JPS63280792A - Antistatic agent - Google Patents

Abstract

PURPOSE:To obtain a water-soluble antistatic agent for exterior, containing a specific cation (co)polymer and specific sulfonate having long-chain alkyl(aryl) groups, etc., in a specific proportion and having excellent adhesive property and durability without impairing appearance of molded synthetic resin products. CONSTITUTION:The aimed antistatic agent obtained by using (A) 1mol. cationic polymer expressed by formula I (R1 is H, CH3, C2H5 or C3H7; R2-R4 are CH3, C2H5 or C3H7; l is 100-10,000; X<-> is halogen, CH3SO4<-> or C2H5SO4<->) or copolymer containing the monomer units and (B) 0.02-0.10mol. sulfonate or sulfate expressed by formula II (R5 is 8-22C alkyl, hydroxyalkyl, alkenyl or alkylaryl having 6-22C alkyl group; R6 is H or CH3; m is 0 or 1; n is 0-30; M is alkali metal, ammonium or alkanolamine).

Description

Detailed Description of the Invention [Industrial Application Field] The present invention provides a method for preparing a polymer having a specific structure and a sulfonic acid salt or a sulfuric acid ester salt having a long-chain alkyl group or a long-chain alkylaryl group in a specific ratio. Can be used together. Excellent adhesion, without damaging the appearance of synthetic resin molded products.
This invention relates to a water-soluble external antistatic agent for synthetic resins that provides a durable antistatic effect.

[Prior art]

In general, synthetic resins have high electrical insulation properties and tend to accumulate static electricity. This charging phenomenon not only impairs the appearance of synthetic resins, but also impedes working processes and secondary processing such as printing and painting. For this reason, 4! synthetic resin products have traditionally been used. F Many electric protection methods have been proposed.

Easy antistatic methods for synthetic resin molded products include (i) kneading an antistatic low molecular weight surfactant into the synthetic resin, and applying one low molecular weight surfactant to the outside. Separated.

Polymethyl methacrylate, polycarbonate.

When the former method is used to prevent static electricity on a resin with a high glass transition point such as hard vinyl chloride, it is difficult for the surfactant to bleed out onto the resin surface, making it difficult to exhibit antistatic performance. Furthermore, problems such as deterioration of transparency and physical properties of the resin may occur, so the latter method is widely used.

When applying an antistatic agent to the outside of a synthetic resin, it is necessary that the appearance of the resin, such as transparency and one color, not be impaired due to uneven coating, and that the antistatic performance has durability such as washability.

As antistatic agents for external use, cationic, anionic, and nonionic monoampholytic low-molecular surfactants are widely used, but they have poor adhesion to resins, lack water wash resistance, and lack durability. I haven't been able to get anything satisfactory.

Furthermore, as disclosed in Japanese Patent Publication No. 54-11347, a water-soluble cationic polymer has been proposed as an antistatic agent for synthetic resin molded articles for external use. However, although a certain degree of improvement in durability is observed, it is insufficient and also has the drawback that it has poor uniform adhesion to the resin, resulting in uneven coating. Antistatic compositions have also been proposed in which a cationic polymer is used in combination with an anionic surfactant such as p-toluenesulfonate or polycarboxylate. (Tokuko Sho 57-4267
0, Special Publication No. 58-144176, Special Publication No. 50-1759
8) Although these antistatic compositions are durable, they are intended for surface modification of special synthetic papers and synthetic fibers, and when applied to transparent resins such as the aforementioned polymethyl methacrylate and polycarbonate. is impractical because the appearance of the resin surface is impaired.

〔the purpose〕

An object of the present invention is to provide a water-soluble antistatic agent that has excellent adhesion to resins and provides a durable antistatic effect without impairing appearance such as transparency.

〔composition〕

According to the present invention, a cationic polymer represented by the following general formula (I) (or a copolymer containing monomer units thereof) and a sulfonic acid salt or a sulfuric acid ester salt represented by the general formula (II), 0.02 to 0 of the compound of general formula (II) per mol of monomer unit of formula (I)
．． A water-soluble antistatic agent characterized in that 10 mol of the antistatic agent is used is provided.

R1; H, CH3, C, H6, C, H.

R2, R, R4; each is the same or different,
Cl-13, C2H,,C,H.

R: 100-10,000 X-; halogen, CI-I, SO, -1C2H,,5O
4-R6; Cl1-C22 long-chain alkyl group, hydroxyalkyl group, alkenyl group, or alkylaryl group R, having a CG to C22 long-chain alkyl group; H, CH.

mho, 1 An integer from neo to 30.

M: Alkali metal salt, ammonium, alkanolamine water-soluble salt In the present invention, a compound represented by the above general formula (I) is used as the cationic polymer (or a copolymer containing one unit thereof).

In this case, R is Il, CI+3, C, H5, or C
, 117. R2, R3, and R4 are each the same or different, and Cl-1,, C2119, (
I: 311□. X-, which represents the counter ion of the quaternary ammonium group, is, for example, a halogen such as chlorine or bromide ion,
C11,SO, -1C2+1,504- is shown.

The cationic polymer (or copolymer containing monomer units thereof) represented by the above general formula (I) is produced by a known method. For example, it can be obtained by polymerizing dialkylaminoethyl methacrylate alone or with other polymerizable monomers in the presence of a polymerization initiator, and then quaternizing it with dialkyl sulfuric acid.

Other polymerizable monomers include, for example, styrene, α
- Styrenes having substituents such as methylstyrene, substituted acrylamides such as acrylonitrile, acrylamide, and N-hydroxyethylacrylamide, vinyl acetate esters, or acrylic acid esters such as acrylic acid, methyl methacrylate, or ethyl methacrylate. etc.

As another method for producing the above polymer, it is also possible to obtain it by previously polymerizing a monomer having a quaternary ammonium group.

The degree of polymerization of the above polymer is not particularly limited as long as it has a molecular weight that is acceptable for use at the treatment concentration, but
The viscosity of a 15% aqueous solution at 25°C is s, oo.

-io, ooocp is practically suitable, and the degree of polymerization Q is preferably 100-10,000.

The above polymers themselves have antistatic properties, but when used alone, they have insufficient durability.

In the present invention, in order to eliminate such drawbacks, a sulfonate salt or a sulfate ester salt, which is an anionic surfactant represented by the general formula (n), is blended into the polymer in a specific ratio, so that the surface of the resin surface can be improved. It is possible to obtain an antistatic agent that has improved adhesion to the polymer and has durability that cannot be achieved only by using the polymer represented by the general formula (I) alone.

The sulfonate or sulfate ester salt having a long-chain alkyl group or a long-chain alkylaryl group, which is an anionic surfactant represented by general formula (II), is shown as follows.

However, R1 is an alkylaryl group having a long chain alkyl group of 08 to co alkyl group, hydroxyalkyl group, alkenyl group, or C, -C, and R6 is 11
Or C113. A long-chain alkyl group or a hydroxyalkyl group (alkenyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms). The number used is 8 to 22, preferably IO to 18.ell is 0 or 1.
n is an integer of 0-30, and particularly preferably 10-30. In addition, a is an alkali metal salt, ammonium,
Water-soluble salts of alkanolamines are shown, and sodium salts are particularly preferably used.

In the present invention, the sulfonic acid salt or sulfuric acid ester salt used is a normal 11N type salt.

In this case, examples of the sulfonate include alkyl sulfonate, olefin sulfonate, alkylbenzene sulfonate, and alkylnaphthalene sulfonate.

Further, examples of the sulfuric ester salts include long chain alcohol sulfuric ester salts, polyoxyethylene alkyl ether sulfuric ester salts, and polyoxyethylene alkyl phenyl ether sulfuric ester salts.

These sulfonic acid salts or sulfuric ester salts may be used alone or in combination with the cationic polymer as a mixture of two or more thereof.

When a sulfonate having no long chain alkyl group such as p-toluenesulfonate is used as a compound used in combination with the polymer represented by the general formula (I), a certain degree of durability can be obtained. Not only does it cause uneven coating on the resin surface, but when used on a transparent resin, the appearance is impaired and the effects of the present invention cannot be expected.Also, other anions such as polycarboxylate and phosphate Similarly, when a surfactant and the above-mentioned polymer are used together, the excellent durability as in the present invention cannot be obtained, and there is also the problem that the appearance is impaired.

Furthermore, in the antistatic agent of the present invention, the compound of general formula (II) is contained in an amount of 0.02 to 0.10 mol, preferably 0.05 to 0.0 mol, per 1 mol of monomer units represented by general formula (I).
．． It is necessary to use it in a range of 0.8 mol. General formula (
If the usage ratio of the compound (ii) is less than this range, the antistatic performance will lack durability. In addition, when the usage ratio of the compound of general formula (n) exceeds this range, the cation-anion complex formed by the above polymer and the above sulfonate or sulfate salt becomes water-insoluble, resulting in antistatic performance. Not only is this method reduced, but it also requires the use of other solvents and emulsifiers, making the operation complicated and lacking in workability.

The antistatic agent of the present invention is generally applied to synthetic resin molded articles as an aqueous solution, but it can also be used as a solution in a water-soluble organic solvent such as isopropanol or a lower alcohol such as ethanol.

The concentration of the antistatic agent treatment liquid of the present invention is determined depending on the required degree of antistatic performance and the properties of the object to be coated, but a range of 0.5 to 5% is usually suitably used.

41' of the present invention; the anti-static agent has the above-mentioned polymer and the above-mentioned long-chain alkyl group or long-chain alkylaryl nor-containing sulfonate or sulfuric acid ester salt as essential components; Other surfactants may be added as necessary for the purpose of improving the properties.

Examples of such surfactants include low molecular weight cationic surfactants such as dihydroxyethyl monomethyl palm ammonium chloride and dihydroxyethylstearylammonium 11 chloride, and amphoteric and nonionic surfactants.

Examples of synthetic resin molded articles to which the VtF antistatic agent of the present invention can be applied include sheets and molded articles of polycarbonate, polymethyl methacrylate, hard vinyl chloride, polystyrene, polypropylene, polyethylene, etc., and laminates thereof.

As a method for applying the antistatic agent of the present invention, a commonly used method can be used. For example, a dipping method, a roll coater, a doctor blade, a knife blade, an applicator, and a spray coating method are used. The coating method is determined depending on the shape, physical properties, etc. of the molded product.

〔effect〕

In the present invention, by using a specific water-soluble cationic polymer represented by the general formula (I) and a specific anionic activator represented by the general formula (n) in a specific ratio,
It is possible to obtain an antistatic agent that has excellent adhesion to resin and excellent durability without impairing the appearance of the resin to be coated.

Therefore, the durability of the antistatic effect of molded products treated with this antistatic agent is significantly improved, and the appearance of the molded products is not impaired and uneven coating does not occur.

Example Next, the present invention will be explained in detail with reference to Examples.

Examples 1-11. Comparative Examples 1 to 15 A plate made of polymethyl methacrylate (Kyowa Gas Chemical Exhibition, Como Glass) was immersed in a 0.5% aqueous solution of the antistatic agent shown in Table 1 for 3 seconds and dried at 50°C for 30 minutes to prepare the sample. The evaluation was conducted using the following method.

Evaluation method 1: Antistatic effect After conditioning the sample in a constant temperature and humidity condition with a relative humidity of 65% and a temperature of 23°C, the sample was tested with a Kyokuho megohmmeter [5M-1 manufactured by Toa Denpa Co., Ltd.]
The surface resistivity was measured at 0E). Surface specific resistance value is 1
012Ω or less was considered effective.

2. Durability The antistatic performance was measured under the conditions of 1 after washing the sample in running water at a flow rate of 10+++1/sec for 5 minutes. If the surface resistivity value does not change by two orders of magnitude or more after washing with water, it is considered durable.

3. Appearance The unevenness of coating was visually determined.

0...No uneven coating, Δ: Slight unevenness of coating occurs.

X: Uneven coating occurred Examples 12 to 15 Using the antistatic agent shown in Example 3 in Table 1, antistatic treatment was performed on the resin shown in Table 2, and the same as Example 1 was applied. The evaluation was conducted using the following method. The resins used in the evaluation are as follows.

Polycarbonate; Polyvinyl chloride manufactured by Idemitsu Petrochemical Co., Ltd.; Polystyrene manufactured by Takiron Co., Ltd.; Stylon ABS manufactured by Asahi Kasei Corporation;
Comparative Example 1
The polystyrene resin was subjected to antistatic treatment using a 'F'M inhibitor. The results of the same evaluation are shown in Table-2.

Examples 17 to 21 Acrylic resins were subjected to antistatic treatment using a diethyl sulfate quaternized product of polydiethylaminoethyl methacrylate and an anionic activator shown in Table 3, and evaluated in the same manner as in Example 1. The results are shown in Table-3.

Examples 22 to 30 Antistatic treatment of acrylic resin was performed using various copolymers containing diethyl sulfate quaternized product of diethylaminoethyl methacrylate and the anionic activator shown in Table 4 in the same manner as in Example 1. The evaluation was carried out. The results are shown in Table 4.

Claims (1)

[Claims] A cationic polymer represented by the following general formula (I) (or a copolymer containing monomer units thereof) and a general formula (I)
It consists of a sulfonate salt or a sulfuric acid ester salt shown in I), and is characterized in that 0.02 to 0.10 mol of the compound of the general formula (II) is used per 1 mol of the monomer unit of the general formula (I). Water-soluble antistatic agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) R1:H, CH_3, C_2H_5, C_3H_7R_
2, R_3, R_4; Each is the same or different, CH_3, C_2H_5, C_3H_7l: 100
~10,000 X^-;Halogen, CH_3SO_4^-, C_2H_
5SO_4＾−▲There are mathematical formulas, chemical formulas, tables, etc.▼(I
I) R_5; C_6 to C_2_2 long chain alkyl group, hydroxyalkyl group, alkenyl group, or C_6 to C_2
Alkylaryl group with a long chain alkyl group of _2 R_6; H, CH_3 m; 0, 1 n; an integer from 0 to 30. M; Alkali metal salt, ammonium, alkanolamine water-soluble salt