JPH04288390A - Antistatic agent - Google Patents

Abstract

PURPOSE:To obtain an antistatic agent excellent in compatibility with a material to which it is applied and in antistatic effect by using, as the constituent, a charge-transfer complex prepared by reacting a specified nonionic compound with a semi-polar compound. CONSTITUTION:An antistatic agent which contains a charge-transfer complex obtained by reacting a nonionic compound having at least one basic nitrogen (e.g. monoethanolamine) with a semi-polar compound having one atomic group of formula I (wherein R1, R2, R3, and R4 are each H, CH3, methoxymethyl or ethoxymethyl, or when one of R1 and R2 and one of R3 and R4 are each methoxy or ethoxy, the others are each H, or when one of R1 and R2 and one of R3 and R4 are each CH3, the others are each methoxymethyl or ethoxymethyl, or when one of R1 and R2 and one of R3 and R4 are each C2H5, the others are each H, methoxymethyl or ethoxymethyl; n is 0 or 1) (e.g. a compound of formula II).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an antistatic agent that is used for plastics, fibers, paper, composite products thereof, etc., to remove static electricity and prevent electrostatic damage.

0002

[Prior Art and Problems to be Solved by the Invention] Conventionally, insulating materials such as plastics and fibers are charged with electricity.
Antistatic agents mainly using surfactants are used for the purpose of preventing dust from adhering and reducing the product value. Antistatic agents are broadly classified into two types: internally kneaded types, which are mixed into the target insulator material during manufacture, and so-called surface-applied types, which are applied to the finished product.

[0003] However, with the internal kneading type, it is impossible to accurately create a close-packed state on the surface of the target molded product, so it has not been possible to reduce the surface resistivity to 1010 Ω or less (that is, in the semiconductor region). . Therefore, it has not been possible to create a material that is completely uncharged.

[0004] Furthermore, since the antistatic agent mixed in is essentially a surface-active substance, it is distributed non-uniformly within the material into which it is mixed. For this reason, when a material mixed with an internally kneaded antistatic agent is subjected to secondary processing and then stretched or cut, static electricity is generated on the newly generated surface, fundamentally modifying the electrical properties. I couldn't do that.

On the other hand, with surface-applied antistatic agents, it is possible to properly align them on the surface depending on the concentration, and achieve a close-packed state where the distances between polar groups are close and uniform. be able to. Therefore, if an adsorbed water film is present thereon, the surface resistivity value of the target material can be significantly reduced. However, when the humidity is low, the antistatic properties are extremely reduced and the antistatic purpose cannot be achieved. In addition, under high humidity conditions, the antistatic effect is good while the oriented adsorption is maintained, but water particles in the adsorbed water film enter between the polar groups over time, resulting in the surface The orientation state of the polar groups becomes irregular, and the distance between the polar groups becomes uneven. Therefore, the antistatic effect tends to gradually decrease.

[0006]

[Means for Solving the Problems] In order to solve the drawbacks of the above-mentioned conventional antistatic agents, namely the insufficiency and instability of the antistatic effect, the present inventors first developed a semipolar organic boron polymer. It has been found that a nitrogen-boron complex (hereinafter referred to as "N.B complex") consisting of a reaction product between a compound and a monoamine can serve as a charge leakage agent with a stable effect (Japanese Patent Application Laid-open No. 1-185329). As a result of further intensive studies, the present inventors determined that basic nitrogen and semipolar boron, which contribute to the charge transfer reaction, should each be used as the N and B components forming the N-B complex.
It has been found that when a 1:1 charge transfer type conjugate is selected, it has better compatibility with the target material and at the same time exhibits a better antistatic effect.

That is, the antistatic agent of the present invention is obtained by reacting 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. It is characterized by containing a charge transfer type conjugate obtained by

[0008]

[Case 2]

(Here, R1 and R2, R3 and R4 are both hydrogen, methyl group, methoxymethyl group or ethoxymethyl group, or when one is methoxy group or ethoxy group, the other is hydrogen) or when one is a methyl group, the other is a methoxymethyl or ethoxymethyl group, or when one is an ethyl group, the other is hydrogen,
A methoxymethyl group or an ethoxymethyl group, n
is 0 or 1. ) Examples of the nonionic compound having one basic nitrogen used as the N component of the N/B complex contained in the antistatic agent of the present invention include ammonia, monomethylamine, dimethylamine,
Trimethylamine, triethylamine, methylnidi(hydroxyethyl)amine, dimethylaminoethanol,
Diethylaminoethanol, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, methylmorpholine, ethylmorpholine, pyridine, picoline, N,N-di(hydroxyethyl)laurylamine, N,N -di(polyoxyethylene)laurylamine, N,N-di(hydroxyethyl)stearylamine, N,N-di(polyoxyethylene)stearylamine, N,N-di(hydroxyethyl)oleylamine, N,N- Di(polyoxyethylene)oleylamine, diallylamine, diallyldihydroxyethylamine, diallyldihydroxypropylamine, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacramide, dimethyl Aminopropyl methaclamide, diethylaminopropyl acramide, diethylaminopropyl methacramide, dimethylaminoethyl stearate, dimethylaminopropyl stearamide, diethylaminoethyl stearate, diethylaminopropyl stearamide, triethanolamine monostearate, triethanolamine distearate , triethanolamine tristearate, di(stearamidopropyl)amine, di(stearamidopropyl)dimethylamine, vinylpyridine, and dimethylaminomethylstyrene.

On the other hand, as a semipolar compound having one atomic group represented by the general formula I, which is component B, oil chemistry,
9, No. 12, pp. 893-900 (1980), a polyvalent compound having two to three adjacent hydroxyl groups or two hydroxyl groups facing each other in the α-position and γ-position. Di(glycerin)borate and its monovalent carboxylic acid ester, 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(2,2,4-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,
Examples include boric acid esters such as 2-di(ethoxymethyl)-1,3-propylene glycol}borate.

[0011] The N/B complex used in the present invention contains the above-mentioned N component and B component at a concentration of 20 to 20% under normal pressure.
At 0°C, preferably from 50 to 150°C, both components were mixed 1:1 (
molar ratio). At this time, the reaction can be carried out more easily by adding a polar solvent such as alcohol, ether or ketone.

The antistatic agent of the present invention can be used in the same manner as conventional antistatic agents. For example, (1) an internal kneading method in which it is added during molding of the target insulator material, (2) a surface application method in which a diluted solution of the antistatic agent of the present invention is treated on an already molded insulator material;
Alternatively, either one of the external permanent antistatic treatment methods is applied to semi-processed or final processed insulator materials with a mixed solution of the antistatic agent of the present invention and a polymer compound compatible with it. Can be adopted.

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 processing temperatures of various insulating materials, and the range of applications is extremely wide. .

[0014] When carrying out a 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. When mixed with a binder resin and applied, it is preferable to use a water-soluble or water-dispersible binder resin.

[0015] The antistatic agent of the present invention has the characteristic that when applied to a film or sheet, the antistatic effect is exhibited even on the opposite side of the coated side by simply applying it to one side. Such characteristics are not observed in conventionally known antistatic agents, and therefore the antistatic agent of the present invention has an extremely wide range of applications.

[0016] In this way, in order for the antistatic effect to be exhibited also on the side opposite to the coated surface, the molecules of the antistatic agent must be properly oriented and present in the coated layer. In order to control the orientation of the antistatic agent molecules, the coated film or sheet may be subjected to heat treatment, corona discharge treatment, or the like.

Tables 1 and 2 show examples of N/B complex type charge transfer type conjugates that can be used as antistatic agents of the present invention.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Action] N/B that can be used as an antistatic agent in this invention
The mechanism by which the complex type charge transfer conjugate exhibits an excellent antistatic effect is that the semipolar bond portion of the semipolar compound and the basic nitrogen bond as shown in the reaction formula [Chemical formula 3] below. As a result, an ion pair is formed, and the acidic protons generated at this time move in a form that leaves bonding properties on both the boron side and the nitrogen side, resulting in a resonant structure and the insulator material in contact with it. This is thought to be the driving force that causes the movement of multiple electrons, gives the Fermi level, and allows the material to be transformed into something that exhibits semiconductor-type electrical properties.

[0021]

[Chemical formula 3]

[0022]

[Examples] Next, examples and comparative examples of the present invention will be shown.

The evaluation methods used in the Examples and Comparative Examples will be explained below. (1) Surface specific resistance Applied voltage 500V, 2 using a specific resistance measuring device manufactured by Takeda Riken Co., Ltd.
Measurement was carried out under the conditions of 3°C and 50% RH.

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

[0025] Saturation voltage (V1) immediately after rubbing for 1 minute
) and the charged voltage (V2) after 30 seconds had elapsed, and the decay rate (D) was calculated using the following formula.

[0026]

[Math 1]

(3) Forced charging static honest meter manufactured by Shishido Trading Company (trade name)
Using 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 a height of , the film was charged, and the discharge was stopped after 1 minute.

The amount of charge on the sample was measured with an electrometer placed 2 cm above the sample. The amount of charge immediately after discontinuation of discharge (V1) and the amount of charge after 30 seconds (V2) were measured, and the attenuation rate (D
) was calculated using the following formula.

[0029]

[Math 2]

Examples 1 to 7 Antistatic agents 1 to 7 shown in Tables 1 and 2 were added to the corona discharge treated surface of a 12 μm biaxially stretched polyester film (Toyobo E5100) treated with water-isopropanol. It was dissolved in a mixed solution, and this solution was applied so that the thickness after drying would be 0.5 μm, and dried at 130° C. for 30 seconds to obtain a polyester film coated with an antistatic agent. Table 3 shows the properties of the obtained coated film.

Comparative Example 1 The film used in Examples 1 to 7 above before being coated with an antistatic agent is referred to as Comparative Example 1, and its properties are shown in Table 3.

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

[0033]

[Table 3]

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

Comparative Example 2, in which a conventional antistatic agent was used, showed some effect on the coated surface, but no antistatic effect was observed on the opposite side to the coated surface.

Examples 8 to 10 Using antistatic agents 1, 3, and 4 shown in Table 1, each antistatic agent and a water-dispersible polyester binder (Vylonal resin manufactured by Toyobo Co., Ltd.) were mixed in a weight ratio of 2:8. Table 4 shows the properties of the film obtained by mixing the solution in the same proportion as in Example 1, and then subjecting the coated surface of the coated film to a corona discharge treatment.

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

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

Examples 11 to 13 A water-isopropanol solution of antistatic agents 3, 4, and 5 in Table 1 was applied to a biaxially stretched polypropylene film (Pylene Film P2601 manufactured by Toyobo Co., Ltd.) with a thickness of 25 μm, and the solution was heated at 100°C. 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 Comparative Example 4 was prepared by applying no antistatic agent to the biaxially oriented polypropylene film used in Examples 11 to 13. The film properties of Comparative Example 4 are shown in Table 3.

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

[0042]

[Table 4]

Example 14 Low density polyethylene pellets (average molecular weight approximately 200,000) 1
After mixing 1 part of antistatic agent 5 shown in Table 2 to 00 parts, extrusion molding was performed at 160°C using a twin-screw kneading extruder to obtain a film with a thickness of 50 μm. Table 5 shows the properties of the obtained film.

Comparative Example 5 In Example 14, a low-density polyethylene film containing no antistatic agent was prepared and designated as Comparative Example 5. The film properties of Comparative Example 5 are shown in Table 5.

[0045]

[Table 5]

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

[0047]

[Effect of the invention] As explained above, N according to this invention
-Antistatic agents containing B complex have excellent properties not found in conventional antistatic agents.

[0048] Therefore, the antistatic agent according to the present invention can remove the static electricity from insulating materials such as films, sheets, fibers, molded articles, paper, and composites thereof, and convert them into materials that do not cause electrostatic damage. It can be used effectively in a wide range of fields.

Claims (1)

[Claims] Claim 1: A charge transfer type conjugate obtained by reacting 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. An antistatic agent characterized by containing. [Formula 1] (Here, R1 and R2, R3 and R4 are both hydrogen, methyl group, methoxymethyl group, or ethoxymethyl group, or when one is methoxy group or ethoxy group, the other is 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, n is 0 or 1
It is. )