JP6913014B2 - Antistatic agent - Google Patents

Description

The present invention relates to an antistatic agent.

Phosphoric acid ester-based surfactants are used in various applications as detergents, antistatic agents, and gelling agents. Further, the acidic phosphoric acid ester has been developed as an antistatic agent for ink (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2011-046838

However, even with the above technology, it cannot be said that the performance such as antistatic property is sufficiently satisfactory, and the development of a more excellent antistatic agent has been required. An object of the present invention is to provide an antistatic agent having more excellent antistatic properties.

［式（１）中、Ｒは炭素数８〜３０の炭化水素基；ＡＯは炭素数２〜３のアルキレンオキシ基であり、ＡＯが複数である場合、同一であっても、異なっていてもよい；ｎは、１分子当たりのＡＯ単位数の数平均であり、３〜１０の数；Ｍはアルカリ金属である。］

Ｒ²−Ｏ−（ＡＯ）_m−Ｈ （２）

［式（２）中、Ｒ²は炭素数８〜３０の炭化水素基、ＡＯは炭素数２〜３のアルキレンオキシ基であり、ＡＯが複数である場合、同一であっても、異なっていてもよい；ｍは、１分子当たりのＡＯ単位数の数平均であり、３〜１０の数である。］ The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems. That is, the present invention contains an anionic surfactant (A) represented by the following general formula (1) and a nonionic surfactant (B) represented by the following general formula (2). , The antistatic agent (X) having a weight ratio [(A) / (B)] of (A) and (B) of 75/25 to 98/2.

[In the formula (1), R is a hydrocarbon group having 8 to 30 carbon atoms; AO is an alkyleneoxy group having 2 to 3 carbon atoms, and when there are a plurality of AOs, they may be the same or different. Good; n is the number average of the number of AO units per molecule, 3 to 10; M is the alkali metal. ]

R ^2- O- (AO) _m- H (2)

[In the formula (2), R ² is a hydrocarbon group having 8 to 30 carbon atoms, AO is an alkyleneoxy group having 2 to 3 carbon atoms, and when there are a plurality of AOs, they are different even if they are the same. May; m is the number average of the number of AO units per molecule, which is a number of 3-10. ]

The antistatic agent (X) of the present invention has the following effects.
(1) Excellent antistatic property.
(2) Further, it imparts excellent storage stability to the ink composition in a wide temperature range.

<Anionic surfactant (A)>
The anionic surfactant (A) in the present invention is represented by the general formula (1).

In the general formula (1), R is a hydrocarbon group having 8 to 30 carbon atoms [hereinafter, may be abbreviated as C], and examples thereof include an alkyl group of C8 to 30 and an alkenyl group of C8 to 30. , Preferably an alkyl group of C8-30.

Examples of the alkyl group of C8 to 30 include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group and a henicosyl group. Examples thereof include a group, a docosyl group, a tricosyl group, a tetracosyl group and the like, which are linear or branched, respectively.
Of these, from the viewpoint of antistatic property and storage stability, an alkyl group having 9 to 20 carbon atoms is preferable, an alkyl group having 10 to 18 carbon atoms is more preferable, and an alkyl group having 12 to 13 carbon atoms is particularly preferable. It is an alkyl group.

Examples of the alkenyl group of C8 to 30 include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadesenyl group, an icosenyl group and a henicosenyl group. Examples thereof include a group, a docosenyl group, a tricosenyl group, a tetracosenyl group and the like. These are linear or branched, respectively, and have double bonds at arbitrary positions.
From the viewpoint of antistatic property and storage stability, an alkenyl group having 9 to 20 carbon atoms is preferable, an alkenyl group having 10 to 18 carbon atoms is more preferable, and an alkenyl group having 12 to 13 carbon atoms is particularly preferable.

In the general formula (1), AO is an alkyleneoxy group having 2 to 3 carbon atoms, and examples thereof include an ethyleneoxy group and a propyleneoxy group. When there are a plurality of AOs, they may be the same or different. Of these, ethyleneoxy groups are preferable from the viewpoint of antistatic properties.
The AO is preferably derived from alkylene oxide [ethylene oxide (EO), propylene oxide (PO)] in the industry.

In the general formula (1), n is the average number of AO units per molecule, which is 3 to 10, preferably 3 to 9 from the viewpoint of antistatic property, and more preferably 4 to 8. be.

In the general formula (1), M is an alkali metal, and examples thereof include lithium, sodium, potassium, rubidium, and cesium. Of these, lithium, sodium, and potassium are preferable, and sodium is more preferable, from the viewpoint of antistatic property and storage stability.

<Nonionic surfactant (B)>
The nonionic surfactant (B) in the present invention is represented by the general formula (2).

R ^2- O- (AO) _m- H (2)

In the general formula (2), R ² is a hydrocarbon group having 8 to 30 carbon atoms [hereinafter, may be abbreviated as C], for example, an alkyl group of C8 to 30 and an alkenyl group of C8 to 30. Preferred are C8-30 alkyl groups.

Examples of the alkyl group of C8 to 30 of R ² include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group and an icosyl group. Examples thereof include a group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group and the like, and they are linear or branched, respectively.
Of these, from the viewpoint of antistatic property and storage stability, an alkyl group having 9 to 20 carbon atoms is preferable, an alkyl group having 10 to 18 carbon atoms is more preferable, and an alkyl group having 12 to 13 carbon atoms is particularly preferable. It is an alkyl group.

Examples of the alkenyl group of C8 to 30 of R ² include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadesenyl group and an icosenyl group. Examples thereof include a group, a henicosenyl group, a docosenyl group, a tricosenyl group, a tetracosenyl group and the like. These are linear or branched, respectively, and have double bonds at arbitrary positions.
From the viewpoint of antistatic property and storage stability, an alkenyl group having 9 to 20 carbon atoms is preferable, an alkenyl group having 10 to 18 carbon atoms is more preferable, and an alkenyl group having 12 to 13 carbon atoms is particularly preferable.

In the general formula (2), AO is an alkyleneoxy group having 2 to 3 carbon atoms, and examples thereof include an ethyleneoxy group and a propyleneoxy group. When there are a plurality of AOs, they may be the same or different. Of these, ethyleneoxy groups are preferable from the viewpoint of antistatic properties.
The nonionic surfactant (B) is industrially preferable in which an alkylene oxide [ethylene oxide (EO), propylene oxide (PO)] is added to a monohydric alcohol having 8 to 30 carbon atoms.

In the general formula (2), m is the number average of the number of AO units per molecule [hereinafter, may be abbreviated as the average of AO units. ], The number is 3 to 10, preferably 3 to 9, and even more preferably 4 to 8 from the viewpoint of antistatic properties.

<Antistatic agent (X)>
The antistatic agent (X) of the present invention contains the anionic surfactant (A) and the nonionic surfactant (B).
The weight ratio [(A) / (B)] between (A) and (B) is 75/25 to 98/2. If the weight ratio [(A) / (B)] is less than 75/25, the antistatic property is inferior, and if it exceeds 98/2, the storage stability is inferior.
The weight ratio [(A) / (B)] is preferably 80/20 to 97/3, more preferably 85/15 to 95/5, from the viewpoint of antistatic property and storage stability.

The antistatic agent (X) of the present invention can be produced, for example, by mixing the anionic surfactant (A) and the nonionic surfactant (B).
Further, the antistatic agent (X) can be used for various purposes (ink application, kneading into resin for molding, coating, etc.), and is particularly suitable as an antistatic agent for ink.

<Ink composition (Y)>
The ink composition (Y) of the present invention contains the antistatic agent (X). The (X) is preferably 0.1 to 5% by weight, more preferably 0.2 to 4% by weight, based on the weight of the ink composition (Y), from the viewpoint of antistatic property and storage stability. Particularly preferably, it is 0.3 to 3% by weight.

The ink composition (Y) contains, for example, the antistatic agent (X), a resin, a solvent, and a pigment. In addition, an auxiliary agent according to other purposes may be contained within a range that does not impair the effects of the present invention.

Examples of the resin include those used for solvent-based inks, such as polyurethane resin, acrylic resin, maleic acid resin, styrene / maleic acid resin, polyester resin, polyamide resin, vinyl chloride-vinyl acetate copolymer, and chlorine. Examples thereof include modified polyolefin resin, alkyd resin, rosin-modified phenol resin, cured rosin, and nitrocellulose.

Examples of the solvent include toluene, ethyl acetate, isopropyl alcohol, methyl ethyl ketone and the like, and from the viewpoint of storage stability, toluene and ethyl acetate are preferable.

Examples of the pigment include azo pigments, phthalocyanine pigments, titanium oxide, carbon black, aluminum powder, copper powder and the like.

Examples of other auxiliaries include antifoaming agents, viscosity modifiers, antioxidants and the like.

Examples of the printing method of the ink composition (Y) include letterpress printing, intaglio printing, lithographic printing, and stencil printing, and can be printed on a plastic film or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In the following, "part" indicates a part by weight, and "%" indicates a weight%. In the following, Examples 31 to 37 are Reference Examples 1 to 7, respectively.

<Examples 1 to 5 and Comparative Examples 1 to 2>
Anionic surfactant (A) and nonionic surfactant (B) are charged in a container according to the compounding composition (part) of Table 1, and the mixture is stirred for 1 minute to prepare each antistatic agent (X-1). (X-5), (ratio X-1) to (ratio X-2) were obtained.

<Examples 11 to 17, Comparative Examples 11 to 12>
In the container, each antistatic agent (X) obtained, polyurethane resin solution ["Samplen IB-915" manufactured by Sanyo Kasei Kogyo Co., Ltd., resin component 30% by weight, solvent, according to the compounding composition (part) in Table 2 70 parts by weight] 100 parts, pigment [β-type phthalocyanine blue] 30 parts, solvent [toluene] 100 parts are charged and mixed, and then the whole amount is mixed with 150 parts of glass beads using a paint conditioner [manufactured by Red Devil]. After kneading for 1 hour, the glass beads were removed by filtration to obtain each ink composition (Y).
Table 2 shows the results of evaluating each of the obtained ink compositions (Y) by the following evaluation methods.

(1) Evaluation of antistatic property The obtained ink composition was applied to an OPP film [biaxially stretched polypropylene film, 0.04 mm thick] with a bar coater so as to have a solid content of 2 to 3 μm, and the temperature was 70 ° C. A printed matter was obtained by drying in 1 minute.
After 10 minutes, the surface specific resistance value (unit: Ω) of the obtained printed matter was measured with Mitsubishi Chemical Analytech's High Restor-UP MCP-HT450 in an environment of 25 ° C. and 50% RH. It was evaluated according to the <evaluation criteria> of.
<Evaluation criteria>
⊚: 1.0 × 10 ^{less than 11} Ω ○: 1.0 × 10 ¹¹ Ω or more, ^{less than 5.0 × 10 11} Ω Δ: 5.0 × 10 ¹¹ Ω or more, ^{less than 1.0 × 10 12} Ω ×: 1.0 x 10 ¹² Ω or more

(2-1) Evaluation of storage stability (high temperature: 50 ° C)
30 g of the obtained ink composition was placed in a 50 mL screw tube bottle, the temperature was adjusted to 50 ° C., and the state of the contents after 5 days was visually observed and evaluated according to the following <evaluation criteria>.
<Evaluation criteria>
⊚: No precipitation or separation ○: Almost no precipitation or separation Δ: Slight precipitation or separation ×: Precipitation or separation

(2-2) Evaluation of storage stability (low temperature: 5 ° C)
30 g of the obtained ink composition was placed in a 50 mL screw tube bottle, the temperature was adjusted to 5 ° C., and the state of the contents after 5 days was visually observed and evaluated according to the following <evaluation criteria>.
<Evaluation criteria>
⊚: No precipitation or separation ○: Almost no precipitation or separation Δ: Slight precipitation or separation ×: Precipitation or separation

<Examples 31 to 37, Comparative Examples 31 to 32>
According to the compounding composition (parts by weight) shown in Table 3, the compounding components are mixed with a Henschel mixer for 3 minutes, and then melt-kneaded and charged in a twin-screw extruder with a vent under the conditions of 100 rpm, 250 ° C. and a residence time of 5 minutes. An antistatic resin composition was obtained. Using the injection molding machine "PS40E5ASE" [manufactured by Nissei Resin Industry Co., Ltd.], a molding test piece was prepared from the antistatic resin composition at a cylinder temperature of 250 ° C. and a mold temperature of 50 ° C., and the following performance test was performed. evaluated. The results are shown in Table 3.

The contents of the symbols in Table 3 are as follows.
(D-1):
PP (polypropylene) resin "PM771M" [manufactured by SunAllomer Ltd.]
(D-2):
PMMA (polymethyl methacrylate) "Acrypet VH" [manufactured by Mitsubishi Rayon Co., Ltd.]

<Performance test> Antistatic property (1) Surface specific resistance value (unit: Ω)
In accordance with ASTM D257, the test piece (100 x 100 x 2 mm) was measured using a super insulation meter "DSM-8103" [manufactured by Toa Denpa Kogyo Co., Ltd.] in an atmosphere of 23 ° C. and 50% humidity RH. ..
<Evaluation criteria>
⊚: 1.0 × 10 ^{less than 11} Ω ○: 1.0 × 10 ¹¹ Ω or more, ^{less than 5.0 × 10 11} Ω Δ: 5.0 × 10 ¹¹ Ω or more, ^{less than 1.0 × 10 12} Ω ×: 1.0 x 10 ¹² Ω or more

From the results in Tables 1 and 2, the antistatic agent (X) of the present invention is superior in antistatic property as compared with the comparative one, and further imparts excellent storage stability in a wide temperature range to the ink composition. I understand.
Further, from the results in Table 3, it can be seen that not only the ink composition but also the thermoplastic resin composition is imparted with excellent antistatic properties.

Since the antistatic agent of the present invention has excellent antistatic properties and further gives the ink composition excellent storage stability in a wide temperature range, it is suitably used as an antistatic agent for various applications, especially inks. NS.

Claims (2)

It contains an anionic surfactant (A) represented by the following general formula (1) and a nonionic surfactant (B) represented by the following general formula (2). An antistatic agent (X) for ink having a weight ratio [(A) / (B)] of (B) of 80/20 to 97/3.

[In the formula (1), R is a hydrocarbon group having 8 to 30 carbon atoms; AO is an alkyleneoxy group having 2 to 3 carbon atoms, and when there are a plurality of AOs, they may be the same or different. Good; n is the number average of the number of AO units per molecule, the number of 4-8 ; M is sodium . ]
R ^2- O- (AO) _m- H (2)
[In the formula (2), R ² is a hydrocarbon group having 8 to 30 carbon atoms, AO is an alkyleneoxy group having 2 to 3 carbon atoms, and when there are a plurality of AOs, they are different even if they are the same. May; m is the number average of the number of AO units per molecule, 4-8 . ] The ink composition (Y) containing the antistatic agent (X) for ink according to claim 1.