣＦ₃ＳＯ₂）₃およびトリス（トリフルオロメタンスルホニル）メタンナトリウムＮａ・Ｃ（ＣＦ₃ＳＯ₂）₃である群から選ばれる１つ又はそれ以上の金属塩 ０．００１〜５重量部
を含む事を特徴とする制電性熱可塑性樹脂組成物である。 [Means for Solving the Problems]
That is, the present invention includes the following components:
(A) 100 parts by weight of a thermoplastic elastomer having a polar group,
(B) a copolymer of ethylene and (meth) acrylic acid or an alkyl ester or salt thereof having 1 to 10 carbon atoms, and / or the following formula

[Wherein X and D are each independently a divalent hydrocarbon group] 0.01-15 parts by weight of a cyclic iminoether compound, and (c) lithium perchlorate LiClO ₄ , perchloric acid Sodium NaClO ₄ , magnesium perchlorate Mg (ClO ₄ ) ₂ , potassium perchlorate KClO ₄ , lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), bis (trifluoromethanesulfonyl) imidolithium Li · N (CF ₃ SO _{2) 2,} bis (trifluoromethanesulfonyl) imide potassium _{K · N (CF 3 SO 2} ) 2, bis (trifluoromethanesulfonyl) imide sodium _{Na · N (CF 3 SO 2} ) 2, tris (trifluoromethanesulfonyl) methane lithium _{li · C (CF 3 SO 2} ) 3 and tris (trifluoromethane ) Methane sodium _{Na · C (CF 3 SO 2} ) 1 or antistatic thermoplastic resin composition characterized by comprising a further metal salt 0.001 parts by weight selected from the group of ₃ It is.

DETAILED DESCRIPTION OF THE INVENTION
Each component of the thermoplastic resin of this invention is demonstrated below.
Component (a): Thermoplastic elastomer having a polar group The component (a) used in the composition of the present invention may be any as long as it has a polar group in its molecular structure. amide resins, polyester elastomers, polyurethane elastomers, and polyamide elastomer are preferable.

(A-1): Polyetheresteramide resin (a-1) The polyetheresteramide resin of the present invention is a kind of a polymeric nonionic surfactant having a polyether segment. Specific examples include antistatic elastomers having polyether segments such as polyethylene glycol polyesteramide copolymers.

(A-2): Polyester-based elastomer The polyester-based elastomer which is the component (a-2) of the present invention is a polyether or polyester having a low glass transition temperature (Tg) as a soft segment and a polyester as a hard segment in the molecule. Is a multi-block copolymer. Specifically, as a hard segment, an aromatic crystalline polyester such as polybutylene terephthalate, a polyester / polyether type using polyether as a soft segment, an aromatic crystalline polyester as a hard segment, as a soft segment Examples include polyester / polyester molds using aliphatic polyester.

The polyester / polyether type is synthesized by a transesterification reaction or a polycondensation reaction using, for example, dimethyl terephthalate, 1,4-butanediol and polytetramethylene ether glycol as starting materials. As the component (a-2) of the present invention, all ordinary polyester elastomers can be used, and one kind can be used alone, or two or more kinds can be used in combination.

(A-4): Polyurethane elastomer The polyurethane elastomer (a-4) of the present invention is a thermoplastic elastomer having a urethane group. Specifically, it is a linear multi-block copolymer of a polyurethane obtained by the reaction of a long-chain glycol and an isocyanate as a soft segment and a polyurethane composed of a short-chain glycol and an isocyanate as a hard segment. Depending on the case, a crosslinking agent (chain extender) is also used.
Here, examples of the long-chain glycol include polyether oxides such as polyethylene oxide, polypropylene oxide, and copolymers thereof, polyesters such as polyadipate, polylactone, polycarbonate, aliphatics such as polybutadiene and polyisoprene. It is done.

Short chain glycols include aliphatic glycols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, alicyclic glycols such as cyclohexanedimethanol, and hydroquinone bis (2-hydroxyethyl). Aromatic glycols such as ethers are usually used.
On the other hand, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'- and 2,6-toluene diisocyanate (TDI) are used as the isocyanate.
In addition, as the cross-linking agent (chain extender), aromatic diamines such as 3,3-dichloro-4,4-diaminodiphenylmethane (MOCA) are used.
The (a-4) polyurethane elastomer may be used alone or in combination of two or more.

(A-5): Polyamide-based elastomer The polyamide which is the component (a-5) of the present invention is a generic term for amide-based resins having an amide bond in the repeating unit. For example, nylon 6 and nylon 6 , 6, nylon 12 and the like, polyamide polyester copolymer, polyamide polyether copolymer and the like.
The polyamide-based elastomer which is the component (a-5) of the present invention is a generic term for a thermoplastic elastomer having a polyamide constrained phase which is a hard segment and a polyether and / or polyester structure as a soft segment. For example, a polyamide-based elastomer using a PA12 component as a polyamide (PA) constrained phase is obtained by reacting laurolactam, dicarboxylic acid, and polyether diol with water as a lactam ring-opening catalyst under pressure and heating. A telechelic nylon 12 oligomer is obtained and then obtained by a condensation reaction with a polyether diol. In addition to this, PA6 or the like is also used as the polyamide constrained phase.

The polyamide-based elastomer is basically in the form of a polyether block polyamide elastomer or a polyether ester block polyamide elastomer by the above synthesis method, and has various properties depending on the type of diol used. An elastomer is obtained.
Polyamide-based elastomers are excellent in high temperature characteristics, mechanical characteristics, oil resistance, low temperature characteristics, and the like, and are therefore used in a wide range of equipment such as machine parts, automobile parts, and sports goods.

Further, for the purpose of modifying processability and characteristics, it is also possible to mix other resins with polyamide or polyamide-based elastomer and use them in the form of polymer alloy, polymer blend or the like.
The component (a) in the present invention preferably has a glass transition temperature of room temperature or lower.

Component (b): Copolymer of ethylene and (meth) acrylic acid or an alkyl ester or salt thereof having 1 to 10 carbon atoms and a cyclic imino ether compound Component (b) will be described below. A copolymer of ethylene and (meth) acrylic acid or an alkyl ester or salt thereof having 1 to 10 carbon atoms and / or a cyclic imino ether compound can be used.

(B-1): Copolymer of ethylene and (meth) acrylic acid or an alkyl ester or salt thereof having 1 to 10 carbon atoms In the present invention, ethylene and (meth) acrylic acid or an alkylene ester thereof having 1 to 10 carbon atoms Copolymers with alkyl esters or salts are:
Ethylene and general formula (I):

[Chemical 1]
_{CH 2 = C (R 1)} -COOM (I)

[Wherein R ₁ represents hydrogen or a methyl group, M represents a metal such as Li, Na, K, Zn, Mg, Ag, Cu, Ca, Ba, Fe, an alkyl group having 1 to 10 carbon atoms or hydrogen. Represents. ] Is a copolymer with a monomer represented by Examples of the monomer represented by the general formula (I) include methacrylic acid metal salts, acrylic acid metal salts, methacrylic acid esters, acrylic acid esters, methacrylic acid, and acrylic acid. Of these, metal methacrylate is preferred. This copolymer is an ionic copolymer having an ionic crosslink having a high rebound resilience, and specifically a copolymer of ethylene and an unsaturated organic acid such as acrylic acid or methacrylic acid. In addition, it is preferable that all or part of the carboxyl group is neutralized or crosslinked with a metal ion. M in the general formula (I) is preferably Na or Zn.

In the copolymer with ethylene, the monomer preferably occupies 3 to 20% by weight, particularly 4 to 15% by weight. In particular, an ethylene-methacrylic acid metal salt copolymer having a methacrylic acid metal salt content of 3 to 20% by weight, particularly 4 to 15% by weight is preferred. If the monomer is less than 3% by weight, there is a problem that the monomer is not sufficiently dispersed in the resulting composition. If the monomer exceeds 20% by weight, the required resilience cannot be obtained. The copolymer preferably has a melt flow rate of 0.5 to 15 g / 10 min (measured at a temperature of 190 ° C. and a load of 2160 g according to JISK 6760). Here, if necessary, an ethylene-vinyl acetate copolymer and an ethylene-α-olefin copolymer can be blended, and a mixture of three or more kinds of resins can also be used.

(B-2): Cyclic imino ether compound As the cyclic imino ether compound in the present invention, those represented by the following formula (II) are used.

（II）

[Chemical 2]

(II)

In the formula (II), X is a divalent hydrocarbon group, and specific examples include ethylene, substituted ethylene, trimethylene, substituted trimethylene and the like. Examples of the substituent of substituted ethylene or substituted trimethylene include an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and an aralkyl group having 8 to 20 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, isopropyl and the like. Examples of the aryl group include phenyl, naphthyl, diphenyl and the like. Furthermore, the aryl group of the following (III) may be used.

(III)

[Chemical 3]

(III)

(Where R is —O—, —CO—, —S—, —SO ₂ —, —CH ₂ —, —CH ₂ .CH ₂ —, —C (CH ₃ ) ₂ —). Examples of alkyl include cyclohexyl.

Among these, ethylene and trimethylene are particularly preferable as X. The two Xs in the formula (II) are preferably the same as each other, but may be different groups.

D in the formula (II) is a divalent hydrocarbon group, and specific examples thereof include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, and a cycloalkylene having 5 to 12 carbon atoms. Group, an aralkylene group having 8 to 20 carbon atoms, and the like. More specifically, examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexamethylene, octamethylene, nonamethylene and decamethylene, and examples of the cycloalkylene group include cyclohexylene. Examples of the arylene group include phenylene, naphthylene, diphenylene, and the following groups. This D may be the same hydrocarbon group as X described above, or may be different.

(IV)

[Formula 4]

(IV)

(Where R ′ is —O—, —CO—, —S—, —SO ₂ —, —CH ₂ —, —CH ₂ .CH ₂ —, —C (CH ₃ ) ₂ —). In formula (II),

(Ｖ)

[Chemical formula 5]

(V)

The cyclic imino ether represented by the formula forms a 5-membered ring or a 6-membered ring. The 5-membered ring is a compound called bisoxazoline, and the 6-membered ring is a compound called bisoxazine. Specific examples of these compounds include the following compounds.

(I) Bisoxazolines: 2,2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline) ), 2,2'-p-phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4-dimethyl-2-oxazoline), 2,2'-m-phenylene Bis (4-methyl-2-oxazoline), 2,2'-m-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2 ' -Tetramethylenebis (2-oxazoline), 2,2'-hexamethylenebis (2-oxazoline), 2,2'-octamethylenebis (2-oxazoline), 2,2'-decamethylenebis (2-o Sazoline), 2,2'-ethylenebis (4-methyl-2-oxazoline), 2,2'-tetramethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-3,3'- Diphenoxyethane bis (2-oxazoline), 2,2'-cyclohexylene bis (2-oxazoline), 2,2'-diphenylene bis (2-oxazoline).

(Ii) Bisoxazines: 2,2'-methylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-ethylenebis (5,6-dihydro-4H-1,3-oxazine ), 2,2'-propylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-butylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2 '-Hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2' -M-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-naphthylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2'-p. p'-diphenylenebis (5,6-dihydro-4H 1,3-oxazine).

As the cyclic imino ether compound represented by the formula (II) in the present invention, 2,2′-m-phenylenebis (2-oxazoline) is particularly preferable.

By blending the component (b), it is possible to suppress a decrease in the viscosity of the component (a), that is, a decrease in molecular weight.
The compounding quantity of a component (b) is 0.01-15 weight part with respect to 100 weight part of component (a).
The preferred blending amount varies depending on the component (b) used, and when the component (b-1) is used alone, it is preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight, particularly preferably 3 ~ 5 parts by weight. When component (b-2) is used alone, it is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight. When using together component (b-1) and (b-2), it is preferably 0.1 to 15 parts by weight.
When the component (b) is less than the lower limit value, the required viscosity reduction preventing effect cannot be obtained.

Component (c): As the alkali metal or alkaline earth metal cation in the metal salt component (c) composed of an alkali metal or alkaline earth metal cation and an anion capable of ion dissociation , for example, Li ⁺ , Examples thereof include Na ⁺ , K ⁺ , Mg ²⁺ and Ca ²⁺ . Li ⁺ , Na ⁺ and K ⁺ having a small ionic radius are preferable, and lithium ion (Li ⁺ ) is particularly preferable.

Examples of anion capable of ion dissociation include Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ , NO ₃ ⁻ , SCN ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , (CF ₃ SO ₂ ) _{2. ^{N -, (CF 3 SO 2}} ) 3 C - , and the like. ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ and (CF ₃ SO ₂ ) ₃ C ⁻ are preferable, and ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ and (CF ₃ are particularly preferable. ^{_{SO 2) 2 N -, (}} CF 3 SO 2) 3 C - is.

There are many metal salts composed of the above cations and anions. Preferably, lithium perchlorate LiClO ₄ , sodium perchlorate NaClO ₄ , magnesium perchlorate Mg (ClO ₄ ) ₂ , potassium perchlorate KClO ₄ , lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), bis (trifluoro) Lomethanesulfonyl) imidolithium Li · N (CF ₃ SO ₂ ) ₂ , potassium bis (trifluoromethanesulfonyl) imide K · N (CF ₃ SO ₂ ) ₂ , sodium bis (trifluoromethanesulfonyl) imide Na · N (CF ₃ SO _{2) 2,} tris (trifluoromethanesulfonyl) methane lithium Li · C (CF ₃ SO _{2) 3,} tris (trifluoromethanesulfonyl) methane sodium Na · C (CF ₃ SO _{2) 3.} More preferred are lithium perchlorate, sodium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide and lithium tris (trifluoromethanesulfonyl) methane. Particularly preferred are lithium perchlorate, sodium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, and tris (trifluoromethanesulfonyl) methanelithium.

  By adding the component (c), the surface resistivity and volume resistivity of the resulting resin composition can be reduced. The compounding amount of component (c) is 5 parts by weight, preferably 3 parts by weight, more preferably 2 parts by weight with respect to 100 parts by weight of component (A). The lower limit is 0.001 part by weight, preferably 0.01 part by weight, more preferably 0.02 part by weight. If the amount is less than the above lower limit, it is difficult to obtain sufficient conductivity. On the other hand, if the amount exceeds the above upper limit, the progress of crystallization, material deterioration, etc. are caused and the antistatic effect is lowered.

  The thermoplastic resin composition of the present invention can further contain the following component (d).

Component (d): The organic compound component (d ) that dissolves the component (c) is used in the resin composition of the present invention, the solubility of the metal salt of the component (c) in the component (a) and the alkali metal or alkaline earth. This improves the dissociation stability of the metal cation.

Preferably, component (d) has a-{O (AO) n}-group (A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 7), and all molecular chains. It is an organic compound whose terminal is a CH ₃ group and / or a CH ₂ group. The CH ₂ group at the end of the molecular chain has a carbon atom having a double bond.

  Component (d) is, for example, an alcohol obtained by adding 1 to 7 moles of an alkylene oxide having 2 to 4 carbon atoms to 1 mole of a linear or branched aliphatic alcohol having 1 to 9 carbon atoms, a dibasic acid, Can be produced by a general method for producing an ester compound.

  Examples of the alcohol include 1 to 7 mol of ethylene oxide, 1 to 4 mol of propylene oxide, or 1 to 3 mol of butylene oxide to 1 mol of propanol, and 1 to 6 mol of ethylene oxide or 1 to 3 mol of propylene oxide to 1 mol of butanol. 1 mol of hexanol, 1 to 2 mol of ethylene oxide, 1 mol of ethylene oxide to 1 mol of propylene oxide, 1 to 2 mol of propylene oxide, 1 to 2 mol of butylene oxide, 1 mol of ethylene oxide to 1 mol of octanol, propylene oxide 1 to 3 mol, or 1 to 3 mol of butylene oxide, 1 mol of nonanol, and 1 to 4 mol of ethylene oxide, 1 to 2 mol of propylene oxide, or 1 to 2 mol of butylene oxide are added.

  Of these compounds, 2- (2-butoxyethoxy) ethanol in which 2 mol of ethylene oxide is added to 1 mol of butanol, and 2-butoxyethanol in which 1 mol of ethylene oxide is added to 1 mol of butanol, It is preferable in terms of balance.

  Examples of the dibasic acid include carboxylic acids such as adipic acid, sebacic acid, phthalic acid, and succinic acid, and carboxylic acid anhydrides thereof.

  The component (d) produced using the above raw material is preferably a compound that is an alkyl group having no hydroxyl group at the terminal.

More preferably, component (d) is a compound represented by the following general formula (VI).

[Chemical 6]
COO (AO) _n Q
｜
Z (VI)
｜
COO (AO) _n Q

In the above formula, Z represents a linear or branched alkylene group having 1 to 9 carbon atoms, a divalent hydrocarbon group containing an aromatic group, or a divalent alicyclic hydrocarbon group, and A is each independently Represents an alkylene group having 2 to 4 carbon atoms, Q represents independently a linear or branched alkyl group having 1 to 9 carbon atoms, and n represents an integer of 1 to 7 each independently. .

Particularly preferably, dibutoxyethoxyethyl adipate represented by the following chemical formula (VII) (bis [2- (2butoxyethoxy) ethyl] adipate) or bis (2-butoxyethyl) phthalate represented by the following chemical formula (VIII) It is.

[Chemical 7]
COO (CH ₂ CH ₂ O) ₂ C ₄ H ₉
│
(CH ₂ ) ₄ (VII)
│
COO (CH ₂ CH ₂ O) ₂ C ₄ H ₉

[Chemical 8]
COOCH ₂ CH ₂ OC ₄ H ₉
│
Ph (VIII)
│
COOCH ₂ CH ₂ OC ₄ H ₉

Component (d) is preferably blended so that the weight ratio of component (d) / component (c) is in the range of 1/1 to 99/1. More preferably, it is in the range of 2/1 to 19/1, and more preferably 3/1 to 9/1. By setting the blending amount of the component (d) within the above range, stable conductivity without bleeding can be obtained. If the above upper limit is exceeded, the viscosity of the resulting composition is remarkably lowered, the moldability such as drawdown is lowered, the dimensional stability of the molded product is deteriorated, and the physical properties are lowered.
In order to facilitate handling, an organic compound that is liquid at room temperature is preferred.

The thermoplastic resin composition of the present invention can further contain the following component (e) as long as the antistatic property is not impaired, and can enhance the thermal stability of the resin composition.
Component (e): Nonpolar thermoplastic elastomer and polar resin component (e) having a glass transition temperature of room temperature or higher include, for example, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), etc. Vinyl monomer polymers or copolymers of polystyrene resins, acrylate / methacrylate resins, etc .; low density polyethylene, medium density polyethylene, high density polyethylene, low pressure low density polyethylene, polypropylene, polybutene-1, poly 4-methylpentene Polyolefins such as -1; copolymers of α-olefins or α-olefins with other monomers, such as propylene-ethylene block copolymers and propylene-ethylene random copolymers; other polyolefin resins ; Nylon 6, nylon 6, polyamides such as nylon 12; aromatic polyesters and aliphatic polyesters such as polyethylene terephthalate and polybutylene terephthalate; liquid crystal polyesters; aromatic polyethers such as polyphenylene oxide; polyacetal resins and polycarbonate resins; polyimides, polysulfones, poly Examples include sulfone polymers such as ether sulfone; epoxy resins, phenol resins, diallyl phthalate resins, melamine resins, and the like.

In the present invention, one or a mixture of two or more of the above thermoplastic resins is appropriately selected according to the purpose.
Among them, from the viewpoint of moldability, vinyl monomer polymers or copolymers such as polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymers (ABS resins); polypropylene, crystalline propylene-ethylene copolymers and crystals Preferred are crystalline propylene copolymers such as crystalline propylene-butene 1 copolymer, nylon, polybutylene terephthalate, etc., and vinyls such as polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene terpolymers (ABS resin) in particular. Monomer polymers or copolymers are preferred.
From the viewpoint of heat resistance, polycarbonate, polyethylene terephthalate, aromatic polyimide, aromatic polyether and the like are preferable.
By forming the antistatic resin composition of the present invention in the form of a polymer alloy with the component (e), the antistatic resin composition is dispersed in the component (e), and as a result, the antistatic effect is obtained. A resin composition having thermal stability is obtained.

The range of the amount of component (e) added to 100 parts by weight of component (a) is preferably 50 to 3500 parts by weight, more preferably 100 to 3500 parts by weight.
In particular, when the component (a) is a polyether ester amide, 200 to 3500 parts by weight are preferable.

The antistatic thermoplastic resin composition of the present invention includes various fillers, stabilizers, colorants, reinforcing rubbers, elastomer components, plasticizers, dispersants, ultraviolet absorbers, antioxidants, flame retardants, stabilizers. Additives such as reinforcing agents, lubricants, foaming agents, weathering (light) agents, and metal powders can be appropriately blended.

The thermoplastic resin composition of the present invention can be used as a pellet compound which is a normal secondary processing raw material form by premixing each component, melt-kneading them. By processing the pellets, various components can be uniformly pre-dispersed and stability as a polymer characteristic can be obtained.
As a premixer used in the processing of the pellet compound, a blender for the purpose of predispersion, distribution and diffusion mixing is used. Typical examples of the blender include a ribbon blender, a Henschel mixer (super mixer), a tumbler mixer, a tumble mixer, and an air blender. These premixers are selected according to the form and diffusion level of each compound and the melt kneader. Further, without using the premixer, each component may be charged into the melt-kneader using a quantitative cutting machine such as a different Brabender or a quantitative liquid adding device.
Generally as a melt kneader, a single screw, a twin screw extruder, a Banbury type, a roll type etc. are mentioned. These can also be selected according to the form, purpose and productivity of the composition, and melt-kneaded to produce a pellet-shaped raw material.

The thermoplastic resin composition of the present invention can also be used as a powder obtained by dry blending each component. It is also possible to produce a raw material of a powdery mixture by dry blending using a premixer used in the processing of the pellet compound.

The thermoplastic resin composition of the present invention can be applied to all molding methods, and can be molded by various molding machines such as extrusion molding including profile extrusion, injection molding, blow molding, calendar molding, vacuum molding, and emboss molding.
The above-mentioned various molding machines can adopt general specifications that are usually used.

The thermoplastic resin composition of the present invention makes use of its excellent characteristics, that is, makes use of medium uniform and stable conductivity, and can be used for various applications. As described above, the carbon black-containing resin has a drawback that a medium uniform and stable conductivity cannot be obtained. Conventionally, the thermoplastic resin of the present invention is suitable for the following various uses that require moderate conductivity, which has been used for carbon black-containing resins because there are no substitutes, while recognizing the drawbacks. A composition may be used. For example, LCD-related fields, LSI-related fields, IC-related fields, OA equipment, AV equipment, home appliances and other fields that require electrical conductivity or antistatic properties, especially printers and copiers using electrophotographic technology It can be used very favorably for charging, developing and transfer rolls. The conductive roll is suitable for applications such as printers using electrophotography and electrostatic recording. In recent years, with the advancement of electrophotographic technology, a semiconductive elastic roll has attracted attention as a transfer material of a dry electrophotographic apparatus, a contact charging member for toner, and the like, and is used for a developing roll, a transfer roll, and the like. It can be suitably used for home appliance cover, OA device cover, FD case cover, antistatic cover, antistatic thin plate, antistatic bag, IC cover tape, antistatic clothing, aseptic clothing and the like.

【Example】
EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited by these Examples. In the examples, parts and% are based on weight unless otherwise specified.

The components used in Examples and Comparative Examples are as follows.
<Component (a)>
(1) Perprene P-70B (trademark): manufactured by Toyobo Co., Ltd.
Type: Polyether / ester thermoplastic polyester elastomer (TPEE)
(Tg: -10 ° C or less)

(2) Pandex T-8180N (trademark): DIC Bayer Co., Ltd. Type: Thermoplastic polyurethane elastomer (TPUE)
(Tg: -10 ° C or less)

(3) Pelestat NC6321 (trademark): Sanyo Chemical Industries, Ltd. Type: Polyetheresteramide (PEEA)
(Tg: −45 to −55 ° C.)

(4) Pebax 2533SA01 (trademark): Toray Industries, Inc. Type: Thermoplastic polyamide elastomer (TPAE)
(Tg: -60 to -70 ° C)

<Component (b)>
(B-1): High Milan 1605 (trademark); Mitsui DuPont Polychemical Co., Ltd. Type: Ethylene-methacrylic acid copolymer ionomer (Na ion system)
(B-2): CP Resin A (trademark); Mikuni Pharmaceutical Co., Ltd. Type: 2,2 ′-(1,3) -phenylene-bis (2-oxazoline)
(Abbreviation: 1,3-PBO)

<Component (c):>
(1) LiClO ₄ : lithium perchlorate (2) LiN (CF ₃ SO _{2) 2} : bis (trifluoromethanesulfonyl) imide lithium (3) LiCF ₃ SO ₃ : lithium trifluoromethanesulfonate:

<Component (d)>
Dibutoxyethoxyethyl adipate (compound represented by the following formula (IX)); manufactured by Sanko Chemical Co., Ltd.

[Chemical 9]
COO (CH ₂ CH ₂ O) ₂ C ₄ H ₉
│
(CH ₂ ) ₄ (IX)
│
COO (CH ₂ CH ₂ O) ₂ C ₄ H ₉

<Component (e):>
(1) KODA PETG 6763 (trademark): manufactured by Eastman Chemical Type: polar resin, PETG (compound represented by the following formula (X))
(Tg: 81 ° C)

(Ｘ)

（２）ユーピロンＳ−１０００Ｒ （商標）：三菱ガス化学製
種類：極性樹脂、ポリカーボネート
（Ｔｇ：１４５〜１５５℃）
[Chemical Formula 10]

(X)

(2) Iupilon S-1000R (trademark): manufactured by Mitsubishi Gas Chemical Type: polar resin, polycarbonate (Tg: 145 to 155 ° C.)

Examples According to the formulation shown in the table below, components (a) to (e) were melt kneaded at a kneading temperature of 190 ° C. to 230 ° C. in a twin screw extruder having a diameter of 47 mm. Examples 1-4 and Comparative Examples 1-4 were 220 ° C., Examples 5-7 and Comparative Examples 5-6 were 200 ° C., Examples 8 and 7 were 220 ° C., Examples 9 and 8 were 210 ° C. C., Example 10 and Comparative Example 9 were 230.degree. Tables 1 and 2 below show the results of the antistatic properties (volume resistivity, surface resistivity) and moldability (foamability) of the obtained resin composition.

The evaluation methods used in the examples and comparative examples are as follows.
<Preparation of test piece and moldability (foaming property)>
The sample pellets were supplied to an injection molding machine having a clamping force of 120 ton and retained at a predetermined temperature in the injection molding machine, and then molded, and the state of the molded product was observed. The molding conditions were: cylinder temperature = 200 or 230 ° C., mold temperature = 40 ° C., and a film gate having a width of 40 × thickness of 0.5 mm was used as the gate. The specimen shape is a plate having a thickness of 3 mm, and the outer dimension is 80 × 40 mm. The presence or absence of foaming of the molded product was confirmed visually.

<Surface specific resistivity, volume specific resistivity (antistatic)>
Measurement was performed according to ASTM D257 using Hiresta manufactured by Mitsubishi Chemical Corporation using an injection-molded test piece of width 6 × length 6 × thickness 0.3 (cm). The measurement conditions were a temperature of 23 ° C., a humidity of 50%, and an applied voltage of 500V.

[Table 1]

[Table 2]

As is apparent from the table, the thermoplastic resin compositions according to the present invention of Examples 1 to 10 have a volume resistivity of 10 ¹¹ Ω · cm or less and a surface resistivity of 10 ¹¹ Ω / sq. In addition, foaming did not occur in molding at 200 ° C. or 230 ° C.
On the other hand, all of the resin compositions of Comparative Examples 1 to 3 and 5 to 9 that do not contain the component (b) cause foaming at the time of molding, and cannot accurately measure the volume resistivity and surface resistivity. It was. Further, Comparative Example 4 not containing the component (c) has a volume resistivity of 10 ¹² Ω · cm or more and a surface resistivity of 10 ¹² Ω / sq. That is the above, and the antistatic property was inferior.

【Effect of the invention】
The present invention provides a thermoplastic resin composition having excellent antistatic properties and excellent heat stability during molding, physical properties, and the like.

Claims (6)

The following ingredients:
(A) 100 parts by weight of a thermoplastic elastomer having a polar group,
(B) a copolymer of ethylene and (meth) acrylic acid or an alkyl ester or salt thereof having 1 to 10 carbon atoms, and / or the following formula

[Wherein X and D are each independently a divalent hydrocarbon group] 0.01-15 parts by weight of a cyclic iminoether compound, and (c) lithium perchlorate LiClO ₄ , perchloric acid Sodium NaClO ₄ , magnesium perchlorate Mg (ClO ₄ ) ₂ , potassium perchlorate KClO ₄ , lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), bis (trifluoromethanesulfonyl) imidolithium Li · N (CF ₃ SO _{2) 2,} bis (trifluoromethanesulfonyl) imide potassium _{K · N (CF 3 SO 2} ) 2, bis (trifluoromethanesulfonyl) imide sodium _{Na · N (CF 3 SO 2} ) 2, tris (trifluoromethanesulfonyl) methane lithium _{li · C (CF 3 SO 2} ) 3 and tris (trifluoromethane ) Methane sodium _{Na · C (CF 3 SO 2} ) 1 or antistatic thermoplastic resin composition characterized by comprising a further metal salt 0.001 parts by weight selected from the group of ₃ . Component (a) is a polyether ester amide elastomer, polyester elastomer, Polyurethane elastomers, and antistatic according to claim 1, wherein a is at least one or more selected from the group of polyamide elastomer Thermoplastic resin composition.
The component (d) further contains an organic compound that dissolves the component (c). The component (d) is a — {O (AO) _n } — group (A is an alkylene group having 2 to 4 carbon atoms, n is 1 The antistatic thermoplastic resin composition according to claim 1, wherein the composition is an organic compound having all of the molecular chain terminals composed of CH ₃ groups.
The antistatic thermoplastic resin composition according to claim 3, wherein the weight ratio of component (d) / component (c) is from 1/1 to 99/1.
Component (c) is lithium perchlorate LiClO ₄ , sodium perchlorate NaClO ₄ , lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), bis (trifluoromethanesulfonyl) imidolithium Li · N (CF ₃ SO ₂ ) ₂ , Sodium bis (trifluoromethanesulfonyl) imide Na · N (CF ₃ SO ₂ ) ₂ , tris (trifluoromethanesulfonyl) methane lithium Li · C (CF ₃ SO ₂ ) ₃ and tris (trifluoromethanesulfonyl) methane sodium Na · C (CF ₃ SO ₂₎ 1 or antistatic thermoplastic resin composition according to any one of claims 1 to 4, characterized in that more than is possible selected from ₃ at which the group.
The non-polar thermoplastic elastomer and / or the polar resin having a glass transition temperature of room temperature or higher is further contained as a component (e) in an amount of 100 to 3 parts by weight of the component (a). The antistatic thermoplastic resin composition according to any one of 1 to 5.