JP2023125696A - Antistatic composition for polymer material - Google Patents

Abstract

To provide an antistatic composition that can express antistatic performance with stable electric resistance values without altering the properties of a polymer material.SOLUTION: An antistatic composition includes an antistatic agent including an imidazoline-based nonionic surfactant and Bronsted acid and a nano material. According to the inventor's findings, such an antistatic composition can express antistatic performance with stable electric resistance values without altering the properties of a polymer material.SELECTED DRAWING: None

Description

The main object of the present invention is to exhibit antistatic performance with a stable electrical resistance value without changing the properties of the polymer material.

Antistatic agents are attracting attention in various fields as materials that eliminate problems caused by static electricity. Among them, attention is increasing from the viewpoint of unpleasant phenomena such as the adhesion of dust due to static electricity generated when human bodies move or come into contact with each other, and the possibility of causing disasters such as dust explosions. In addition, as equipment becomes more sophisticated, problems related to static electricity are increasing, such as causing serious system failures due to malfunctions of electronic equipment in the information, electronics, and precision fields, and indirectly affecting precision production lines. With the evolution of civilization, this has become an increasingly important issue, and quite sophisticated countermeasures are now required. Therefore, in recent years, various anti-static products have been appearing at a rapid pace, and a recent trend that has attracted particular attention is the ability to stably develop electrical resistance values in the intermediate region between antistatic and conductive levels. It is a product that can. In addition, polymer materials are used in a wide variety of forms in various industries, and are one of the most convenient materials, but because they are insulating materials, they require measures such as adding antistatic agents. Measures against static electricity are being taken.

Surfactants have been used as antistatic agents for a long time, and it is known that various hydrophilic groups such as nonionic, anionic, cationic, and amphoteric groups exhibit antistatic properties. It is known that among these hydrophilic groups, cationic surfactants have particularly excellent antistatic properties. Regarding the mechanism of antistatic effect by surfactants, when a surfactant is applied to a certain base material, the surfactant applied to the surface is arranged on the surface of the base material in the form of a continuous phase. By adsorbing moisture in the air, this array of surfactants exhibits conductivity and antistatic properties.

On the other hand, there are concerns that the addition of surfactants as antistatic agents may cause changes in the properties of polymeric materials due to stickiness and the like. From the above, there is a need to develop antistatic performance with a stable electrical resistance value without changing the properties of the polymer material (Non-Patent Document 1).

Surface Technology Volume 56, No. 8, 447 (2005)

The main object of the present invention is to exhibit antistatic performance with a stable electrical resistance value without changing the properties of the polymer material.

The present inventors have made extensive studies to solve the various problems mentioned above, and have found that an antistatic agent consisting of an imidazoline type nonionic surfactant and a Brønsted acid is excellent. Furthermore, we have discovered that by using this antistatic agent supported on nanomaterials, it is possible to suppress changes in the properties of polymeric materials due to the antistatic agent, and have completed the present invention.

That is, the present invention is as follows.
An antistatic agent for polymeric materials, consisting of an imidazoline type nonionic surfactant represented by the following general formula (1) and a Brønsted acid represented by the following general formula (2) in a molar ratio, An antistatic agent composition comprising an antistatic agent and a nanomaterial, characterized in that they are contained in a ratio of (1):(2)=30:70 to 50:50.

However, in the general formula (1), R ¹ represents an alkyl group having 7 to 21 carbon atoms or an alkylene group having a linear or branched structure, and in the general formula (2), R ² represents a linear or branched structure. An alkyl group having a branched structure having 1 to 22 carbon atoms, an alkylene group, or a phenyl group, a hydroxyalkyl group having a primary or secondary hydroxyl group having 1 to 3 carbon atoms, a hydroxyphenyl group, or at least one or more An antistatic agent that represents either an alkyl group or an alkylene group in which a hydrogen atom is substituted with a fluorine atom, and A represents any one of a carboxylic acid group, a sulfonic acid group, a monovalent phosphoric acid group, and a phosphoric ester group.

An antistatic agent composition for polymeric materials, in which a nanomaterial supports 1.0 parts by mass or more of the antistatic agent.

An antistatic agent composition for a polymeric material, wherein the nanomaterial is at least one selected from titanium oxide, silicon dioxide, iron oxide, zirconium dioxide, zinc oxide, aluminum oxide, pseudoboehmite, and cerium oxide.

The antistatic agent for polymeric materials and the antistatic agent composition of the present invention can exhibit antistatic performance with a stable electrical resistance value without changing the properties of the polymeric material.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail. The present embodiment below is an illustration for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be implemented with appropriate modifications within the scope of its gist.

The present inventors have made extensive studies to solve the various problems mentioned above, and have found that an antistatic agent consisting of an imidazoline type nonionic surfactant and a Brønsted acid is excellent. We have also discovered that by supporting this antistatic agent on nanomaterials, it is possible to suppress changes in the properties of polymeric materials caused by the antistatic agent.

(Imidazoline type nonionic surfactant)

The type of imidazoline type nonionic surfactant is not particularly limited, and any suitable one can be selected as appropriate. For example, an imidazoline type nonionic surfactant represented by the general formula (1) which is generally easily available can be mentioned.

Although R ¹ in the general formula (1) is not particularly limited, it preferably has 1 to 22 carbon atoms from the viewpoint of easy availability. The lower limit is more preferably 7 or more, still more preferably 11 or more, even more preferably 13 or more, even more preferably 15 or more, even more preferably 17 or more. More preferred. Moreover, it is more preferable that the upper limit is 22 or less.

Specifically, for example, 2-(2-heptyl-2-imidazolin-1-yl)ethanol, 2-(2-octyl-2-imidazolin-1-yl)ethanol, 2-(2-nonyl-2-yl) imidazolin-1-yl)ethanol, 2-(2-decyl-2-imidazolin-1-yl)ethanol, 2-(2-undecyl-2-imidazolin-1-yl)ethanol, 2-(2-dodecyl-2 -imidazolin-1-yl)ethanol, 2-(2-tridecyl-2-imidazolin-1-yl)ethanol, 2-(2-tetradecyl-2-imidazolin-1-yl)ethanol, 2-(2-pentadecyl- 2-imidazolin-1-yl)ethanol, 2-(2-hexadecyl-2-imidazolin-1-yl)ethanol, 2-[2-(2-hexyldecyl)-2-imidazolin-1-yl]ethanol, 2 -(2-heptadecyl-2-imidazolin-1-yl)ethanol, 2-[2-(8-heptadecenyl)-2-imidazolin-1-yl]ethanol, 2-(2-henicosyl-2-imidazolin-1-yl) (il) ethanol, etc.

The imidazoline type nonionic surfactants may be used alone or in combination of two or more.

(Bronsted acid)

A and R ² of the Brønsted acid represented by the general formula (2) that can be used in the antistatic agent of this patent are not particularly limited, and are determined based on the types of other components used, desired physical properties, etc. It can be selected as appropriate.

R ² in the general formula (2) is generally easily available, so R 2 is a linear or branched alkyl group having 1 to 22 carbon atoms, an alkylene group, or a phenyl group having 1 to 3 carbon atoms. Examples include a hydroxyalkyl group having a primary or secondary hydroxy group, a hydroxyphenyl group, an alkyl group or alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.
A in general formula (2) can represent a carboxylic acid group, a sulfonic acid group, a monovalent phosphoric acid group, a phosphoric ester group, and the like. The combination of R ² and A is also not particularly limited.

Specifically, for example, aliphatic carboxylic acids, aliphatic sulfonic acids, aliphatic phosphoric esters, aromatic carboxylic acids, aromatic sulfonic acids, aromatic phosphoric esters, aliphatic hydroxy acids, aromatic hydroxy acids, sulfuric acid Examples include esters, vinyl group-containing sulfonic acids, fluorine atom-containing carboxylic acids, fluorine atom-containing sulfonic acids.

Specific examples of aliphatic carboxylic acids include methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, and hexadecanoic acid. , heptadecanoic acid, octadecanoic acid, (Z)-octadec-9-enoic acid, (9Z,12Z)-octadec-9,12-dienoic acid, (9Z,12Z,15Z)-9,12,15-octadecatriene acid, (5Z,8Z11Z,14Z)-5,8,11,14-icosatetraenoic acid, 2-propenyl acrylic acid, and the like.

Specific examples of aliphatic sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, and decanesulfonic acid. acids, dodecanesulfonic acid, tetradecanesulfonic acid, hexadecanesulfonic acid, octadecanesulfonic acid, and the like.

Specific examples of aliphatic phosphate esters include dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, bis(2-ethylhexyl) phosphate, dioctyl phosphate, dinonyl phosphate, Examples include didecyl phosphate, didodecyl phosphate, ditridecyl phosphate, ditetradecyl phosphate, dihexadecyl phosphate, diotadecyl phosphate, and the like.

Specific examples of aromatic carboxylic acids include benzenecarboxylic acid, benzene-1,2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, 2-hydroxybenzenecarboxylic acid, Examples include 3,4,5-trihydroxybenzenecarboxylic acid, benzenehexacarboxylic acid, and 3-phenylprop-2-enoic acid.

Specific examples of aromatic sulfonic acids include dodecylbenzenesulfonic acid, para-toluenesulfonic acid, and the like.

Specific examples of aromatic phosphate esters include diphenyl phosphate.

Specific examples of aliphatic hydroxy acids include hydroxyacetic acid, 2-hydroxypropionic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, ricinoleic acid, and the like.

Specific examples of aromatic hydroxy acids include 2-hydroxybenzoic acid, 4-hydroxy-3-methoxybenzoic acid, diphenylglycolic acid, 2-methoxycinnamic acid, and (E)-3,4-dihydroxycinnamic acid. acid, 3-hydroxy-4-methoxycinnamic acid, 4-hydroxy-3,5-dimethoxycinnamic acid, and the like.

Specific examples of sulfuric esters include dodecyl sulfate.

Specific examples of vinyl group-containing sulfonic acids include 2-acrylamido-2-methylpropanesulfonic acid, parastyrenesulfonic acid, and the like.

Specific examples of the fluorine atom-containing carboxylic acid include perfluorooctanoic acid.

Specific examples of the fluorine atom-containing sulfonic acid include trifluoroacetate, perfluorooctane sulfonic acid, and the like.

Among these, one selected from the group consisting of aliphatic carboxylic acids, aliphatic sulfonic acids, aliphatic phosphoric acid esters, aromatic carboxylic acids, aromatic sulfonic acids, aromatic phosphoric acids, etc. due to ease of availability. Preferably, it is methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, Octadecanoic acid, (Z)-octadec-9-enoic acid, (9Z,12Z)-octadec-9,12-dienoic acid, (9Z,12Z,15Z)-9,12,15-octadecatrienoic acid, (5Z , 8Z, 11Z, 14Z) -5,8,11,14-icosatetraenoic acid, 2-propenyl acrylic acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptane Sulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, tetradecanesulfonic acid, hexadecanesulfonic acid, octadecanesulfonic acid, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dipentyl phosphate, dihexyl phosphate , bis(2-ethylhexyl) phosphate, dioctyl phosphate, dinonyl phosphate, didecyl phosphate, didodecyl phosphate, ditridecyl phosphate, ditetradecyl phosphate, dihexadecyl phosphate, dioctadecyl phosphate, benzenecarboxylic acid, benzene-1 , 2-dicarboxylic acid, benzene-1,3-dicarboxylic acid, benzene-1,4-dicarboxylic acid, 2-hydroxybenzenecarboxylic acid, 3,4,5-trihydroxybenzenecarboxylic acid, benzenehexacarboxylic acid, 3- More preferably, it is at least one selected from the group consisting of phenylprop-2-enoic acid, dodecylbenzenesulfonic acid, para-toluenesulfonic acid, and diphenyl phosphate.

One type of Brønsted acid may be used alone, or two or more types may be used in combination.

A reaction product of an imidazoline type nonionic surfactant and a methylating agent is also expected to exhibit antistatic properties similar to those of the present invention. However, when using a methylating agent, Brønsted acid is more preferred since it is more expensive and requires complicated synthetic operations compared to Brønsted acid.

(molar ratio)

In the antistatic agent of the present invention, the molar ratio of the imidazoline type nonionic surfactant and the Brønsted acid is 30:70 to 50:50. It is preferable that there be. The molar ratio is more preferably 30:70, still more preferably 35:65, even more preferably 40:60, even more preferably 45:55, and even more preferably 50:50. Even more preferably.

(Method for producing antistatic agent)

The antistatic agent according to this embodiment can be manufactured by mixing the above-mentioned components. The method for producing an antistatic agent according to the present embodiment includes a step of mixing an imidazoline type nonionic surfactant and a Brønsted acid. At this time, it may turn into salt. Alternatively, it may be manufactured by mixing in advance the solvents described in the section of other solvents, other additives, etc., which will be described later.
The method for producing the antistatic agent according to the present embodiment includes, for example, mixing an imidazoline type nonionic surfactant and a Brønsted acid in a dispersing machine such as a stirrer or a rotation/revolution mixer within the above-mentioned molar ratio range. It is preferable to mix using.

(Support on nanomaterials)

When using the antistatic agent of the present invention, it may be supported on nanomaterials. By supporting the antistatic agent, bleed-out of the antistatic agent kneaded into the polymer material can be suppressed.
The nanomaterial to be used is not particularly limited, and a suitable one can be selected in consideration of the types of components to be used, the intended use, and the like. Examples include titanium oxide, silicon dioxide, iron oxide, zirconium dioxide, zinc oxide, aluminum oxide, pseudoboehmite, cerium oxide, etc., which are widely used. Pseudo-boehmite is particularly preferred in terms of availability, cost, and effectiveness.

The average primary particle diameter of the nanomaterial is not particularly limited as long as it can be dispersed in a polymer material, but it is preferably 5 nm to 100 nm. The upper limit of this average primary particle diameter is more preferably 80 nm or less, even more preferably 60 nm or less, even more preferably 50 nm or less, even more preferably 30 nm or less, and 20 nm or less. Even more preferably. The average primary particle diameter here is a value calculated from specific surface area data by the BET method.

One type of nanomaterial may be used alone, or two or more types may be used in combination.

The amount of antistatic agent supported on the nanomaterial is not particularly limited, but it is preferable that the amount of the nanomaterial be 1.0 parts by mass or more relative to the antistatic agent. From the viewpoint of the bleed-out suppressing effect, it is more preferably 2.0 parts by mass or more.

(Method of supporting on nanomaterial)

The antistatic agent can be supported on the nanomaterial according to this embodiment by mixing each component. It includes a step of mixing an antistatic agent made of an imidazoline type nonionic surfactant and a Brønsted acid, and a nanomaterial. For example, in the presence of an antistatic agent and other additives obtained by mixing a nanomaterial, an imidazoline type nonionic surfactant, and a Brønsted acid, the nanomaterial is added to a solvent using a stirrer or a dispersion machine. Dispersion and stabilization are preferred.

Mixing into the polymer material can be performed by a known method. For example, general methods such as a dispersing machine such as an autorotation-revolution mixer, a homogenizer, an ultrasonic stirring device, a rocking mill device, a ball mill device, a jet mill device, a spike mill device, etc. can be used. Suitable mixing conditions can be selected as appropriate, taking into consideration the proportions, properties, etc. of each component used.

(polymer material)

There are no particular restrictions on the polymeric material to which the antistatic agent of the present invention can be applied, and a suitable material can be determined by taking into consideration the type of antistatic agent to be used, the intended use, etc. For example, ABS resin, AS resin, EVA resin, polyethylene resin, PET resin, acrylic resin, polypropylene resin, polystyrene resin, polyvinyl alcohol, polyvinyl chloride resin, vinylidene chloride resin, etc. are widely used and easily available. Can be mentioned.

(Application of antistatic agent to polymer materials)

Application of the antistatic agent of the present invention to polymer materials includes, but is not particularly limited to, coating or kneading.
As the coating method, for example, general methods such as dip coating, spin coating, spray coating, roll coating, and bar coating can be used.
Examples of kneading methods include kneading an antistatic agent into a heated and melted polymer material, adding an antistatic agent when polymerizing monomers and oligomers that are raw materials for polymer materials, and adding antistatic agents to polymer materials. A method of preparing a solution by mixing an antistatic agent with an appropriate solvent and then removing the solvent from the solution to form a polymer material, using roll kneading, bumper kneading, an extruder, a kneader, etc. , mixing and kneading.

(Amount of antistatic agent added to polymer material)

The antistatic agent of the present invention can be suitably applied depending on the type of polymeric material and other components, and can be applied without any upper limit as long as there is no problem with the application of the applied polymeric material. From the viewpoint of antistatic effect, the amount is preferably 0.3 parts by weight or more, more preferably 0.5 parts by weight or more, and even more preferably 1.0 parts by weight or more based on the polymer material composition (100 parts by weight).

(Other solvents, other additives, etc.)

There are no particular restrictions on the solvent that can be used in the antistatic agent according to the present embodiment, and it can be appropriately selected depending on the type of polymer material to which it is applied. For example, ether solvents such as dibutyl ether, tetrahydrofuran, and dioxane; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and N-methyl-2-pyrrolidone; ethyl acetate, isopropylacetate, propylene glycol monomethyl ether acetate, Ester solvents such as methyl acrylate, methyl methacrylate, and isobornyl acrylate; aromatic solvents such as xylene, toluene, and styrene; and hydrocarbon solvents such as hexane, methylcyclohexane, and mineral spirit.

Among these, from the viewpoint of handling properties, one or more solvents selected from the group consisting of ester solvents, aromatic solvents, hydrocarbon solvents, etc. are preferred, and methyl acetate, isopropylacetate, propylene glycol monomethyl ether More preferably, it is at least one selected from the group consisting of acetate, methyl acrylate, methyl methacrylate, isobornyl acrylate, xylene, toluene, styrene, hexane, methylcyclohexane, and mineral spirit.

Other known additives may also be used. Examples include leveling agents, ultraviolet absorbers, antioxidants, viscosity modifiers, and the like.

The content of each additive is not particularly limited, and can be determined under suitable conditions in consideration of the types of components used, intended use, and the like.

The present invention will be explained in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited to the following Examples. The reagents used were all special grade or first grade reagents manufactured by Tokyo Chemical Industry Co., Ltd. unless otherwise specified.

(Preparation of antistatic agent)

The imidazoline type nonionic surfactant represented by the general formula (1) was synthesized by a known method (Japanese Patent Laid-Open No. 10-17554). Thereafter, an imidazoline type nonionic surfactant and 1 mol of ethanoic acid per 1 mol of the imidazoline type nonionic surfactant were added to an ointment jar. Subsequently, using a rotation and revolution mixer (equipment name: Awatori Rentaro (registered trademark) ARE-310, manufactured by Thinky) under room temperature conditions, mixing treatment was performed for 10 minutes and defoaming treatment was performed for 5 minutes. Antistatic agents (Examples 1 to 8, Comparative Examples 4 to 9) which are mixtures of imidazoline type nonionic surfactants and Bronsted acids or salts thereof were obtained. In Comparative Examples 2 and 3, only an imidazoline type nonionic surfactant was used.

Details of the surfactant used are as follows.

Imidazoline type nonionic surfactants

In the formula, the -CR ¹ group represents a lauric acid residue, an oleic acid residue, or a coconut oil fatty acid residue.

(Preparation of antistatic agent composition)

Powdered pseudo-boehmite particles (particle diameter (breadth axis x long axis): 10 x 50 nm (arithmetic mean determined by observation with an electron microscope) of 1.0 to 2.0 times the weight of the prepared antistatic agent diameter)) (manufactured by Kawaken Fine Chemical Co., Ltd., Aluminum Sol-10A) was mixed in a toluene solution.

(Kneading into polymer materials)

Pellets of PS resin (average molecular weight 2,000, manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in toluene by heating and stirring while adjusting the concentration to 20 wt% to obtain a PS resin toluene solution. Add various antistatic agents of the present invention or nanomaterial-supported antistatic agents to the obtained PS resin toluene solution to make them compatible, and then pour 4g of the solution into a Teflon mold measuring 70 mm long, 70 mm wide, and 1 mm thick. By drying at room temperature overnight, PS resin films containing an antistatic agent were obtained (Examples 1 to 8). For comparison, Comparative Examples 1 to 9 in which no nanomaterial was added were also obtained.

(Antistatic performance evaluation)

The antistatic performance was evaluated using a super megohmmeter (SM-8220, Hioki Electric Co., Ltd.) and a flat plate sample electrode (SME-8311, Hioki Electric Co., Ltd.) at a temperature of 25°C and a relative Measurement was performed under conditions of humidity 25%, applied voltage 500V, and measurement time 60 seconds, and evaluation was made based on the following criteria.
〇: Surface resistance value (Ω/□) is 1E+9 or more, less than 1E+12 △: Surface resistance value (Ω/□) is 1E+12 or more, less than 1E+13 ×: Surface resistance value (Ω/□) is 1E+13 or more

(Adhesion evaluation)

Films obtained by applying the antistatic agent of this patent were stacked together, and the presence or absence of adhesion was visually confirmed and evaluated based on the following criteria.
〇: No adhesive property △: Some adhesive property ×: Adhesive property

Antistatic agent composition example

Comparative example of antistatic agent composition

From the above, the antistatic agent compositions of each example prepared within the scope of the present invention all have low surface resistance values, antistatic performance evaluations of ○, and polymeric materials that are not sticky or The adhesion evaluation was △ or higher. From this, the antistatic agent for polymeric materials and the antistatic agent composition of the present invention were able to exhibit antistatic performance with a stable electrical resistance value without changing the properties of the polymeric material.

Claims (3)

An antistatic agent for polymeric materials, consisting of an imidazoline type nonionic surfactant represented by the following general formula (1) and a Brønsted acid represented by the following general formula (2) in a molar ratio, An antistatic agent composition comprising an antistatic agent and a nanomaterial, characterized in that they are contained in a ratio of (1):(2)=30:70 to 50:50.
However, in the general formula (1), R ¹ represents an alkyl group having 7 to 21 carbon atoms or an alkylene group having a linear or branched structure, and in the general formula (2), R ² represents a linear or branched structure. An alkyl group having a branched structure having 1 to 22 carbon atoms, an alkylene group, or a phenyl group, a hydroxyalkyl group having a primary or secondary hydroxyl group having 1 to 3 carbon atoms, a hydroxyphenyl group, or at least one or more An antistatic agent that represents either an alkyl group or an alkylene group in which a hydrogen atom is substituted with a fluorine atom, and A represents any one of a carboxylic acid group, a sulfonic acid group, a monovalent phosphoric acid group, and a phosphoric ester group. 2. The antistatic agent composition for polymeric materials according to claim 1, wherein the nanomaterial supports 1.0 parts by mass or more of the antistatic agent. Charge for polymeric materials, wherein the nanomaterial according to claims 1 and 2 is at least one selected from titanium oxide, silicon dioxide, iron oxide, zirconium dioxide, zinc oxide, aluminum oxide, pseudoboehmite, and cerium oxide. Inhibitor composition.