JPS5849334A - Polybasic acid salt compound and antistatic agent comprising it - Google Patents

Abstract

NEW MATERIAL:A salt of tetra-or pentacarboxylic acid shown by the formula I(n and n' are 4-10; X is H or COOZ; Z is H, lower alkyl, alkali metal or ammonium ion; at least three Z are alkali metal or ammonium ion). EXAMPLE:Tetrasodium 1, 9, 10, 12-octadecanetetracarboxylate. USE:An antistatic agent. Effectively applied to cloth, plastic, and paper. Having improved heat resistance and hard water resistance. PROCESS:An acid or ester shown by the formula II (Y is H or COOH; R is H or 1-4C alkyl) is neutralized or saponified to give a compound shown by the formulaI. The compound shown by the formula II is obtained by ozonizing a fatty acid derivative containing a cyclohexene ring as a raw material and oxidizing it with oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polybasic acid salt compound and an antistatic agent comprising the same.More specifically, the present invention relates to a novel polybasic acid salt compound and an antistatic agent comprising the same. and n' is a number from 4 to 10; The present invention relates to a sodium, potassium, lithium or ammonium salt of a tetra or pentacarboxylic acid represented by the above formula, and an antistatic agent comprising the same.

A wide variety of antistatic agents have been proposed in the past, but generally they are cationic, amphoteric, some nonionic (amines, amides, phosphate esters, etc.), and some antistatic agents. Ionic (phosphate-based) surfactants are used alone or in mixtures. However, such surfactant-based antistatic agents are (1) generally expensive, (2) need to be added in large amounts, and (3) cannot be used in both water and oil (including plastics). (4) Limited to 4I-specified objects; (5) Few products are durable; (6) Many products bleed when applied to plastics. (η There are very few products that are effective against vinyl chloride resin, f
3) In general, the effectiveness is considerably reduced under low temperature and low humidity conditions. (9) Cationic and amphoteric surfactants are highly effective but have poor heat resistance. QI cationic surfactants are toxic. It has drawbacks such as limited use, and has not yet been satisfactory.

The present inventors have conducted various studies to overcome these drawbacks of conventional surfactant-based antistatic agents. As a result, we have discovered that ionic surfactant-based antistatic agents contain only alkyl phosphates. Although there were very few compounds with excellent antistatic effects, as a result of repeated research into the production and application of novel tetrapentacarboxylic acid ester derivatives developed by one of the inventors, many of them were discovered. We have discovered that salts of basic acids have practical advantages such as low toxicity and stability, as well as excellent antistatic properties against various types of fibers and plastics, and based on this knowledge, we have developed the present invention. It's arrived.

The salt of the tetra or pentacarboxylic acid represented by the general formula (1) of the present invention can be produced by neutralizing or saponifying the acid or ester of the general formula (1) below by a conventional method. Examples of the alkali used for neutralization include sodium hydroxide, potassium hydroxide, lithium hydroxide, and ammonia.

・------Qi) (where n and I are numbers from 4 to 10, Y is a hydrogen atom or C
0OR%R and I each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ) In the production of the tetra- or pentacarboxylic acid salt, it goes without saying that esterification can be carried out as appropriate to convert the carboxyl group at a desired position into an ester group.

Conventionally, well-known polycarboxylic acids or esters include tricarboxylic acids having three carboxyl groups in the molecule and tetracarboxylic acids having four carboxyl groups, as well as some two of these carboxyl groups. There are polycarboxylic acid esters that are esterified.

However, these polycarboxylic acids and their ester derivatives generally have short molecular chains, or have a structure with one or two carboxyl groups or ester groups at both ends of the molecular chain, that is, at the α and ω positions. Many of them were thought to be derivatives of the basic linear dicarboxylic acid.

The tetra or pentacarboxylic acid and the tetra or pentacarboxylic acid di- or triester represented by the general formula (1) used in the present invention have one carboxyl group or ester group at one end of the molecular chain, that is, at the α-position carbon. The other end is an alkyl group, and the other carboxyl group or ester group is a polycarboxylic acid or polycarboxylic acid ester bonded to the middle ν element of the molecular chain. Therefore, these are novel polycarboxylic acids and polycarboxylic acid esters which are considered to be derivatives of ordinary linear basic acids. These tetra- or pentacarboxylic acids and tetra- or pentacarboxylic acid di- or tri-esters are produced by ozonation and oxygen oxidation using fatty acid derivatives having a cyclohexene ring as raw materials.

The antistatic agent of the present invention can be applied to or impregnated onto objects such as fibers and plastics in the form of an aqueous solution, or
It is used after being elaborated. When an aqueous solution is used, the concentration used is usually 0.1 to 3.0%, preferably 0.3 to 1.5%.
And when kneading into the object, ijO, 2~3.01!
, preferably Fio, 3 to 2.0.

The characteristics of the antistatic agent of the present invention are as follows.

(1) It has an excellent temporary antistatic effect.
Good long-lasting effect.

(3) It is highly compatible with water, some oils, and plastics, so it can be used in a very wide range of applications.

(4) It is economical because it is effective at low concentrations.

(5) Since it is colorless, it is less likely that objects will be colored.

(Since it is low in boron, there is no need to worry about problems caused by foxtail.)

(η External application, spraying, and internal line embedding can all be used.

(8) Effectively applied to cloth (nylon, acrylic, Tetron, etc.), plastic (polyethylene, polypropylene, other polyolefins, latex, etc.), and paper.

(9) It is extremely convenient to use because it has excellent heat resistance and hard water resistance.

α・Low toxicity and can be used safely over a wide range of areas.

Next, the present invention will be explained in more detail based on Examples and Reference Examples.

The esters of teto-2- or pentacarboxylic acids used in the examples were prepared according to the method of the reference examples, and the antistatic power test method was 11NI as described below.

In addition, the raw materials used in the reference examples are fatty acid derivatives having a cyclohexene ring with the structures of the following general formulas A and B. Each is shown below.

"α℃C■ (R, R': H or alkylene group) Reference pH Raw material B (n = 5, n' = 7, both R and R' are OH,) 3
．． 01? 30 - ml of glacial acetic acid was weighed out into 50 pear-shaped solid flasks. , the flask has a gas blowing tube,
A cooler and a stirrer were installed. The reaction takes 10 to 14 flasks.
The solution was placed in a constant temperature bath at 0.degree. C., and ozone-oxygen mixed gas (ozone concentration: 3 wt %) was blown into the solution for 38 minutes while stirring to effect ozonation. After ozonation, manganf acetate (M
Add 0.02F of n(C)ImCO*)* ・4H10), raise the temperature to 80°C while stirring, and blow oxygen gas (flow rate 270d1 min) at 80°C for 1.5 hours to decompose and oxidize osinide. I did it. After the reaction, the reaction solution was filtered to remove the manganese compound, and then the acetic acid was distilled off.
The reaction product was collected with ether, washed with water, and the ether was distilled off to obtain reaction product 3.18F. This reaction product gave the following analytical values. That is, acid value 144.6 (theoretical value: 2
52.4), IR spectrum k (am-ri:2SGO-
2700 (carboxyl group), 1710 (carbonyl group), River-NMR spectrum (PPm): 0.9 (terminal methyl group) 1.2-1.3 (methylene group) 3.4 (methyl ester group), 8. 5-8.6 (carboxyl group),"
C-NMRx vector (ppm): 14.3 (terminal methyl group), 23.0 to 35.5 (methylene group), 4G (methyl ester group), 174.2 to 181.1 (carboxyl group).

From these analysis results, it was confirmed that the reaction product was tetracarboxylic acid dimethyl ester having the following structure.

Reference example 2 10.03f of raw material A (n=5.n'=7, both R and R' are CH,) and 100d each of 80yd'ft of glacial acetic acid
A pear-shaped three-white flask was weighed. 7 y score rtc
A gas blowing pipe, cooler, and agitator were installed. The reaction was carried out by placing the flask in a constant temperature bath at 10-13°C, stirring the solution, and adding an ozone-oxygen mixed gas (ozone concentration: 3.f).
Ozonation was carried out by blowing wt. After ozonation, manganese acetate [:Mn (C
Add o and o7t of HsCO*)* ・4HsD),
While stirring, raise the temperature of the reaction solution to 80°C.
Oxygen gas (flow rate: 2107/min) was blown into the reactor for 3 hours to oxidize and decompose oscinide. After the reaction, the reaction solution was filtered to remove the manganese compound, then the acetic acid was distilled off, and the reaction product was extracted with ether and washed with water to obtain reaction product 10.33F. Various analyzes were conducted on this reaction product and the following results were obtained.

Neutralization value: 218.8 (theoretical value 223.3), IR spectrum (prepared): 2500-2700 (carboxyl group), 1710 (carbonyl group), H-NMR spectrum (ppm) 20.8 g ( terminal methyl group), 1.3
(meter/group), 3.65 (methyl ester group), 8
．． 08 (carboxyl group), 'C-NMR scale (ppm): 14,0 (terminal methyl group), 22.4-3
4.1 (methylene group), 51.5-52.0 (methyl ester group), 171.8-178.4 (carbonyl group) From these analysis results, the reaction product is pentacarbozai)limethyl with the following structure. It was confirmed that it was an ester.

Example 1 Tetracarboxylic acid dimethyl ester obtained in Reference Example 13. Of was dissolved in 50% of ethanol, 50wt of an aqueous solution of sodium hydroxide was added thereto, and the mixture was reacted at 80 to 85°C for 2 hours. After the reaction, the solution was concentrated by evaporation, 5 to 10-m water was added to it, and the whole volume was diluted with methanol to about 200-
The mixture was sealed and the precipitated inorganic salt was filtered off. Next, about 50% of ether was added to the filtrate, and the precipitated soap was filtered off. The obtained soap was mixed with water/methanol/ether (1:20:5).
) Reprecipitation is performed several times with the mixed solution to purify white crystals 2.
I got 42.

The spectral data of this product is shown below.

IR spectrum (a--Li: 1570 (carboxylald ion) IH-NMR spectrum);, 1.3
0 (terminal methyl), 1.70 (methylene) 'C-NMR spectrum (PPm): 14.3 (
Terminal methyl) 22.6-38.6 (methylene), 52.0 (methine), 167.5-185.0 (carbonyl) From these analysis results, the reaction product is 1,9.10°12
-Tetrasodium octadecanetetracarboxylate ([I(
It was confirmed that it was 0d4Na (hereinafter abbreviated as 0d4Na).

(2) Example 2 3.67f of pentacarboxylic acid trimethyl ester obtained in Reference Example 2 was dissolved in ethanol 50-, and a 2-1 aqueous solution of sodium hydroxide [ Add Od, 89-85℃
The reaction was allowed to proceed for 172 hours. After the reaction, the reaction solution was concentrated by evaporation, 5 to 1 G of water was added thereto, the total volume was made up to about 200 mg with methanol, and the precipitated inorganic salts were filtered out. Approximately 50% of ether was added and the precipitated soap was filtered out.The obtained soap and soap were mixed with water/methanol/ether (
1:20:5) Purify by reprecipitation several times with a mixed solution,
White crystals 3.82 were obtained. The spectral data of this product is shown below.

IR spectrum (all-〇: 1570 (carboxilade ion) IH-NMR spectrum δ): 1.32
(terminal methyl), 1.70 (methylene) "C-NMR spectrum (PPm): 14.5 (terminal methyl), 22.6-38.5 (methylene/), 51.7 (methine), 167.7 ~184.7 (carbonyl) From these analysis results, the reaction products are 1,9,10,12
- Pentasodium octadecanepentacarboxylate (conversion) (
It was confirmed that 0dSN &)'.

---01,-0OM Example 3 3. of tetracarboxylic acid. Of was dissolved in 50 m of ethanol, and to this was added 52 m of an aqueous solution of hydroxide with stirring, and then a reflux condenser was attached and the solution was gently boiled on a water bath. When reacted in this state for 1 hour, it was found that even raw materials in which part of the raw material was an acid anhydride were converted into soap.

Next, bring the temperature to room temperature, add ethanol, and reduce the total volume of the solution to about 2
00-stitched, and about 50 wt of ↓-chill was gradually added thereto to precipitate soap. - After standing overnight, the precipitated soap was filtered off. Furthermore, the liquid is evaporated and concentrated to 5~1O-
When the soap was dissolved in water and ethanol was added to bring the total volume to about 106 m, then 30 m of ether III was added, and even more soap could be precipitated. Combine both soaps and mix with water/ethanol/ether (1:20:5).
) The mixed solution was purified by reprecipitation several times to obtain white crystal tetracarboxylic acid tetrasodium salt 3.15F.

The sous vector of this product completely matched that of the soap shown in Example IK.

Od4Nm and 0dNaO01 obtained in Examples 1 to 3
- and 1.0- were prepared, and the antistatic power against each extreme right was measured. The results are shown in the table below. In addition,
The test method is as follows.

Antistatic Power Test Method Two pieces each of 4 x 5 m test cloths [nylon cloth (taffeta, plain weave: polyamide type), cashmilon cloth (plain weave: polyacrylic type), and Tetron cloth (taffeta, plain weave: polyester type)] were placed on a polypropylene plate. , 0.2 t of a 1.0% sample aqueous solution was dropped so as to uniformly wet the entire surface, dried, and kept at constant humidity (n, H, 93- (on dihydrogen phosphate-ammonium saturated aqueous solution), R, H, : <1% (on silica gel)] After keeping K (<IIs: 2hr193qk=2
4hr) 20~22℃% F8 status scope type (
Measure the surface leakage resistance value (Ω) of the fabric (manufactured by Kochu Sangyo Co., Ltd.) by 2 each on the front and back sides.
Measurements were taken at each location and the average value was taken. The smaller the resistance, the better the antistatic ability was obtained.

As is clear from the results in this table, even when used alone, the antistatic agent of the present invention exhibits an antistatic effect that is approximately equal to or greater than that of commercially available products. It can be seen that the antistatic agent of the present invention exhibits an excellent antistatic effect even at a particularly low concentration.

Patent applicant Makoto Ishiita, Director of the Agency of Industrial Science and Technology

Claims (1)

[Claims] (1) General formula % formula % () (in the formula, n and n' are numbers from 4 to 10, and at least 2 of which are at least 3 thin alkali metal or ammonium ions. (General formula % formula % (1) (where n and n' are numbers from 4 to 10, At least three of them are alkali metal or ammonium ions.) An antistatic agent comprising a salt of a tetra or pentacarboxylic acid represented by