JP2011153301A - Resin composition for molded article for living material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for molded articles for living materials, which gives the molded articles for the living materials, having a sufficiently permanent antistatic property without deteriorating the excellent mechanical characteristics and good appearance of thermoplastic resin molded articles, even when the content of an antistatic agent is smaller than those of conventional resin compositions. <P>SOLUTION: There are provided the resin composition for: molded articles for living materials, comprising an antistatic agent (A) and a thermoplastic resin (B), wherein the melt-viscosity ratio of (B) to (A) at 220°C is 0.5-5, and the absolute value of a difference between solubility parameters is 1.0-3.0; and the molded article for living materials, formed from the composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a resin composition for molded articles for living materials. More specifically, the present invention relates to a resin composition for molded articles for living materials that imparts excellent permanent antistatic properties to the molded article without impairing the excellent mechanical properties and good appearance of the thermoplastic resin molded article.

  Conventionally, as resins for molded articles for living materials, impact-resistant polystyrene (HIPS), polycarbonate (PC), acrylonitrile / butadiene / styrene copolymer (ABS resin), alloys thereof (PC / ABS resin, etc.), Thermoplastic resins such as polypropylene (PP) and polyethylene (PE) have been commonly used. However, since molded products obtained from these resins have high surface resistivity, once they are charged, there is a drawback that static electricity disappears slowly and dirt such as dust tends to adhere due to electrostatic interaction. Particularly in recent years, the surface of molded articles has become highly glossy, and there has been an increasing demand for preventing the adhesion of dirt. In view of this, various methods for imparting antistatic performance have been proposed in order to prevent dust from adhering to the molded article for living materials.

Known methods for imparting antistatic properties to highly insulating thermoplastic resins include (1) a method of kneading a low molecular weight surfactant and (2) a method of kneading a metal filler or conductive carbon black. However, since the molded product formed by molding the resin composition obtained by the method (1) exhibits an effect by bleeding out of the low molecular weight surfactant, the antistatic effect is lost by wiping the surface, etc. There is a drawback that surface roughness occurs over time.
In particular, in the molded article for daily use, the user frequently wipes the surface for the purpose of cleaning, and the antistatic performance is often lost. Moreover, although the molded article by the method (2) is excellent in the sustainability of the antistatic effect, there is a problem that impact resistance is lowered because a large amount of metal filler or the like is required. Furthermore, as another method, (3) a proposal has been made that a paint containing an antistatic agent is applied to the surface of a molded article and cured on the surface. However, this method further requires a painting process and a curing process, which is problematic in productivity.

  Therefore, as a method for solving these problems, (4) a method of kneading a polymer type antistatic agent such as polyether ester amide in a resin has been proposed. Furthermore, a method of kneading a polyether ester amide having a specific dicarboxylic acid as a structural unit into the resin (for example, see Patent Document 1) or a method in which an ionic polymer is incorporated into the polyether ester amide in a relatively small amount in the resin. A method of kneading (see, for example, Patent Document 2) has been proposed.

JP-A-11-255894 Japanese Patent Laid-Open No. 5-140541

  However, in the method of kneading the polyether ester amide (4) in the resin, sufficient antistatic properties cannot be imparted with an addition amount of 10% or less, and antistatic properties are satisfactory when added in an amount exceeding 10%. However, there was a drawback that the mechanical properties were lowered. In addition, the method of kneading a small amount of polyether ester amide having a specific structure as exemplified in Patent Documents 1 and 2 does not impair the mechanical properties and appearance of the molded product, but satisfactory antistatic properties. There was a problem that could not be granted.

  The object of the present invention is to provide a molded article having sufficient permanent antistatic properties without impairing the excellent mechanical properties and good appearance of the thermoplastic resin molded article, and even when the content of the antistatic agent is smaller than that of the conventional one. The object is to provide a resin composition for molded articles for living materials.

  The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises an antistatic agent (A) and a thermoplastic resin (B), the melt viscosity ratio at 220 ° C. of (B) and (A) is 0.5 to 5, and the solubility parameter is It is an antistatic resin composition having an absolute difference of 1.0 to 3.0. It contains an antistatic agent (A) and a thermoplastic resin (B), the melt viscosity ratio at 220 ° C. of (B) and (A) is 0.5 to 5, and the absolute value of the difference in solubility parameter is 1. It is a resin composition for molded articles for living materials that is 0.0 to 3.0.

The resin composition for molded articles for living materials of the present invention has the following effects.
(1) A molded article for a living material having excellent permanent antistatic properties is provided even when the content of the antistatic agent in the composition is smaller than that in the prior art.
(2) A molded article for living material formed by molding the composition is excellent in appearance and mechanical properties.

[Antistatic agent (A)]
The antistatic agent (A) in the present invention has a melt viscosity ratio at 220 ° C. of the thermoplastic resin (B) and (A) described later of 0.5 to 5, preferably 0.7 to 3.5, more preferably. 0.8 to 2.5, particularly preferably 0.9 to 1.5, and the absolute value of the difference between the solubility parameters of (B) and (A) (hereinafter abbreviated as SP) is 1.0 to 3.0, The antistatic agent is preferably 1.1 to 2.5, more preferably 1.2 to 2.0.
When either the absolute value of the difference in the melt viscosity ratio or the solubility parameter, or both are out of the above ranges, either the appearance, mechanical properties or antistatic properties of the molded product described later, or any of them Deteriorate.
The point that the effects of the present invention are exhibited when (B) and (A) satisfy the above-described conditions of the absolute value of the difference between the melt viscosity ratio and the SP is not clear about the mechanism, but [1] SP Is within the above range, the dissolution of the antistatic agent in the resin is suppressed, and the antistatic agent easily migrates to the surface layer portion of the molded product, and the antistatic agent concentration in the surface layer portion increases, and [ 2] Even when the concentration of the antistatic agent is increased, if the melt viscosity ratio is in the above range, the dispersibility of the antistatic agent in the resin is good and the appearance and mechanical properties of the molded product are not adversely affected. It is presumed to be caused by

The above melt viscosity is in compliance with JIS K 7199, a capillary rheometer [model number "capillary rheometer PD-C type", Ltd. Toyo Seiki Seisakusho Ltd.] by using, 220 ° C., shear rate 600 sec ^- it can be measured at ^one of the conditions, the melt viscosity ratio of the (B) and (a) can be obtained by the following equation.

Melt viscosity ratio = ρ (B) / ρ (A)

In the formula, ρ (A) and ρ (B) indicate the melt viscosities (unit: Pa · s / shear rate 600 sec ⁻¹ ) of (A) and (B) at 220 ° C. respectively.

Further, SP means an amount defined by the following formula when the cohesive energy density is ΔE (unit is cal / mol) and the molecular volume is V (unit is cm ³ / mol). In the following, each SP in (A) and (B) is denoted as SP _A and SP _B , and the absolute value of the difference between SPs in (A) and (B) is denoted as | SP _A −SP _B |. There is a case.

SP = (ΔE / V) ^1/2 [the unit is (cal / cm ³ ) ^1/2 ]

For example, the Fedors method is known as a specific method for obtaining the SP, and this method, together with the SP obtained by the method, is “A Method for Estimating”.
both the Solubility Parameters and Molecular
Volumes of Liquids, POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, vol. 14, Issue 2, p. 147-154 ", and these can be used in the present invention.

Of the antistatic agents (A) satisfying the absolute value of the difference between the melt viscosity ratio and the SP, a volume specific resistance value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm is preferable from the viewpoint of antistatic properties. At least one block selected from the group consisting of an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond and an imide bond, wherein the block of the hydrophilic polymer (a) and the block of the hydrophobic polymer (b) are It is a block polymer having a structure in which bonds are alternately bonded via bonds.

[Hydrophilic polymer (a)]
Examples of the hydrophilic polymer (a) constituting the block polymer include at least one selected from the group consisting of polyether (a1), cationic polymer (a2), and anionic polymer (a3).

Examples of the polyether (a1) include polyether diol (a11), polyether diamine (a12), and modified products (a13) thereof.
Examples of the cationic polymer (a2) include a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated by a nonionic molecular chain (c1) in the molecule. .
As the anionic polymer (a3), a dicarboxylic acid (e1) having a sulfonyl group and a diol (a0) or a polyether (a1) are essential structural units, and 2 to 80, preferably 3 to Examples include anionic polymers having 60 sulfonyl groups.

The polyether (a1) will be described.
Among (a1), the polyether diol (a11) has a structure obtained by addition reaction of alkylene oxide (hereinafter abbreviated as AO) to the diol (a0). The general formula: H- (OA ¹ ) those represented by ^{_{m -O-E 1 -O- (A}} 1 O) m '-H and the like.
In the formula, E ¹ is a residue obtained by removing a hydroxyl group from diol (a0), A ¹ is an alkylene group having 2 to 4 carbon atoms (hereinafter abbreviated as C), and m and m ′ are per hydroxyl group of diol (a0). Represents the AO addition number. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used. m and m ′ are generally integers of 1 to 300, preferably 2 to 250, and more preferably 10 to 100. M and m ′ may be the same or different.

Examples of the diol (a0) include dihydric alcohols (for example, C2-12 aliphatic, alicyclic and aromatic ring-containing dihydric alcohols), C6-18 dihydric phenols, and tertiary amino group-containing diols.
Examples of the aliphatic dihydric alcohol include alkylene glycol [ethylene glycol, propylene glycol (hereinafter abbreviated as EG and PG, respectively)], 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter 1 each). , 4-BD, 1,6-HD, abbreviated as NPG), 1,12-dodecanediol;
Examples of the alicyclic dihydric alcohol include cyclohexanedimethanol;
Examples of the aromatic ring-containing dihydric alcohol include xylylene diol.
Examples of the dihydric phenol include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenols (bisphenol A, -F and -S).
4,4′-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl and the like) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol and the like).

Examples of the tertiary amino group-containing diol include C1-12 aliphatic or alicyclic primary monoamines (methylamine, ethylamine, 1- and 2-propylamine, hexylamine, decylamine, dodecylamine, cyclopropylamine, And bishydroxyalkylated products of C6-12 aromatic ring-containing primary monoamines (aniline, benzylamine, etc.).
Of these, aliphatic dihydric alcohols and bisphenols are preferred from the viewpoint of antistatic properties, and EG and bisphenol A are more preferred.

The polyether diol (a11) can be produced by adding AO to the diol (a0).
AO includes C2-4 AO [ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, BO, respectively), and Two or more of these combined systems are used, and if necessary, other AO or substituted AO (hereinafter collectively referred to as AO) such as C5-12 α-olefin, styrene oxide, epihalohydrin (epichlorohydrin). Etc.) can be used in a small proportion (for example, 30% or less based on the weight of the total AO).
When two or more kinds of AO are used in combination, the coupling form may be random and / or block. Preferred as AO is EO alone or a combination of EO and another AO (random and / or block addition). The addition number of AO is usually an integer of 1 to 300, preferably 2 to 250, more preferably 10 to 100 per hydroxyl group of the diol (a0).

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. The content of C2-4 oxyalkylene units in (a11) is usually 5 to 99.8%, preferably 8 to 99.6%, more preferably 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is usually 5 to 100%, preferably 10 to 100%, more preferably 50 to 100%, and particularly preferably 60 to 100%.

The polyether diamine (a12) has the general formula: H ₂ N—A ² — (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —A ² —NH ₂ (symbol E in the formula ¹ , A ¹ , m and m ′ are the same as above,
A ² is a C2-4 alkylene group. A ¹ and A ² may be the same or different. ) Can be used.
(A12) can be obtained by changing the hydroxyl group of (a11) to an amino group by a known method. For example, the terminal obtained by cyanoalkylating the hydroxyl group of (a11) is reduced to an amino group. Can be used.
For example, it can be produced by reacting (a11) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

Examples of the modified product (a13) include aminocarboxylic acid modified products (terminal amino groups), isocyanate modified products (terminal isocyanate groups) and epoxy modified products (terminal epoxy groups) of (a11) or (a12). It is done.
The modified aminocarboxylic acid can be obtained by reacting (a11) or (a12) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (a11) or (a12) with a polyisocyanate as described below or reacting (a12) with phosgene.
The epoxy-modified product is obtained by reacting (a11) or (a12) with a diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (a11) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  Number average molecular weight of the polyether (a1) [hereinafter abbreviated as Mn. The measurement is performed by a gel permeation chromatography (GPC) method described later] is usually 150 to 20,000, and preferably 300 to 20,000 from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (b) described later. It is 18,000, more preferably 500 to 15,000, particularly preferably 1,200 to 8,000.

The measurement conditions of Mn are as follows. Hereinafter, Mn is measured under the same conditions.
Equipment: High temperature GPC
Solvent: Orthodichlorobenzene reference material: Polystyrene sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B [Polymer Laboratories
Manufactured by]
Column temperature: 135 ° C

Next, the cationic polymer (a2) will be described. (A2) is a hydrophilic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated in the molecule by a nonionic molecular chain (c1).
Examples of the cationic group (c2) include a group having a quaternary ammonium salt or a phosphonium salt. Examples of the counter anion of (c2) include a super strong acid anion and other anions.
The super strong acid anion includes an anion of a super strong acid (tetrafluoroboric acid, hexafluorophosphoric acid, etc.) derived from a combination of a protonic acid (d1) and a Lewis acid (d2), a super strong acid anion such as trifluoromethanesulfonic acid, etc. Examples include strong acid anions.
Examples of other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^{− and the} like. Can be mentioned.
Specific examples of the protonic acid (d1) that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, and the like.
Specific examples of the Lewis acid (d2) include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.

The nonionic molecular chain (c1) includes a divalent hydrocarbon group, or an ether bond, a thioether bond, a carbonyl bond, an ester bond, an imino bond, an amide bond, an imide bond, a urethane bond, a urea bond, a carbonate bond, and / or Or a divalent organic group such as at least one divalent hydrocarbon group selected from the group consisting of a hydrocarbon group having a siloxy bond and a hydrocarbon group having a heterocyclic structure containing a nitrogen atom or an oxygen atom; These two or more types are used in combination.
Among these (c1), a divalent hydrocarbon group and a divalent hydrocarbon group having an ether bond are preferable.

  Mn of the cationic polymer (a2) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (b) described later. Preferably, it is 1,200 to 8,000.

  Specific examples of the cationic polymer (a2) include cationic polymers described in JP-A No. 2001-278985.

Next, the polymer (a3) having an anionic group will be described. (A3) comprises dicarboxylic acid (e1) having a sulfonyl group and diol (a0) or polyether (a1) as essential structural units, and 2 to 80, preferably 3 to 60 sulfonyls in the molecule. An anionic polymer having a group.
As the dicarboxylic acid (e1), an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, or a salt of only these sulfonyl groups can be used.

Examples of the aromatic dicarboxylic acid having a sulfonyl group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid, and ester-forming derivatives thereof [lower Alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and ester-forming derivatives thereof [lower alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the salts in which only these sulfonyl groups are converted include salts of alkali metals (lithium, sodium, potassium, etc.), salts of alkaline earth metals (magnesium, calcium, etc.), ammonium salts, hydroxyalkyl (C2-4). ) Amine salts, such as mono-, di- and tri-amines having organic groups (organic amine salts such as mono-, di- and tri-ethylamine, mono-, di- and tri-ethanolamine, diethylethanolamine), these Examples include quaternary ammonium salts of amines and combinations of two or more of these.
Among these, preferred are aromatic dicarboxylic acids having a sulfonyl group, more preferred are 5-sulfoisophthalic acid salts, and particularly preferred are 5-sulfoisophthalic acid sodium salt and 5-sulfoisophthalic acid potassium salt.

Among (a0) and (a1) constituting (a3), C2-10 alkanediol, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2-20), bisphenol (bisphenol A, etc.) EO adduct (number of added moles 2 to 60) and a mixture of two or more thereof.
As a manufacturing method of (a3), a normal polyester manufacturing method can be applied as it is. The polyesterification reaction is usually performed in a temperature range of 150 to 240 ° C. under reduced pressure, and the reaction time is 0.5 to 20 hours. Moreover, in this esterification reaction, you may use the catalyst used for normal esterification reaction as needed.
Examples of esterification catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide and dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), and metal acetate. Examples thereof include salt catalysts (such as zinc acetate).

  Mn of (a3) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1 from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (b) described later. , 200-8,000.

[Hydrophobic polymer (b)]
The hydrophobic polymer (b) in the present invention includes at least one hydrophobic polymer selected from the group consisting of polyolefin (b1), polyamide (b2), polyamideimide (b3) and polyester (b4). Here, the hydrophobic polymer means a polymer having a surface resistivity of 1 × 10 ¹⁴ to 1 × 10 ¹⁷ Ω.

As the polyolefin (b1), a polyolefin (b11) having a carbonyl group (preferably a carboxyl group, the same shall apply hereinafter) at both ends of the polymer, a polyolefin (b12) having a hydroxyl group at both ends of the polymer, and an amino group as a polymer The polyolefin (b13) having both ends thereof and the polyolefin (b14) having isocyanate groups at both ends of the polymer can be used.
Further, a polyolefin (b15) having a carbonyl group at one end of the polymer, a polyolefin (b16) having a hydroxyl group at one end of the polymer, a polyolefin (b17) having an amino group at one end of the polymer, and an isocyanate group as a piece of polymer. Polyolefin (b18) having a terminal can be used.
Of these, polyolefins (b11) and (b15) having a carbonyl group are preferable because of easy modification.

As (b11), a carbonyl group is present at both ends of the polyolefin (b10) whose main component (preferably the content is 50% or more, more preferably 75% or more, particularly preferably 80 to 100%). What introduced group is used.
As (b12), those having hydroxyl groups introduced at both ends of (b10) are used.
As (b13), those in which amino groups are introduced at both ends of (b10) are used.
As (b14), those obtained by introducing isocyanate groups at both ends of (b10) are used.

As (b15), one end of a polyolefin (b100) containing a polyolefin whose one end can be modified as a main component (preferably a content of 50% or more, more preferably 75% or more, particularly preferably 80 to 100%) A group into which a group is introduced is used.
As (b16), one obtained by introducing a hydroxyl group at one end of (b100) is used.
As (b17), one obtained by introducing an amino group at one end of (b100) is used.
As (b18), an isocyanate group introduced at one end of (b100) is used.

(B10) means (co) polymerization (polymerization or copolymerization) of one or a mixture of C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And a degraded polyolefin [a product obtained by mechanically, thermally or chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 150,000)] (reduced) Method).
From the viewpoint of easy modification and availability of introduction of a carbonyl group, a hydroxyl group, an amino group or an isocyanate group, a degraded polyolefin, particularly a thermally degraded polyolefin is preferred.
The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804).
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene, C4-12 α-olefin and two or more of these are preferable. More preferred are ethylene, propylene, C4-10 α-olefins and mixtures of two or more thereof, particularly preferred are ethylene, propylene, and mixtures of two or more thereof.

Examples of the C2-30 olefin used for the production of the polyolefin (polymerization method) include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin and C4-30. A diene of (preferably 4-18, more preferably 4-8) is used.
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene.
Examples of the diene include butadiene, isoprene, cyclopentadiene, 1,11-dodecadiene, and the like.
Of these, ethylene, propylene, C4-12 α-olefin, butadiene and isoprene are preferred, ethylene, propylene, C4-10 α-olefin and butadiene are more preferred, and ethylene, propylene and butadiene are particularly preferred. is there.

Mn of polyolefin (b10) mainly composed of polyolefin which can be modified at both ends is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. is there. When Mn is within this range, the antistatic property is further improved.
The amount of double bonds in (b10) is preferably 1 to 40 per 1,000 carbon atoms, more preferably 2 to 30, and particularly preferably 4 to 20. When the amount of the double bond is within this range, the antistatic property is further improved.
The average number of double bonds per molecule is preferably 1.1 to 5.0, more preferably 1.3 to 3.0, particularly preferably 1.5 to 2.5, and most preferably 1.8. ~ 2.2. When the average number of double bonds is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
With low molecular weight polyolefins by thermal degradation, low molecular weight polyolefins with an average terminal double bond amount of 1.5 to 2 per molecule can be easily obtained with Mn in the range of 800 to 6,000 [Katsuhide Murata Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

(B100) can be obtained in the same manner as (b10), and Mn of (b100) is usually 2,000 to 50,000, preferably 2,500 to 30,000, more preferably 3,000 to 20,000.
(B100) has 0.3 to 20 double bonds per 1,000 carbon atoms, preferably 0.5 to 15 and more preferably 0.7 to 10 double bonds. From the viewpoint of easy modification, low molecular weight polyolefins (particularly polyethylene and / or polypropylene having Mn of 2,000 to 20,000) by thermal degradation are preferred.
In the low molecular weight polyolefin by the thermal degradation method, those having an average terminal double bond amount of 1 to 1.5 per molecule are obtained with Mn in the range of 5,000 to 30,000.

  In addition, (b10) and (b100) are usually obtained as a mixture of these, but these mixtures may be used as they are, or may be used after purification and separation. From the viewpoint of production cost and the like, it is preferably used as a mixture.

  Hereinafter, (b11) to (b14) having a carbonyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (b10) will be described, but these groups are present at one end of the polyolefin (b100) (b15). About (b18), (b10) can be replaced with (b100) and similarly obtained according to (b11) to (b14).

As the polyolefin (b11) having carbonyl groups at both ends of the polymer, the end of (b10) is α, β unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, C1-4 alkyl ester thereof) Or an anhydride thereof. The same applies hereinafter.) Polyolefin (b11-1) having a structure modified with (b11-1) and polyolefin (b11-2) having a structure obtained by secondary modification of (b11-1) with lactam or aminocarboxylic acid. ), (B10) a polyolefin (b11-3) having a structure modified by oxidation or hydroformylation, and (b11-3) a polyolefin (b11-4) having a structure secondarily modified with a lactam or aminocarboxylic acid A mixture of two or more of these can be used.

(B11-1) can be obtained by modifying (b10) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid, alkyl (C1-4) ester thereof and anhydride thereof can be used, for example, (meth) acrylic acid (Means acrylic acid or methacrylic acid; the same shall apply hereinafter), methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride) , Diethyl itaconate and citraconic acid (anhydride).
Among these, preferred are dicarboxylic acids, their alkyl esters and their anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably 2 based on the weight of the polyolefin (b10). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
The modification with α, β-unsaturated carboxylic acid (anhydride) can be performed by various methods. For example, the terminal double bond of (b10) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (b10) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(B11-2) can be obtained by secondarily modifying (b11-1) with a lactam or an aminocarboxylic acid.
As the lactam used for the secondary modification, a C6-12 (preferably 6-8, more preferably 6) lactam or the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Among these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferable, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferable. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1-50, more preferably 0.3-20, per carboxyl group of α, β unsaturated carboxylic acid (anhydride). The number is particularly preferably 0.5 to 10, most preferably 1 to 2. When the amount is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.

(B11-3) can be obtained by introducing (b10) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation with an oxo method.
The introduction of the carbonyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, see Macromolecules, Vol. 31, 5943 page.
(B11-4) can be obtained by secondarily modifying (b11-3) with a lactam or an aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (b11-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn in (b11) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.
The acid value of (b11) is preferably 4 to 280 (unit is mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, from the viewpoint of reactivity with (a). Especially preferably, it is 5-50.

As the polyolefin (b12) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying the polyolefin (b11) having a carbonyl group at both ends of the polymer with hydroxylamine and a mixture of two or more of these are used. it can.
Hydroxylamines that can be used for modification include C2-10 hydroxylamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-amino. Examples include hexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.

The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
Mn of (b12) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500, from the viewpoints of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.
The hydroxyl value of (b12) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (a). Preferably it is 5-50.

As the polyolefin (b13) having amino groups at both ends of the polymer, a polyolefin having an amino group obtained by modifying the polyolefin (b11) having the carbonyl group at both ends of the polymer with a diamine (Q1), and two or more of these Mixtures can be used.
As diamine (Q1) used for this modification | denaturation, C2-12 diamine etc. can be used, For example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc. are mentioned.
Among these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.

The amount of diamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, and still more preferably, per residue of α, β unsaturated carboxylic acid (anhydride). 0.5 to 1.2, particularly preferably 1. When the amount of diamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved.
In actual production, 2 to 1,000, more preferably 5 to 800 per residue of α, β unsaturated carboxylic acid (anhydride) are used to prevent polyamide (imide) formation. Particularly preferably, 10 to 500 diamines are used, and it is preferable to remove unreacted excess diamine under reduced pressure (usually 120 ° C. to 230 ° C.).

Mn of (b13) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.
In addition, the amine value of (b13) is preferably 4 to 280 (unit is mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (a), more preferably 4 to 100, Especially preferably, it is 5-50.

  As the polyolefin (b14) having isocyanate groups at both ends, a polyolefin having an isocyanate group obtained by modifying (b12) with poly (2 to 3 or more) isocyanate (hereinafter abbreviated as PI), and a mixture of two or more of these. Can be used. As PI, C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI, C2 to 18 aliphatic PI, C4 to 15 alicyclic PI, and C8 to 15 araliphatic PI , Modified products of these PIs, and mixtures of two or more thereof.

  Specific examples of the aromatic PI include 1,3- and / or 1,4-phenylene diisocyanate (diisocyanate is hereinafter abbreviated as DI), 2,4- and / or 2,6-tolylene DI (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane DI (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI and the like can be mentioned.

  Specific examples of the aliphatic PI include ethylene DI, tetramethylene DI, hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethyl carbonate. Examples include proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Specific examples of the alicyclic PI include isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane DI.

  Specific examples of the araliphatic PI include m- and / or p-xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified PI include urethane-modified, urea-modified, carbodiimide-modified, uretdione-modified, and the like.
Of these, TDI, MDI and HDI are preferred, and HDI is more preferred.

The reaction between (b12) and PI can be carried out in the same manner as a normal urethanization reaction.
The equivalent ratio (NCO / OH ratio) between PI and (b12) in forming the isocyanate-modified polyolefin is usually 1.8 / 1 to 3/1, preferably 2/1.
In order to accelerate the reaction, a catalyst usually used for polyurethane may be used if necessary. Examples of such catalysts include metal catalysts such as tin catalysts [dibutyltin dilaurate, stannous octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal naphthenates] (Cobalt naphthenate, etc.), phenylmercuric propionate, etc.]; amine catalysts such as triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (San Apro Corporation) Manufactured, registered trademark)], etc.], dialkylaminoalkylamine [dimethylaminoethylamine, dimethylaminooctylamine, etc.], heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2 -Hexylamine etc.] carbonates and organic acid salts (eg formate), N-methyl Beauty - ethylmorpholine, triethylamine, diethyl - and dimethylethanolamine; and use of two or more types of system thereof.
The amount of these catalysts used is usually 3% or less, preferably 0.001 to 2%, based on the total weight of PI and (b12).

  Mn in (b14) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2,500 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (a). -10,000.

Among the hydrophobic polymers (b), examples of the polyamide (b2) include those obtained by ring-opening polymerization or polycondensation of amide-forming monomers.
Examples of amide forming monomers include lactam (b21), aminocarboxylic acid (b22), and diamine (b23) / dicarboxylic acid (b24).
Examples of the lactam (b21) include C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of the ring-opening polymer (b21) include nylon 4, -5, -6, -8 and -12.

As aminocarboxylic acid (b22), C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid and mixtures thereof.
Examples of the self-polycondensate of (b22) include nylon 7 by polycondensation of ω-aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid. .

Diamine (b23) includes C2-40, such as aliphatic, alicyclic and aromatic (aliphatic) diamines, and mixtures thereof.
Aliphatic diamines include C2-40, such as ethylene diamine, propylene diamine, hexamethylene diamine, decamethylene diamine, 1,12-dodecane diamine, 1,18-octadecane diamine and 1,20-eicosane diamine.
Alicyclic diamines include C5-40, such as 1,3- and 1,4-cyclohexanediamine, isophorone diamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) propane. It is done.
Examples of araliphatic diamines include C7-20, such as (para or meta) xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (aminobutyl) benzene.
Aromatic diamines include C6-40, such as p-phenylenediamine, 2,4- and 2,6-toluylenediamine and 2,2-bis (4,4'-diaminophenyl) propane.

  Examples of the dicarboxylic acid (b24) include C2-40 dicarboxylic acids such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, derivatives of these dicarboxylic acids [for example, acid anhydrides, lower (C1-4 ) Alkyl esters and dicarboxylates [alkali metal (eg, lithium, sodium and potassium) salts]] and mixtures of two or more thereof.

Examples of the aliphatic dicarboxylic acid include C2-40 (preferably 4 to 20, more preferably 6-12 from the viewpoint of antistatic properties), such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples include sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid and itaconic acid.
Examples of the aromatic ring-containing dicarboxylic acid include C8-40 (preferably 8 to 16, more preferably 8-14 from the viewpoint of antistatic properties), such as ortho-, iso- and terephthalic acid, 2,6- and -2, Examples include 7-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid and 5-sulfoisophthalic acid alkali metal (same as above) salts.
As alicyclic dicarboxylic acid, C5-40 (preferably 6-18, more preferably 8-14 from the viewpoint of antistatic properties), for example, cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, Examples include dicyclohexyl-4,4'-dicarboxylic acid and camphoric acid. Of these, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferable from the viewpoint of antistatic properties, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and sodium 3-sulfoisophthalate are more preferable.
Among the dicarboxylic acid derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride and phthalic anhydride; examples of lower (C1-4) alkyl esters include lower alkyl esters of the above dicarboxylic acids, such as Mention is made of dimethyl adipate and ortho-, iso- and dimethyl terephthalate.

Polycondensates of diamines and dicarboxylic acids include nylon 66, -610, -69 or -612, respectively, and tetramethylene by polycondensation of hexamethylenediamine and adipic acid, sebacic acid, azelaic acid or dodecanedioic acid. Mention may be made of nylon 46 or MXD6 by polycondensation of diamine or metaxylylenediamine and adipic acid.
Examples of the copolymer nylon include nylon 6/66 (adipic acid / hexamethylenediamine nylon salt and caprolactam copolymer) and nylon 6/12 (12-aminododecanoic acid and caprolactam copolymer). .

  Among the amide-forming monomers, caprolactam, 12-aminododecanoic acid, adipic acid / metaxylylenediamine and adipic acid / hexamethylenediamine are more preferable, and caprolactam is more preferable from the viewpoint of antistatic properties.

The production method of the polyamide (b2) is one or more of the dicarboxylic acid (b24) (C2-40, preferably 4-20) or the diamine (b23) (C2-40, preferably 4-20). May be used as a molecular weight modifier, and in the presence thereof, the amide-forming monomer may be subjected to ring-opening polymerization or polycondensation.
Examples of the C2-40 diamine include those exemplified as the above (b23). Of these, aliphatic diamines are preferable from the viewpoint of reactivity with other amide-forming monomers, and hexamethylenediamine is more preferable. And decamethylenediamine.
Examples of the C2-40 dicarboxylic acid include those exemplified as the above (b24). Among these, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferable from the viewpoint of reactivity with other amide-forming monomers. Acids, more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

  The amount of the molecular weight regulator used is preferably based on the total weight of the amide-forming monomer and the molecular weight regulator, the lower limit is from the viewpoint of antistatic properties of the molded product described later, and the upper limit is from the viewpoint of heat resistance of the molded product. Is from 2 to 80%, more preferably from 4 to 75%.

  Mn of the polyamide (b2) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoint of moldability and production of an antistatic antistatic agent.

  Of the hydrophobic polymer (b), the polyamideimide (b3) includes the amide-forming monomer, and a trivalent or tetravalent aromatic polymer that can form at least one imide ring with the amide-forming monomer. Carboxylic acid or its anhydride [hereinafter abbreviated as aromatic polycarboxylic acid (anhydride). (Hereinafter sometimes referred to as an amidoimide-forming monomer), and mixtures thereof. The diamine (b23) and the dicarboxylic acid (b24) can also be used as a molecular weight modifier during polymerization.

  Examples of the aromatic polycarboxylic acid (anhydride) include monocyclic (C9-12) and polycyclic (C13-20) carboxylic acids such as trivalent [monocyclic (trimellitic acid, etc.), polycyclic (1,2 , 5- and 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-biphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, Diphenyl ether-3,3 ′, 4-tricarboxylic acid and the like, and their anhydrides] carboxylic acid; and tetravalent [monocyclic (pyromellitic acid etc.), polycyclic (biphenyl-2,2 ′, 3,3 ′] -Tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid, diphenylether-2,2 ', 3,3 - tetracarboxylic acid, etc.), and these anhydrides], and carboxylic acids.

As a method for producing the polyamideimide (b3), as in the case of the polyamide (b2), one or more of the dicarboxylic acid (C2-40) or the diamine (C2-40) is used as a molecular weight modifier, Examples thereof include a method of ring-opening polymerization or polycondensation of the amidoimide-forming monomer in the presence thereof. Preferred among the dicarboxylic acid and diamine are the same as in the case of (b2).
The amount of the molecular weight modifier used is preferably based on the weight of the amide imide-forming monomer and the total molecular weight modifier, the lower limit is from the viewpoint of antistatic properties of the molded product described later, and the upper limit is from the viewpoint of heat resistance of the molded product. Is from 2 to 80%, more preferably from 4 to 75%.

  Mn of (b3) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoint of moldability and production of an antistatic agent.

Among the hydrophobic polymers (b), examples of the polyester (b4) include those obtained by subjecting an ester-forming monomer to ring-opening polymerization, polycondensation or transesterification by a conventional method.
Examples of the ester-forming monomer include lactones, hydroxycarboxylic acids, combinations of the diol (a0) and the dicarboxylic acid (b24), and mixtures thereof.

  Examples of the lactone include C4-20, such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthlactone, laurolactone, undecanolactone, and eicosanolactone. Is mentioned.

  Examples of the hydroxycarboxylic acid include C2-20, such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid, ω-hydroxycapric acid, 11- Examples include hydroxyundecanoic acid, 12-hydroxydodecanoic acid and 20-hydroxyeicosanoic acid, tropic acid, and benzylic acid.

  As a method for producing the polyester (b4), one or more of the above diol (a0) or the above dicarboxylic acid (b24) is used as a molecular weight modifier, and the above ester-forming monomer is used in the usual manner. Can be used for ring-opening polymerization, polycondensation or transesterification.

  Mn of (b4) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoint of moldability and production of an antistatic agent.

  The Mn of the hydrophobic polymer (b) is preferably 200 to 25,000, more preferably 500 to 20,000, and particularly preferably 1,000 to 15,000.

[Block polymer]
The block polymer of the antistatic agent (A) in the present invention is such that the block of the hydrophilic polymer (a) and the block of the hydrophobic polymer (b) are an ester bond, an amide bond, an ether bond, a urethane bond, It has a structure in which they are alternately bonded via at least one bond selected from the group consisting of a urea bond and an imide bond. The proportion of the block (a) based on the weight of the block polymer is preferably 20 to 80%, more preferably 30 to 70% from the viewpoint of antistatic properties and moldability of the antistatic resin composition described later. .

  Of the bonds between the blocks (a) and (b), the ester bond, amide bond and imide bond are, for example, polyether (a1) [(a11) or (a12)] and the hydrophobic polymer (b) [ (B11) or (b15) etc.], and the ether bond is, for example, the above-mentioned epoxy modified product obtained by reacting a polyether diol (a11) with an epihalohydrin, and a polyolefin having a hydroxyl group at both ends of the polymer (b12 ). The urethane bond is formed, for example, by a reaction between a polyether diol (a11) and a polyolefin (b14) having an isocyanate group at both ends, and a urea bond is formed by, for example, polyether diamine (a12) and an isocyanate group at both ends. It is formed by the reaction with polyolefin (b14).

The structure (a)-(b) type, (a)-(b)-(a) type, (a)-(b) type, b)-(a)-(b) type and (ab) n type (n is an integer of 2 or more). The structure of the block polymer is
From the viewpoint of antistatic properties, an (ab) _n- type structure is preferable. The average repeating number (Nn) of the repeating unit (a-b) _n- type structure is preferably 2 to 50, more preferably 2.3 to 30, particularly from the viewpoint of antistatic properties and mechanical properties of the molded product. Preferably it is 2.7-20, most preferably 3-10. Nn can be determined by Mn and ¹ H-NMR analysis of the block polymer.

  The Mn of the block polymer is preferably from 2,000 to 100,000, more preferably from 5,000 to 60,000, particularly preferably from 10,000 to 40,000, from the viewpoint of melt viscosity.

[Thermoplastic resin (B)]
As the thermoplastic resin (B), polyphenylene ether (PPE) resin (B1); vinyl resin [polyolefin resin (B2) [for example, polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate copolymer resin (EVA), Ethylene-ethyl acrylate copolymer resin], poly (meth) acrylic resin (B3) [for example, polymethyl methacrylate], polystyrene resin (B4) [vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, Copolymers having at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylonitrile and butadiene as structural units, such as polystyrene, high-impact polystyrene (HIPS), styrene / acrylonitrile copolymers ( AN resin), acrylonitrile / butadi / Styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin)], etc.]; polyester resin (B5) [for example, polyethylene Terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; polyamide resin (B6) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6 / 66, nylon 6/12]; polycarbonate resin (B7) [eg polycarbonate (PC), polycarbonate (PC) / ABS alloy resin]; polyacetal resin (B8), and two or more of these Compounds, and the like.

  Of these, (B1), (B2), (B3), (B4), (B), (B1), (B4), (B) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the antistatic agent of the present invention in (B). B7) and more preferable are (B2), (B4), and (B7).

Examples of the polyphenylene ether resin (B1) include poly (1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether, and poly (2,6-diethyl-1,4-phenylene). ) Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4) -Phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1, 4-phenylene) ether, poly (2,6-dibromo-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly 2,6-dichloro-1,4-phenylene) ether, poly (2,6-dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether.
Further, (B1) includes those obtained by grafting the above styrene and / or a monomer thereof (modified polyphenylene ether) onto (B1).

  As the vinyl resins [(B2) to (B4)], those obtained by (co) polymerizing the following vinyl monomers by various polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.) Is mentioned.

Examples of vinyl monomers include unsaturated hydrocarbons (aliphatic hydrocarbons, aromatic ring-containing hydrocarbons, alicyclic hydrocarbons, etc.), acrylic monomers, other unsaturated mono- and dicarboxylic acids and their derivatives, and carboxylic acids of unsaturated alcohols. Examples include acid esters, alkyl ethers of unsaturated alcohols, halogen-containing vinyl monomers, and combinations (random and / or block) of two or more thereof.

  Aliphatic hydrocarbons include C2-30 olefins [ethylene, propylene, C4-30 α-olefins (1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1 -Dodecene etc.), etc.], C4-30 dienes [alkadiene (butadiene, isoprene etc.), cycloalkadiene (cyclopentadiene etc.) etc.] and the like.

  Examples of the aromatic ring-containing hydrocarbon include C8-30 styrene and derivatives thereof, such as o-, m- and p-alkyl (C1-10) styrene (vinyltoluene, etc.), α-alkyl (C1-10) styrene ( α-methylstyrene and the like) and halogenated styrene (chlorostyrene and the like).

Acrylic monomers include C3-30, such as (meth) acrylic acid and its derivatives.
Examples of (meth) acrylic acid derivatives include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.], mono- and di-alkyl ( C1-4) aminoalkyl (C2-4) (meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.], (meth) acrylonitrile and (meth) acrylamide.

  Other unsaturated mono- and dicarboxylic acids include C2-30 (preferably 3-20, more preferably 4-15) unsaturated mono- and dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid and itacon. Examples thereof include C5-30, such as mono- and dialkyl (C1-20) esters, acid anhydrides (maleic anhydride, etc.) and acid imides (maleic imide, etc.).

Examples of carboxylic acid esters of unsaturated alcohols include carboxylic acids (C2-4, such as acetic acid and propionic acid) esters (such as vinyl acetate) of unsaturated alcohols [C2-6, such as vinyl alcohol, (meth) allyl alcohol]. It is done.
Examples of the alkyl ether of the unsaturated alcohol include alkyl (C1-20) ethers of the above unsaturated alcohol (methyl vinyl ether, ethyl vinyl ether, etc.). Halogen-containing vinyl monomers include C2-12, such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (B2) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate Copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40 ].
Among these, from the viewpoint of imparting antistatic properties, polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization] Ratio (weight ratio) = 90/10 to 10/90, random and / or block addition].

The melt flow rate (hereinafter abbreviated as MFR) of (B2) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of imparting resin physical properties and antistatic properties. Here, MFR is measured according to JISK7210 (1994) (in the case of polypropylene: 230 ° C., load 2.16 kgf, in the case of polyethylene: 190 ° C., load 2.16 kgf).
The crystallinity of (B2) is preferably 0 to 98%, more preferably 0 to 80%, and particularly preferably 0 to 70% from the viewpoint of antistatic properties.
Here, the degree of crystallinity is measured by methods such as X-ray diffraction and infrared absorption spectrum. ].

  Examples of the poly (meth) acrylic resin (B3) include one or two or more (co) polymers [poly (meth) methyl acrylate, poly (meth) butyl butyl, etc.] and the like of the acrylic monomers. Copolymer with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of the monomers [copolymerization ratio (weight ratio) is preferably 5/95 to 95/5, more preferably 50 from the viewpoint of resin physical properties. / 50 to 90/10] [however, those included in (B2) are excluded].

  The MFR of (B3) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. Here, the MFR is measured according to JIS K7210 (1994) [230 ° C., load 1.2 kgf for poly (meth) acrylic resin].

As the polystyrene resin (B4), vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene Examples thereof include a copolymer as a structural unit.
Examples of vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives,
For example, o-, m-, and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.) can be mentioned. .
Specific examples of (B4) include polystyrene, polyvinyltoluene, styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene / methyl methacrylate copolymer. (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to 95/5], acrylonitrile / butadiene / Styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [Copolymerization ratio (weight ratio) = (20-30) / (5-40) / (40-70)].

  The MFR of (B4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. Here, the MFR is measured in accordance with JIS K7210 (1994) (in the case of polystyrene resin, 230 ° C., load 1.2 kgf).

  Examples of the polyester resin (B5) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.).

  The intrinsic viscosity [η] of (B5) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and antistatic properties. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

  The polyamide resin (B6) includes a lactam ring-opening polymer (B61), a dehydration polycondensation product of diamine and dicarboxylic acid (B62), a self-polycondensation product of aminocarboxylic acid (B63), and a poly (condensation) combination thereof. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (B61) include those exemplified as the above (b21), and examples of (B61) include nylon 4, -5, -6, -8 and -12.
Examples of the diamine and dicarboxylic acid in (B62) include those exemplified as the above (b23) and (b24). Examples of (B62) include nylon 66 and hexamethylenediamine obtained by condensation polymerization of hexanemethylenediamine and adipic acid. Examples thereof include nylon 610 by polycondensation of sebacic acid.
Examples of the aminocarboxylic acid in (B63) include those exemplified as the above (b22). Examples of (B63) include nylon 7 by polycondensation of aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 and the like by polycondensation of 12-aminododecanoic acid.

In the production of (B6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the diamines and / or dicarboxylic acids exemplified as the above (b23) and (b24).
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and 3- Sodium sulfoisophthalate. Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

  The MFR of (B6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. Here, MFR is measured in accordance with JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Polycarbonate resins (B7) include bisphenol compounds (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene or Examples include condensates with carbonic acid diesters. Of the bisphenol compounds, bisphenol A is preferable from the viewpoint of dispersibility of the block polymer (A).
The MFR of (B7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. Here, MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (B8) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [the above-mentioned AO (EO, PO, dioxolane, etc.)] (polyoxy). And methylene / polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer and the like].
The MFR of (B8) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and antistatic properties. Here, MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
Intrinsic viscosity [η] of (B8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, and particularly preferably from 0.3 to 3, from the viewpoint of resin physical properties and antistatic properties.

[Resin composition for molded articles for living materials (X)]
Resin composition (X) for molded articles for living materials of the present invention contains an antistatic agent (A) and a thermoplastic resin (B), and the melt viscosity ratio at 220 ° C. of (B) and (A). 0.5 to 5, preferably 0.7 to 3.5, more preferably 0.8 to 2.5, particularly preferably 0.9 to 1.5, and (B) from the viewpoint of antistatic properties. The absolute value of the difference of SP from (A) is 1.0 to 3.0, preferably 1.1 to 2.5, more preferably 1.2 to 2.0 from the viewpoint of antistatic properties and mechanical properties. It is a certain antistatic resin composition.

In the specific combination of (B) and (A) that constitutes the resin composition (X), although the melt viscosity ratio needs to satisfy the above range, the melt viscosity that (B) has, or charging Each of the melt viscosities possessed by the inhibitor (A) may be arbitrary, and is not particularly limited.
The same applies to SP, and in the specific combination of (A) and (B) constituting the resin composition (X), the absolute value of the difference between these SPs must satisfy the above range. Each of the SP possessed by the antistatic agent (A) or the SP possessed by (B) may be arbitrary and is not particularly limited.

  The melt viscosity ratio at 220 ° C. of (B) and (A) can be set within the above range by selecting a combination of (B) and (A), and antistatic properties can be set within this range. It can be set as the resin composition (X) excellent in.

  The absolute value of the difference between the SPs of (A) and (B) can be set within the above range by selecting the combination of (A) and (B). It can be set as the resin composition (X) excellent in.

  The weight ratio of (A) to (B) in the resin composition (X) is preferably 0.5 / 99.5 to 10/90, more preferably 1/99 to 7 from the viewpoint of antistatic properties and mechanical properties. / 93, particularly preferably 3/97 to 5/95.

In the resin composition (X) of the present invention, an antistatic property improver (C1), a compatibilizer (C2), a flame retardant (C3) other than the above (A) is necessary, as long as the effects of the present invention are not impaired. ) And other additives for resin (C4), one or more additives (C) selected from the group consisting of additives may be contained.
Antistatic property improvers (C1) include alkali metal or alkaline earth metal salts (C11
), A surfactant (C12) and / or an ionic liquid (C13), or one or a mixture of two or more thereof.

  (C11) include alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids (C1-7 mono- and dicarboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-7 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid) A salt of perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.

The use amount of (C11) is preferably 0.001 to 3%, based on the total weight of (A) and (B), from the viewpoint of giving a resin molded article having a good appearance without precipitating on the resin surface. Preferably it is 0.01 to 2.5%, Especially preferably, it is 0.1 to 2%, Most preferably, it is 0.15 to 1%.
The method of adding (C11) is not particularly limited, but it is preferable to disperse it in the antistatic agent (A) in advance because it is easy to effectively disperse it in the composition.
Further, when (C11) is dispersed in (A), it is particularly preferable to add (C11) in advance during the production (polymerization) of (A). The timing for adding (C11) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

Surfactant (C12) includes nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
Examples of the nonionic surfactant (C121) include EO addition type nonionic surfactants [for example, higher alcohols (C8-18, the same shall apply hereinafter), higher fatty acids (C8-24, the same shall apply hereinafter) or higher alkylamines ( C8-24) EO adduct (molecular weight 158 or more and Mn 200,000 or less); polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) higher fatty acid ester which is an EO adduct of glycol; polyhydric alcohol (C2 18 divalent to octavalent or higher, for example EG, PG, glycerin, pentaerythritol and sorbitan) higher fatty acid ester EO adduct (molecular weight 250 or more and Mn 30,000 or less); higher fatty acid amide EO adduct (molecular weight) 200 or more and Mn 30,000 or less); and polyhydric alcohol EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn30,000 or less)], and polyhydric alcohol (above) (C3-60) type nonionic surfactant [For example, fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

The anionic surfactant (C122) is represented by the following general formula (1).

R−X ⁻ · Z ⁺ (1)

In the formula, R represents a C8-30 (preferably C10-24, more preferably C12-21) monovalent hydrocarbon group. When R is less than C8, the appearance of the molded product described later is deteriorated, and when it exceeds 30, the antistatic property is deteriorated.
Examples of R include an alkyl group, an alkenyl group, an alkylaryl group, and an arylalkyl group.
Examples of the alkyl group include octyl, decyl, dodecyl, pentadecyl and octadecyl groups;
Examples of alkenyl groups include octenyl, decenyl, dodecenyl, pentadecenyl and octadecenyl groups;
Examples of the alkylaryl group include ethylphenyl, pentylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, pentadecylphenyl and octadecylphenyl groups;
Examples of the arylalkyl group include phenylethyl, phenylpentyl, phenyldecyl, phenylnonyl, phenyldodecyl, phenylpentadecyl and phenyloctadecyl groups.
Of the above R, from the viewpoint of antistatic properties, alkyl groups and alkylaryl groups are preferred, C12-21 alkylaryl groups are more preferred, and dodecylphenyl and pentadecylphenyl groups are particularly preferred.

In the formula, X ⁻ represents an anion obtained by removing a proton from at least one group selected from the group consisting of a sulfonic acid group, a sulfinic acid group, a sulfate ester group, a carboxyl group, a phosphate ester group and a phosphite ester group. To express. Of these groups, sulfonic acid groups, sulfinic acid groups and sulfate ester groups are preferred from the viewpoint of antistatic properties, sulfonic acid groups and sulfate ester groups are more preferred, and sulfonic acid groups are particularly preferred.

Wherein Z ⁺ is a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations, metals [alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and IIB Group metals (such as zinc) etc.] or amines [alkylamines (C1-720) and alkanolamines (C2-12, such as mono-, di- and triethanolamine) etc.].

The following are mentioned as an amidinium cation.
(1) imidazolinium cation C5-15, such as 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
(2) imidazolium cation C5-15, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;

(3) Tetrahydropyrimidinium cation C6-15, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6 -Tetrahydropyrimidinium;
(4) Dihydropyrimidinium cation C6-20, such as 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium [these are 1,3-dimethyl-1,4 (6) -dihydro This is expressed as pyrimidinium, and the same notation is used hereinafter. ], 8-Methyl-1,8-diazabicyclo [5,4,0] -7,9 (10) -undecadienium.

  Examples of the pyridinium cation include C6-20, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.

  Examples of the pyrazolium cation include C5-15, such as 1,2-dimethylpyrazolium and 1-n-butyl-2-methylpyrazolium.

The following are mentioned as a guanidinium cation.
(1) Guanidinium cation having an imidazolinium skeleton C8-15, such as 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium;
(2) Guanidinium cation having an imidazolium skeleton C8-15, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium;

(3) Guanidinium cation having a tetrahydropyrimidinium skeleton C10-20, such as 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
(4) Guanidinium cation having a dihydropyrimidinium skeleton C10-20, such as 2-dimethylamino-1,3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1, 3-Dimethyl-4-ethyl-1,4 (6) -dihydropyrimidinium.

  Of these, an amidinium cation is preferable from the viewpoint of antistatic properties, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

Among the anionic surfactant (C122), specific examples of the sulfonate include imidazolium salts of alkanesulfonic acid (1-ethyl-3-methylimidazolium salt of dodecanesulfonic acid and pentadecanesulfonic acid, and 1, 3-dimethyl-2-ethylimidazolium salt, etc.), alkene sulfonic acid imidazolium salt (dodecenesulfonic acid and pentadecenesulfonic acid 1-ethyl-3-methylimidazolium salt and 1,3-dimethyl-2- Ethyl imidazolium salts, etc.), imidazolium salts of alkylarene sulfonic acids (1-ethyl-3-methyl imidazolium salt and 1,3-dimethyl-2-ethyl imidazolium of dodecylbenzene sulfonic acid and pentadecyl benzene sulfonic acid, respectively) Salt), arylalkanesulfonic acid Midazolium salts (such as 1-ethyl-3-methylimidazolium salt and 1,3-dimethyl-2-ethylimidazolium salt of phenyldodecanesulfonic acid and phenylpentadecanesulfonic acid), and the above metals and amines of these sulfonic acids And the like.
Of these, imidazolium salts and metal salts of alkylarene (C8-30) sulfonic acids are preferred from the viewpoint of antistatic properties and appearance of molded articles, and more preferred is 1-ethyl-3 of dodecylbenzenesulfonic acid. -Methylimidazolium salt, 1,3-dimethyl-2-ethylimidazolium salt and alkali metal (sodium etc.) salt, 1-ethyl-3-methylimidazolium salt of pentadecanebenzenesulfonic acid, 1,3-dimethyl- 2-ethylimidazolium salts and alkali metal (sodium) salts.

Examples of the cationic surfactant (C123) include quaternary ammonium salts such as alkyltrimethylammonium salts.
Examples of the amphoteric surfactant (C124) include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
Examples of the salt in the amphoteric surfactant (C124) include metal salts such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); And ammonium salts [alkylamine (C1-720) salts and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts] and quaternary ammonium salts.
These surfactants may be used alone or in combination of two or more.

The amount of the surfactant (C12) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, particularly preferably 0.1 based on the total weight of (A) and (B). ~ 2.5%.
The method of adding (C12) is not particularly limited, but it is preferable to disperse in (A) in advance in order to effectively disperse it in the resin composition. Further, when (C12) is dispersed in (A), it is particularly preferable to add (C12) in advance during the production (polymerization) of (A). The timing for adding (C12) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

  The ionic liquid (C13) is a compound other than (C12), has a melting point of room temperature or lower, and at least one of the cations or anions constituting (C13) is an organic ion, and the initial conductivity is 1. A room temperature molten salt of ˜200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572.

Examples of the cation constituting (C13) include a cation represented by Z ⁺ in the general formula (1), that is, a cation selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations.
The cation may be used alone or in combination of two or more. Of these, an amidinium cation is preferable from the viewpoint of antistatic properties, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (C13), examples of the organic acid or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfuric acid ester, sulfonic acid, and phosphoric acid ester; and examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluorocarbon, Fluorinated antimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the organic acids and inorganic acids, from the viewpoint of antistatic property of (C13), a conjugate base of a super strong acid, in which the Hammett acidity function (—H ₀ ) of the anion constituting (C13) is 12 to 100, is preferred. , Acids that form anions other than the conjugate bases of super strong acids and mixtures thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1-12) benzenesulfonic acid (for example, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ions and poly (n = 1-25) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [for example, methanesulfonic acid, dodecanesulfonic acid, etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (for example, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropane) Sulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid.
Of these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.

Examples of protonic acids used in combination with Lewis acids include hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (C13).

Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (C13).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Of the above anions, (C13) from the viewpoint of antistatic properties, a super strong acid conjugate base (a super strong acid comprising a proton acid and a super strong acid comprising a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

  Of the ionic liquids (C13), from the viewpoint of antistatic properties, preferred are ionic liquids having an amidinium cation, and more preferred are ionic liquids having a 1-ethyl-3-methylimidazolium cation. Preferred is 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.

The amount of (C13) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, and particularly preferably 0.1 to 2.% based on the total weight of (A) and (B). 5%.
The method of adding (C13) is not particularly limited, but it is preferable to disperse it in (A) in advance in order to effectively disperse it in the resin composition. Further, when (C13) is dispersed in (A), it is particularly preferable to add (C13) in advance during the production (polymerization) of (A). The timing for adding (C13) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

As the compatibilizing agent (C2), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The amount of (C2) used is usually 20% or less based on the total weight of (A) and (B), preferably from 0.1 to 15%, more preferably from the viewpoint of the compatibilizing effect and the mechanical properties of the molded product. Is 1 to 10%, particularly preferably 1.5 to 8%.
The method for adding (C2) is not particularly limited, but it is preferable to disperse it in the antistatic agent (A) in advance because it can be effectively dispersed or dissolved in the composition.
When (C2) is dispersed or dissolved in (A), it is particularly preferable to add (C2) in advance during the production (polymerization) of (A). The timing for adding (C2) during the production of (A) is not particularly limited, and may be any before, during or after polymerization.

  The flame retardant (C3) includes a halogen-containing flame retardant (C31), a nitrogen-containing flame retardant (C32), a sulfur-containing flame retardant (C33), a silicon-containing flame retardant (C34), and a phosphorus-containing flame retardant (C35). 1 type or 2 types or more of flame retardants chosen from these are included.

  Examples of the halogen-containing flame retardant (C31) include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, and the like;

Examples of the nitrogen-containing flame retardant (C32) include a salt of urea compound, guanidine compound or triazine compound (melamine, guanamine, etc.) and cyanuric acid or isocyanuric acid;
Examples of the sulfur-containing flame retardant (C33) include sulfuric ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and salts, esters and amides thereof;
Examples of the silicon-containing flame retardant (C34) include polyorganosiloxane;
Examples of the phosphorus-containing flame retardant (C35) include phosphorus-containing acids and esters thereof (C2-20) such as phosphoric acid, phosphate, halogen-containing phosphate, phosphorous acid, phosphonate, and ammonium phosphate.
These flame retardants may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.

  Of these flame retardants, (C32) is preferred from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

  The total amount of (C3) used is usually 30% or less based on the total weight of (A) and (B), preferably from 0.1 to 20%, more preferably from the viewpoint of flame retardancy and mechanical properties of the molded product Is 1 to 10%.

  Other resin additives (C4) are one or more selected from the group consisting of pigments, dyes, nucleating agents, lubricants, plasticizers, mold release agents, antioxidants, ultraviolet absorbers and antibacterial agents. These additives may be mentioned.

  The total use amount of (C4) is usually 45% or less based on the total weight of (A) and (B), preferably 0.001 to 40% from the viewpoint of the effect of each additive and the mechanical properties of the molded product, More preferably, it is 0.01 to 35%, and particularly preferably 0.05 to 30%.

The antistatic resin composition (X) of the present invention can be obtained by melt-mixing the antistatic agent (A), the thermoplastic resin (B) and, if necessary, (C).
As a method of melting and mixing, generally, a method in which pellets or powdery components are mixed with an appropriate mixer such as a Henschel mixer and then melted and mixed with an extruder to be pelletized can be applied.
There is no particular limitation on the order of addition of each component during melt mixing, for example,
(1) A method of melt-mixing the antistatic agent (A), the thermoplastic resin (B), and (C) if necessary,
(2) A part of the antistatic agent (A) and the thermoplastic resin (B) is previously melt-mixed to prepare a high-concentration resin composition (masterbatch resin composition) of the antistatic agent, and then the remaining ( B) and a method of melt-mixing (C) if necessary.
The concentration of the antistatic agent of the present invention in the masterbatch resin composition in the method (2) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Among these, the method (2) is a method called a master batch method, which is a preferable method from the viewpoint of efficient dispersion of the antistatic agent (A) into (B).

  The molded article for living material of the present invention is obtained by molding the antistatic resin composition (X). Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, film molding (casting method, tenter method, inflation method, etc.). Depending on the method, it can be formed by any method.

The molded product has excellent permanent antistatic properties, mechanical properties, and heat resistance, and also has good paintability and printability. Therefore, the molded product is molded for daily use by coating and / or printing. Articles can be obtained.
Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method. Examples of the paint include various paints such as polyester melamine, epoxy melamine, acrylic melamine, and acrylic urethane resin paint.
Although a coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, it is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of physical properties of the coating film.
Examples of the method for printing on the molded product include various printing methods such as gravure printing, flexographic printing, screen printing, and offset printing. Examples of the printing ink include those usually used for printing plastics.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example is a weight part. % Represents% by weight.

Production Example 1 [Production of acid-modified polyolefin (b1-1)]
To a stainless steel autoclave, 410 ± 0.1% of an ethylene / propylene (random addition) copolymer (ethylene content 2%) having a density of 0.90 g / cm ^{3 at} 23 ° C. and an MFR of 6.0 g / 10 min was added to a stainless steel autoclave. Low molecular weight ethylene / propylene random copolymer (Mn 3,500, density 0.89 g / cm ³ , amount of double bonds per 1,000 C 1 unit, average number of double bonds per molecule 1.8, content of polyolefin that can be modified at both ends 90%) 95 parts, maleic anhydride 10 parts, xylene 30 parts, nitrogen gas atmosphere (sealed) Then, it was melted at 200 ° C. and reacted at 200 ° C. for 20 hours. Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain an acid-modified polyolefin (b1-1). The acid value of (b1-1) was 27.2, and Mn was 3,700.

Production Example 2 [Production of secondary modified polyolefin (b1-2)]
A stainless steel autoclave was charged with 88 parts of (b1-1) and 12 parts of 12-aminododecanoic acid, melted at 200 ° C. in a nitrogen gas atmosphere, and reacted at 200 ° C. for 3 hours under a reduced pressure of 1.3 kPa or less. Secondary modified polyolefin (b1-2) was obtained. The acid value of (b1-2) was 24.0, and Mn was 4,200.

Production Example 3 [Production of Modified Polyolefin (b1-3) Having Hydroxyl Groups at Both Ends of Polymer]
In a stainless steel autoclave, 95 parts of acid-modified polyolefin (b1-1) and 5 parts of ethanolamine were melted at 180 ° C. in a nitrogen gas atmosphere and reacted at 180 ° C. for 2 hours. Thereafter, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polyolefin (b1-3) having hydroxyl groups at both ends of the polymer. The hydroxyl value of (b1-3) was 26.0, the amine value was 0.01, and Mn was 3,900.

Production Example 4 [Production of Modified Polyolefin (b1-4) Having Amino Groups at Both Ends of Polymer]
In a stainless steel autoclave, 95 parts of acid-modified polyolefin (b1-1) and 40 parts of bis (2-aminoethyl) ether were melted at 200 ° C. with stirring in a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours. . Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polyolefin (b1-4) having amino groups at both ends. The amine value of (b1-4) was 25.5, and Mn was 4,000.

Production Example 5 [Production of polyamide (b2-1) having carboxyl groups at both ends]
In a stainless steel autoclave, 173 parts of ε-caprolactam, 33.2 parts of terephthalic acid, an antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and so on. ] 0.4 parts and 10 parts of water were charged, and the inside of the autoclave was purged with nitrogen. A polyamide (b2-1) having a group was obtained. Mn of (b2-1) was 1,000 and the acid value was 111.

Production Example 6 [Production of Cationic Polymer (a2-1)]
A glass autoclave was charged with 41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate. After purging with nitrogen, the temperature was raised to 220 ° C. over 2 hours and reduced to 0.13 kPa over 1 hour. The polyesterification reaction was performed. After completion of the reaction, the mixture was cooled to 50 ° C. and 100 parts of methanol was added and dissolved. While stirring, the temperature of the solution was maintained at 120 ° C., 31 parts of dimethyl carbonate was gradually added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 110 parts of dioctyl phosphoric acid was added and stirred at room temperature for 1 hour. Subsequently, methanol was distilled off under reduced pressure to obtain a cationic polymer (a2-1) having an average of 12 quaternary ammonium groups in one molecule. The hydroxyl value of (a2-1) was 16.5, the acid value was 0.5, Mn was 6,800, and the volume resistivity value was 1 × 10 ⁵ Ω · cm.

Production Example 7 [Production of anionic polymer (a3-1)]
A stainless steel autoclave is charged with 67 parts of PEG of Mn300, 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide, heated to 190 ° C. under a reduced pressure of 0.67 kPa, and methanol produced by the reaction. An anionic polymer (a3-1) having an average of 5 sodium sulfonate bases in one molecule was obtained by performing an ester exchange reaction for 6 hours while distilling off. The hydroxyl value of (a3-1) was 29.6, the acid value was 0.4, Mn was 3,500, and the volume resistivity value was 2 × 10 ⁶ Ω · cm.

Production Example 8 [Production of Antistatic Agent (A-1)]
Stainless steel autoclave, secondary modified polyolefin (b1-2) 60.9 parts, PEG (a1-1) (Mn 3,000, volume resistivity 1 × 10 ⁷ Ω · cm) 39.1 parts, antioxidant 0.3 parts and 0.5 parts of zirconyl acetate were charged and polymerized for 4 hours under the reduced pressure of 230 ° C. and 0.13 kPa or less to obtain a viscous polymer. The polymer was taken out in the form of a strand on a belt and pelletized to obtain an antistatic agent (A-1) comprising a block polymer. The melt viscosity of (A-1) was 180 Pa · s, SP was 8.8, and Mn was 30,000. (Average repeat number Nn is 4.2)

Production Example 9 [Production of Antistatic Agent (A-2)]
In Production Example 8, an antistatic agent (A-2) comprising a block polymer was obtained in the same manner as in Production Example 8 except that the polymerization time was changed from 4 hours to 3 hours. The melt viscosity of (A-2) was 40 Pa · s, SP was 8.8, and Mn was 22,000. (Average repeat number Nn is 3.1)

Production Example 10 [Production of Antistatic Agent (A-3)]
In Production Example 8, an antistatic agent (A-3) comprising a block polymer was obtained in the same manner as in Production Example 8 except that the polymerization time was changed from 4 hours to 3.5 hours. The melt viscosity of (A-3) was 110 Pa · s, SP was 8.8, and Mn was 26,000. (Average repeat number Nn is 3.6)

Production Example 11 [Production of Antistatic Agent (A-4)]
In Production Example 8, an antistatic agent (A-4) comprising a block polymer was obtained in the same manner as in Production Example 8 except that the polymerization time was changed from 4 hours to 10 hours. The melt viscosity of (A-4) was 280 Pa · s, SP was 8.8, and Mn was 41,000. (Average repeat number Nn is 5.7)

Production Example 12 [Production of Antistatic Agent (A-5)]
In Production Example 8, in place of 60.9 parts of secondary modified polyolefin (b1-2) and 39.1 parts of PEG (a1-1), modified polyolefin (b1-3) 59.0 having hydroxyl groups at both ends of the polymer Part, (a1-1) 41.0 parts and dodecanedioic acid 6 parts were used in the same manner as in Production Example 8 to obtain an antistatic agent (A-5) comprising a block polymer. The melt viscosity of (A-5) was 130 Pa · s, SP was 8.8, and Mn was 25,000. (Average repeat number Nn is 3.6)

Production Example 13 [Production of Antistatic Agent (A-6)]
In Production Example 8, instead of 60.9 parts of secondary modified polyolefin (b1-2) and 39.1 parts of PEG (a1-1), modified polyolefin (b1-4) having amino groups at both ends of the polymer 59. An antistatic agent (A-6) comprising a block polymer was obtained in the same manner as in Production Example 8, except that 5 parts, 40.5 parts of PEG (a1-1), and 6 parts of dodecanedioic acid were used. The melt viscosity of (A-6) was 150 Pa · s, SP was 8.8, and Mn was 28,000. (Average repeat number Nn is 4.0)

Production Example 14 [Production of Antistatic Agent (A-7)]
In Production Example 8, instead of 60.9 parts of secondary modified polyolefin (b1-2) and 39.1 parts of PEG (a1-1), 40.7 parts of (b1-2), cationic polymer (a2-1) ) An antistatic agent (A-7) comprising a block polymer was obtained in the same manner as in Production Example 8 except that 59.3 parts were used. The melt viscosity of (A-7) was 210 Pa · s, SP was 8.7, and Mn was 29,000. (Average repeat number Nn is 2.6)

Production Example 15 [Production of Antistatic Agent (A-8)]
In Production Example 8, instead of 60.9 parts of secondary modified polyolefin (b1-2) and 39.1 parts of PEG (a1-1), 55.2 parts of (b1-2), anionic polymer (a3-1) ) An antistatic agent (A-8) comprising a block polymer was obtained in the same manner as in Production Example 8 except that 44.8 parts were used. The melt viscosity of (A-8) was 190 Pa · s, SP was 9.4, and Mn was 28,000. (Average repeat number Nn is 3.6)

Production Example 16 [Production of Antistatic Agent (A-9)]
In Production Example 8, 20.3 parts of polyamide (b2-1) having carboxyl groups at both ends instead of 60.9 parts of secondary modified polyolefin (b1-2) and 39.1 parts of PEG (a1-1) From the block polymer in the same manner as in Production Example 8, except that 79.7 parts of EO product of bisphenol A (Mn 4,000, volume resistivity 2 × 10 ⁷ Ω · cm) (a1-2) was used. An antistatic agent (A-9) was obtained. The melt viscosity of (A-9) was 250 Pa · s, SP was 11.0, and Mn was 23,000. (Average repeat number Nn is 4.6)

Production Example 17 [Production of Antistatic Agent (A-10)]
A stainless steel autoclave was charged with 85.7 parts of PEG (a1-1) and 14.3 parts of MDI and reacted at 90 ° C. to make a terminal isocyanate group-modified PEG (a1-3) (NCO content 3.0%, volume resistivity). Value 1 × 10 ⁷ Ω · cm) was obtained. Thereafter, 47.3 parts of (a1-3) and 52.7 parts of modified polyolefin (b1-3) having hydroxyl groups at both ends of the polymer were melt-kneaded at 200 ° C. and a residence time of 30 seconds using a twin-screw extruder. This was taken out into a strand shape and pelletized to obtain an antistatic agent (A-10) comprising a block polymer. The melt viscosity of (A-10) was 140 Pa · s, SP was 9.2, and Mn was 25,000. (Average repeat number Nn is 3.6)

Production Example 18 [Production of Antistatic Agent (A-11)]
In Production Example 17, instead of (a1-3) 47.3 parts and (b1-3) 52.7 parts, (a1-3) 38.9 parts, a modified polyolefin having amino groups at both ends of the polymer (b1 -4) An antistatic agent (A-11) comprising a block polymer was obtained in the same manner as in Production Example 17 except that 61.1 parts were used. The melt viscosity of (A-11) was 150 Pa · s, SP was 9.3, and Mn was 24,000. (Average repeat number Nn is 3.4)

Comparative Production Example 1 [Production of Antistatic Agent (Ratio A-1)]
In Production Example 8, an antistatic agent (ratio A-1) comprising a block polymer was obtained in the same manner as in Production Example 8 except that the polymerization time was changed from 4 hours to 2 hours. The melt viscosity of (Ratio A-1) was 20 Pa · s, SP was 8.8, and Mn was 16,000. (Average repetition number Nn is 2.2)

Comparative Production Example 2 [Production of Antistatic Agent (Ratio A-2)]
In Production Example 8, an antistatic agent composed of a block polymer (Ratio A-2) was obtained in the same manner as in Production Example 8 except that the polymerization time was changed from 4 hours to 40 hours. The melt viscosity of (Ratio A-2) was 400 Pa · s, SP was 8.8, and Mn was 72,000. (Average repeat number Nn is 10.0)

Examples 1-18, Comparative Examples 1-11
In accordance with the formulation shown in Tables 1 and 2, after blending each component for 3 minutes with a Henschel mixer, the mixture was melt-kneaded in a twin screw extruder with a vent at 100 rpm, a residence time of 5 minutes, and a melting temperature of 220 ° C. Examples 1 to 18 and Comparative Examples 1 to 11) were obtained.

Example 19
After blending 60 parts of (A-1), 40 parts of (B-1), 3 parts of (C1-1), 2 parts of (C4-1) with a Henschel mixer for 3 minutes, in a twin screw extruder with a vent, The mixture was melt kneaded at 100 rpm and a residence time of 5 minutes at a melting temperature of 220 ° C. to obtain a master batch resin composition (M-1).
Thereafter, 95 parts of (B-1) was blended with 5.25 parts of (M-1) for 3 minutes using a Henschel mixer, and then 100 rpm, residence time of 5 minutes, melting temperature of 220 ° C. in a twin screw extruder with a vent. And kneaded to obtain a resin composition.

The contents of symbols in Tables 1 and 2 are as follows.
B-1: HIPS resin [trade name “HIPS 433”, manufactured by PS Japan Ltd.]
Melt viscosity 160Pa · s, SP10.6
B-2: ABS resin [trade name “Cebian 680SF”, manufactured by Daicel Polymer Co., Ltd.]
Melt viscosity 400Pa · s, SP11.7
B-3: PC / ABS resin [trade name “Psycholoy C6600”, SABIC Inove
Made by Tive Plastics Japan GK]
Melt viscosity 550 Pa · s, SP11.4
B-4: Modified PPE resin [trade name “Noryl V-095”, SABIC Innovative
Made by Plastics Japan GK]
Melt viscosity 580 Pa · s, SP11.2
B-5: PP resin [trade name “PM771M”, manufactured by Sun Allomer Co., Ltd.]
Melt viscosity 170 Pa · s, SP 8.0
C1-1: 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonate
) Imido C1-2: sodium dodecylbenzenesulfonate C2-1: epoxidized polystyrene elastomer [trade name “Epofriend AT501”
Manufactured by Daicel Chemical Industries, Ltd. ]
C4-1: Antioxidant [trade name “Irganox 1010”, Ciba Specialty
Tetrakis [methylene-3- (3 ′, 5′-di-t-, manufactured by Chemicals Co., Ltd.]
Butyl-4′-hydroxyphenyl) propionate] methane

<Performance test>
The resin composition obtained above was injected into an injection molding machine [model number “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd. The same shall apply hereinafter, and molded articles (100 × 100 × 2 mm and 100 × 10 × 3.2 mm) were produced under conditions of a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C., and performance evaluation of the following items was performed. The results are shown in Tables 1 and 2.

<Performance evaluation items>
(1) Surface specific resistance value Conforms to ASTM D257 (1984). Using a test piece (100 × 100 × 2 mm), measurement was carried out in an atmosphere of 23 ° C. and humidity 50% RH with a super insulation meter [model number “DSM-8103”, manufactured by Toa Denpa Co., Ltd.].
(2) Impact strength Conforms to ASTM D256 Method A (with notch, 3.2 mm thickness).
(3) Appearance (3-1) Surface appearance The appearance of the front and back surfaces of an injection molded product (100 × 100 × 2 mm) was observed and evaluated according to the following criteria.
(Evaluation criteria)
○ Good with no abnormalities (equivalent to thermoplastic resin containing no antistatic agent)
× Surface roughness, swelling, etc. are observed

(3-2) Cross-sectional appearance It cut | disconnected with the cutter perpendicularly | vertically to the surface so that it might pass through the surface center part of a test piece (100x100x2mm), the cross section was observed, and the following reference | standard evaluated.
(Evaluation criteria)
○ Cross section is uniform and good (equivalent to thermoplastic resin containing no antistatic agent)
× Cross section is non-uniform

  As is apparent from Tables 1 and 2, the resin composition for molded articles for living materials of the present invention is a molded article having excellent permanent antistatic properties even when the content of the antistatic agent in the composition is smaller than that in the prior art. It can be seen that the appearance and mechanical properties are excellent over a wide range of contents.

The resin composition for molded articles for living materials according to the present invention does not impair the mechanical properties and good appearance of the thermoplastic resin molded article, and is sufficient for permanent antistatic even when the content of the antistatic agent is smaller than the conventional one. Since it gives a molded product having properties, it can be suitably used as a resin composition for a molded product for living materials, and is extremely useful.
Examples of the molded article for living materials include furniture (chairs, desks, hangers, etc.), hobby goods [sports equipment (racquets, skis, snowboards, etc.), gardening equipment (planters, etc.), outdoor equipment (fishing rods, etc.)] And other daily necessities [tableware, toys, stationery, oral care products, toiletries (bath units, toilets, etc.), health appliances, etc.].

Claims (8)

It contains an antistatic agent (A) and a thermoplastic resin (B), the melt viscosity ratio at 220 ° C. of (B) and (A) is 0.5 to 5, and the absolute value of the difference in solubility parameter is 1. Resin composition for molded articles for living materials that is 0.0 to 3.0. The composition according to claim 1, wherein the weight ratio of (A) to (B) is 0.5 / 99.5 to 10/90. The block of hydrophilic polymer (a) having a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm and the block of hydrophobic polymer (b) are ester bonds and amide bonds (A). 3. The composition according to claim 1, which is a block polymer having a structure in which they are alternately bonded through at least one bond selected from the group consisting of an ether bond, a urethane bond, a urea bond and an imide bond. The composition according to claim 3, wherein (a) is at least one selected from the group consisting of polyethers, cationic polymers and anionic polymers. The composition according to claim 3 or 4, wherein (b) is at least one selected from the group consisting of polyolefin, polyamide, polyamideimide and polyester. In the masterbatch resin composition (M) containing (A) and (B) for the composition according to any one of claims 1 to 5, the concentration of (A) in (M) is 40 to 40. Masterbatch resin composition (M) which is 80% by weight. A molded article for living material formed by molding the composition according to any one of claims 1 to 5. A molded article for living material, which is obtained by coating and / or printing the molded article according to claim 7.