WO1995011948A1 - Antistatic composition and thermoplastic resin composition containing the same - Google Patents

Abstract

An antistatic composition (I) comprising a mixture of two specified sulfonic acid salts, another antistatic composition (II) comprising a mixture of a specified sulfonic acid salt, a specified glycol and at least one member selected from the group consisting of a fatty acid glyceride containing a given proportion of a monoglyceride, a fatty acid diethanolamide and an N-(alkyl or alkenyl)diethanolamine, and still another antistatic composition (III) comprising the mixture mentioned above in the composition (II) and a metal salt of a sulfonic acid. These compositions, when added to a thermoplastic resin, can impart thereto a stable and excellent antistatic performance and improve the moldability of the resin. Furthermore, the two compositions (II) and (III) enable the resin to exhibit a stable antistatic performance immediately after the injection molding even in a small amount of addition and can suppress smoking in the molding step. Especially, even when a transparent resin such as an acrylic resin is used as the thermoplastic resin, the transparency is not impaired. The invention also provides a thermoplastic resin composition containing the antistatic composition.

Description

 Description Antistatic agent composition and thermoplastic resin composition containing the same

 The present invention relates to a novel antistatic agent composition and a thermoplastic resin composition containing the same. More specifically, the present invention has excellent antistatic properties, does not impair moldability, does not impair the transparency of molded articles when molded with a transparent resin, and has a special composition. When blended with a transparent resin such as acryl resin, not only in extrusion molding but also in injection molding, an antistatic agent composition capable of exhibiting antistatic performance immediately after molding, and containing it, antistatic properties, moldability and in some cases The present invention relates to a thermoplastic resin composition having excellent transparency. Background art

 Thermoplastic resins, especially acrylic resins, are widely used as materials for films, fibers, molded products, etc. due to their excellent transparency and optical properties, good mechanical properties, processing properties, and appearance. It is widely used in products. However, such thermoplastics are generally hydrophobic and have a high electrical insulation, so they tend to be charged by the accumulation of static electricity-resulting in poor appearance, processes such as processing, packaging, printing, painting, etc. Inevitably leads to a decrease in work efficiency, and also causes an accident due to spark discharge. Therefore, various antistatic methods for thermoplastic resins, particularly acrylic resins, have been studied.

 By the way, cationic, anionic, and nonionic surfactants are known as internal addition type antistatic agents for general synthetic resins, and these surfactants are synthesized by the antistatic effect. It is said that this phenomenon occurs by pre-drilling on the resin surface.

However, for acrylic resin, the processing temperature of the resin is relatively high. Therefore, it is difficult to use a cationic surfactant having poor thermal stability, and since the resin has a higher glass transition temperature than polyethylene or polypropylene, a nonionic surfactant is used. In such a case, a large amount of addition is necessary, but in this case, the heat distortion temperature and the transparency are reduced, the basic characteristics of the resin are impaired, and the surfactant excessively bleeds out to the resin surface. It is inevitable that the molded products will be tackled and become unusable. On the other hand, when heat stability is required as the antistatic surfactant, an anionic surfactant such as a metal salt of an alkyl sulfonic acid or a metal salt of an alkyl benzene sulfonic acid has been proposed (Japanese Patent Application Laid-Open No. 49-49). - 7 3 4 4 3 JP, Sho 5 2 - 4 7 0 7 2 JP, Sho 5 4 - 3 7 1 5 4 No.) _c However, these internal kneading-type electrification preventing property surfactant Activators have the drawback that the transparency is reduced and the appearance is impaired because the compatibility with the inherently hydrophobic acryl resin is not sufficient.

 In addition, alkane sulfonate, alkylbenzene sulfonate and fatty acid monoglyceride are used in combination with the acrylic resin, and the decrease in transparency is improved by using a sulfonate-based anionic surfactant as an antistatic composition. Although a method has been proposed (Japanese Unexamined Patent Publication No. Hei 11-199552), the improvement effect is not always satisfactory.

 On the other hand, as an antistatic composition for polyolefin or polystyrene, a metal salt of a sulfonic acid having a free carboxyl group neutralized with an amine compound (Japanese Patent Publication No. 58-19692) and fats A sulfonic acid metal salt having a carboxyl group esterified with an aliphatic alcohol or polyethylene glycol (Japanese Patent Publication No. 58-53658) has been proposed.

 However, when these antistatic agent compositions are applied to an acrylic resin, it is inevitable that the appearance becomes poor due to a decrease in transparency and dispersibility.

On the other hand, to date, anti-static methods for acryl resin molded products, especially injection molded products, have been studied by using nonionic surfactants having a carbon chain length of 12 or less, using monoglyceride laurate instead of other nonionic surfactants. A method in which a surfactant is used in combination with an ionic surfactant (Japanese Patent Publication No. 2-143777), A method of blending min (JP-A-62-295944) has been proposed.

 However, in these methods, injection molding is required unless the amount of the nonionic surfactant added to the acrylic resin is 4 parts by weight or more. Sufficient antistatic effect cannot be obtained immediately after molding. Not only that, it lowers the thermal deformation temperature of the acrylic resin and the high volatility of the surfactant causes a silver mark on the surface of the molded product, degrading the appearance of the surface of the molded product, and intense smoke during molding. There are many disadvantages, such as inconvenience in the work environment.

 Under these circumstances, the present invention has superior antistatic properties to conventional antistatic agent compositions in thermoplastic resins such as acrylic resins, does not impair moldability, and is particularly blended with transparent resins. The molded product does not impair the transparency of the molded product when it is molded, and when it is blended with a transparent resin such as acryl resin due to its special composition, the antistatic performance is not limited to extrusion molding but also to injection molding. The purpose of the present invention is to provide an antistatic agent composition which is immediately expressed later. Disclosure of the invention

 The present inventors have conducted intensive studies to develop an antistatic agent composition having the above-mentioned preferable characteristics, and as a result, have found that two kinds of sulfonic acid salts having a specific structure or a nonionic surfactant is used. It has been found that the combination can more advantageously achieve the purpose by combining a sulfonate having a specific structure with a specific glycol and a specific nonionic surfactant, The present invention has been accomplished based on this finding.

 That is, the present invention relates to (A) —general formula (I)

0

 II

R ¹ -CH-C-0- (A ¹⁰ ) _m -H… (I)

I

S OgM ¹ And (B) — general formula

R CH— C— 0— (A ² 0) _n — C— CH— R (Π)

S 0 ₃ M ² S 0 ₃ M ³

(Wherein RR ² o I and R ³ are each independently a straight-chain or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and A ¹ and A ² are each independently An alkylene group having 2 to 4 carbon atoms, m and n each independently represent an integer of 6 to 50, and MM ² and M ³ each independently represent an alkali metal atom or a phosphonium group having 4 hydrocarbon groups. Or a combination of the sulfonic acid salt represented by the formula (A) and the component (B) in a weight ratio of 9: 1 to 1: 9, or (Α ') — general formula (m)

0

And (Β ') — general formula (IV)

0 0

 II II

R ² -CH-C-0-{(CH ₂ ) _r O} _s -C-CH-R ³ (IV)

(Wherein RR ² and R ³ are each independently a straight-chain or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and p and r are each independently a 2 to 4 integer, q and s integers each independently 1 to 100, MM ² and M ³ are Hosuhoniumu group having each independently an alkali metal atom or 4 hydrocarbon group)

And (C) a general formula (V) HO {(CH ₂ ) _t O} _u H… (V)

(Where t is an integer of 2 to 4 and u is 2 to 100)

And (D) a fatty acid glyceride derived from a fatty acid having 6 to 14 carbon atoms and having a fatty acid monoglyceride content of 70% by weight or more, and a fatty acid derived from a fatty acid having 6 to 14 carbon atoms. Or a nonionic surfactant selected from the group consisting of a fatty acid genamide and a jetanolamine N-substituted with an alkyl or alkenyl group having 6 to 14 carbon atoms. At least one selected from the sulfonates of component (Α ') and component (Β'), component (C) and component (D), and (Ε)

R- S 0 ₃ Μ ⁴

as well as

(R— S 0 ₃ ) ₂ Μ ⁵

(Wherein R is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 8 to 30 carbon atoms, 、 ⁴ is an alkali metal atom, 、 ⁵ is an alkaline earth metal atom). An antistatic composition comprising at least one selected from metal sulfonic acid salts represented by the following formulas: And a thermoplastic resin composition comprising:

 As described above, the antistatic agent composition of the present invention comprises, as described above, a two-component system of the component (Α) and the component (Β), the component (Α ′) and the component Ζ or (Β ′), the component (C), and the component (D). )), And another multi-component system in which component (II) is further added to this multi-component system.

RR ² and R ³ in the component (Α), the component (Α ′), the component (Β) and the component (Β ′) of the antistatic agent composition are each an alkyl group having 6 to 20 carbon atoms. Or an alkenyl group, which may be linear or branched, and R ¹ , R ² and R ³ may be the same And may be different. These include, for example, hexyl, octyl, decyl, Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, hexadecenyl group, octadecyl group, octadecenyl group and the like. If the number of carbon atoms of Ri, R ² and R ³ is less than 6, the compatibility with the thermoplastic resin is inferior and the transparency may be impaired. If the number exceeds 20, the antistatic performance deteriorates.

Further, A ¹ and A ² in the component (A) and the component (B) are an alkylene group having 2 to 4 carbon atoms, for example, an ethylene group, a propylene group, and the like. may be, also be one or may be allowed combination of two or more, may be mutually identical, which may be the or different, one or both of preferably a ¹ and a ² It is preferred that at least 70% or more of the total number of alkylene groups be ethylene groups. If the number of ethylene groups is too small, the antistatic property tends to decrease. Further, m and n are 6 to 50, preferably 9 to 40, and when these are more than 50, the antistatic property is reduced, and when they are less than 6, the transparency is reduced. C (Α ′) (CH ₂ ) _P and (CH ₂ ) _r in the component and the (Β ′) component are alkylene groups having 2 to 4 carbon atoms, that is, an ethylene group, a propylene group, or a butylene group. Or may be a combination of two or more kinds, and may be the same or different, and preferably one of the alkylene groups of these components Alternatively, it is preferred that at least 70% or more of the total number of both alkylene groups be ethylene groups. If the number of ethylene groups is too small, the antistatic property tends to decrease. In addition, q and s are 1 to 100, preferably 3 to 80, more preferably 6 to 50, and most preferably 9 to 40. If the properties of the blended thermoplastic resin are impaired, or if it is relatively small, there may be some problems in transparency and heat resistance depending on the type and amount of other components to be combined and the type of thermoplastic resin used. There is.

The sulfonate of the component (A), the component () ′), the component (Β) and the component (Β ′) may be a corresponding metal salt of sulfonic acid or four hydrocarbon groups. A Hosuhoniumu salts with the general formula of salt residue (I), (Π), () and ¹ in (IV), M ² and M ³ may be mutually identical, were or It may be different. As the alkali metal salt, a sodium salt, a potassium salt, a lithium salt and the like are preferable.

 As the salt residue of the phosphonium salt, for example, a compound represented by the following general formula (式)

RR ⁶

P… (VI)

R 5 R ⁷

(Wherein R ⁴ , R ⁵ , R ⁶ and R ⁷ are a substituted or unsubstituted linear or branched alkyl group or phenyl group having 1 to 18 carbon atoms). Examples of the substituent include a hydroxyl group, a halogen atom, and an amino group. Such compounds include, for example, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, trimethylstearylphosphonium, trimethyldodecylphosphonium, and trimethylphenylphosphonium. Examples include a dimethyl group, a triphenylmethylphosphonium group, a tetraphenylphosphonium group, a di (2-hydroxyshethyl) dibutylphosphonium group, and a p-hydroxyphenyltriethylphosphonium group. Phosphodimethyl salts are particularly effective as a highly heat-resistant resin composition.

 These components (A), (Α ′), (Β) and (Β ′) may be used each alone or in combination of two or more. In the two-component antistatic agent composition, at least two components of (Α) and (Β) are blended and used, but compared with the case where only the (Α) component or the (Β) component is used alone. This is advantageous because the antistatic property, particularly the stability over time of the performance and the transparency are better.

The compounding weight ratio of the component (ii) to the component (ii) is selected in the range of 9: 1 to 1: 9, preferably 8: 2 to 2: 8. If the ratio is higher than 9: 1, the antistatic property is reduced, and if the ratio is lower than 1: 9, the transparency is reduced. I do.

 A similar tendency is observed in the multi-component system. That is, when at least two components of (Α ') and (Β') are used in combination, the antistatic property, particularly the performance, is higher than when only the (Α ') component or the (Β') component is used alone. Stability over time and transparency are better, which is advantageous. When used in combination, the compounding weight ratio of each component is in the range of 9: 1 to 1: 9, preferably 8: 2 to 2: 8. To be elected. If this ratio is higher than 9: 1, the antistatic property will decrease, and if it is lower than 1: 9, the transparency will decrease.

 The component (Α) and the component (Β) are represented, for example, by the general formula (ΥΠ)

Η

R ⁸ — C— C OOR ⁹ … (VH)

I

S 0 ₃ Μ

(In the formula, R ⁸ is a linear or branched alkyl 1 or alkenyl group having 6 to 20 carbon atoms, R ⁹ is a hydrogen atom or an alkyl group, Μ is a hydrogen atom or the above salt residue. is there)

The compound represented by the general formula (VI)

 ΗΟ- (ΑΟ) ν-Η… (Cor)

(Where A is an alkylene group having 2 to 4 carbon atoms and V is 6 to 50), or a lower alkyl ester of the compound of the general formula (式) By subjecting the polyalkylene glycol of (VI) to a transesterification reaction, and when Μ is a hydrogen atom, subjecting the sulfonic acid of these reaction products to a predetermined salt-forming reaction to obtain the component (Α ′) And the component (Β ′) are, for example, a compound of the general formula (W) and a compound of the general formula (Κ)

HO- {(CH ₂ ) _x O} _y -H… (K)

(X in the formula is an integer of 2 to 4, and the alkylene group of (CH ₂ ) _X may be one type, or a combination of two or more types, and y is 1 to 100 Wherein the polyalkyleneoxy group in KCH ₂ ) _x O} _y is May be used alone or in combination of two or more) or the lower alkyl ester of the compound of the general formula (VH) is converted to a glycol of the general formula (IX) When M is a hydrogen atom, the compound can be produced by subjecting the sulfonic acid of these reaction products to a predetermined salt-forming reaction. The molar ratio of the compound represented by the general formula (II) and the polyalkylene glycol represented by the general formula (I) or the glycol represented by the general formula (K) is preferably in a range of 0.5: 1 to 2.0: 1. . In this case, these reaction products contain the component (A) and the component (B), or contain the component (Α ′), the component (Β ′) and optionally the glycol (C) described later. However, it is advantageous because it has a suitable composition of the antistatic agent composition of the present invention. Regarding the reaction conditions for obtaining the reaction product, in the case of the dehydration esterification reaction, the reaction temperature is 50 to 150 ° C., preferably 80 to 120 ° C. under normal pressure or reduced pressure, The reaction time is suitably from 30 minutes to 20 hours, preferably from 2 to 12 hours. In the case of a transesterification reaction, the reaction temperature is 50 to 150 ° C, preferably 80 to 120 ° C, and the reaction time is 10 minutes to 20 hours, preferably at normal pressure or reduced pressure. 30 minutes to 6 hours is appropriate.

 These reactions are carried out without solvent or in a solvent such as carbon tetrachloride xylene. The reaction temperature and the reaction time are appropriately selected depending on the molar ratio, the degree of reduced pressure and the like.

 In the transesterification, a conventional catalyst such as an acid catalyst such as p-toluenesulfonic acid and sulfuric acid, and a base catalyst such as sodium hydroxide, potassium hydroxide and sodium hydrogen carbonate are used. When the starting material is an unneutralized product, it is not necessary to add an acid catalyst.

 The salt formation reaction method is not particularly limited, and a conventionally known method can be used. For example, an alkali metal salt of the sulfonic acid can be obtained by allowing a hydroxide, carbonate, bicarbonate or the like of the alkali metal to act on the sulfonic acid of the above reaction product.

Further, the phosphonium salt is obtained by adding phosphonium salt to the alkali metal salt of the sulfonic acid. The compound can be obtained by metathesis by the action of a halogen salt of a platinum compound or by direct action of a phosphonium hydroxide compound.

Next, in the compound of the general formula (V) of the component (C), which is a component of the multi-component antistatic composition, t is an integer of 2 to 4, preferably 2 or 3, The alkylene group of (CH ₂ ) _t may be one type or a combination of two or more types. Also, u is selected in the range of _{2 to} 100, preferably 3 to 80, more preferably 6 to 50, and most preferably 9 to 40, and the polio of KCH ₂ ) _t O} _u is selected. The xyalkylene group may be a single type or a combination of two or more types. Examples of such compounds include polyethylene glycol, polypropylene glycol, and ethylene glycol-propylene glycol copolymer. The specific nonionic surfactant (D) is a fatty acid glyceride derived from a fatty acid having 6 to 14 carbon atoms and having a fatty acid monoglyceride content of 70% by weight or more. At least one selected from fatty acid diethanolamide derived from fatty acids having 6 to 14 carbon atoms and jetanolamine N-substituted with an alkyl or alkenyl group having 6 to 14 carbon atoms Is a main component. If the number of these carbon atoms is too small, the volatility becomes high, and problems such as smoke are generated. If the number is too large, the immediate effect of antistatic performance cannot be obtained.

 The fatty acid glyceride of the component (D) needs to have a fatty acid monoglyceride content of 70% by weight or more, and is a mixture of fatty acid monoglyceride ゃ and fatty acid diglyceride ゃ fatty acid triglyceride. Are used. If the content of the fatty acid monoglyceride is less than 70% by weight, immediate effect of antistatic performance cannot be obtained.

These specific nonionic surfactants include, for example, glyceride monoproic acid, diglyceride cabronate, triglyceride proproate, monoglyceride octylate, diglyceride octylate, triglyceride octylate, decanoate. Monodaliceride, decanoic acid diglyceride, decanoic acid triglyceride, lauric acid monoglyceride, lauric acid diglyceride Triglyceride, lauric acid monoglyceride, myristic acid monoglyceride, myristic acid diglyceride, myristic acid triglyceride, caproic acid diethanolamide, octylic acid diethanolamide, decanoic acid diethanolamide, lauric acid jetanolamide , Gentanolamide myristate, diethanolhexylamine, diethanoloctylamine, jetanolylarylamine, and jetanolmyristylamine.

Then, another multi-component antistatic agent composition of above, by its having a composition component (E) component, the surface resistance of the molded after immediate can be less than 10 ^U Q. Examples of the component (E) include sodium paraffin sulfonate, and linear or branched d ₂ alkyl-benzene sulfonate sodium.

 In the antistatic agent composition of the present invention, as an auxiliary component, for example, ethylene glycol stearate, polyethylene glycol stearate, polyethylene glycol laurate, palmitic acid monoglyceride, palmitic diglyceride, palmitic acid Triglyceride, monoglyceride stearate, diglyceride stearate, triglyceride stearate, pentaerythritol monostearate ester, pentaerythritol dilaurate, stearyl alcohol, lauryl alcohol, octyl alcohol, glycerin Monostearic acid succinate, diethanolstearylamine, diethanol palmitylamine, panolemitic acid jetanolamide, It may be contained, such as ants phosphate diethanolamine de. These may be used alone or in combination of two or more.

In the multi-component antistatic agent composition of the present invention, a suitable compounding ratio of each component is such that {(Α ′) + (Β ′)} / (C) is from 90/10 to 30/70 on a weight basis. 85 715-40 60 60, {(Α ') + (Β')} + (C) / (D) is in the range of 20Ζ80-80Ζ20, preferably 25Ζ75-75Ζ25, and if it deviates from this range, a sufficient effect can be obtained. It becomes difficult. Further, in another multi-component antistatic composition, a suitable mixing ratio of each component is as follows: ((Α ′) + (Β ′)) / (C) is 90Z10 to 30Z70, preferably 85 / 15~ 40 60, {(Α ' ) + (Β') + (C)} / (D) is 20/80 to ^80/20 preferably ^{25 / / 75~75 25, {(} Α ') + (Β ') + (C) + (D)} / (Ε) is in the range of 99Ζ1 to 50Ζ50, and if it deviates from this range, it is difficult to obtain a sufficient effect. The antistatic agent composition of the present invention can impart an antistatic property to a thermoplastic resin without impairing its original properties and moldability. The thermoplastic resin is not particularly limited, but a transparent resin such as an acrylic resin, a vinyl chloride resin, a polyethylene terephthalate resin, a polybutylene terephthalate resin, or a polycarbonate resin is impaired in transparency. Not preferred. Examples of the acryl resin of these transparent resins include, for example, methyl methacrylate homopolymer or methyl methacrylate, and 50% by weight or less of an acrylate or methacrylate other than methyl methacrylate, acrylic acid, methacryl. Copolymers with acid, styrene, acrylonitrile, butadiene, etc. are listed. For the purpose of further improving the strength of molded products, rubber components such as polybutadiene, styrene-butadiene rubber, acrylonitrile rubber, etc. Butadiene rubber or the like may be blended by a conventional method. Examples of the acrylate include methyl acrylate, ethyl acrylate, and butyl acrylate. Examples of the methacrylate include ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate.

The antistatic agent composition of the present invention is prepared by preparing a masterbatch kneaded in a thermoplastic resin at a concentration higher than the concentration in a target thermoplastic resin composition in advance and adding the calculated amount at the time of molding. Can be used. This master batch can be prepared by blending 6 to 50 parts by weight, preferably 10 to 40 parts by weight, of the antistatic composition of the present invention with 100 parts by weight of the thermoplastic resin. If the amount is more than 50 parts by weight, In addition, it becomes difficult to uniformly disperse at the time of fabricating, and the concentration of the antistatic agent composition is too high, resulting in poor dispersibility at the time of addition.

 By blending the antistatic agent composition of the present invention with a thermoplastic resin, a thermoplastic resin composition having excellent antistatic properties and moldability is prepared. In particular, when a transparent resin is used as the thermoplastic resin, A resin composition having excellent transparency is prepared. In this case, the amount of the antistatic agent composition is usually 0.5 to 6.0% by weight, preferably 1% by weight, based on 100 parts by weight of the thermoplastic resin. It is preferable to add so that the amount is from 0 to 4.0 parts by weight. If the amount is less than 0.5 part by weight, the effect of imparting antistatic properties is not sufficiently exhibited, and if it exceeds 6 parts by weight, no further improvement in the antistatic effect is observed, and the physical properties of the thermoplastic resin are adversely affected. Influence, not preferred.

 As this preparation method, it is preferable to knead a predetermined compounding component into a thermoplastic resin. There is no particular limitation on the kneading method, and a conventionally known method, for example, a method of blending a thermoplastic resin such as an acryl resin with a blended component, followed by melt-kneading with an extruder and then extruding the blended component, A method of preparing a master patch kneaded with a resin at a high concentration and adding this at the time of molding can be used.

When preparing the thermoplastic resin composition, various commonly used additives can be used in combination, if necessary. Examples of such additional components include phosphorus-based antioxidants such as tri (nonylphenyl) phosphite and triphenylphosphite, dioctadecyl 3,3′-thiodipropionate, and didodecyl 3,3′-thiodipropionate. Sulfur-based antioxidants, such as butylated hydroxytoluene, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methinol-based oxidation, such as methane Inhibitors, UV absorbers, nucleating agents, ethylene bisamides, monoalkyl amides, polyolefin waxes such as montanic acid wax, polyethylene resin, lubricants such as higher fatty acid metal salts, and fluorescent brightening agents such as oxazole and coumarins Agent, barium sulfate, titanium oxide 4 Includes resin reinforcing or light scattering inorganic fillers such as tan and calcium carbonate, and other colorants.

 The thermoplastic resin composition thus prepared can be molded by various molding methods such as injection molding, extrusion molding, blow molding, and the like. And parts, meter covers, films, sheets, panels, and molded products such as fine fibers such as optical fibers.

 Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

 The performance of the molded article was obtained and evaluated for each test piece as follows.

(1) Evaluation of surface resistance and antistatic performance

 Toa Denpa Co., Ltd. Using a super insulation meter SM-10E, immediately after molding, or maintain the molded product in a constant temperature / humidity room at 23 ° C and 65% RH for 1 month or 6 months. After that, the surface resistance was measured for each. In addition, depending on the sample, when this measured value was X (Ω), the antistatic performance was evaluated according to the following criteria.

A: X <1 X 1 0 ^{1 1}

B: 1 X 1 0 ^{1 1} ≤ X <1 X 1 0 ^{1 2}

C: 1 X 1 0 ^{1 2} ≤ X <1 1 0 ^{1 3}

D: X≥ 1 X 1 0 ^{1 3}

 (2) Cloudiness

 It was determined in accordance with JISK 713.

Examples 1 to 11, Comparative Examples 1 to 6

 To the acrylic resin [SUMIPEX B-EX, manufactured by Sumitomo Chemical Co., Ltd.], the ingredients of the types shown in Table 1 were added in the amounts shown in Table 2, and premixed with a Henschel mixer. This mixture was melt-kneaded at 230 ° C. using a vented twin-screw extruder, and the resulting strand was pressed with a pelletizer to form a pellet.

After the pellets were dried, the vented extruder was used to produce a width of 130 Omm, An extruded plate having a thickness of 2 mm was obtained. The plate was pressed to make a 100 x 100 x 2 mm plate. Table 2 shows the results of measuring the surface resistance and haze of this plate after conditioning it for 1 day in a constant temperature and humidity room at 23 ° C and 65% RH.

Blending composition (A) Component (B) Component

No. R ¹ A ^! 0 m M ¹ R ² = R ³ A ² 0 n M ² = M ⁸ (A) / (B)

 1 then 10 EO 9 Na C 10 EO 9 Na 85/15

2 16 E0 14 N a C 16 EO 14 N a 40/60

3 16 E0 23 Na C 16 EO 23 Na 30/70

4 then 16 EO 23 K C 16 EO 23 K 60/40

5 then 14 1 O EO 23 L i C 14 EO 23 L i 80/20

6 then 14 23 N a C 1 23 N a 50/50

7 c ₈ EO 35 N ac ₈ EO 35 N a 80/20

8 18 EO / PO = 28/7 35 i C 18 EO / PO = 28/7 35 L i 40/60

9 1B EO 35 Na C 18 EO 35 Na 35/65

10 12 EO 35 Na C l 2 EO 35 Na 25/75

11 16 EO 9 DDP C 16 EO 9 DDP 50/50

12 EO 9 N a C 12 EO 9 N a 100/0

13 EO 9 N a C l 2 EO 9 N a 0/100

14 16 EO 23 Na C l 6 EO 23 Na 95/5

15 o 23 Na Co

 16 E 16 E IIO 23 Na 5/95

16 then 12 EO 5 K C 12 EO 5 K 10/90

17 then 14 EO 68 N a C i EO 68 Na 80/20

RR ² and R ³ are represented as C _k (k is the number of carbon atoms) according to the number of carbon atoms in the alkyl group.

EO: ethyleneoxy; PO: propyleneoxy; DDP: dibutyldiphenylphosphonium

7 Table 2 Blending amount Blending amount, performance of an an composition Composition Surface resistance (Ω)

 Value

No. (wt%) After molding 1 After molding 6 months

^{1 - 2 7. 8x 10 11 8.} 9xl0 10 4. 3

2 2 1.5 9.5x ^{10 11} 7.4 xl0 ¹⁰ 4.6

3 3 1.5 8.8 X 10 ¹¹ 6.7 X 10 ¹⁰ 4.4

4 4 2 2.3 x 10 ¹¹ 2.8 10 ¹⁰ 6.5

5 5 28.4 xlO ⁿ 6.3X10 ¹⁰ 3.9 Application 6 6 2 2 .3xl0 ¹² 3.lxlO ¹¹ 6.7

7 7 29.8 xlO ⁿ 4.3 x 10 ^U 4.7

8 8 2 1.2 x 10 ¹² 2.7 x 10 ¹¹ 5.5 Example 9 9 2 5.6 xlO ⁿ 6.9 xl0 ¹⁰ 4.6

1h ¹⁰ 27.3 xlO ⁿ 5.8xl0 ¹⁰ 4.8

^{11 11 2 8. 6xlO n 9. 6x} 10 10 4. 9 ratio ^{1 12 3 7. 3xl0 13 1. 9x} 10 13 5. 3

2 13 2 8.7xlO ^u 1.8X10 ¹¹ 20.3

^{3 14 3 5. 9x 10 13 1.} Ox 10 13 5. 7

^{4 15 2 7. 9x 10 11 9.} 8x 10 10 15. 1 Example ^{5 16 3 6. 5xlO n 9. 6x} 1 O 10 35. 8

^{6 17 3 8. 7x 10 14 6.} 3xl0 13 4. 3

If the surface resistance is 10 ¹³ Ω or more, the desired antistatic effect cannot be obtained. Example 12-; I 8 ′, Comparative Example 7-: I 3

To the acryl resin [Kuraray Co., Ltd., Para-Gl-II], the components shown in Table 1 or the comparative substances were added in the amounts shown in Table 3, and premixed with a Henschel mixer. A mixture or a non-added acryl-based resin 8 itself was melt-kneaded at 230 ° C using a vented twin-screw extruder and extruded, and the resulting strand was pressed with a pelletizer to form a pellet. After the pellets were dried, they were injection-molded at 260 ° C. using an injection molding machine to form a 100 × 100 × 2 mm plate. This plate was evaluated in the same manner as in Example 1. Table 3 also shows the results. Table 3

PS: sodium paraffin sulfonate (average carbon chain length 14)

DS: Sodium dodecylbenzenesulfonate 9 Examples 19-26

 In Examples 19 to 22, 2% by weight of the antistatic agent composition having the composition No. 1 was added to the various transparent resins shown in Table 4, and in Examples 23 to 26, the mixed components of the composition No. 1 were mixed. 2.5% by weight of an equal weight mixture of styrene and polyethylene glycol having an average degree of polymerization of 9 to prepare various resin compositions, which were molded according to the method of Example 1 to determine the performance of the molded articles. Table 4 shows the results. Table 4

表中の樹脂の種類における記号は次の意味を有する。

The symbols for the types of resin in the table have the following meanings.

 MS: Estyrene MS-600 (trade name, manufactured by Nippon Steel Chemical Co., Ltd., methyl methacrylate-styrene copolymer)

 AS: Sebian-N (trade name, Daicel Chemical Co., Atarilonitrile-styrene copolymer)

 PVC: Zeon 103EP-8 (trade name, manufactured by Zeon Corporation, vinyl chloride resin)

PC: Panlite L-1225 (trade name, Teijin Chemicals, polycarbonate resin) Examples 27 to 41, Reference Examples 1 to 6

 (C) The blending weight ratio of polyethylene glycol (9) as a component and each of the components shown in Table 5 is shown in Table 5 ((Α ') / (Β') = 80/20; In parentheses in the column of ") is the blending weight ratio of each component when two types of component (D) are used]), and the blended composition is shown in Table 5. Indicated by

 In the acryl resin [Kuraray Co., Ltd., G1-Ρ], in Examples 27 to 39, 2.5% by weight of the antistatic agent composition having the composition No. 18 to 30 shown in Table 5 was used. In Examples 40 and 41, 3.0% by weight of the antistatic agent composition of the composition No. 31 and No. 32 shown in Table 5 was used. In Reference Examples 1 to 6, the composition of No. 33 to 38 shown in Table 5 was used A mixture obtained by adding 2.5% by weight of the composition having the mixed composition and premixing with a Hensile mixer was melt kneaded at 230 ° C. using a vented twin-screw extruder and then extruded. At that time, the degree of smoke emission from the vent was visually determined.

Next, the obtained strand is pressed with a pelletizer, the pelletized _c- pellet is dried, and then is injection-molded at 240 ° C by an injection molding machine, and a lO Ox l O Ox 2 mm test piece is formed. Created. The surface resistance of the test piece was measured immediately after molding and 6 months after molding. As for the moldability of the test piece, the surface condition of the molded article was visually judged. As a result, the surface resistance of each molded product of each example was evaluated as B immediately after molding, and A after 6 months from molding, indicating excellent antistatic performance, good moldability, and good moldability. Smoke emission was also low. On the other hand, as shown in Table 6, the molded articles of each comparative example had at least one type of inconvenience, such as poor antistatic performance, poor moldability, and smoke generation during molding. . Table 5 Composition (Α ') Ingredient (Β') Ingredient (D) Ingredient Ingredient weight ratio

No.R ¹ P q M ¹ R ² = R3 rs M ² = M ³ LMG (Α ') + (B') / (C) / (D)

18 16 2 9 Na C l β 29 Na LMG 25/25/50

 19 and 12 2 9 Na C l 2 9 Na LMG 25/25/50

20 c ₈ 2 9 Na c ₈ 2 9 Na LMG 25/25/50

 21 and 16 2 3 Na C l 6 2 3 Na LMG 25/25/50

 22 16 16 2 35 Na C l β 235 Na LMG 25/25/50

 23 16 16 2 9 L i C l β 29 L i LMG 25/25/50

 24 16 2 9 K C l β 29 K LMG 25/25/50

 25 to 16 29 Na Cl 1 29 Na LMG 20/30/50

 26 and 16 2 9 Na C 16 2 9 Na LMG 40/10/50

 27 16 2 9 Na C l 6 2 9 Na LMG 15/15/70

 28 16 2 9 Na C l 6 2 9 Na LDAd 25/25/50

 29 16 2 9 Na C l 6 2 9 Na LDAn 25/25/50

 30 to 16 2 9 Na C i 6 2 9 Na LMG + LDG 25/25/50 (40/10)

31 16 2 80 Na C l 6 2 80 Na LMG 25/25/50

 32 16 2 9 Na C l β 29 Na LMG + SA 25/25/50 (30/20)

33 16 16 2 119 Na C l β 2 110 .Na LMG 25/25/50

 34 and 16 2 9 Na C l β 29 Na LMG + SMG 25/25/50 (20/30)

35 to 16 29 NaCl 6 29 Na LMG + LDG 25/25/50 (25/25)

36 LMG 0/50/50

 37 16 16 9 NaCl 6 29 Na LMG 50 / 0/50

38 16 2 9 Na Cl 6 29 Na 50/50/0

Each symbol in Table 5 has the following meaning.

 LMG: monoglyceride laurate, SA: stearyl alcohol, LDG: diglyceride laurate, SMG: monoglyceride stearate, LDAd: diethanolamide laurate, LDAn: lauryldiethanolamine

In the table, RR ² and R ³ are represented as C _k (k is the number of carbon atoms) according to the number of carbon atoms in the alkyl group. Table 6

実施例 42〜47

Examples 42-47

Acryl-based resin [G1-P, manufactured by Kuraray Co., Ltd.] was added to the four types of components shown in Table 5 for the composition No. 18 and various metal salts of sulfonate (E) shown in Table 7 Were added in the proportions shown in Table 7 to add 2.5% by weight of each antistatic agent composition, and each molded article was prepared in the same manner as in Example 27. The surface resistance of each of the molded products was evaluated as A immediately after molding and 6 months after molding, indicating excellent antistatic performance, good moldability, and little smoke during molding. 7

表 7中、 AB Sは分岐 d 2アルキルベンゼンスルホン酸ナトリウム、 P Sは C ₁₄パラフィンスルホン酸ナトリウム、 LASは直鎖 C 1₂アルキ ルベンゼンスルホン酸ナトリゥムをそれぞれ示す。

In Table 7, AB S denotes branched d 2 sodium alkylbenzene sulfonate, PS is C ₁₄ sodium paraffin sulfonate, LAS is a linear C 1 ₂ alkyl Le benzenesulfonic acid Natoriumu respectively.

Examples 48-49

 A 300 ml three-necked flask was equipped with a stirrer, Dimroth condenser, and thermometer, and 200 g of methyl methacrylate and 1 g of benzoyl peroxide were added.Then, the mixture was heated to 90 ° C in a water bath to polymerize. When the viscosity became 100 centi-boise, it was quenched with ice water to obtain a dry mouth.

 On the other hand, a silicone rubber tube and a spacer with a thickness of 2 mm were sandwiched between two glass plates (100 x 100 x 5 mm) to create a mold for putting syrup.

To the above syrup was added 3% by weight of an antistatic agent having a composition of mixture No. 18 shown in Table 5 or a mixture of 60% by weight of this mixture and 40% by weight of PEG (9). After casting in a water bath at 70 ° C for 3 hours and then at 95 ° C for 2 hours, the cast resin plate produced from the mold was taken out and the performance of the molded product was determined. As a result, when the former antistatic agent was used, the surface resistance was 6 X 10 Ω one day after molding. 5 X 10 ^{! 1} Ω six months after molding. The haze was 7.8, and the latter antistatic agent was used. If you were, surface resistance molding 1曰後3 X 10 ^U Q, a 4x 10 ^Micromax Omega after molding 6 months, The haze was 4.7.

Comparative Example 1 4

 Sodium paraffin sulfonate was used in place of the antistatic agent composition of Example 48, and this was added to the same syrup as in Example 48, but did not dissolve in the syrup. Industrial applicability

 When the antistatic agent composition of the present invention is blended with a thermoplastic resin, the antistatic agent composition can stably provide excellent antistatic performance and also improve the moldability. Further, the multi-component antistatic composition can also exhibit a stable antistatic performance immediately after molding with a small amount of addition even in injection molding, and can reduce smoke during molding. When a transparent resin such as an acryl resin is used for the thermoplastic resin, a remarkable effect that the transparency is not deteriorated is exerted.

Claims

The scope of the claims 1. (A) General formula 0  II R ¹ -CH-C-0- (A ¹⁰ ) _D1 -H

And (B) — general formula 0 0  II R ² — CH— C— 0— (A ² 0) _n — C— CH— R ³  I I so ₃ M ² so ₃ M ³ (Wherein RR ² and R ³ are each independently a straight-chain or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and A ¹ and A ² are each independently a carbon atom An alkylene group of numbers 2 to 4, m and n are each independently an integer of 6 to 50, and MM ² and M ³ are each independently an alkali metal atom or a phosphonium group having 4 hydrocarbon groups. An antistatic composition comprising the sulfonate represented by the formula (C) in a weight ratio of the component (A) to the component (B) of 9: 1 to 1: 9. 2. A ¹ or antistatic agent composition of at least 70% Gae styrene and is described claim 1, wherein groups of the total number of alkylene groups represented by A ^2.  3. (Α ') — general formula 0  II R 1 _ CH-C-0-{(CH ₂ ) pO} ₀ -H

And (Β ') — general formula 0 0  II R ² -CH-C-0-{(CH ₂ ) _r O} _s -C-CH-R ³  I I S 0 ₃ M ² S 0 ₃ M ³ (wherein RR ² and R ³ are each independently a straight-chain or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and p and r are independently an integer of 2 to 4 their respective, Q and s are integers independently 1 to 100, Hosuhoniumu with each MM ² and M ³ are independently a alkali metal atom or 4 hydrocarbon group Is the base) And at least one selected from the sulfonates represented by the formula (C): HO {(CH ₂ ) _t O} _u H  (Where t is an integer from 2 to 4, u is from 2 to: L00) And (D) a fatty acid glyceride derived from a fatty acid having 6 to 14 carbon atoms and having a fatty acid monoglyceride content of 70% by weight or more, and a fatty acid derived from a fatty acid having 6 to 14 carbon atoms. An antistatic agent comprising a fatty acid gel and a nonionic surfactant selected from N-substituted diethanolamines having 6 to 14 alkyl or alkenyl groups. Composition. 4. Furthermore, (E) —general formula RS 0 ₃ M ⁴ as well as (RS 0 ₃ ) ₂ M ⁵ (In the formula, R is a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms, or an alkylaryl group having 8 to 30 carbon atoms, and M ⁴ is an alkali metal atom. , M ⁵ antistatic agent composition of at least one formed by blending the claims 3 claims selected from among a sulfonic acid metal salt represented by a is) Al force Li earth metal atom. 5. Each component (Α '), (Β'), (C), (D) is Relational expression  {(Α ') + (Β')} / (C) = 90 10-30Z70 And relational expressions  4. The antistatic agent according to claim 3, which satisfies {(Β ′) + (Β ′) + (C)} / (D) = 20−80−20.  6. Each component (Α '), (Β'), (C), (D), (E) is the compounding weight ratio, and the following relational expression  {(Α ') + (Β')} / (C) = 90 / 10〜30 ノ 70 Relational expression  {(Α ') + (Β') + (C)} / (D) = 20Z80-80Z20 and relational expressions  The antistatic agent according to claim 4, wherein {(Α ') + (Β') + (C) + (D)} / (E) = 99Z1 to 50Z50.  7. A thermoplastic resin composition comprising a thermoplastic resin and the antistatic agent according to any one of claims 1 to 6.  8. The thermoplastic resin composition according to claim 7, wherein the compounding amount of the antistatic agent is 0.5 to 6.0% by weight based on the thermoplastic resin.  9. The thermoplastic resin composition according to claim 7, wherein the thermoplastic resin is an acryl-based resin. 10. The thermoplastic resin composition according to claim 7, wherein the thermoplastic resin is a vinyl chloride resin, a polyester resin, or a polycarbonate resin.