JP2968061B2 - Antistatic agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic agent which is used to remove static electricity from plastics, fibers, papers and composites thereof, so as not to cause electrostatic damage.

[0002]

2. Description of the Related Art Conventionally, insulating materials such as plastics and fibers are electrically charged,
For the purpose of preventing dust from adhering and reducing the commercial value, an antistatic agent mainly using a surfactant is used. Antistatic agents are broadly classified into two types: an internal kneading type that is mixed in the production of the target insulator material, and a so-called surface coating type that is applied to the finished product.

However, in the internal kneading type, it is impossible to form a close-packed state accurately on the surface of the object to be molded, so that the surface specific resistance can be reduced to 10 ¹⁰ Ω or less (that is, a semiconductor region). Did not. Therefore, a material that was not completely charged could not be obtained.

Further, since the kneaded antistatic agent is essentially a surfactant, it is unevenly distributed inside the kneaded target material. For this reason, when a material mixed with an internal kneading type antistatic agent is subjected to secondary processing and stretched or cut, static electricity is generated on a newly generated surface, and the electrical characteristics are fundamentally modified. I couldn't do that.

On the other hand, a surface coating type antistatic agent can be correctly oriented on the surface depending on its concentration, realizes a close-packed state, and makes the distance between polar groups close and uniform. be able to. Therefore, if an adsorbed water film is present thereon, the surface resistivity of the target material can be considerably reduced. However, when the humidity is low, the antistatic property is extremely reduced, and the antistatic purpose cannot be achieved. In addition, under conditions of high humidity, the antistatic effect is good while orientation adsorption is maintained, but water particles in the adsorbed water film enter between the polar groups with time, and as a result, on the surface Has an irregular orientation state, and the distance between the polar groups varies. For this reason, the antistatic effect tends to gradually decrease.

[0006]

In order to solve the above-mentioned drawbacks of the conventional antistatic agent, namely, insufficient antistatic effect and instability, the present inventors have first prepared a semipolar organoboron polymer. It has been found that a nitrogen-boron complex (hereinafter, referred to as "NB complex") comprising a reaction product between a compound and a monoamine can be a charge leaking agent having a stable effect (JP-A-1-185329).
As a result of further intensive studies, the present inventors have found that as an N component and a B component that form an NB complex, a basic nitrogen and a semipolar boron given to the charge transfer reaction are each one.
It has been found that when only one compound is selected and a 1: 1 charge-transfer type conjugate is used, the compatibility with the target material is more excellent, and at the same time, a more excellent antistatic effect is exhibited.

That is, the antistatic agent of the present invention reacts a nonionic compound having one basic nitrogen with a semipolar compound having one atomic group represented by the following general formula I in the molecule. And a charge transfer type conjugate obtained by the above method.

[0008]

Embedded image

(Where R ₁ and R ₂ , R ₃ and R
₄ is a hydrogen, a methyl group, a methoxymethyl group or an ethoxymethyl group, or when one is a methoxy group or an ethoxy group, the other is hydrogen, or when one is a methyl group, The other is a methoxymethyl group or an ethoxymethyl group, or when one is an ethyl group, the other is hydrogen, a methoxymethyl group or an ethoxymethyl group, and n is 0 or 1. ) NB contained in the antistatic agent of the present invention
Nonionic compounds having one basic nitrogen used as the N component of the complex include, for example, ammonia, monomethylamine, dimethylamine, trimethylamine, triethylamine, methylnidi (hydroxyethyl) amine, dimethylaminoethanol, diethylaminoethanol, Monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methyl morpholine, ethyl morpholine, pyridine,
Picoline, N, N-di (hydroxyethyl) laurylamine, N, N-di (polyoxyethylene) laurylamine, N, N-di (hydroxyethyl) stearylamine, N, N-di (polyoxyethylene) stearyl Amines, N, N-di (hydroxyethyl) oleylamine,
N, N-di (polyoxyethylene) oleylamine, diallylamine, diallylhydroxyethylamine, diallylhydroxypropylamine, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl Aclamide, dimethylaminopropyl methclamide, diethylaminopropyl acrylamide, diethylaminopropyl methclamide, dimethylaminoethyl stearate, dimethylaminopropyl stearamide, diethylaminoethyl stearate, diethylaminopropyl stearamide, triethanolamine monostearate, triethanol Amine distearate, triethanolamine tristearate, (Stearamide propyl) amine,
1 such as di (stearamidopropyl) dimethylamine, vinylpyridine and dimethylaminomethylstyrene
Primary, secondary and tertiary amines.

On the other hand, semi-polar compounds having one atomic group represented by the general formula I, which is the component B, are described in Oil Chem.
9, No. 12, pages 893 to 900 (1980), showing two or three adjacent hydroxyl groups or α-positions,
di (glycerin) borate of a 2: 1 type polyol borate comprising a polyhydric alcohol residue having two hydroxyl groups opposed to each other in a γ-position and a monovalent carboxylic acid ester thereof, di (catechol) borate, Di (1,
2- (propylene glycol) borate, di (1,3-propylene glycol) borate, di (1,3-butylene glycol) borate, di (2-methyl-2,4-pentanediol) borate, di (2,2,2) 4-trimethyl-1,3-pentanediol) borate, di (2-ethyl-1,3-hexanediol) borate, di (2-methoxy-1,3-propylene glycol) borate, di (2-ethoxy-1) , 3-propylene glycol) borate, di (2-methyl-2-methoxymethyl-1,3-
Propylene glycol) borate, di (2-methyl-2)
-Ethoxymethyl-1,3-propylene glycol) borate, di (2-ethyl-2-methoxymethyl-1,3)
-Propylene glycol) borate, di (2-ethyl-
2-ethoxymethyl-1,3-propylene glycol)
Borate, di {2,2-di (methoxymethyl) -1,3
Propylene glycol borate and di 2,2
And boric esters such as -di (ethoxymethyl) -1,3-propylene glycol diborate.

The NB complex used in the present invention is obtained by combining the above-mentioned N component and B component under normal pressure for 20 to 20 minutes.
At 0 ° C., preferably 50-150 ° C., the components are 1: 1
(Molar ratio). At this time, if a polar solvent such as alcohol, ether or ketone is added, the reaction can be performed more easily.

The antistatic agent of the present invention can be used in the same manner as the usual method for using a known antistatic agent.
For example, an internal kneading method to be added at the time of molding the target insulator material, a surface coating method of treating a diluted solution of the antistatic agent of the present invention on the already molded insulator material,
Alternatively, any one of the external permanent antistatic treatment methods of treating the semi-processed or final processed insulator material with a mixed solution of the antistatic agent of the present invention and a polymer compound compatible therewith is employed. I can do it.

In this case, since the antistatic agent of the present invention has a higher heat resistance temperature than conventionally known antistatic agents, it can withstand the processing temperature of various insulator materials, and its application range is extremely wide. .

In the case of the surface coating method, the antistatic agent of the present invention comprising a charge transfer binder may be used alone, or may be mixed with a binder resin. It is preferable to use a water-soluble or water-dispersible binder resin when the mixture is applied to the binder resin.

The antistatic agent of the present invention is characterized in that, when applied to a film or sheet, the antistatic effect is exerted on the surface opposite to the coated surface only by applying it on one surface. Such characteristics are not observed in the conventionally known antistatic agents, and therefore, the application range of the antistatic agent of the present invention is extremely wide.

As described above, in order for the antistatic effect to be exerted on the surface opposite to the coating surface, it is necessary that molecules of the antistatic agent be present in the coating layer in an appropriate orientation. In order to control the orientation of the antistatic agent molecules, the applied film or sheet may be subjected to heat treatment or corona discharge treatment.

Tables 1 and 2 show examples of the NB complex type charge transfer type conjugate which can be used as the antistatic agent of the present invention.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

The NB which can be an antistatic agent in the present invention
The mechanism of action of the complex type charge transfer conjugate exhibiting an excellent antistatic effect is that the semipolar bond part of the semipolar compound and the basic nitrogen bond as shown in the following reaction formula [3]. In this way, an ion pair is formed, and the acidic protons generated at this time move in a manner that leaves bonds on both the boron side and the nitrogen side. It is considered that this causes the movement of a plurality of electrons to give a Fermi level, which is a driving force that can be converted to one having semiconductor-type electric characteristics.

[0021]

Embedded image

[0022]

Next, examples of the present invention and comparative examples will be described.

The evaluation methods used in the examples and comparative examples will be described below. (1) Surface specific resistance Takeda Riken's specific resistance measuring instrument applied voltage 500 V, 2
The measurement was performed at 3 ° C. and 50% RH.

(2) Triboelectricity JIS-L-1094 using a rotary static tester (RST-201) manufactured by Koa Shokai Co., Ltd.
It measured according to. A stainless steel plate was used as the friction body, and the measurement was performed at a load of 500 gf and 23 ° C.-50% RH.

Saturation charge voltage (V ₁ ) immediately after rubbing for 1 minute
After 30 seconds, the charged voltage (V ₂ ) was measured, and the decay rate (D) was calculated by the following equation.

[0026]

(Equation 1)

(3) Forced electrification Static honest meter (trade name) manufactured by Shishido Shosha Co., Ltd.
And a sample of 2 cm in an atmosphere of 23 ° C. and 50% RH.
A voltage of 10 kV was applied to the discharge electrode at the height of the film to charge the film, and after 1 minute, the discharge was stopped.

The charge amount of the sample was measured with an electrometer at a position 2 cm above the sample. The charge amount (V ₁ ) immediately after the discharge was stopped and the charge amount (V ₂ ) after 30 seconds were measured, and the decay rate (D) was calculated by the following equation.

[0029]

(Equation 2)

Examples 1 to 7 Antistatic agents 1 to 7 shown in Tables 1 and 2 were added to water-isopropanol on the corona discharge treated surface of a biaxially stretched polyester film of 12 μm (E5100 manufactured by Toyobo Co., Ltd.) which had been subjected to corona discharge treatment. Dissolve in a mixed solution, apply this solution to a thickness of 0.5 μm after drying, and
After drying for 2 seconds, a polyester film coated with an antistatic agent was obtained. Table 3 shows the properties of the obtained coated film.

Comparative Example 1 The film before application of the antistatic agent used in Examples 1 to 7 above was Comparative Example 1, and the characteristics are shown in Table 3.

Comparative Example 2 Table 3 shows properties of a film obtained in the same manner as in Example 1 using a commercially available anionic antistatic agent composed of sodium sulfonate as an antistatic agent.

[0033]

[Table 3]

As is apparent from the results in Table 3, all of the coated films of Examples 1 to 7 according to the present invention have excellent antistatic properties. In addition, the coated films of these examples also have antistatic properties on the surface opposite to the surface on which they are applied, and it is an extremely interesting property that the antistatic properties can be imparted to the entire coated film only by coating on one side. have. The surface resistivity of the surface opposite to the coating surface is
Although the level is the same as that of a normal polyester film, the triboelectric charging property and the forced charging property reach almost the same level as the coated surface.

In the case of using the conventional antistatic agent of Comparative Example 2, although the effect was slightly recognized on the coated surface, no antistatic effect was recognized on the surface opposite to the coated surface.

Examples 8 to 10 Using the antistatic agents 1, 3 and 4 shown in Table 1, the respective antistatic agents and a water-dispersible polyester binder (Vylonal resin manufactured by Toyobo Co., Ltd.) were used in a weight ratio of 2: 8. Table 4 shows the characteristics of the film obtained by applying the solution in the same manner as in Example 1 and applying a corona discharge treatment to the coated surface of the coated film.

Comparative Example 3 Table 4 shows the properties of the coated films obtained in Examples 8 to 10 by applying only the vironal resin without using an antistatic agent.

As is clear from the results in Table 3, all of the coated films of Examples 8 to 10 coated with the antistatic agent according to the present invention have excellent antistatic properties.

Examples 11 to 13 Water-isopropanol solutions of the antistatic agents 3, 4 and 5 shown in Table 1 were applied to a biaxially stretched polypropylene film (Pyrene film P2601 manufactured by Toyobo Co., Ltd.) having a thickness of 25 μm. After drying for 60 seconds, the coated surface was subjected to corona discharge treatment to obtain a polypropylene film coated with an antistatic agent. The thickness of the coating was 0.5 μm after drying. Table 4 shows the properties of the obtained coated film.

Comparative Example 4 The biaxially stretched polypropylene films used in Examples 11 to 13 were coated with no antistatic agent as Comparative Example 4, and the film properties of Comparative Example 4 are shown in Table 4.

As is clear from the results in Table 4, the coated films of Examples 11 to 13 according to the present invention all have excellent antistatic properties.

[0042]

[Table 4]

Example 14 Low density polyethylene pellets (average molecular weight: about 200,000) 1
After mixing 1 part of the antistatic agent 5 shown in Table 2 with respect to 00 parts, the mixture was extruded at 160 ° C. using a biaxial kneading extruder to obtain a film having a thickness of 50 μm. Table 5 shows the properties of the obtained film.

Comparative Example 5 A low-density polyethylene film in which an antistatic agent was not mixed in Example 14 was prepared. This film was referred to as Comparative Example 5, and the film characteristics of Comparative Example 5 are shown in Table 5.

[0045]

[Table 5]

As apparent from Table 5, the polyethylene film mixed with the antistatic agent according to the present invention has excellent antistatic properties.

[0047]

As described above, according to the present invention, the N
-The antistatic agent containing the B complex has excellent properties not found in conventional antistatic agents.

Therefore, the antistatic agent according to the present invention removes the chargeability of insulating materials such as films, sheets, fibers, molded articles, papers and composites thereof, and converts them into materials which do not cause electrostatic damage. It can be used effectively in a wide range of fields.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-185329 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09K 3/16 CA (STN) WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. A nonionic compound having one basic nitrogen and an atomic group represented by the following general formula I in the molecule:
An antistatic agent comprising a charge-transfer type conjugate obtained by reacting the compound with a semipolar compound. Embedded image (Where R ₁ and R ₂ , R ₃ and R ₄ are each hydrogen, methyl, methoxymethyl or ethoxymethyl, or when one is methoxy or ethoxy, the other is Is hydrogen, or the other is a methoxymethyl group or an ethoxymethyl group when one is a methyl group, or the other is a hydrogen, a methoxymethyl group or an ethoxymethyl group when one is an ethyl group, n is 0 or 1.)