JPH0995471A - Cationic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new cationic compound capable of providing an antistatic agent, having excellent antistatic performances and useful as extremely strong countermeasures for preventing static electricity having high reliability. SOLUTION: This cationic compound is represented by formula I (R1 to R4 are each a 1-22C hydrocarbon, a hydroxy-substituted hydrocarbon, dihydroxypropyl, etc., with the proviso that at least one of R1 to R4 is a >=6C hydrocarbon or a group prepared by connecting the hydrocarbon and at least one thereof is hydroxymethyl or 2-hydroxy-substituted hydrocarbon), e.g. the one represented by formula II. The new cationic compound is obtained by reacting, e.g. 1mol one or more of a primary amine in which a substituent group is a >=6C hydrocarbon group or a group prepared by connecting the hydrocarbon group or a secondary or a tertiary amine in which at least one substituent group is the >=6C hydrocarbon group or the group prepared by connecting the hydrocarbon group with 1mol methanesulfonic acid and then reacting the resultant reactional product with formalin, glycidol, a 2-22C olefin oxide, etc., in a number of reactional mol capable of converting all the N-H bonds in the produced ammonium group into N-C bonds.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel cationic compound, and more particularly to a cationic compound having extremely excellent performance as an antistatic agent. Here, the antistatic agent is an agent that changes an insulating material such as plastic, fiber, paper, or ceramic into a material that is not charged.

[0002]

[Related Art] Conventionally, various types of plastic products, synthetic fibers, etc. may be charged with dust and adhere to them, and in order to prevent the decrease in commercial value due to that, charging mainly using known surfactants. Inhibitors are used.

Most of the antistatic agents currently used are those obtained by directly applying the surfactant or compounds having a hydrophilic group structure similar to that of the surfactant. Therefore, they are among the polymeric substances. It can be construed that the surface-active effects such as penetration, diffusion, and wetting as shown indirectly bring about the antistatic effect. The type and structure of the antistatic agent differ depending on which one of the actions is emphasized.

The antistatic agents are classified into the following four types according to how they are applied to polymer products. 1) An internal kneading antistatic agent, which is added when processing a polymer substance, and whose components are appropriately dispersed in a finished molded product to provide an antistatic effect. 2) A surface coating type antistatic agent which forms a conductive film on the surface of a polymer product by preparing a solution of the antistatic agent reagent and immersing the polymer product in the solution or performing a spray operation.

3) An internal permanent antistatic agent that is added as a copolymerization component during the synthesis of a polymer substance and is therefore chemically bonded in the finished polymer product. 4) Thermally polymerize the conductive material on the surface of the polymer product,
Alternatively, an external permanent antistatic agent that forms an insoluble conductive surface by adhering a mixture of a conductive substance with another polymer on the surface of a polymer product.

Among these, the internal kneading antistatic agent is most often used mainly for polymer moldings, and then the surface coating type antistatic agent is a special polymer film coating or synthesis. It is used when finishing fibers.

Further, as antistatic agents for fibers, washing resistance is particularly desired, so that the tendency toward permanent antistatic agents for internal use has been strengthened, and some of them have already been put to practical use as a copolymerization component of synthetic fibers. It has been done. The external permanent antistatic agent also has no problem in terms of washing resistance, but an increase in the number of steps for carrying out an antistatic treatment later is disadvantageous, so that it is not so much emphasized at present.

Further, since the internal kneading type antistatic agent cannot accurately form the closest packed state on the surface, the surface specific resistance value is 10 ¹⁰ Ω in order to make the target insulator product a semiconductor region. Cannot be less than

Moreover, because of the characteristics of the surface-active substance, the insulating product is unevenly distributed inside the product, so that the product needs to be subjected to secondary processing. Therefore, it cannot be said that the antistatic product is completely manufactured.

On the other hand, in the case of the surface coating type antistatic agent, it is possible to form a close-packed state in which the surface of the target insulator product is correctly oriented depending on the treatment concentration, and therefore the distance between hydrophilic groups is close. However, since they are aligned, the surface resistivity of the target product can be set to 10 ¹⁰ Ω or less if an adsorbed water vein exists on it, but if the humidity is low, the surface resistance will be extremely low. The specific resistance value becomes high, and the desired antistatic performance is considerably reduced.

On the other hand, under high humidity conditions, the antistatic performance is good while the oriented adsorption is maintained, but with the passage of time, the water particles in the adsorbed water vein are separated from the hydrophilic groups of the antistatic agent layer. If a lot of gaps get in between and the orientation on the surface becomes irregular, the electrical conductivity is not originally extremely superior, and there is a tendency for the antistatic performance to gradually decrease. , Not preferable.

[0012]

On the other hand, in recent years, when synthetic resin products, rubbers, and fibers have been increasingly incorporated into computer equipment or used in contact with each other, it is no matter what case they are. It is very important that even if the state of reaching the semiconductor region is not maintained, it may cause a malfunction of the computer, and in that sense, an antistatic agent with better antistatic performance is obtained. Was sought after in the world.

In addition to the surfactant-type antistatic agent, as an antistatic product made of an insulating material, metal powder, metal fiber, carbon powder or tin oxide, indium oxide, etc. have been used in the inorganic type. Kneading the conductive material of, or vapor deposition of metal has been done,
In the former method, the effect does not come out unless it is added in a large amount so that the conductive materials can come into contact with each other.
There is a drawback that molding workability is significantly reduced, and
Even in the latter method, unless a large amount is processed at one time, it is not possible to meet the utility cost such as the amount of electric power, and it is difficult to produce a product with good reproducibility.

In the organic system, polyacetylene, polyene of conjugated double bond type and charge transfer complex such as TCNQ.TTF are known as those having electron conductivity. , For example, the entire plastic must be transformed, and the charge transfer complex must be mixed in a large amount in order to transmit its effect.
From an economical point of view, it is difficult to put it into practical use.

Accordingly, it is an object of the present invention to provide a novel cationic compound, and further a novel and strong antistatic agent in which the above-mentioned drawbacks of conventional products are improved. Further, the present invention aims to provide an antistatic liquid, an antistatic spray, an antistatic writing instrument, an antistatic paint, an antistatic adhesive, an antistatic adhesive, and an antistatic sealing material having excellent antistatic properties. And Furthermore,
The present invention is applied to an insulating product such as a whiteboard, a plastic toy, an insulating pipeline, and other plastic products by applying, spraying, or adding the antistatic agent, antistatic liquid, or antistatic paint of the present invention. It is an object of the present invention to provide an insulating product having various antistatic effects.

[0016]

As a result of various studies, the present inventor has found that a cationic compound using a synthetic organic monobasic acid, methanesulfonic acid, which has an acidity 10 times or more that of existing natural or synthetic acids as a reaction raw material. By newly synthesizing and contacting them with a small amount of insulating material such as plastic, fiber, paper, ceramic, etc., each material is stable, completely made into a semiconductor, and even under various conditions. The inventors have found that the non-charged state is maintained for a long period of time and have reached the present invention.

That is, the present invention is a cationic compound represented by the following general formula I.

[0018]

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(However, in the formula, R ₁ , R ₂ , R ₃ and R ₄
Is a hydrocarbon group having a carbon number of 1 to 22 and a hydroxy-substituted hydrocarbon group, a dihydroxypropyl group, a hydrocarbon group having a total of 12 to 25 carbon atoms having 2 or less amide bonds and / or ester bonds in the group, 1 in the middle with ether oxygen
A hydrocarbon group having a total of 2 to 25 carbon atoms, an O-hydrocarbon group substituted 3-oxy-2-hydroxypropyl group having a total of 4 to 25 carbon atoms, and a terminal hydroxyl-substituted polyoxy having a total carbon number of 2 to 122 A hydrocarbon group, a central nitrogen atom in the same atomic group and another N-substituent are residues forming a morpholine ring or a C-hydrocarbon group-substituted imidazoline ring having a total of 4 to 20 carbon atoms, R ₁ , R ₂ , R ₃ and R ₄
It is necessary that at least one of them is a hydrocarbon group having 6 or more carbon atoms, or a group connecting them, and at least another is a hydroxymethyl group or a 2-hydroxy-substituted hydrocarbon group. . )

The antistatic agent of the present invention is constituted by containing, as an active ingredient, one or more cationic compounds of the above formula I.

The antistatic solution of the present invention contains 0.001 to 50% by weight, preferably 0.01 to 50% by weight, of the above antistatic agent in water and / or a solvent comprising one or more hydrophilic solvents.
It is composed by being dissolved by 5% by weight.

The antistatic spray of the present invention comprises a container filled with the antistatic solution and a spraying means for spraying the antistatic solution so that the antistatic solution can be sprayed on a desired site. Composed. The spraying mechanism is not particularly limited in its spraying mechanism, and any conventionally known spraying means can be applied.

The antistatic writing tool of the present invention is filled with the above antistatic solution so that it can be written or applied, and the antistatic solution can be written or applied to a desired site. As the structure of the writing instrument, in addition to the felt pen described below, a conventionally known writing instrument, for example, a writing instrument mechanism such as a writing pen, a ballpoint pen, and a fountain pen can be applied. In the case of a ballpoint pen, a known adhesive material may be added to increase the viscosity of the antistatic solution.

The antistatic felt pen of the present invention comprises a long body portion having a hollow portion inside and an opening communicating with the hollow portion at one end or both ends, and a hollow body portion. A felt pen having a felt filled in a portion and a felt core inserted into the opening so that one end projects from the opening and the other end contacts the felt. The core is impregnated with the above antistatic solution, and the antistatic solution can be used for writing or coating on a desired site.

The antistatic coating material of the present invention is obtained by adding the above antistatic agent, and is 0.1% with respect to the total amount of the coating material.
It is suitable to add in the range of -25 wt%, preferably 1-10 wt%. Conventionally known paints may be used as the paint, and examples thereof include acrylic paint, urethane paint, vinyl acetate paint, and vinyl acetate ester paint.

The antistatic pressure-sensitive adhesive of the present invention is obtained by adding the above-mentioned antistatic agent, and is in the range of 0.1 to 25% by weight, preferably 1 to 10% by weight, based on the total amount of the pressure-sensitive adhesive. It is preferable to add it. As the pressure-sensitive adhesive, conventionally known ones may be used, and examples thereof include a rubber-based pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive.

The antistatic adhesive of the present invention is prepared by adding the above antistatic agent, and is in the range of 0.1 to 25% by weight, preferably 1 to 10% by weight, based on the total amount of the adhesive. It is preferable to add it. As the adhesive, a conventionally known adhesive may be used, and examples thereof include a water-based adhesive, a rubber-based adhesive, and a reactive adhesive (epoxy-based, acrylic-based, urethane-based) elastic adhesive and the like.

The antistatic sealing material of the present invention contains the above antistatic agent and is added in an amount of 0.1 to 25% by weight, preferably 1 to 10% by weight, based on the total amount of the sealing material. It is preferable to add it. As the sealing material, conventionally known materials may be used, such as silicone-based sealing materials, polysulfide-based sealing materials, modified silicone-based sealing materials, urethane-based sealing materials,
Butyl sealants can be used.

The antistatic plastic film laminate structure of the present invention is a plastic film laminate structure formed by laminating a plurality of plastic films, and is obtained by laminating each film using the above-mentioned pressure-sensitive adhesive or adhesive. . As the plastic film, any of conventionally known ones can be used, such as a polyethylene film, a vinyl chloride film, a polypropylene film,
A polyester film etc. can be mentioned. In addition, it also includes a structure in which an aluminum foil is used as one of the constituent layers of the laminate film.

The whiteboard of the present invention has been subjected to antistatic treatment by applying or spreading the above-mentioned antistatic agent or the above antistatic paint on the back surface and / or surface of the whiteboard body or by adding it to the whiteboard body. Is. The whiteboard can be applied to a conventionally known structure.

The insulator pipeline of the present invention is obtained by applying or spreading the above-mentioned antistatic agent on the outer surface of the pipeline main body to perform antistatic treatment. The insulator pipeline has a conventionally known structure, and is made of a plastic material such as vinyl chloride or polypropylene.

In the plastic toy of the present invention, the above antistatic agent is applied or spread on the back surface of the toy body or added to the toy body for antistatic treatment. The plastic toy can be applied to various forms, and the kind of the plastic material is not limited, and any known plastic material such as polyethylene or vinyl chloride can be applied.

The insulator roll of the present invention is obtained by adding the above-mentioned antistatic agent to the roll body and performing antistatic treatment. As the insulator roll, any conventionally known one, for example, a take-up roll or the like can be applied, and a roll made of a rubber material or a plastic material, for example, SBR rubber, polyurethane or the like is targeted.

The plastic product of the present invention has been subjected to antistatic treatment by applying or spreading the antistatic agent on the back surface and / or the surface of the product body or by adding it to the product body.

The method of applying the antistatic solution of the present invention comprises applying or spreading a very small amount of the above-mentioned antistatic solution to such an extent that a two-dimensional film is not formed on the surface to be coated or spread. The processing surface is formed. This coating method can be effectively used for coating or spreading the antistatic solution of the present invention on the front surface and / or the back surface of the above-mentioned whiteboard, insulator pipeline, plastic toy, and plastic product. When carrying out this coating method, it is preferable to use the above-mentioned writing instrument or spray of the present invention.

The method for producing a novel cationic compound or cationic surfactant (hereinafter referred to as a predetermined cation) that can serve as the antistatic agent of the present invention will be described below. The predetermined cation has a substituent having 6 carbon atoms. A primary amine which is the above hydrocarbon group or a group in which it is linked, or a secondary amine in which at least one substituent is a hydrocarbon group having 6 or more carbon atoms, or a group in which it is linked. Alternatively, after reacting 1 mol of one or more tertiary amines with 1 mol of methanesulfonic acid and 1 mol of methanesulfonic acid, the number of reaction mols such that all NH bonds in the resulting ammonium group are converted into NC bonds. By reacting with formalin, glycidol, a glycidyl ester having a total of 5 to 25 carbon atoms, or an olefin oxide having 2 to 22 carbon atoms. That.

In that case, the reaction is carried out under atmospheric pressure or under pressure at 20 to 200 ° C., preferably 0 to 10 Kg / cm.
² , it can be performed smoothly and accurately at 50 to 100 ° C. in the presence of water and other polar solvents. The given cations having a hydroxymethyl group or a 2-hydroxy substituted hydrocarbon group thus produced are novel compounds.

Here, the predetermined cation is, for example, water and / or lower alcohols such as methanol, ethanol and isopropanol, glycols such as ethylene glycol, propylene glycol, 1,3-butanediol and diethylene glycol, and ethylene glycol monomethyl ether. , Ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monoisopropyl A Glycol ethers such as diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol It is well soluble in diglymes such as diethyl ether, and hydrophilic solvents such as acetone, methyl ethyl ketone, furfural, and dioxane.

Further, one or two or more kinds of the above-mentioned water and / or hydrophilic solvent and one or more kinds of predetermined cations are added together, and a system in which 0.01 to 50% is dissolved is sprayed or The material filled in the pen is very useful as a surface coating type antistatic agent for a small amount of certain cations.

Here, the merit of the surface coating type antistatic agent that is not found other than the predetermined cation is that it is converted to an uncharged material even when it is not spread on the entire surface of the target insulator. It can be done.

In connection with the present invention, quaternary ammonium methylsulfate obtained by reacting 1 mol of a tertiary amine with 1 mol of dimethylsulfate as a peripheral substance of a predetermined cation, and primary and secondary compounds. A quaternary ammonium p-toluenesulfonate obtained by reacting 1 mol of a primary or tertiary amine with 1 mol of p-toluenesulfonic acid and further reacting with an alkylene oxide has long been used as an antistatic agent. Although they have been subjected to application tests, both have poor dissociation degrees, so that they have poor antistatic performance and also have poor thermal stability, so both cannot be put to practical use.

Certain cations which can be used as the antistatic agent of the present invention are ionized to enhance the basicity so that the quaternary ammonium group and the methylsulfate ion of a strong acid residue enhance the ionic dissociation of each other. It is a compound with a structure that is bound by Coulomb force, and therefore, it becomes a substance that has extremely higher electrical conductivity than existing antistatic agents to which commonly known cationic surfactants are applied. Antistatic performance can be exhibited even when the closest packed state cannot be created. Therefore, if a certain amount is present, regardless of the type of the target insulator, even if the orientation state on the surface collapses a little, and even if the temperature and humidity conditions change, the substantial antistatic performance It is speculated that a good semiconductor region can be created without decreasing

[0043]

EXAMPLES First, an example of producing a predetermined cation will be described, and then the preparation and performance as an antistatic agent of the present invention will be described by examples.

[Manufacturing Example 1] 213.3 g (1 mol) of dodecyldimethylamine was charged into a pressure reactor equipped with a stirrer, a thermometer, a dropping funnel, a gas inflow tube and a condenser to obtain 353.5 g of isopropyl. After being dissolved in alcohol, 96.1 g (1 mol) of methanesulfonic acid was added dropwise under stirring at 30 to 40 ° C. over 1 hour. Next, inject 176.8 g of water to increase the internal temperature to 70
After the temperature was raised to 75 ° C., 44.1 g (1 mol) of ethylene oxide was introduced over 1 hour under the conditions of 75 to 80 ° C. and 1 to ² Kg / cm ² . After that, the contents were transferred to a rotary evaporator, and 90-
Isopropyl alcohol and water were removed from the system over 3 hours at 95 ° C. to give a predetermined cation 1 having the following structure as a white solid.
I got

The characteristic absorption band of the obtained cation 1 was confirmed by elemental analysis and IR absorption spectrum analysis, and the results are shown below.

[0046]

[Table 1]

[0047]

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[Production Example 2] According to the method of Production Example 1, the following predetermined cations 2 to 21 were produced.
Confirmation of the obtained cations 2 to 21 was made by ν of the characteristic absorption band in IR absorption spectrum analysis as in Production Example 1.
_In addition to checking for the presence of _{s = 0} (1350 cm ⁻¹ , 1150 cm ⁻¹ ), it was carried out because it was a water-soluble substance and the amine value was 0.

[0049]

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[0050]

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[0051]

[Chemical 6]

[0052]

[Chemical 7]

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

[Chemical 12]

[0058]

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[0059]

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[0060]

[Chemical 15]

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

[Chemical 21]

[0067]

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[0068]

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Example 1 100 parts of vinyl chloride resin having an average degree of polymerization of 1350, 40 parts of dioctyl phthalate, and 0.7 parts of calcium stearate.
Part and 170 parts of lead stearate
Soft PV obtained by calendar molding under kneading conditions of 5 ° C for 5 minutes
After spreading an ethanol solution of the antistatic agent of the present invention comprising the predetermined cations obtained in Production Examples 1 and 2 on one side of a C film (thickness: 100 μm) in an amount of 5 g / m ² , respectively, Spread evenly with gauze, 23 ℃, 50%
It was allowed to stand for 24 hours under the constant temperature and humidity conditions of RH. After a while
The surface specific resistance was measured under the same conditions, and the surface specific resistance was also measured for those left to stand for one year under the same conditions.

Further, the following three comparative samples were selected including the conventionally known cationic type antistatic agent stearamidopropyldimethyl-2-hydroxyethylammonium nitrate and subjected to the same test. Comparative sample I: Stearamidopropyldimethyl-2-hydroxyethylammonium nitrate Comparative sample II: Dodecyltrimethylammonium methylsulfate Comparative sample III: Dodecyldimethyl-2-hydroxy Ethyl ammonium-p-toluene sulfonate

The results are shown in Table 2, and it was confirmed that the cationic compound of the present invention exhibited an excellent antistatic effect even when used in a small amount.

[0072]

[Table 2]

Example 2 The antistatic agent of the present invention comprising the predetermined cations obtained in Production Examples 1 and 2 was 0.5% acetone-methanol (1:
1) Add a low-polymerization degree polyethylene film having an average molecular weight of 200,000 (thickness: 50 μm) to the mixed solution 5
After immersing in s, it was left to stand under constant temperature and humidity conditions of 15 ° C. and 30% RH for 24 hours and air dried. Then, the surface resistivity was measured under the same conditions. Next, the amount of charge and the half-life when an applied voltage of 5000 V was applied and forced charging was measured. Furthermore, each test sample was inserted into a bag consisting of two low-polymerization degree polyethylene films of the same kind as described above, which were previously triboelectrically charged to electrostatically adsorb tobacco ash over the entire surface, and the volume-propagation antistatic performance was evaluated. Existence was checked.

As a comparative sample, the three kinds of cation compounds used in Example 1 were selected, and 0.5% of each was selected.
Make an acetone-methanol (1: 1) mixed solution,
The same experiment was performed.

The results are shown in Table 3, and the antistatic agent of the present invention not only makes the treated low density polyethylene film non-charged but also exerts a function on the untreated low density polyethylene film brought into contact therewith. It was found to have sufficient volume-propagation antistatic performance.

Further, by applying this result, for example, the antistatic effect can be exerted on the inner surface only by treating the outer side of the insulating plastic pipe with the antistatic agent of the present invention. Static electricity in pipelines will be removed, and powders will be transported smoothly.

[0077]

[Table 3]

Note) * The evaluation criteria for the presence / absence of the volume-propagation antistatic property are as follows. Existence: All tobacco ash electrostatically adsorbed on the outer low-density polyethylene film falls off No ... Cigarette ash electrostatically adsorbed on the outer low-density polyethylene film does not fall at all, or only What falls only partly

Example 3 In an adhesive in which a polyalkyl acrylate (having both ethyl alcohol residue and butyl alcohol residue) was made into a 50% emulsion in water using an ethylene oxide adduct of nonylphenol. After adding 2.0% each of the predetermined cations obtained in Production Examples 1 and 2, to a PET film (with a thickness of 50 μm)
2 μm was applied to each side of Next, a polyethylene copolymer film containing 8% vinyl acetate segment (EVA film, with a thickness of 30 μm) was pressure-bonded onto it, and allowed to stand at 23 ° C. and 50% RH constant temperature and humidity for 1 month. I put it. Thereafter, a weight of 300 g was applied, and rotational friction was applied to both surfaces of each laminated film to measure the triboelectric charge amount.

As a comparative sample, the three kinds of cationic compounds used in Examples 1 and 2 were selected and each contained 2.0%.
Each of them was added to the polyalkyl acrylate emulsion adhesive and then subjected to the same test.

The results are shown in Table 4, which shows that the antistatic agent of the present invention has a superior volume-propagation antistatic property.
It was found that triboelectric charging did not occur at all on the EVA surface. That is, the volume-propagation antistatic performance of the antistatic agent of the present invention has been developed as a method for producing a novel antistatic laminate film or sheet, and at the same time, for example, even in a whiteboard which is highly used in stationery, the drug is completely on the surface. It is suggested that it will be a safe antistatic product that does not exist, and here, a new antistatic adhesive,
Contributing to the acquisition of industrial fields such as adhesives and sealing materials.

[0082]

[Table 4]

Example 4 3 kg of polypropylene glycol having an average molecular weight of 3000
The antistatic agent of the present invention comprising the predetermined cations obtained in Production Examples 1 and 2 was added thereto in an amount of 120 g each, and 2,4-tolylene diisocyanate 174 was added to the homogeneously mixed system. .2g was added and reacted at 125 ° C for 10 minutes to synthesize a polyurethane resin. Subsequently, the obtained polyurethane resin mass was left standing at 23 ° C. and 50% RH constant temperature and constant humidity for 24 hours, then the central part was cut to form a flat surface, and the surface specific resistance of the part was measured.

Comparative samples I and III used in Examples 1 to 3 were selected as urethane reactivity comparative samples, added in the same manner as the antistatic agent of the present invention, and subjected to the same test.

The results are shown in Table 5, and it was confirmed that the antistatic agent of the present invention exhibited an excellent antistatic effect as a reactive type.

[0086]

[Table 5]

Example 5 To a system of 100 parts of methyl methacrylate and 0.3 part of azodiisobutyronitrile, 0.25 parts each of the antistatic agent of the present invention was added, and then injected between two pressure-resistant glass plates. Then, a 20 cm × 20 cm acrylic resin plate was prepared by the monomer casting method at 120 ° C. for 4 hours. Then, at 23 ° C and 50% RH constant temperature and humidity, 24
It was allowed to stand for a period of time and the surface resistivity was measured.

Further, as a comparative sample, Comparative sample II used in Examples 1 to 4 having compatibility with methyl methacrylate
I was selected and subjected to the same test.

The results are shown in Table 6, and it was found that the antistatic agent of the present invention exhibited a good antistatic effect both as a reactive type and an internally kneaded type.

[0090]

[Table 6]

Example 6 To 100 parts of polyethylene pellets polymerized with 4% octene added, 0.5 part of the antistatic agent of the present invention was added, respectively, and then blow molded to obtain 4 parts at 160 ° C.
A 0 μm film was prepared and allowed to stand for 24 hours at 23 ° C. and 50% RH constant temperature and humidity, and the surface specific resistance was measured.
Further, the surface specific resistance was measured again after being left standing for one year under the same conditions.

As the comparative samples, the following nonionic comparative samples IV and comparative samples I to III used in the above-mentioned examples were selected and subjected to the test with the same addition amount. Comparative sample IV ... N, N-di (2-hydroxyethyl) stearylamine

The results are shown in Table 7, and it was confirmed that the antistatic agent of the present invention was an internal kneading type and had good performance retention for a long time.

[0094]

[Table 7]

Example 7 Two parts of each antistatic agent of the present invention was added to 100 parts of medium impact type ABS resin (however, Styrac 121 manufactured by Asahi Kasei Co., Ltd.) pellets, followed by injection molding at 220 ° C. 2 mm thick plate (however, 10 cm x 1
0 cm) was prepared and allowed to stand for 24 hours under the conditions of 23 ° C. and 50% RH constant temperature and constant humidity, and then the surface resistivity was measured under the same conditions. Further, after applying a weight of 500 g and rubbing with a Tetoron cloth for 1 minute, the presence or absence of adsorption of tobacco ash was observed.

As comparative samples, comparative samples I to IV used in Example 6 were selected and subjected to the test with the same addition amount.

The results are shown in Table 8 and it was confirmed that the antistatic agent of the present invention showed good performance.

[0098]

[Table 8]

Example 8 31.5 ml of a 1% ethanol solution of the antistatic agent of the present invention comprising the predetermined cation 1 obtained in Production Example 1 and LPG
After filling with 38.5 ml of gas to make a 70 ml spray, white plain nylon taffeta (however, 10 cm
X 10 cm), white plain Teflon taffeta (however, 10 cm x 10 cm), and fine paper for copying (however, A-4 size). It was allowed to stand for 24 hours under constant temperature and humidity conditions of 23 ° C. and 50% RH. Then, the surface specific resistances of the treated surface and the back surface were measured.

As a comparative sample, comparative sample I used in each of the above-mentioned examples was selected and subjected to the same test.

The results are shown in Table 9, and it was confirmed that the antistatic agent of the present invention imparted sufficiently effective antistatic properties not only to the treated side but also to the back side.

[0102]

[Table 9]

Example 9 1% of antistatic agent according to the invention consisting of a given cation 9
(Water: isopropanol = 3: 2 weight ratio mixture) 5 g of the solution was filled in the felt pen 20 shown in FIG. 1 to prepare an antistatic writing instrument.

In FIG. 1, the writing instrument or felt-tip pen 20 has an elongated body 2 having a hollow portion 22 inside and an opening 24 communicating with the hollow portion 22 at one end.
6, the felt 28 filled in the hollow portion 22 of the body 26, and one end protruding from the opening 24 and the other end being inserted into the opening 24 so as to contact the felt 28. A felt core 30 is provided, and the felt 28 and the felt core 30 are impregnated with the antistatic solution 42 of the present invention. The openings 24 may be provided at both ends of the body 26.

Thereafter, as shown in FIG. 2, A-4 version O
The antistatic solution 42 of the present invention is applied or spread by drawing a plurality of lines 44 on one surface of the HP PET film 40 using the writing instrument 20 at 23 ° C., 50% R
It was allowed to stand for 24 hours under the conditions of H constant temperature and constant humidity.

By coating or spreading the antistatic solution in this manner, a very small amount of the antistatic solution, which is not enough to form a two-dimensional film, can be applied to the surface of the PET film 40. When applying this very small amount,
It goes without saying that, as shown in FIG. 2, in addition to drawing a plurality of lines 44, it is possible to apply by various modes.

Then, the surface resistivity of the back surface was measured. Moreover, after applying a weight of 500 g and rubbing with a Teflon cloth for 1 minute, it was observed whether or not tobacco ash was adsorbed.

As the comparative sample, the comparative sample I used in each of the above-mentioned examples was selected and subjected to the same test as a 5% (water: isopropanol = 3: 2 weight ratio mixture) solution.

The results are shown in Table 10. It was confirmed that the antistatic agent of the present invention had a sufficiently effective antistatic property even by partial coating, and at the same time, the antistatic agent used in this example was used. Writing instruments have also proved to be of practical utility.

[0110]

[Table 10]

Example 10 Each of the predetermined cations obtained in Production Examples 1 and 2 was added to a coating material composed of an emulsion of an ethylene oxide adduct of lauryl alcohol of polyvinyl acetate (however, 40% pure content). Then, 5 μm on each side of the poly (difluorinated butadiene) film (thickness 40 μm)
Applied. Then, heat treatment was performed at 105 ° C. for 10 minutes, and the mixture was allowed to stand for 24 hours at 23 ° C. and 50% RH constant temperature and constant humidity. Then, the surface resistivity of the polyvinyl acetate layer was measured. Furthermore, a load of 300 g was applied to the poly (difluorinated butadiene) layer on the back surface for rotational friction, and the triboelectric charge amount was measured.

As comparative samples, the three kinds of cationic compounds (I, I) used in the above-mentioned several examples were used.
I and III) were selected and added to each of the polyvinyl acetate emulsion-based paints, and then subjected to the same test.

The results are shown in Table 11. The antistatic agent of the present invention shows a very effective antistatic effect even when used in a small amount, and at the same time, the antistatic coating composition containing the antistatic agent of the present invention is added. It was also confirmed that the product had good performance and had a sufficient volume-propagating antistatic effect. Further, the poly (difluorinated butadiene) film having the back surface coated with the antistatic coating material in this example has a chemical agent on the front surface,
It can be used as a safe and highly hygienic whiteboard material that does not adhere to dust.

[0114]

[Table 11]

[0115]

As described above, the cationic compound of the present invention has an excellent antistatic property and can provide an extremely strong antistatic agent.

The antistatic agent of the present invention contains a small amount of quaternary ammonium methylsulfate, which has a very high dissociation property, as compared with an antistatic agent comprising a conventional cationic surfactant having a known anion as an opposite ion. In the presence of the above, since the electrical properties of the insulator can be efficiently changed and lowered to the range of the semiconductor, by using the antistatic agent of the present invention, highly reliable antistatic measures can be taken.

According to the antistatic agent of the present invention, various insulating materials, which have been disadvantageous in use due to the occurrence of electrostatic damage, can be reliably drawn into the area of the semiconductor material, and the adhesion of dust, etc. It not only prevents the product value from declining but also contributes to the safety and security of social life by eliminating one of the harmful effects of malfunctioning computer functions.

Furthermore, by utilizing the volume-propagation antistatic performance exhibited by the antistatic agent of the present invention, it is possible to prevent the static charge on the side to which no chemical is added. Therefore, a new means for smooth transportation in an existing insulating pipeline. Or again,
For writing utensils, toys, etc., it is possible to provide an antistatic product that is safe from the viewpoint of safety and hygiene.

[Brief description of drawings]

FIG. 1 is a side view showing a felt-tip pen filled with an antistatic solution of the present invention.

FIG. 2 is an explanatory diagram showing an example of a mode of applying or spreading the antistatic solution of the present invention on the film surface.

[Explanation of symbols]

 20 felt pen and writing instrument 22 hollow part 24 opening part 26 body part 28 felt 30 felt core 40 PET film 42 antistatic solution

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 219/08 C07C 219/08 233/36 9547-4H 233/36 309/04 309/04 C07D 233 / 22 C07D 233/22 C08J 7/04 C08J 7/04 D C09J 5/00 JGW C09J 5/00 JGW 9/00 JAX 9/00 JAX 11/06 JAX 11/06 JAX C09K 3/10 C09K 3/10 Z 3/16 108 3/16 108D

Claims (17)

[Claims] 1. A cationic compound represented by the following general formula I: Embedded image (However, in the formula, R ₁ , R ₂ , R ₃ and R ₄ have 1 to 1 carbon atoms.
22 hydrocarbon groups and hydroxy-substituted hydrocarbon groups, dihydroxypropyl groups, hydrocarbon groups having a total of 12 to 25 amide bonds and / or ester bonds within the group, and a hydrocarbon group having 12 to 25 carbon atoms, and ether oxygen in the middle. 1-containing hydrocarbon group having 2 to 25 carbon atoms in total, 3-oxy-2-hydroxypropyl group having 4 to 25 carbon atoms in total substituted by O-hydrocarbon group, terminal hydroxyl substitution having 2 to 122 carbon atoms in total A polyoxyhydrocarbon group, a residue forming a morpholine ring or a C-hydrocarbon group-substituted imidazoline ring having a total of 4 to 20 carbon atoms with a central nitrogen atom in the same atomic group and another N-substituent, R _{At least one of 1} , R ₂ , R ₃ and R ₄ is a hydrocarbon group having 6 or more carbon atoms, or is a group in which it is linked, and at least another is a hydroxy group. It must be a chill group or a 2-hydroxy substituted hydrocarbon group. ) 2. An antistatic agent, which comprises, as an active ingredient, one or more compounds of the formula I according to claim 1. 3. The antistatic agent according to claim 2 is added to water and / or a hydrophilic solvent in a solvent comprising one or more of 0.0 and 0.0.
An antistatic solution characterized by being dissolved in 1 to 50% by weight. 4. An antistatic spray comprising a container filled with the antistatic solution according to claim 3 and a spraying means for spraying the antistatic solution. 5. An antistatic writing instrument comprising the antistatic solution according to claim 3 so that it can be written or applied. 6. A long body part having a hollow part inside and an opening communicating with the hollow part at one end or both ends, and felt filled in the hollow part of the body part, A felt pen having a felt core inserted into the opening so that one end projects from the opening and the other end comes into contact with the felt, and the felt and the felt core are charged according to claim 2. An antistatic felt pen characterized by being impregnated with an antistatic solution. 7. An antistatic paint comprising the antistatic agent according to claim 2. 8. An antistatic pressure-sensitive adhesive comprising the antistatic agent according to claim 2. 9. An antistatic adhesive comprising the antistatic agent according to claim 2. 10. An antistatic sealing material comprising the antistatic agent according to claim 2. 11. A plastic film laminate structure formed by laminating a plurality of plastic films,
An antistatic plastic film laminate structure, characterized in that the films are attached using the pressure-sensitive adhesive or the adhesive according to claim 8 or 9. 12. The antistatic agent according to claim 2 or the antistatic paint according to claim 7 is applied to the back surface of the whiteboard body and / or
Alternatively, a whiteboard characterized by being applied or spread on the surface or added to the main body of the whiteboard for antistatic treatment. 13. An insulating pipeline, characterized in that the antistatic agent according to claim 2 is applied or spread on the outer surface of a pipeline main body to carry out an antistatic treatment. 14. A plastic toy, wherein the antistatic agent according to claim 2 is applied or spread on the back surface of the toy body or added to the toy body to perform antistatic treatment. 15. An insulator roll, wherein the antistatic agent according to claim 2 is added to the roll body to perform antistatic treatment. 16. A plastic product characterized by being subjected to an antistatic treatment by applying or spreading the antistatic agent according to claim 2 on the back surface and / or the front surface of the product body or by adding it to the product body. 17. An antistatic treated surface is formed by applying or spreading a very small amount of the antistatic solution according to claim 3 on the surface to be applied or spread so as not to form a two-dimensional film. A characteristic method of applying an antistatic solution.