JP2020033483A - Antistatic agent and application thereof - Google Patents

Abstract

To provide an antistatic agent not only exhibiting excellent antistatic effect when added to a polypropylene resin, but also capable of exhibiting the antistatic effect over long time by suppressing performance reduction by an adhesive used for laminate, a polymer film by milling the same, and a laminate film thereof.SOLUTION: There is provided an antistatic agent contains a component (A) which is diglycerol fatty acid ester, a component (B) which is aliphatic amine-ethylene oxide addition product fatty acid ester, a component (C) which is glycerine fatty acid ester, and a component (D) which is an aliphatic amine-ethylene oxide added article, in which the component (A) contains a component (A-1) which is diglycerol fatty acid monoester, and a component (A-2) which is ester of diglycerol and two or more aliphatic acids, and a weight ratio of the component (A-1) and the component (A-2); (A-1/A-2) is 80/20 to 20/80.SELECTED DRAWING: Figure 3

Description

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

  BACKGROUND ART Thermoplastic resins such as polyolefins are used in a wide range of fields such as a fiber field and a packaging field because of their ease of processing and excellent appearance. A typical example of the packaging material is a polyolefin film. Polyolefin films are often used alone or laminated to other films.

  On the other hand, a drawback of thermoplastic resins such as polypropylene is that static electricity is generated due to hydrophobicity of the resin. When static electricity is generated, not only does the dust and dirt adhere to the product to impair the appearance, but also may adversely affect productivity such as generation of sparks and discomfort of the operator. In order to solve these problems, it has been widely practiced to suppress the generation of static electricity by using an antistatic agent.

  In order to solve these problems, in general, a method of changing the physical properties of the film surface using a surfactant and giving it an antistatic property has been adopted. Is a method of applying to the resin surface or a method of melting and mixing with the resin.

  The method of applying the antistatic agent has advantages such as being superior to the initial antistatic agent, but it is often pointed out that there is a problem in sustainability, and that the number of processing steps increases and becomes economically disadvantageous. I have. Therefore, a method of kneading an antistatic agent which can maintain the antistatic property for a relatively long time and is economical is often adopted, and various methods using sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester and the like are used. Has been attempted with a complex formulation.

  In food packaging, a laminated film in which a plurality of synthetic resin films are laminated is widely used in order to improve physical properties such as gas barrier properties, film strength, and heat sealing properties. Polypropylene films are often used after being laminated with other synthetic resin films. However, when a polypropylene film containing an antistatic agent is laminated with another film using a polyurethane-based adhesive or a polyether-based adhesive, the antistatic agent is adsorbed by the adhesive and the antistatic performance is not exhibited. There are problems. Also, increasing the amount of the antistatic agent leads to whitening of the film and attenuation of the antistatic performance.

  Patent Literature 1 discloses that an antistatic property is exhibited by providing a coating layer containing an ester of a polyhydric alcohol and a fatty acid, but the amount of addition is large and sufficient transparency cannot be maintained.

  Patent Literature 2 discusses separately kneading and laminating a specific surfactant and a polyglycerin fatty acid ester on a plurality of film layers. However, since it is necessary to laminate at least three or more films, it can be applied. Is limited.

  In Patent Document 3, an ester of a polyhydric alcohol, a fatty acid and an N-acyl sarcosine salt are kneaded to maintain the antistatic property after lamination, but the salt of the anionic activator has poor compatibility with the polyolefin resin. This may lead to poor appearance and long-term performance degradation.

  In Patent Document 4, low-molecular-weight glycerin fatty acid ester and polyglycerin fatty acid ester are used to maintain the immediate antistatic effect and maintain the antistatic effect after lamination, but in Examples, the effect was confirmed only by polyethylene resin. No mention is made as to whether it can be applied to polypropylene resin, and it is not economical because a large amount of expensive polyglycerin fatty acid ester is used.

JP-A-10-34 JP-A-5-96694 Patent No. 5184331 JP 2017-179350 A

  The object of the present invention is not only to show an excellent antistatic effect when added to a polypropylene resin, but also to suppress the performance deterioration due to the adhesive used in the lamination, and to continue to exhibit the antistatic effect for a long time. An object of the present invention is to provide a novel antistatic agent, a polymer film into which the same is kneaded, and a laminated film thereof.

The present inventors have conducted intensive studies, and have found that an antistatic agent containing component A, which is a diglycerin fatty acid ester having a specific configuration, and another specific component can solve the above problems, The present invention has been reached.
That is, the antistatic agent of the present invention comprises a component (A) that is a diglycerin fatty acid ester, a component (B) that is an aliphatic amine ethylene oxide adduct fatty acid ester, a component (C) that is a glycerin fatty acid ester, and an aliphatic amine. A component (A-1) comprising a component (D) which is an ethylene oxide adduct, wherein the component (A) is a diglycerin fatty acid monoester, and a component (A-) which is an ester of diglycerin and two or more fatty acids. 2), and the weight ratio (A-1 / A-2) of the component (A-1) to the component (A-2) is 80/20 to 20/80.

  A component (B-1) in which the component (B) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1); and an aliphatic amine ethylene oxide represented by the following general formula (2). A component (B-2) which is an adduct difatty acid ester, and the weight ratio (B-1 / B-2) of the component (B-1) to the component (B-2) is 50/50 to 50/50. It is preferably 90/10.

(Wherein, R ¹ and R ² are each independently an alkyl group, an alkenyl group, an alkadienyl group or an alkanyl group. N and m are 0 or more, and n + m is a number satisfying 2-3. .)

(Wherein, R ³ , R ⁴ and R ⁵ are each independently an alkyl group, an alkenyl group, an alkadienyl group or an alkanyl group. O and p are 0 or more, and satisfy o + p = 2 to 3. It is a number.)

The component (A) preferably contains diglycerin laurate, and the weight ratio of the diglycerin laurate in the component (A) is preferably 40% by weight or more.
20 to 70% by weight of the component (A), 10 to 50% by weight of the component (B), 5 to 50% by weight of the component (C), and 1 to 20% by weight of the component (D). It is preferred that it comprises.
It is preferable that the ratio (OHv / Sv) between the hydroxyl value (OHv) and the saponification value (Sv) is in the range of 1.8 to 2.4.

The polyolefin-based resin composition of the present invention contains a polyolefin-based resin and the above antistatic agent.
The weight ratio of the polyolefin resin antistatic agent in the resin composition is preferably 0.01 to 30% by weight.
It is preferable that the polyolefin resin is polypropylene.
The film of the present invention is obtained by molding the above-mentioned polyolefin-based resin composition.
The laminated film of the present invention is obtained by bonding the above antistatic film and another base film.

The antistatic agent of the present invention not only exhibits an excellent antistatic effect when added to a polypropylene-based resin, but also suppresses performance degradation due to the adhesive used for lamination, and exhibits an antistatic effect over a long period of time. Is possible.
ADVANTAGE OF THE INVENTION The polyolefin resin composition of this invention is excellent in the antistatic effect over a long period, without the antistatic performance being reduced by an adhesive.
The film of the present invention does not decrease the antistatic performance due to the adhesive, and has an excellent antistatic effect over a long period of time.

Schematic diagram of component (A). Sectional drawing which bleed out the component (A) to the monolayer film surface. Sectional drawing in which some hydrophilic groups of component (A) were adsorbed on the hydrophilic layer. Sectional drawing of the film bonded together using the adhesive. Sectional drawing of a co-extruded film.

(Antistatic agent)
The antistatic agent of the present invention comprises a component (A) which is a diglycerin fatty acid ester, a component (B) which is a fatty acid amine ethylene oxide adduct fatty acid ester, a component (C) which is a glycerin fatty acid ester, and an aliphatic amine ethylene oxide. A component (A-1) comprising a component (D) which is an adduct, wherein the component (A) is a diglycerin fatty acid monoester, and a component (A-2) which is an ester of diglycerin and two or more fatty acids. And the weight ratio (A-1 / A-2) between the component (A-1) and the component (A-2) is 80/20 to 20/80.

[Component (A)]
Generally, a film using a kneading type antistatic agent tends to have a reduced antistatic performance when laminated, and the component (A) is a component that contributes to the development of the antistatic property of the film in the present invention, It is a composite of components that contribute to suppressing the attenuation of the antistatic property when the film is laminated.
Component (A) is a diglycerin fatty acid ester.
Examples of the fatty acid constituting the diglycerin fatty acid ester include butyric acid, valeric acid, caproic acid, heptyl acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, and stearic acid. , Arachidic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, and saturated fatty acids such as melicic acid; crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadolinic acid, erucic acid, nervonic acid Unsaturated fatty acids such as acids, linoleic acid, α-linolenic acid, eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, succinic acid, and docosahexaenoic acid.
Among them, lauric acid, myristic acid, and palmitic acid are preferable, and lauric acid is particularly preferable, from the viewpoint of achieving the effects of the present invention.

  Component (A) preferably contains diglycerin laurate from the viewpoint of antistatic performance. When the component (A) contains diglycerin laurate, the weight ratio of the diglycerin laurate in the component (A) is preferably 40% by weight or more, and more preferably 50% by weight or more from the viewpoint of antistatic performance. Is more preferably 60% by weight or more, further preferably 90% by weight or more.

(Component (A-1))
Component (A-1) is a component that mainly contributes to exhibiting antistatic properties. Component (A-1) is a diglycerin fatty acid monoester.
Examples of the component (A-1) include diglycerin fatty acid monolaurate, diglycerin fatty acid monostearate, and diglycerin fatty acid monooleate. Among them, diglycerin fatty acid monolaurate is preferable from the viewpoint of exhibiting the effects of the present invention. .

(Component (A-2))
Component (A-2) is a component that mainly contributes to maintaining the antistatic property after lamination. Component (A-2) is an ester of diglycerin and two or more fatty acids. Specifically, it is at least one selected from diglycerin fatty acid diester, diglycerin fatty acid triester, and diglycerin fatty acid tetraester.
The fatty acid constituting the component (A-2) may be one type, or two or more types.

  The weight ratio (A-1 / A-2) between the component (A-1) and the component (A-2) is 80/20 to 20/80, preferably 75/25 to 25/75, 70/30 to 30/70 is more preferred, and 60/40 to 40/60 is even more preferred. When it exceeds 80/20, the antistatic property of the film after lamination is insufficient, and when it is less than 20/80, the immediate antistatic property of the kneaded film is insufficient.

[Component (B)]
The component (B) is a component having excellent compatibility with the polyolefin resin, and is used for controlling the dispersion state of the antistatic agent in the polyolefin resin. Component (B) is an aliphatic amine ethylene oxide adduct fatty acid ester.
When the antifogging agent of the present invention contains the component (B-1) represented by the general formula (1) and the component (B-2) represented by the general formula (2), the balance between resin compatibility is improved. It is preferable because it is easy to take.

[Component (B-1)]
Component (B-1) is a monofatty acid ester of an aliphatic amine ethylene oxide adduct, and 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 alkadienyl group or an alkynyl group. R ¹ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and is preferably a linear chain from the viewpoint of exhibiting the effects of the present invention.
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 polypropylene resin is poor and stickiness and yellowing due to excessive bleeding are caused. On the other hand, when the number of carbon atoms exceeds 22, the bleed control effect is too strong and the antistatic property is impaired.

The carbon number of R ² is 7 to 21, preferably 11 to 17, more preferably 13 to 17, and particularly preferably 15 to 17. If the number of carbon atoms is less than 7, the compatibility with the polypropylene resin is poor and stickiness or yellowing due to excessive bleeding may be caused. On the other hand, if the number of carbon atoms exceeds 21, the bleed control effect is too strong, which impairs the antistatic property.

  n and m represent the average number of moles of oxyethylene groups added. n and m are 0 or more, and n + m is a number satisfying 2-3.

  Although it does not specifically limit as a component (B-1), For example, lauryl diethanolamine monolaurate, lauryl diethanolamine monomyristate, lauryl diethanolamine monopalmitate, lauryl diethanolamine monostearate, lauryl diethanolamine monooleate, myristyl diethanolamine monolaurate, Myristyl diethanolamine monomyristate, myristyl diethanolamine monopalmitate, myristyl diethanolamine monostearate, myristyl diethanolamine monooleate, palmityl diethanolamine monolaurate, palmityl diethanolamine monomyristate, palmityl diethanolamine monopalmitate, palmityl diethanolamine monostearete , Palmityl diethanolamine monooleate, stearyl diethanolamine monolaurate, stearyl diethanolamine monomyristate, stearyl diethanolamine monopalmitate, stearyl diethanolamine monostearate, stearyl diethanolamine monooleate, oleyl diethanolamine monolaurate, oleyl diethanolamine monomyristate, oleyl Examples thereof include diethanolamine monopalmitate, oleyldiethanolamine monostearate, oleyldiethanolamine monooleate, and the like, and one or more types may be used.

[Component (B-2)]
The component (B-2) is a diamine ester of an aliphatic amine ethylene oxide adduct, and is a compound represented by the above general formula (2).
In the general formula (2), R ³ is an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group. R ³ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and is preferably a linear chain from the viewpoint of exhibiting the effects of the present invention.
The number of carbon atoms of R ³ is from 8 to 22, 12 to 18, more preferably 14 to 18, more preferably 16 to 18. If the number of carbon atoms is less than 8, the compatibility with the polypropylene resin is poor and stickiness or yellowing due to excessive bleeding may be caused. On the other hand, when the number of carbon atoms exceeds 22, the bleed control effect is too strong and the antistatic property is impaired.

The carbon number of R ³ is preferably 7 to 21, more preferably 13 to 17, and still more preferably 15 to 17. If the number of carbon atoms is less than 7, the compatibility with the polypropylene resin is poor and stickiness or yellowing due to excessive bleeding may be caused. If the number of carbon atoms exceeds 22, the bleed control effect is too strong, which may impair the antistatic property.

  o and p show the average number of moles of oxyethylene groups added. o and p are 0 or more, and o + p is a number satisfying 2-3.

  Specific examples of the component (B-2) include lauryl diethanolamine dilaurate, lauryl diethanolamine dimyristate, lauryl diethanolamine dipalmitate, lauryl diethanolamine distearate, lauryl diethanolamine dioleate, myristyl diethanolamine dilaurate, myristyl diethanolamine dimyristate, and myristyl. Diethanolamine dipalmitate, myristyl diethanolamine distearate, myristyl diethanolamine dioleate, palmityl diethanolamine dilaurate, palmityl diethanolamine dimyristate, palmityl diethanolamine dipalmitate, palmityl diethanolamine distearate, palmityl diethanolamine dioleate , Stearyl diethanolamine dilaurate, stearyl diethanolamine dimyristate, stearyl diethanolamine dipalmitate, stearyl diethanolamine distearate, stearyl diethanolamine dioleate, oleyl diethanolamine dilaurate, oleyl diethanolamine dimyristate, oleyl diethanolamine dipalmitate, oleyl diethanolamine distearate, Oleyldiethanolaminediolate and the like may be mentioned, and one or more kinds may be used. The method for synthesizing the component (B-1) and the component (B-2) is not particularly limited, but a mixture may be obtained by adjusting the reaction ratio of the fatty acid during the esterification reaction between the alkyldiethanolamine and the fatty acid. And the fatty acids are reacted and then purified to obtain each separately.

  The weight ratio (B-1 / B-2) of the component (B-1) to the component (B-2) is preferably 50/50 to 90/10, more preferably 53/47 to 90/10, and 55/45. ~ 90/10 is more preferred. If the ratio is less than 50/50, the hydrophobicity of the antistatic component becomes so strong that bleeding of the antistatic component occurs and the antistatic property may be insufficient. On the other hand, if it exceeds 90/10, stickiness and yellowing may occur due to a decrease in compatibility of the antistatic component.

[Component (C)]
Component (C) is a glycerin fatty acid ester, which itself has an antistatic effect and promotes immediate bleed-out of the entire antistatic component among the components used in the present invention.

The component (C) is classified into glycerin monofatty acid ester, glycerin difatty acid ester, and glycerin trifatty acid ester according to the difference in the degree of esterification, and may be any one, and is a mixture of glycerin monofatty acid ester and glycerin difatty acid ester. Certain glycerin sesqui fatty acid esters may be used. However, from the viewpoint of hydrophilicity of the antistatic agent, glycerin monofatty acid ester or glycerin sesquifatty acid ester is preferable.
It is preferable that the component (C) has a fatty acid residue having 8 to 22 carbon atoms because the compatibility with the thermoplastic resin is good, the transparency is high, and the antistatic property is excellent.
The carbon number of the fatty acid residue of the component (C) is preferably 12 to 18, more preferably 14 to 18, and particularly preferably 16 to 18. When the number of carbon atoms is less than 8, the compatibility with the polyolefin resin is poor, and poor transparency due to excessive bleeding and stickiness of the molded product surface may be caused. On the other hand, when the number of carbon atoms exceeds 22, the immediate effect cannot be sufficiently exhibited, and the antistatic property may be insufficient.

Component (C) includes, for example, glycerin monolaurate, glycerin sesquilaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monopalmitate, glycerin sesquipalmitate, glycerin monostearate, glycerin sesquistearate, glycerin monostearate Olate, glycerin sesquiolate, glycerin monobehenate, glycerin sesquibehenate and the like may be mentioned, and one or more kinds may be used.
The method for synthesizing the component (C) is not particularly limited, and examples thereof include a method of subjecting glycerin and a fatty acid to an esterification reaction, and a method of subjecting a glycerin ester to a transesterification reaction of a fatty acid ester. At this time, a mixture can be obtained by adjusting the reaction ratio. The compositions obtained by the respective reactions may be used by mixing purified products obtained separately.

[Component (D)]
Component (D) is a component that assists bleeding and is a component that prevents aggregation of the antistatic agent. When the component (D) is not contained, the bleeding of the entire antistatic agent is delayed in a short term, so that the antistatic property is not sufficiently exhibited, and in the long term, aggregation of the antistatic component on the surface of the resin composition. And crystallization may occur, and the antistatic property and the transparency may decrease.
Component (D) is an aliphatic amine ethylene oxide adduct. It is preferable that the component (D) is represented by the general formula (3) from the viewpoint of compatibility with the resin and transparency of the resin.

In the general formula (3), R ⁶ is an alkyl group, an alkenyl group, an alkadienyl group or an alkynyl group. R ⁶ has 8 to 22 carbon atoms.
The alkyl group may be linear or branched, and is preferably a linear chain from the viewpoint of exhibiting the effects of the present invention.
R ⁶ has 8 to 22 carbon atoms, and particularly preferably 12 to 18 carbon atoms. If the number of carbon atoms is less than 8, excessive bleeding occurs on the surface, which causes stickiness of the molded product. On the other hand, when the number of carbon atoms exceeds 22, the bleeding speed is too slow, so that the antistatic effect and the aggregation preventing effect are not exhibited.
q and r show the average number of moles of oxyethylene groups added. q and r are 0 or more, and q + r is a number satisfying 2-3.

  As the component (D), for example, lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, behenyl diethanolamine and the like can be mentioned, and one or more kinds may be used.

About the weight ratio of component (A), component (B), component (C) and component (D) contained in the antistatic agent of the present invention, component (A), component (B), component (C) and When the total amount of component (D) is 100 parts by weight, component (A) is 20 to 70 parts by weight, component (B) is 10 to 50 parts by weight, component (C) is 5 to 50 parts by weight, component (C) D) is preferably 1 to 20 parts by weight, component (A) is 30 to 60 parts by weight, component (B) is 20 to 40 parts by weight, component (C) is 10 to 40 parts by weight, component (D). Is more preferably 5 to 15 parts by weight. If the weight ratio is outside the above range, the effects of the present invention may not be exhibited.
From the viewpoint of increasing the effective component per unit weight, the total weight ratio of the components (A), (B), (C) and (D) in the antistatic agent is preferably from 80 to 100. %, More preferably 85 to 95% by weight.

  The ratio (OHv / Sv) between the hydroxyl value (OHv) and the saponification value (Sv) of the antistatic agent of the present invention is preferably 1.8 to 2.4, and more preferably 1.85 to 2.35. And particularly preferably 1.9 to 2.3. If OHv / Sv is less than 1.8, immediate antistatic properties may decrease due to insufficient hydrophilicity, and if it exceeds 2.4, transparency over time may decrease due to excess bleed due to excessive hydrophilicity. There is. Here, the hydroxyl value and the saponification value are determined by the method described in Examples described later.

  When the ratio (OHv / Sv) between the hydroxyl value (OHv) and the saponification value (Sv) of the antistatic agent of the present invention is within the above range, the antistatic properties when the film is laminated on another film. Is also good. Although the details of this principle are unknown, it can be considered as follows in consideration of the effects of the hydroxyl value and the saponification value on the thermoplastic resin. When laminating a film, a hydrophilic adhesive is usually applied to the back side of the surface where the antistatic property is desired to be exhibited, and the film is adhered. If the hydrophilicity of the antistatic agent is too high, the antistatic agent diffuses inside the film. The agent is excessively fixed on the adhesive surface, and the antistatic property of the antistatic surface is impaired. Conversely, if the compatibility with the resin is too high, the antistatic agent does not bleed to the film surface, and the antistatic property is not exhibited. Therefore, by balancing the hydroxyl value and the saponification value and satisfying the range of OHv / Sv = 1.8 to 2.4, it is possible to impart and maintain the antistatic property to the laminate film. Conceivable.

  The antistatic agent of the present invention may contain other components other than the component (A), the component (B), the component (C), and the component (D) as long as the effects of the present invention are not impaired. . Other components are not particularly limited, and include, for example, polyoxyalkylene alkyl ether, polyoxyalkylene aryl ether, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyalkylene glycol fatty acid ester, and a polymerization degree of 3 or more. Nonionic surfactants other than component (A), component (B), component (C) and component (D) such as esterified product of polyglycerin and fatty acid, sorbitan fatty acid ester, etc .; alkyl sulfate and salts thereof, alkyl aryl sulfate And anionic surfactants such as salts thereof, higher fatty acid salts, polyoxyethylene alkyl ether sulfates and salts thereof, alkyl sulfonic acids and salts thereof, dialkyl sulfosuccinic acids and salts thereof, alkyl ether phosphoric acids and salts thereof; higher fatty acids; Alcohols; sorbitol, polyhydric alcohols polyglycerol and the like; aliphatic hydrocarbons, and the like. In addition, it is a raw material used when manufacturing the component (A), the component (B), the component (C), and the component (D), and glycerin, diglycerin, aliphatic amine, fatty acid, etc. which remain unreacted and remain. Is included in other components.

  The antistatic agent of the present invention is produced by mixing each of the components described above. The mixing method is not particularly limited, and the components may be mixed at once or sequentially, or some components may be mixed in advance and mixed with the remaining components. The components may be mixed by melt mixing, may be mixed with a thermoplastic resin, or may be mixed at the time of forming the thermoplastic resin.

(Polyolefin resin composition)
The polyolefin resin composition of the present invention contains a polyolefin resin and the above-mentioned antistatic agent.
Examples of the polyolefin resin include, but are not particularly limited to, for example, polypropylene, low density polyethylene, high density polyethylene, linear low density polyethylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer. Examples thereof include a polymer, an ethylene-methacrylic acid copolymer, an ethylene-maleic anhydride copolymer, and a propylene-maleic anhydride copolymer. As the polyolefin resin, one type may be used alone, or two or more types may be used in combination.
Among these, it is preferable that the polyolefin resin is polypropylene from the viewpoint that the effects of the present invention are remarkably exhibited.

  The polyolefin-based resin composition contains, in addition to the polyolefin-based resin and the antistatic agent described above, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antioxidant, an antifogging agent, a lubricant, It may contain additives such as a burning agent, a coloring agent, a pigment, an inorganic filler, a plasticizer, and a nucleating agent. Conventionally known additives can be used as these additives, and the amount of the additives may be appropriately set according to the purpose.

The polyolefin-based resin composition may be a masterbatch which is an intermediate material of the molding material, or a molding material used for molding.
The weight ratio of the antistatic agent in the polyolefin resin composition (hereinafter, sometimes referred to as “antistatic agent concentration”) varies depending on whether the resin composition is a masterbatch or a molding material, and is particularly limited. However, it is preferably 0.01 to 30% by weight.
The mixing ratio of the polyolefin resin and the antistatic agent is not particularly limited, but from the viewpoint that the effects of the present invention are remarkably exhibited, the antistatic agent of the present invention is used with respect to 100 parts by weight of the polyolefin resin. It is preferable to add 0.015 to 45 parts by weight of an agent.
Hereinafter, the production method and the like will be described separately for the case where the polyolefin-based resin composition is a masterbatch and the case for a molding material.

〔Master Badge〕
The masterbatch is an intermediate raw material in the process of manufacturing a molded article, and is a resin composition containing additives such as a coloring agent and a resin performance modifier at a high concentration. When the master batch is mixed with the resin pellets, the mixing can be performed with better handleability than when the additive is mixed alone with the resin pellets containing no additive. In addition, by using a master batch, even a low-concentration additive can be uniformly mixed in a resin with good dispersibility.

  When the polyolefin-based resin composition is a masterbatch, the concentration of the antistatic agent is preferably from 1 to 30 for the purpose of improving the uniformity of dispersion and the handleability in producing a molding material using the masterbatch as a raw material. %, More preferably 5 to 20% by weight. If the concentration of the antistatic agent is less than 1% by weight, mixing properties at a uniform concentration cannot be ensured when producing molding materials or molded products, and a large amount of master batch is required when producing molding materials, which leads to cost reduction. Will be high. On the other hand, when the concentration of the antistatic agent exceeds 30% by weight, the production of a master batch becomes difficult due to insufficient compatibility.

  As a method for producing a masterbatch, for example, a conventional plastic molding machine, that is, a Banbury mixer, a Henschel mixer, a screw extruder with a vent, a kneader, or the like, is used to melt a polyolefin resin and the antistatic agent of the present invention. After kneading and cooling, a method of pelletizing to prepare a master batch can be used.

(Molding material)
In the present invention, the molding material means a material which is processed into a final product such as a film or a sheet by itself.
When the polyolefin resin composition is a molding material, the concentration of the antistatic agent is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight. If the concentration of the antistatic agent is less than 0.01% by weight, sufficient antistatic performance may not be exhibited. On the other hand, if the concentration of the antistatic agent exceeds 10% by weight, further improvement in antistatic performance is not recognized, and the transparency of the polyolefin resin may be impaired.

Examples of the method for producing a molding material include: (1) a method of simply melt-kneading an antistatic agent and a polyolefin-based resin; (2) a method of melt-kneading a masterbatch containing an antistatic agent and a thermoplastic resin. Can be mentioned. In the method for producing a molding material, the same ordinary plastic molding machine as that used for producing the master batch can be used.
In the above method (2), at least one of the resin contained in the master batch and the thermoplastic resin used for melt-kneading may contain a polyolefin resin, and both resins are necessarily the same type of resin. Although it is not necessary, it is preferable that the resin contained in the masterbatch and the thermoplastic resin have compatibility in order to improve the uniformity of dispersion of both, and the bulk specific gravity of the masterbatch and the bulk specific gravity of the thermoplastic resin are preferable. It is more preferable that the values substantially match.

(Molded body)
The molded article of the present invention is obtained by molding the above-mentioned polyolefin-based resin composition. Examples of the molded article include molded articles of various shapes such as films such as inflation films and biaxially stretched films, sheets, injection molded articles, blow molded articles, and the like. Among these, from the viewpoint that the effects of the present invention are most remarkably exhibited, it is particularly preferable that the molded article is a film. The thickness of the film is not particularly limited, but is preferably 1 to 500 μm.
Examples of the method for producing a molded article include a method of injection molding, blow molding, extrusion molding, thermoforming (such as biaxial stretching) in a state where the molding material is heated and melted, and the like. A similar method of molding may be used.
The production of the molding material and the molded body may be performed continuously, for example, a method in which the master batch and the thermoplastic resin are melt-kneaded by an extruder, and then processed into a film by a T-die, an inflation die, or the like. Can be
Examples of uses of these molded articles include packaging materials for foods and the like, electric wire covering materials, agricultural materials such as houses and tunnels, miscellaneous goods and daily necessities such as toys and stationery, and building materials such as wallpaper.

(Laminated film)
Although the film of the present invention can be used alone, it can be more suitably used by forming a laminated film in combination with a base film or a base resin. Other configurations are not particularly limited as long as the laminated film of the present invention has at least a layer formed from the above-mentioned polyolefin-based resin composition (hereinafter, sometimes referred to as “antistatic layer”). And those having the antistatic layer as a surface layer are preferred. In addition, a surface layer means the outermost layer of a laminated film. Preferred embodiments of the laminated film include the following (a), (b) and (c).
(A) A laminated film obtained by dry laminating the film of the present invention and a base film with a polyurethane-based adhesive or a polyether-based adhesive.
(B) A laminated film obtained by extrusion laminating the polyolefin resin composition of the present invention on a base film.
(C) A laminated film obtained by co-extruding the polyolefin-based resin composition of the present invention and a base thermoplastic resin composition.
Such a laminated film is also one of the present invention.

[Dry laminate film]
A dry laminated film is a laminated film manufactured by laminating at least two or more different or similar films via an adhesive. FIG. 4 is a sectional view showing an example of the dry laminate film of the present invention. The dry laminate film 10 has a structure in which the antistatic layer 3 and the base material layer 6 are laminated via the adhesive layer 5. As the adhesive used for the dry laminate film, a commercially available adhesive such as a polyurethane-based adhesive or a polyether-based adhesive can be appropriately used.

  Conventionally, when a film containing an antistatic agent is dry-laminated on a base film, the bleeding antistatic agent is adsorbed on highly hydrophilic components such as isocyanate and polyether contained in the adhesive as shown in FIG. However, there is a problem that the antistatic performance is impaired.

  As a feature of the present invention, component (B), component (C) and component (D) are used in combination with component (A) in which the weight ratio of components (A-1) and (A-2) is within a specific range. By doing so, the adsorption of the antistatic agent to the adhesive layer is inhibited, and the antistatic performance is maintained even after the film is dry-laminated. When the ratio (OHv / Sv) between the hydroxyl value (OHv) and the saponification value (Sv) of the antistatic agent is in the range of 1.8 to 2.4, the bleed balance of the antistatic agent is maintained. Therefore, it is particularly preferable. There is no particular limitation on the film that can be used as the base film of the whole antistatic agent. it can.

[Extruded laminate film]
The extruded laminate film is a laminated film manufactured by bonding a molten resin to a base film while extruding the resin. In an extruded laminate film, an anchor coat agent is usually used to improve the adhesion between the films. When an anchor coat agent is used, the configuration of the laminated film is the same as that in FIG. The base film used for the extruded laminate film can be the same as the dry laminated film.
When a conventional antistatic agent is used, there is a problem that the antistatic component is adsorbed to the anchor coat adhesive layer, thereby impairing the antistatic performance.
However, when the antistatic agent of the present invention is used, component (B) and component (C) are added to component (A) in which the weight ratio of components (A-1) and (A-2) is in a specific range. When the antistatic agent is used in combination with the component (D), the adsorption of the antistatic agent to the highly hydrophilic anchor coat adhesive layer is suppressed, so that the antistatic agent can be effectively used. When the ratio (OHv / Sv) between the hydroxyl value (OHv) and the saponification value (Sv) of the antistatic agent is in the range of 1.8 to 2.4, the bleed balance of the antistatic agent is maintained. Therefore, it is particularly preferable. As the anchor coating agent, there are a polyurethane-based adhesive and a polyether-based adhesive, and any of them can be used as appropriate.

[Co-extrusion film]
A co-extruded film is a laminated film manufactured by simultaneously extruding and bonding a molten resin and a molten base resin. FIG. 5 is a sectional view showing an example of the co-extruded film of the present invention. The co-extruded film 11 has a structure in which the antistatic layer 3 and the hydrophilic base material layer 7 are directly adhered and laminated. For the co-extruded film, the same base resin as the dry laminated film can be used.
With conventional antistatic agents, when a different thermoplastic resin having a high hydrophilicity to the thermoplastic resin containing the antistatic agent is co-extruded as a base resin, the antistatic component is adsorbed to the base resin layer and charged. There is a problem that the prevention performance is impaired.
When the antistatic agent of the present invention is used, the component (A) containing the component (A-1) is used in combination with the component (B), the component (C), and the component (D) to form a hydrophilic substrate layer. Since the adsorption to the surface is suppressed, it can be used effectively. When the ratio (OHv / Sv) between the hydroxyl value (OHv) and the saponification value (Sv) of the antistatic agent is in the range of 1.8 to 2.4, the bleed balance of the antistatic agent is maintained. Therefore, it is particularly preferable. As the base resin, for example, polyester, polyvinyl alcohol, and polyamide can be appropriately used.

  The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. The evaluation of the physical properties of the antistatic resin composition in the examples was performed by the following methods.

(Hydroxyl value)
The hydroxyl value (OHv) of the anti-fogging agent is measured by a quasi-drug raw material standard hydroxyl value measurement method.
(Saponification value)
The saponification value (Sv) of the antifogging agent is measured by a quasi-drug raw material standard saponification value measuring method.
In addition, the said measuring method shall be the measuring method prescribed at the time of filing this application.

(Antistatic performance evaluation)
The film produced by molding the polyolefin-based resin composition is stored at 40 ° C. for 1 day and at 40 ° C. for 7 days.
In a constant temperature and humidity room controlled at 20 ° C. and 45% RH, the surface specific resistivity of the film piece is measured using a super-insulation meter (SM-8310, manufactured by Toa Denpa Kogyo KK). A surface resistivity of 1 × 10 ¹⁴ Ω / □ or less (1000 × 10 ¹¹ Ω / □ or less) was judged to pass antistatic performance.

(Film transparency evaluation)
The film prepared by molding the polyolefin-based resin composition was stored at 40 ° C. for 30 days after the formation, and then ΔHaze (film) of the film was measured using a color difference / turbidity meter (manufactured by Nippon Denshoku Industries Co., Ltd .; COH-300A). The difference in Haze value before and after lightly rinsing the surface with ethanol) is measured.

(Evaluation of antistatic property of dry laminated film)
After the film produced by molding the polyolefin-based resin composition is dry-laminated with another thermoplastic resin film using a polyurethane-based adhesive, the surface of the laminated film piece obtained in the same manner as in the evaluation of the antistatic property described above is obtained. Measure the resistivity.
The antistatic property was passed when the surface resistivity was 1 × 10 ¹⁴ Ω / □ or less (1000 × 10 ¹¹ Ω / □ or less).

(Production of dry laminated film)
Another polypropylene film is prepared by preparing a polyurethane-based laminating adhesive (manufactured by Sanyo Chemical Industries; Polybond AY-651) in a ratio of 100 parts by weight: 15 parts by weight: 190 parts by weight: hardener: ethyl acetate (solvent) = 100 parts by weight. And then dried at 60 ° C. for 1 minute to evaporate the solvent. The produced polypropylene film was adhered to the bonding surface, pressed with a roller kept at 60 ° C, and stored at 40 ° C for 2 days immediately after curing. Further, it was stored at 40 ° C. for 7 days.

Components (A) to (D) were melt-mixed at the mixing ratios shown in Table 1 to prepare an antistatic agent. Next, a polypropylene homopolymer (MFR = 2.5 g / 10 min) was prepared, and the antistatic agent was mixed so that the concentration of the antistatic agent was 10% by weight with respect to the polypropylene resin. A strand was obtained by melt-kneading at 230 ° C., and cut by a pelletizer to prepare a master batch.

Next, the obtained master batch and a separately prepared polypropylene homopolymer were mixed, melt-kneaded at 230 ° C. using a twin-screw extruder, and extruded from a T-die. The mixing ratio of the polypropylene homopolymer prepared separately from the master batch used was adjusted, and the concentration of the antistatic agent contained in the film was adjusted. Three types of films of 0.8% by weight, 0.5% by weight, and 1.0% by weight of the antistatic agent were prepared only in Production Examples 1, 2 and 3, and 0.8% by weight for the remaining Production Examples and Production Examples. %.
The resin composition extruded from the T-die was uniaxially stretched to produce a film having a thickness of 20 μm, and the obtained film was measured for antistatic properties and transparency. In addition, the surface specific resistivity of the antistatic surface was measured for the film that was dry-laminated by the method described above. The results are shown in Tables 2 and 3.

As can be seen from Tables 1 to 3, the antistatic agents of Examples 1 to 16 are a diglycerin fatty acid ester component (A), an aliphatic amine ethylene oxide adduct fatty acid ester component (B), and a glycerin fatty acid ester. And a component (D) which is an aliphatic amine ethylene oxide adduct, wherein the ratio of the hydroxyl value (OHv) to the saponification value (Sv) (OHv / Sv) Is in the range of 1.8 to 2.4, and a component (A-1) which is a diglycerin fatty acid monoester and a component which is an ester of diglycerin and two or more fatty acids represented by the following general formula (3) ( A-2), and the weight ratio (A-1 / A-2) between (A-1) and (A-2) is in the range of 80/20 to 20/80. Can be solved.
On the other hand, when any of the components (A) to (D) is not contained (Comparative Examples 1 to 4), (A-1 / A-2) is not in the range of 80/20 to 20/80 ( For Comparative Examples 5 and 6), the problem of the present application has not been solved.

1: hydrophilic group 2: hydrophobic group 3: antistatic layer 4: hydrophilic layer 5: adhesive layer 6: substrate layer 7: hydrophilic substrate layer 10: dry laminated film 11: coextruded film

Claims (10)

Component (A) which is a diglycerin fatty acid ester, Component (B) which is a fatty acid amine ethylene oxide adduct fatty acid component, Component (C) which is a glycerin fatty acid ester and component (D) which is an aliphatic amine ethylene oxide adduct Including
The component (A) comprises a component (A-1) which is a diglycerin fatty acid monoester, and a component (A-2) which is an ester of diglycerin and two or more fatty acids,
An antistatic agent, wherein the weight ratio (A-1 / A-2) between the component (A-1) and the component (A-2) is 80/20 to 20/80. A component (B-1) in which the component (B) is an aliphatic amine ethylene oxide adduct mono-fatty acid ester represented by the following general formula (1); and an aliphatic amine ethylene oxide represented by the following general formula (2). A component (B-2) which is an adduct difatty acid ester, and the weight ratio (B-1 / B-2) of the component (B-1) to the component (B-2) is 50/50 to 50/50. The antistatic agent according to claim 1, which is 90/10.

(Wherein, R ¹ and R ² are each independently an alkyl group, an alkenyl group, an alkadienyl group or an alkanyl group. N and m are 0 or more, and n + m is a number satisfying 2-3. .)

(Wherein, R ³ , R ⁴ and R ⁵ are each independently an alkyl group, an alkenyl group, an alkadienyl group or an alkanyl group. O and p are 0 or more, and satisfy o + p = 2 to 3. It is a number.)   The antistatic according to any one of claims 1 to 3, wherein the component (A) contains diglycerin laurate, and a weight ratio of the diglycerin laurate in the component (A) is 40% by weight or more. Agent.   20 to 70% by weight of the component (A), 10 to 50% by weight of the component (B), 5 to 50% by weight of the component (C), and 1 to 20% by weight of the component (D). The antistatic agent according to any one of claims 1 to 3, which comprises an antistatic agent.   The antistatic agent according to any one of claims 1 to 4, wherein a ratio (OHv / Sv) between a hydroxyl value (OHv) and a saponification value (Sv) is in a range of 1.8 to 2.4.   A polyolefin-based resin composition comprising a polyolefin-based resin and the antistatic agent according to claim 1.   The polyolefin resin composition according to claim 6, wherein the weight ratio of the antistatic agent for the polyolefin resin in the resin composition is 0.01 to 30% by weight.   The polyolefin resin composition according to claim 6, wherein the polyolefin resin is polypropylene. A film formed by molding the polyolefin-based resin composition according to claim 6.   A laminated film having at least two layers, wherein the antistatic film according to claim 9 and another substrate film are adhered.

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