JP6893832B2 - Antistatic agents for thermoplastic resins and their use - Google Patents

Description

The present invention relates to an antistatic agent for thermoplastic resins and its use.

Since thermoplastic resins have good transparency, rigidity, and moisture resistance, their films and molded products are widely used in packaging materials such as foods and clothing, home appliance parts, and automobile interior materials. These resins generally have high insulating properties and are used for various purposes by utilizing this excellent property, but on the other hand, static electricity is likely to be generated due to friction and the like, and the generated static electricity is accumulated (charged). It causes various troubles. Conventionally, in order to prevent these troubles, troubles due to static electricity have been prevented by kneading an antistatic agent (various surfactants) into the resin. In this case, it is presumed that the kneaded antistatic agent exerts its effect by sequentially migrating (orienting) the antistatic agent to the surface and forming a conductive film on the surface.

For polypropylene, which is the most commonly used thermoplastic resin, a combination system of fatty acid ester of aliphatic amine ethylene oxide and fatty acid monoglyceride as described in Patent Document 1 is the most suitable and versatile for a long time. Has been used for.

In recent years, the development of catalysts and processes for obtaining highly regular polypropylene resins has made it possible to efficiently obtain polypropylene having higher rigidity and transparency than before. However, on the other hand, due to the increased crystallinity of the resin, it has become a problem that the performance of the kneaded antistatic agent is less likely to be exhibited in the antistatic agent compounding system as in Document 1.
In order to solve this problem, measures have been taken to increase the concentration of these additives and to lengthen the heat setting time after the molded product is produced to accelerate the transfer speed of the internal surfactant to the surface. However, attempts to improve performance by increasing the concentration and extending the heat setting time often cause an excessive bleeding phenomenon on the surface of the surfactant, and the excessive bleeding antistatic agent reduces the transparency of the film. In the sheets and molded products, stains were observed due to the stickiness of the surface.

Patent Document 2 proposes a blending system of alkyldiethanolamine, glycerin monofatty acid ester, polyoxyethylene alkylamine fatty acid ester, and fatty alcohol as an antistatic agent for molded products. In this blending system, molded products, sheets, etc. Although it can exhibit immediate performance for thick subjects, it is expected that whitening phenomenon due to excessive bleeding will occur when used for films.

In this way, in the resin composition kneaded with the antistatic agent, a sufficiently satisfactory compounding system was not found, and the appearance was excellent due to stable performance expression for a wide range of objects such as molded products, sheets, and films. There is a demand for an antistatic agent that has good fast-acting properties and long-lasting properties in a molded product.

Special fair No. 4-43104 Japanese Unexamined Patent Publication No. 2006-143980

An object of the present invention is to provide an antistatic agent that gives an excellent appearance due to the development of stable antistatic properties for a wide range of molding materials.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、アルキル基、アルケニル基、アルカジエニル基またはアルキニル基である。Ｒ^１の炭素数は８〜２２、Ｒ^２の炭素数は７〜２１である。ａ及びｂはオキシエチレン基の平均付加モル数を示し、ａ及びｂは０以上であり、ａ＋ｂは２〜３を満足する数である。）

（式中、Ｒ^３及びＲ^４は、それぞれ独立して、アルキル基、アルケニル基、アルカジエニル基又はアルキニル基である。２つあるＲ^４は互いに同一であっても異なっていてもよい。Ｒ^３の炭素数は８〜２２であり、Ｒ^４の炭素数は７〜２１であり、ｃ及びｄはオキシエチレン基の平均付加モル数を示し、ｃ及びｄは０以上であり、ｃ＋ｄ=２〜３を満足する数である。）

（式中、Ｒ^５はアルキル基、アルケニル基、アルカジエニル基又はアルキニル基であり、その炭素数は８〜２２であり、e及びfはオキシエチレン基の平均付加モル数を示し、ｅ及びｆは０以上であり、ｅ＋ｆ＝２〜３を満足する数である。）
Ｒ ^６ ＣＯＮＨ _２ （４）
（式中、Ｒ ^６ はアルキル基、アルケニル基、アルカジエニル基またはアルキニル基であり、その炭素数は１５〜２１である。） As a result of diligent research, the present inventors have solved the above-mentioned problems if the antistatic agent contains a specific amount of a specific aliphatic amine ethylene oxide adduct fatty acid ester (A) and a specific compound. We found a solution and arrived at the present invention.
That is, the antistatic agent for thermoplastic resins of the present invention includes a component (A) which is an aliphatic amine ethylene oxide fatty acid ester, a component (B) which is a glycerin monofatty acid ester, and an aliphatic amine ethylene oxide adduct. An antistatic agent containing the component (C) and the fatty acid amide represented by the following general formula (4).
The component (A) is a component (A-1) which is an aliphatic amine ethylene oxide adduct monofatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2). Containing a component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) to the component (A-2) is 50/50 to 90/10, and the component (C) is the following general formula (3). ) compound der represented by is,
The weight ratio of the fatty acid amide to the total weight of the component (A), the component (B) and the component (C) is 0.2 to 5% by weight .

(In the formula, R ¹ and R ² are independently alkyl group, alkenyl group, alkazienyl group or alkynyl group. R ¹ has 8 to 22 carbon atoms and R ² has 7 to 21 carbon atoms. A and b indicate the average number of moles of oxyethylene groups added, a and b are 0 or more, and a + b is a number satisfying 2 to 3.)

(Wherein, R ³ and R ⁴ are each independently an alkyl group, an alkenyl group, alkadienyl group or .2 is an alkynyl group There R ⁴ is optionally being the same or different .R ³ Has 8 to 22 carbon atoms, R ⁴ has 7 to 21 carbon atoms, c and d indicate the average number of moles of oxyethylene groups added, c and d are 0 or more, and c + d = 2 to 2. It is a number that satisfies 3.)

(Wherein, R ⁵ is an alkyl group, an alkenyl group, alkadienyl group or an alkynyl group, the carbon number of 8 to 22, e and f represents an average addition molar number of oxyethylene groups, e and f are It is a number that is 0 or more and satisfies e + f = 2 to 3.)
R ⁶ CONH ₂ (4)
(In the formula, R ⁶ is an alkyl group, an alkenyl group, an alkazienyl group or an alkynyl group, and the number of carbon atoms thereof is 15 to 21.)

The weight ratio of the component (A) is 10 to 40% by weight, and the weight ratio of the component (B) is 20 to 40% by weight with respect to the total weight of the component (A), the component (B), and the component (C). 80 wt%, wherein the weight ratio of component (C) is not preferred to be 10 to 40 wt%.
Rights Hitoshitsubu diameter 2~10mm and thickness 0.5~1.5mm flaky, or is a pellet shape having an average particle size of 2~7mm preferred.

It further contains an inorganic powder and / or a fatty acid metal salt, and the average particle size of the inorganic powder and the fatty acid metal salt is 0.1 to 50 μm, and the component (A), the component (B) and the component ( The weight ratio of the inorganic powder and the fatty acid metal salt to the total weight of C) is preferably 0.1 to 10% by weight.

The antistatic resin composition of the present invention contains the above antistatic agent.
It is preferable that the thermoplastic resin is polyolefin.

The molded product of the present invention is obtained by molding the antistatic resin composition.

The antistatic agent for thermoplastic resins of the present invention can exhibit stable antistatic properties having both immediate effect and durability for a wide range of molding materials, and can give an excellent appearance.

[Antistatic agent for thermoplastic resin]
The antistatic agent for thermoplastic resins of the present invention contains a specific component. These components will be described in detail.

[Ingredient (A)]
The component (A) is a component having excellent compatibility with the thermoplastic resin, and is used to control the dispersed state of the antistatic component in the thermoplastic resin. The component (A) is an aliphatic amine ethylene oxide adduct fatty acid ester.
The antistatic agent for a thermoplastic resin of the present invention essentially contains the component (A-1) represented by the above general formula (1) and the component (A-2) represented by the following general formula (2).

[Component (A-1)]
The component (A-1) is an aliphatic amine ethylene oxide adduct monofatty acid ester, which is a compound represented by the above general formula (1).
In the above general formula (1), R ¹ is an alkyl group, an alkenyl group, an alkazienyl group or an alkynyl group. R ¹ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and a linear group is preferable from the viewpoint of exhibiting the effects of the present application.
R ¹ has 8 to 22 carbon atoms, preferably 12 to 18, more preferably 14 to 18, and even more preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the thermoplastic resin is poor, and excessive bleeding causes deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness. On the other hand, when the number of carbon atoms exceeds 22, the antistatic property is lowered.

The number of carbon atoms in R ² is preferably 11 to 17, more preferably 13 to 17, particularly preferably 15 to 17. If the number of carbon atoms is less than 8, the compatibility with the thermoplastic resin is poor, and the film transparency is lowered due to excessive bleeding, and the surface of the sheet or molded product becomes dirty or sticky. May cause. On the other hand, if the number of carbon atoms exceeds 22, the antistatic property may decrease.

a and b indicate the average number of moles of oxyethylene groups added. a and b are 0 or more, and a + b is a number satisfying 2 to 3.

The component (A-1) is not particularly limited, and for example, lauryldiethanolamine monolaurate, lauryldiethanolamine monomillistate, lauryldiethanolamine monopalmitate, lauryldiethanolamine monostearate, lauryldiethanolamine monooleate, myristyldiethanolamine monolaurate, Myristyl Diethanolamine Monomillistate, Myristyl Diethanolamine Monopalmitate, Myristyl Diethanolamine Monostearate, Myristyl Diethanolamine Monoolate, Palmityl Diethanolamine Monolaurate, Palmityl Diethanolamine Monomillistate, Palmityl Diethanolamine Monopalmitate, Palmythyl Diethanolamine Monostearate , Palmytyl Diethanolamine Monooleate, Stearyl Diethanolamine Monolaurate, Stearyl Diethanolamine Monomillistate, Stearyl Diethanolamine Monopalmitate, Stearyl Diethanolamine Monostearate, Stearyl Diethanolamine Monooleate, Oleyl Diethanolamine Monolaurate, Oleyl Diethanolamine Monomillistate, Oleyl Diethanolamine Examples thereof include monopalmitate, oleyldiethanolamine monostearate, and oleyldiethanolamine monooleate, which may be one or more.

[Component (A-2)]
The component (A-2) is an aliphatic amine ethylene oxide adduct difatty acid ester, which is a compound represented by the above general formula (2).
In the above general formula (2), R ³ is an alkyl group, an alkenyl group, an alkazienyl group or an alkynyl group. R ³ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and a linear group is preferable from the viewpoint of exhibiting the effects of the present application.
R ³ has 8 to 22 carbon atoms, preferably 12 to 18, more preferably 14 to 18, and even more preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the thermoplastic resin is poor, and excessive bleeding causes deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness. On the other hand, when the number of carbon atoms exceeds 22, the antistatic property is lowered.

The number of carbon atoms of R ⁴ is preferably 11 to 17, more preferably 13 to 17, particularly preferably 15 to 17. If the number of carbon atoms is less than 8, the compatibility with the thermoplastic resin is poor, and excessive bleeding causes deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness. On the other hand, when the number of carbon atoms exceeds 22, the antistatic property is lowered.

c and d indicate the average number of moles of oxyethylene groups added. c and d are 0 or more, and c + d is a number satisfying 2 to 3.

Specifically, as the component (A-2), for example, lauryl diethanolamine dilaurate, lauryl diethanolamine dimillistate, lauryl diethanolamine dipalmitate, lauryl diethanolamine distearate, lauryl diethanolamine diolate, myristyl diethanolamine dilaurate, myristyl diethanolamine dimillistate, myristyl. Diethanolamine Dipalmitate, Myristyl Diethanolamine Distearate, Myristyl Diethanolamine Diurate, Palmityl Diethanolamine Dilaurate, Palmythyl Diethanolamine Dimillistate, Palmythyl Diethanolamine Dipalmitate, Palmythyl Diethanolamine Distearate, Palmityl Diethanolamine Diolate, Stearyl Diethanolamine Dilaurate, Stearyl Diethanolamine Dimylstate, Stearyl Diethanolamine Dipalmitate, Stearyl Diethanolamine Distearate, Stearyl Diethanolamine Diurate, Oleyl Diethanolamine Dilaurate, Oleyl Diethanolamine Dimylstate, Oleyl Diethanolamine Dipalmitate, Oleyl Diethanolamine Distearate, Oleyl Diethanolamine Geo The rate and the like may be mentioned, and one type or two or more types may be used. The method for synthesizing the component (A-1) and the component (A-2) is not particularly limited, but a mixture can be obtained by adjusting the reaction ratio of the fatty acid when the alkyldiethanolamine and the fatty acid are esterified, or the alkyldiethanolamine can be obtained. After reacting with and fatty acids, they can be purified to obtain each separately.

The weight ratio (A-1 / A-2) of the component (A-1) to the component (A-2) is 50/50 to 90/10, preferably 60/40 to 90/10, and 63/37 to 63. 86/14 is more preferable. If it is less than 50/50, the hydrophobicity of the antistatic agent becomes strong, causing insufficient bleeding of the antistatic agent, and the antistatic property deteriorates. On the other hand, if it exceeds 90/10, the compatibility of the antistatic agent with the resin decreases, which may cause a decrease in film transparency due to excessive bleeding, and a stain or stickiness on the surface of the sheet or molded product.

[Component (B)]
The component (B) is a glycerin monofatty acid ester, which is a component used in the present invention that promotes immediate bleed-out of the entire antistatic agent.

When the component (B) has a fatty acid residue having 8 to 22 carbon atoms, the compatibility with the thermoplastic resin is good, the transparency of the film is high, the appearance of the sheet and the molded product is good, and the antistatic property is excellent. preferable.
The number of carbon atoms of the fatty acid residue of the component (B) is preferably 12 to 18, more preferably 14 to 18, and particularly preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the thermoplastic resin is poor, which may cause deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness. On the other hand, if the number of carbon atoms exceeds 22, the immediate effect cannot be sufficiently exhibited, and the antistatic property may be insufficient.

Examples of the component (B) include glycerin monolaurate, glycerin monomillistate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monooleate, and the like, and one or more of them. Is also good.
The method for synthesizing the component (B) is not particularly limited, and for example, it can be obtained by subjecting glycerin and a fatty acid to an esterification reaction.

[Component (C)]
The component (C) is an aliphatic amine ethylene oxide adduct, and is a component that contributes to continuous antistatic properties among the antistatic components used in the present invention.
The component (C) is an ethylene oxide adduct of an aliphatic amine, which is a compound represented by the above general formula (3).

In the general formula (3), R ⁵ is an alkyl group, an alkenyl group, alkadienyl group or an alkynyl group.
The ^{number of carbon atoms in R 5} is 8 to 22, e and f are 0 or more, and the number satisfies e + f = 2 to 3.
The R ^5, preferably an alkyl group or an alkenyl group, good generally available at ease stability. The carbon number of R ⁵ is 8 to 22, preferably 8 to 18, more preferably 12 to 18, and even more preferably 16 to 18. When ^{the carbon number of R 5} is less than 8, the compatibility with the thermoplastic resin is poor, and excessive bleeding causes deterioration of film transparency, dirt on the surface of the sheet and molded product, and stickiness. On the other hand, if the number of carbon atoms in the R ⁵ is a 22 exceeds, antistatic property is lowered.

Specific examples of the component (C) include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, and the like, and may be one or more.
The method for producing the component (C) is not particularly limited, but for example, it can be produced by subjecting an aliphatic amine to an addition reaction with ethylene oxide. Further, it can be contained as an unreacted product by adjusting the reaction ratio at the time of synthesizing the component (A).

[Antistatic agent for thermoplastic resin]
The antistatic agent for a thermoplastic resin of the present invention indispensably contains the above-mentioned component (A), component (B) and component (C).

The weight ratio of the component (A) is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on the total amount of the component (A), the component (B), and the component (C). Particularly preferably, it is 20 to 30% by weight. If the blending ratio of the component (A) is less than 10% by weight, the compatibility with the thermoplastic resin is deteriorated, and excessive bleeding causes deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness. On the other hand, if the blending ratio of the component (A) exceeds 40% by weight, the antistatic property may decrease.

The blending ratio of the component (B) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total amount of the component (A), the component (B), and the component (C). Particularly preferably, it is 40 to 60% by weight. If the blending ratio of the component (B) is less than 20% by weight, the immediate effect of the bleed may be hindered and the antistatic property may be lowered. On the other hand, when the blending ratio of the component (B) is more than 80% by weight, excessive bleeding of the antistatic component causes deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness.

The blending ratio of the component (C) is preferably 10 to 40% by weight, more preferably 15 to 35% by weight, based on the total amount of the component (A), the component (B), and the component (C). Particularly preferably, it is 20 to 30% by weight. If the blending ratio of the component (C) is less than 10% by weight, the antistatic property may be lowered. On the other hand, if the blending ratio of the component (C) is more than 40% by weight, excessive bleeding may cause deterioration of film transparency, dirt on the surface of the sheet molded product, and stickiness.

When the antistatic agent for thermoplastic resin of the present invention is processed into an antistatic resin composition, the antistatic agent and the thermoplastic resin pellet may be mixed at a predetermined concentration and directly processed, but a wide range of molding materials In order to enable its use in plastics, it is desirable to consider a method of once processing as a high-concentration masterbatch pellet and then mixing it to a predetermined concentration in consideration of the uniformity of concentration and workability.

When the antistatic agent for thermoplastic resin of the present invention is used as a master pellet, the primary fatty acid amide represented by the following general formula (4) is used for the purpose of improving the slipperiness of the master pellet and improving the charging efficiency. Is preferably contained.
R ⁶ CONH ₂ (4)
(In the formula, R ⁶ is an alkyl group, an alkenyl group, an alkazienyl group or an alkynyl group, and the number of carbon atoms thereof is 15 to 21.)
As R ⁶ , an alkyl group or an alkenyl group is generally preferable because it is easily available and stable, and an alkenyl group is further preferable because it has a high smoothing improving effect.
The carbon number of R ⁶ is preferably 15 to 21, more preferably 17 to 21, and even more preferably 17. The ^{smoothness of R 6} is inferior regardless of whether the number of carbon atoms is less than 15 or 22 or more.

Specific examples of the fatty acid amide include palmitate amide, stearic acid amide, oleic acid amide, behenic acid amide, erucic acid amide and the like, and may be one or more.
The method for producing the fatty acid amide is not particularly limited, and for example, it can be produced by reacting an acid anhydride or an acid halide with an amine, or directly reacting an alcohol with an amine in the presence of a catalyst.

The blending ratio of the fatty acid amide is 0.2 to 10% by weight based on the total weight of the component (A), the component (B) and the component (C) so as to improve workability during master pelletization. Yes, preferably 0.3 to 5% by weight, more preferably 0.5 to 2% by weight. If the blending ratio is less than 0.2% by weight, the smoothness is poor, and if it exceeds 10% by weight, the antistatic property may be impaired at the time of producing the final molded product.

The antistatic agent for thermoplastic resins of the present invention can take various forms. For example, it can be powdered, flake-shaped, pellet-shaped, solid-solidified in a molten state, etc., but it is preferably flake-shaped or pellet-shaped, which is excellent in processability when mixed with a thermoplastic resin.

When the antistatic agent for a thermoplastic resin of the present invention has a flake shape, it preferably has an average particle size of 1 to 10 mm and a thickness of 0.5 to 2 mm.
If the average particle size is less than 1 mm or more than 10 mm, the concentration of the antistatic agent in the resin composition may become uneven due to classification when mixed with the thermoplastic resin pellets. If the thickness is less than 0.5 mm, it may be powdered by mixing with the resin, so that the concentration becomes uneven as well. If the thickness exceeds 2 mm, the passability in the automatic weighing machine for mixing deteriorates, which may result in poor preparation. The thickness here means the shortest side when the flakes are regarded as a rectangular parallelepiped.

When the antistatic agent of the present invention has a flake shape or a pellet shape, the antistatic agent preferably contains an inorganic powder or an organic powder for the purpose of preventing blocking of the antistatic agent itself and improving workability. Among the organic powders, fatty acid metal salts are particularly preferable.
Further, from the viewpoint of more effectively preventing blocking, the average particle size of the powder is preferably 0.1 to 50 μm. If the average particle size is less than 0.1 mm, the bulk specific gravity becomes lighter, so that dust generation may become severe and mixing may become difficult. If the average particle size exceeds 50 mm, the blocking prevention effect is reduced.
The blending ratio of the powder is preferably 0.1 to 8% by weight based on the total weight of the component (A), the component (B) and the component (C). If the content is less than 0.1%, the blocking prevention effect may be inferior, and if it exceeds 8%, there is no difference in the blocking prevention effect. I have something to do. Specific examples of the inorganic powder include silica, calcium carbonate, zeolite, mica and the like, but silica having a large specific surface area is preferable. The fatty acid metal salt is preferably solid at room temperature, and specific examples thereof include magnesium stearate, calcium stearate, zinc stearate, and sodium stearate.

The antistatic agent in the present invention can be blended with various commonly used additives. For example, an antioxidant may be added to prevent coloration. Further, for the master batch, stabilizers such as antioxidants and ultraviolet absorbers, lubricants, nucleating agents, pigments, inorganic fillers and the like may be added.

(Antistatic resin composition)
The thermoplastic resin composition of the present invention indispensably contains the antistatic agent for thermoplastic resin and the thermoplastic resin. Stabilizers such as antioxidants and UV absorbers, lubricants, nucleating agents, pigments, inorganic fillers, plasticizers, and other thermoplastic resin additives as necessary, as long as the effects of the present invention are not impaired. May be contained.

The weight ratio of the antistatic agent for a thermoplastic resin to the thermoplastic resin composition is not particularly limited, but from the viewpoint of having both excellent resin physical properties and antistatic properties, 0.01 to 5% by weight is preferable, and 0 .05 to 2% by weight is more preferable, and 0.1 to 1% by weight is particularly preferable. If it is less than 0.01% by weight, the antistatic property may be insufficient, and if it exceeds 5% by weight, excessive bleeding of the antistatic component causes deterioration of film transparency, dirt on the surface of the sheet or molded product, and stickiness.

The thermoplastic resin used in the thermoplastic resin composition of the present invention is not particularly limited, and polyethylene, polypropylene, ethylene-α-olefin copolymer, olefin-diene copolymer, ethylene-vinyl acetate copolymer, and the like. Polyethylene resin such as ethylene- (meth) acrylic acid copolymer, chlorinated polypropylene, maleic acid-modified polypropylene, polystyrene, polymethylstyrene, rubber modified polystyrene (HIPS resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile With polystyrene-based resins such as -butadiene-styrene copolymer (ABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), and ABS resin Polymer alloy containing styrene resin such as polycarbonate alloy, ABS resin and polyamide resin alloy, polystyrene and polyphenylene oxide alloy as one component, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, Polyester resin such as polyethylene naphthalenedicarboxylate, polybutylene naphthalenedicarboxylate, polyhexamethylenenaphthalenedicarboxylate, polyamide resin such as nylon 6 and nylon 66, polyacrylic acid, polymethyl methacrylate, polyacrylonitrile, poly Examples thereof include acrylic resins such as acrylamide, polyvinyl alcohol, polyvinyl acetate, polybutadiene, polyvinyl chloride, polyphenylene oxide resin, polycarbonate resin, alloy of polycarbonate resin and polyester resin, alloy of polycarbonate resin and polyamide resin, and the like.
Among these resins, a polyolefin resin in which the bleeding property of the antistatic component is likely to appear is preferable, and polypropylene having excellent performance control is more preferable.

(Molding)
The molded product of the present invention is obtained by heat-molding the above-mentioned thermoplastic resin composition. The method of adding the antistatic agent for the thermoplastic resin at the time of manufacturing the molded product is not particularly limited, and the molded product is directly added to the thermoplastic resin using various mixers such as an extruder, a kneader, and a Banbury mixer for molding. Alternatively, a masterbatch having a high concentration may be produced by these methods and then processed again to a predetermined concentration to obtain a molded product.
The antistatic resin composition of the present invention can take various forms such as a film, a sheet, and a general molded product, but in order to take advantage of excellent bleeding characteristics, it is preferably in the form of a film or a sheet. Further, the product can be processed by various processing methods such as injection molding, blow molding and extrusion molding.

The present invention will be described in detail in the following Examples and Comparative Examples, but the present invention is not limited to these Examples. The physical property evaluation of the molded product in the examples was carried out by the following method. Hereinafter, Examples 1 to 13, 18 to 29, 31 to 36 and 38 to 43 are referred to as Reference Examples 1 to 13, 18 to 29, 31 to 36 and 38 to 43, respectively.

(Antistatic property)
For films, sheets, and general molded products produced by molding thermoplastic resin compositions, the surface resistivity (Ω / □) after storage at 40 ° C for 8 hours and 2 weeks is measured by Toa Denpa Kogyo's ultra-super insulation meter. Measured using, and evaluated according to the evaluation criteria shown below. The measurement conditions are temperature and humidity 20 ° C x 45% R. H.
○: Less than 5 × 10 ¹³ Ω / □ △: 5 × 10 ^{13 to} 5 × 10 ¹⁴ Ω / □
×: 5 × 10 ¹⁴ Ω / □ Super

(Film transparency)
After storing the polypropylene film at 40 ° C for 2 weeks, the Haze value and ΔHaze of the film (difference between the Haze value before and after lightly rinsing the film surface with ethanol) using a color difference / turbidity measuring device (manufactured by Nippon Denshoku Kogyo). To measure. ΔHaze is evaluated based on the evaluation criteria shown below.
◯: 0.0 or more and less than 0.6 Δ: 0.6 to 0.9
×: Over 0.9

(Sheet, appearance of general molded products)
The sheet and general molded product after storage at 40 ° C. for 2 weeks are visually observed and evaluated based on the evaluation criteria shown below.
◯: Yellowing or powder blowing is not observed Δ: Yellowing or powder blowing is observed.
X: Both yellowing and powder blowing are observed.

(Combined with antistatic agent)
The components (A) to (C) were blended at the blending ratios shown in Table 1 to obtain antistatic agents T-1 to T-16, T-1A to T-3A, and T-1AST.

(Polypropylene film: Examples 1 to 13, Comparative Examples 1 to 6)
The melted antistatic agent is mixed and dispersed so as to be 10% by weight with respect to polypropylene (homopolymer, MFR = 2.5 g / 10 min), melt-kneaded at 230 ° C. in a twin-screw extruder, and strands. Got The obtained strands were cut with a pelletizer to prepare a masterbatch. The masterbatch was obtained as a cylinder-like shape having a diameter of about 3 mm and a height of about 3 mm, and had a bulk specific density of 0.55 to 0.60 g / cm ³ and a water content of less than 1000 ppm.
Next, the obtained masterbatch and a polypropylene homopolymer prepared separately were mixed to prepare an extrusion raw material, melt-kneaded at 230 ° C. in a twin-screw extrusion molding machine, and extruded from a T-die. Here, the extruded raw material was prepared by adjusting the amount of the masterbatch and polypropylene prepared separately so that the content of the antistatic agent was the ratio shown in Table 1 with respect to polypropylene.
The extruded product extruded from the T-die was uniaxially stretched to form a film having a thickness of 20 μm, and the corona discharge treatment was performed so that the surface tension was 40 dyne / cm. The results are shown in Table 2.

(Polypropylene film: Examples 14 to 16)
After processing the molten antistatic agent containing oleic acid amide into flakes having an average particle size of 5 mm and a thickness of 1 mm, a masterbatch was prepared in the same manner as in the above examples, and master pellets having better slipperiness than the tactile sensation were obtained. It was confirmed. The obtained masterbatch was subjected to an extrusion molding machine in the same manner, and the extruded product extruded from the T-die was uniaxially stretched and molded into a film having a thickness of 20 μm. The antistatic property and appearance were evaluated, and the results were evaluated. It is shown in Table 2.

(Polypropylene film: Example 17)
A molten antistatic agent containing oleic acid amide was processed into flakes having an average particle size of 5 mm and a thickness of 1 mm, and then magnesium stearate having an average particle size of 10 μm was mixed in a solid state and uniformly dispersed. Using these flakes, a masterbatch was prepared in the same manner as in the above embodiment, the obtained masterbatch was subjected to an extrusion molding machine in the same manner, and the extruded product extruded from the T-die was uniaxially stretched to a thickness of 20 μm. The antistatic properties and appearance of the film molded into the above film were evaluated, and the results are shown in Table 2.

(Polypropylene sheet: Examples 18 to 30, Comparative Examples 7 to 12)
The master batch obtained by the same method as the polypropylene film (the same method as in Examples 14 to 16 for Example 29) was subjected to an extrusion molding machine in the same manner, and the extruded product extruded from the T-die was subjected to the same method. The antistatic properties and appearance of the uniaxially stretched sheet formed into a sheet having a thickness of 200 μm were evaluated, and the results are shown in Table 3.

(Polypropylene general molded product: Examples 31 to 37, Comparative Examples 13 to 15)
A masterbatch was prepared for the polypropylene resin by the same method (the same method as for Examples 14 to 16 for Example 37) except that a polypropylene homopolymer (MFR = 25) was used, and prepared separately from the obtained masterbatch. Mix with the same polypropylene homopolymer to obtain a predetermined concentration, prepare a disk with a thickness of 3 mm and a radius of 50 mm with an injection molding machine, evaluate the antistatic property and appearance of the obtained product, and the results are shown in Table 4. Shown in.

(Polystyrene general molded product: Examples 38 to 44, Comparative Examples 16 to 18)
Except for the use of polystyrene homopolymer (MFR = 8.0), the same method as for polypropylene general molded products (the same method as for Examples 14 to 16 for the master batch of Example 44) has a thickness of 3 mm and a radius. Table 4 shows the antistatic properties and appearance of a 50 mm disk prepared and stored at 20 ° C. for 8 hours and 40 ° C. for 2 weeks.

As can be seen from Tables 2 to 4, the molded product containing the antistatic agent of the present invention contains a component (A) which is an aliphatic amine ethylene oxide fatty acid ester, a component (B) which is a glycerin monofatty acid ester, and a component (B). An antistatic agent containing a component (C) which is an aliphatic amine ethylene oxide adduct.
The component (A) is a component (A-1) which is an aliphatic amine ethylene oxide adduct monofatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2). Containing a component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) to the component (A-2) is 50/50 to 90/10, and the component (C) is the following general formula (3). ) Is used, it is confirmed that it exhibits stable antistatic properties having both immediate effect and durability because it uses an antistatic agent for thermoplastic resins.
On the other hand, when the component (A) is not contained (Comparative Examples 4 to 6, 10 to 12), when the component (B) is not contained (Comparative Examples 3, 9, 15, 18), and when the component (C) is not contained. (Comparative Examples 2, 5, 8, 11, 14, 17), when the component (A-2) is not contained (Comparative Examples 1, 7, 13, 16), any of the problems of the present application has been solved. Absent.

Claims (7)

The component (A) which is an aliphatic amine ethylene oxide fatty acid ester, the component (B) which is a glycerin monofatty acid ester, the component (C) which is an aliphatic amine ethylene oxide adduct, and the following general formula (4). An antistatic agent containing the fatty acid amide represented by
The component (A) is a component (A-1) which is an aliphatic amine ethylene oxide adduct monofatty acid ester represented by the following general formula (1), and an aliphatic amine ethylene represented by the following general formula (2). Containing a component (A-2) which is an oxide adduct difatty acid ester,
The weight ratio (A-1 / A-2) of the component (A-1) to the component (A-2) is 50/50 to 90/10, and the component (C) is the following general formula (3). ) compound der represented by is,
An antistatic agent for a thermoplastic resin , wherein the weight ratio of the fatty acid amide to the total weight of the component (A), the component (B) and the component (C) is 0.2 to 5% by weight.

(In the formula, R ¹ and R ² are independently alkyl group, alkenyl group, alkazienyl group or alkynyl group. R ¹ has 8 to 22 carbon atoms and R ² has 7 to 21 carbon atoms. A and b indicate the average number of moles of oxyethylene groups added, a and b are 0 or more, and a + b is a number satisfying 2 to 3.)

(Wherein, R ³ and R ⁴ are each independently an alkyl group, an alkenyl group, alkadienyl group or .2 is an alkynyl group There R ⁴ is optionally being the same or different .R ³ Has 8 to 22 carbon atoms, R ⁴ has 7 to 21 carbon atoms, c and d indicate the average number of moles of oxyethylene groups added, c and d are 0 or more, and c + d = 2 to 2. It is a number that satisfies 3.)

(Wherein, R ⁵ is an alkyl group, an alkenyl group, alkadienyl group or an alkynyl group, the carbon number of 8 to 22, e and f represents an average addition molar number of oxyethylene groups, e and f are It is a number that is 0 or more and satisfies e + f = 2 to 3.)
R ⁶ CONH ₂ (4)
(In the formula, R ⁶ is an alkyl group, an alkenyl group, an alkazienyl group or an alkynyl group, and the number of carbon atoms thereof is 15 to 21.) The weight ratio of the component (A) is 10 to 40% by weight, and the weight ratio of the component (B) is 20 to 40% by weight of the total weight of the component (A), the component (B), and the component (C). The antistatic agent for a thermoplastic resin according to claim 1, wherein the weight ratio of the component (C) is 80% by weight and the weight ratio is 10 to 40% by weight. The antistatic agent for a thermoplastic resin according to claim 1 or 2 , which is in the form of flakes having an average particle size of 2 to 10 mm and a thickness of 0.5 to 1.5 mm, or in the form of pellets having an average particle size of 2 to 7 mm. .. It further contains an inorganic powder and / or a fatty acid metal salt, and the average particle size of the inorganic powder and the fatty acid metal salt is 0.1 to 50 μm, and the component (A), the component (B) and the component ( The antistatic agent for a thermoplastic resin according to any one of claims 1 to 3 , wherein the weight ratio of the inorganic powder and the fatty acid metal salt to the total weight of C) is 0.1 to 10% by weight. An antistatic resin composition containing the antistatic agent according to any one of claims 1 to 4. The antistatic resin composition according to claim 5, wherein the thermoplastic resin is polyolefin. A molded product obtained by molding the antistatic resin composition according to claim 5 or 6.