JP2872817B2 - 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 an antistatic agent for insulating materials such as films, sheets, various plastic molded articles, fibers, cloths, papers and composites thereof. Useful for

[0002]

2. Description of the Related Art When an insulating material as described above is charged, dusts are attached to the product, causing a reduction in commercial value, or products are attached to each other to make it difficult to handle, thereby causing an electrostatic trouble. Therefore, various antistatic agents have been used for the purpose of preventing the occurrence of such troubles. A surfactant is mainly used as an antistatic agent, and is used by an internal kneading method in which a resin is mixed during molding of a resin and a part thereof is transferred to a surface, or a surface coating method in which the resin is directly applied to a product. . The antistatic effect of the surfactant is such that a hydrophilic layer formed on the outermost surface adsorbs moisture in the air, and a thin conductive layer is formed by the polarization effect of the absorbed water and the polarization effect of the surfactant itself. It is thought that it is exhibited by doing.

However, since the surfactant layer formed on the surface cannot be brought into a close-packed state by the internal kneading method, the surface resistivity cannot be reduced to 10 ¹⁰ Ω or less (semiconductor area), Cannot be converted to a non-charged material. In this method, when the material is subjected to secondary processing such as stretching and cutting,
The newly formed surface has the disadvantage that the distribution of the surfactant is reduced and static electricity is generated, and this does not fundamentally improve the electrical characteristics.

In the surface coating method, a conductive layer formed on the surface can be brought into a close-packed state, and sufficient conductivity can be obtained with an adsorbed water film. In the humidity condition, the antistatic effect is extremely reduced.In the high humidity condition, the water particles in the adsorbed water film enter the polar groups with time, disturbing the orientation state of the surface, and the antistatic effect gradually decreases. There is a disadvantage that it will.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and aims to solve the insufficiency and instability of the antistatic effect of a surfactant type antistatic agent. Things.

[0006]

The antistatic agent of the present invention is a semipolar compound having a polyamino compound having at least two or more basic nitrogens in a main chain and / or a side chain and an atomic group represented by the following chemical formula (2). There is a gist of a charge transfer type conjugate obtained by reacting with an organic boron compound.

[0007]

Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, a lower alkyl group, a lower alkoxyl group, a lower alkoxy lower alkyl group, and n is 0 or 1) .)

[0008]

According to the present invention, a nitrogen-boron complex (hereinafter abbreviated as NB complex) comprising a reaction product of a semipolar organic boron polymer compound and a monoamine is effective as a means for solving the above problems. Have filed an application for a stable antistatic agent.
185329). However, as a result of further study, they found that a better antistatic effect could be obtained by using a polyamino compound as a raw material of the N component in the NB complex, and reached the present invention.

This will be described more specifically. First, the polyamino compound which is a raw material of the N component of the NB complex has at least two or more basic nitrogens in a main chain and / or a side chain. For example, ethylenediamine, propylenediamine, hexamethylenediamine, dimethyl Aminopropylamine, phenylenediamine, tolylenediamine, methyliminobispropylamine, piperazine, polyethyleneimino and its ethylene oxide adduct, propylene oxide adduct or ethylene oxide
Propylene oxide coadduct, triethylenediamine,
Polyvinyl pyridine, poly (dimethylaminoethyl) acrylate, poly (dimethylaminoethyl) methacrylate, poly (diethylaminoethyl) acrylate, poly (diethylaminoethyl) methacrylate, poly (dimethylaminopropyl) acrylamide, poly (dimethylaminopropyl) methacrylamide, Examples thereof include poly (dimethylaminomethylstyrene), diallylamine-isobutylene alternating copolymer, and diallylamine-sulfur dioxide alternating copolymer.

On the other hand, as a raw material of the component B, a semipolar organic boron compound having an atomic group represented by the above formula (2) is used. The term "lower" in the substituted group represented by R _1, R _2, R ₃ and R ₄ in Naoshiki, it refers to those having 1 to 6 carbon atoms, and more preferably from 1 to 2 carbon atoms. Specific semipolar organoboron compounds include, for example, Oil Chemistry, Vol. 29, No. 1
No. 2, pages 893 to 900 (1980),
Di (glycerin) borate of a 2: 1 type polyol borate comprising a polyhydric alcohol residue having two to three adjacent hydroxyl groups or two hydroxyl groups opposed to each other in a positional relationship of α-position and γ-position, and the same. Monovalent carboxylic acid ester, alkylene oxide adduct of di (glycerin) borate and 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, di (2,2-di (ethoxymethyl) -1,3-propylene glycol) Borate or JP-A-63-37
No. 130, ie,

[0011]

Embedded image Wherein q is 0 or 1, and when q = 1, A is-(X) a-
(Y) b- (Z) c-group wherein X and Z are oxygen-containing hydrocarbon groups having a total of 100 or less carbon atoms having one terminal ether residue,
Y is

[0012]

Embedded image (Where R is a hydrocarbon group having 1 to 82 carbon atoms) or

[0013]

Embedded image (Where R ′ is a hydrocarbon group having 2 to 13 carbon atoms),
a, b, and c are 0 or 1}, and 1 mol or more of the compound represented by the formula (1) is added to 1 mol of boric acid or a boric acid triester of a lower alcohol having 4 or less carbon atoms. Or a 0.5 mol of boric anhydride to carry out a triesterization reaction, or a di (glycerin) borate or a diol having a total of 206 or less carbon atoms containing a di (glycerin) borate residue in the middle.
A polyetherification reaction of one or more species or a dicarboxylic acid having 3 to 84 carbon atoms (hereinafter referred to as a predetermined dicarboxylic acid) or One or two or more esters of a lower alcohol having 4 or less carbon atoms and a predetermined dicarboxylic acid, a predetermined dicarboxylic acid halide or a diisocyanate having 4 to 15 carbon atoms (hereinafter, referred to as a predetermined diisocyanate). For example, a semipolar organoboron polymer compound as shown in Chemical formulas 6 to 11 obtained by reacting a total of 1 mol can be mentioned.

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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Using the raw materials of the N component and the B component,
Various methods can be used for producing the B complex type charge transfer type conjugate, but it is preferable that the following conditions be satisfied.

With respect to one basic nitrogen in the N component, 0.01 to 1, preferably 0.05 to 1, semipolar boron in the B component is used.
20 to 200 under normal pressure
The two components are reacted at a temperature of preferably from 50 to 150 ° C. At this time, if a polar solvent such as alcohol, ether or ketone is added, the reaction proceeds more easily.

The method of using the antistatic agent of the present invention comprising the charge transfer conjugate obtained as described above will be described. The antistatic agent of the present invention can also be used in the same manner as the method of using a generally known antistatic agent, for example, i) an internal kneading method to be added at the time of molding the target insulating material, ii) an already molded product. Surface treatment method in which the processed insulator material is treated with a diluted solution of the antistatic agent of the present invention, iii) the semi-processed or final processed insulator material is mixed with the antistatic agent of the present invention and a polymer compound compatible therewith. A system such as an external permanent antistatic treatment system for processing with a mixed solution can be employed.

Although the mechanism of action of the antistatic agent of the present invention is not clear, an ion pair is formed by binding of the semipolar bond of the semipolar organic boron compound to the basic nitrogen as shown in the following formula (12). The resulting acidic protons move in a manner that leaves a bond on both the boron and nitrogen sides, creating a resonant structure, causing the movement of multiple electrons in the insulator material in contact with it, resulting in a Fermi quasi- Rank,
It is presumed that it is a driving force that can be converted to one that shows semiconductor-type electrical characteristics.

[0024]

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The antistatic agent of the present invention is constituted as described above, and has a higher heat resistance temperature than conventional antistatic agents, so that it can withstand the processing temperature of various insulator materials and has a very wide application range. wide.

Further, since the antistatic agent of the present invention is of a charge transfer type, it is not that the antistatic effect is not exhibited unless orientation and adsorption are accurately performed as in the case of a surfactant type antistatic agent. Also in coating, there is no need to pay attention to create a completely uniform treated surface, so processing becomes easy. Further, this is the reason why a stable antistatic effect can be obtained even when used for a long time.

Further, when the antistatic agent of the present invention is applied to a film or a sheet, the antistatic effect is exerted not only on the coated surface but also on the anti-coated surface by simply applying the antistatic agent to one surface. It has extremely attractive features not possessed by conventionally known antistatic agents and has a very wide range of applications.

[0028]

EXAMPLES Examples and comparative examples are shown below. The specific surface resistance, frictional charging property and forced charging property were measured by the following methods.

<Surface Specific Resistance> An applied voltage of 500 was measured using a specific resistance measurement device manufactured by Takeda Riken Co., Ltd.
V, 23 ° C., 50% RH.

<Triboelectric Charging Property> JIS-L-109 was used by using a rotary static tester (RST-201) of Kyoto University Kaken Co., Ltd. manufactured by Koa Shokai Co., Ltd.
4 was performed. The friction body uses a stainless steel plate,
The saturated electrostatic potential (V ₁ ) immediately after rubbing for 1 minute under the conditions of a load of 500 gf, 23 ° C. and 50% RH and the electrostatic potential (V ₂ ) after a lapse of 30 seconds were measured, and the decay rate (D) was calculated by the following equation. Calculated. D (%) = V ₁ −V ₂ / V ₁ × 100

<Forced Charging> Using a static honest meter manufactured by Shishido Shosha Co., Ltd.
The sample is 2cm high under the atmosphere of 3 ° C and 50% RH.
The sample is banded by applying a voltage of 10 KV to the discharge electrode.
The discharge was stopped after 1 minute. 2cm above the sample
The charge amount (V ₀) And 30
Second charge (V₁), And the attenuation rate (D) is calculated by the following equation.
Was calculated. D (%) = V₀-V₁/ V₀× 100

Examples 1 to 17 and Comparative Examples 1 and 2 The antistatic properties shown in Tables 1 and 2 were applied to the corona discharge treated surface of a 12 μm biaxially stretched polyester film (E5100 manufactured by Toyobo Co., Ltd.) which had been subjected to corona discharge treatment. A solution obtained by dissolving a commercially available anionic antistatic agent composed of agents A to Q and sodium sulfonate in a water-isopropanol mixture, respectively.
After drying, apply to a thickness of 0.5 μm and apply
Dry for 0 seconds.

[0033]

[Table 1]

[0034]

[Table 2]

Tables 3 and 4 show the properties of the coated surface and the non-coated surface of the obtained coated film and the film before coating.

[0036]

[Table 3]

[0037]

[Table 4]

Each of the coated films obtained in these examples had much better antistatic properties than those before coating (Comparative Example 1).

The coating film obtained in this example is
The anti-coated surface also has an antistatic property, and has an extremely interesting characteristic that the antistatic property can be imparted to the entire coated film only by coating on one side. That is, the surface specific resistance of the anti-coated surface was at the same level as that of a normal polyester film, but the triboelectric charging property and forced charging property were improved to the same level as the coated surface.

The film of Comparative Example 2 had a relatively good antistatic property on the coated surface, but had no antistatic property on the anti-coated surface, and was significantly inferior in performance to the antistatic agent of the present invention. I was

Examples 18 to 25 and Comparative Example 3 A solution in which each of the antistatic agents shown in Tables 1 and 2 and a water-dispersible polyester binder (Vylonal resin manufactured by Toyobo Co., Ltd.) were mixed at a weight ratio of 2: 8, Only the vironal resin was applied in the same manner as in Example 1. Table 5 shows the properties of the obtained film.

[0042]

[Table 5]

Each of the coated films obtained in these examples had excellent antistatic properties. On the other hand, in the comparative example in which only the vironal resin was applied, a sufficient antistatic effect was not obtained.

Examples 26 to 29 and Comparative Example 4 Water of various antistatic agents was added to a 25 μm biaxially stretched polypropylene film (Pyrene film P2601 manufactured by Toyobo Co., Ltd.).
An isopropanol solution was applied and dried at 100 ° C. for 60 seconds (applied thickness 0.5 μ after drying). Table 6 shows the properties of the obtained coated film and the film before coating.

[0045]

[Table 6]

Each of the coated films obtained in these examples had excellent antistatic properties as in the case of using the polyester film.

Example 30 and Comparative Example 5 Low density polyethylene pellets (average molecular weight: about 200,000) 1
After mixing 1 part of the antistatic agent A shown in Table 2 with 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 7 shows the properties of the film obtained in this example and the film prepared without using the antistatic agent A.

[0048]

[Table 7] The film obtained in this example had excellent antistatic properties.

[0049]

The present invention is configured as described above,
・ Because the antistatic effect is obtained by the action of the ion pair derived from the B complex, unlike the conventional method using a surfactant, there is no need to orient at the interface, and the effect can be easily obtained, and the stability is improved. Is also excellent.
Further, even when used after being applied, it has an excellent property that an antistatic effect can be imparted not only to the coated surface but also to the anti-coated surface.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI C08L 79/08 C08L 79/08 (58) Investigated field (Int.Cl. ⁶ , DB name) C09K 3/16 C08G 79/08 C08K 5/55 C08L 79/08 CA (STN) WPI / L (QUESTEL)

Claims (1)

(57) [Claims] 1. A compound obtained by reacting a polyamino compound having at least two or more basic nitrogens in a main chain and / or a side chain with a semipolar organoboron compound having an atomic group represented by the following formula 1. An antistatic agent comprising the charge transfer type conjugate obtained. Embedded image (Wherein, R ₁ , R ₂ , R ₃ and R ₄ are the same or different and each is hydrogen, a lower alkyl group, a lower alkoxyl group, a lower alkoxy lower alkyl group, and n is 0 or 1) .)