JPH03243640A - Antistatic agent for synthetic resin - Google Patents

Abstract

PURPOSE:To obtain the title antistatic agent having excellent immediate effects, durability, stability with time and excellent heat resistance, comprising a specific quaternary ammonium compound and a specific ester in a specific ratio. CONSTITUTION:The objective antistatic agent comprising (A) a quaternary ammonium compound shown by the formula (R is 11-21C alkyl or alkenyl; m is 2 or 3; n is 1-5; R<1> is methyl or ethyl) and (B) an ester obtained from a polyglycerin having 2-7 degree of polymerization and 12-22C (unsaturated) saturated fatty acid in the ratio of the component A:B = (10-70):(90-30). The compound A is produced by condensing 1 mol 12-22C (unsaturated) saturated fatty acid (ester) with 0.8-3 mols dialkylaminoalkylamine to give an amide compound, adding an alkylene oxide to the amide compound in the presence of water to give a quaternary ammonium hydroxide compound and then neutral izing the compound with perchloric acid.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to an antistatic agent for synthetic resins, and more specifically, to an antistatic agent that has excellent immediate effect, sustainability, and oral stability in antistatic performance, Furthermore, the present invention relates to an antistatic agent for synthetic resins having excellent silence resistance.

[Prior Art] In recent years, synthetic resins have been widely used in the form of films, sheets, molded products, fibers, and the like. However, although these synthetic resin products have excellent electrical insulation properties, they tend to generate static electricity, resulting in a significant decrease in product value due to decreased workability and dirt adhesion, unpleasant electrical shocks to the human body, and even the generation of static electricity. There is also the risk of causing disasters such as fire and explosion due to static electricity discharge. For this reason, various antistatic agents for synthetic resins have been studied, including nonionic surfactants such as glycerin fatty acid esters, sorbitan fatty acid esters, alkyl alkanolamides, and alkyl alkanolamines, and alkyl sulfonates. Anionic surfactants, various quaternary ammonium compounds, and mixtures thereof are blended into synthetic resins to prevent the generation of static electricity.

However, the problems that this invention aims to solve are that these antistatic agents generally have a sufficient antistatic effect immediately after molding, so-called immediate effect, but lack force or persistence, are not very stable, and impede the heat resistance of the resin. However, there are still some problems with this, and no satisfactory solution has yet been found.

The present invention has been developed with attention to the above points, so it is possible to impart an excellent antistatic effect to synthetic resins, maintain this effect for a long time, and reduce the physical properties of synthetic resins such as heat resistance. The purpose of the present invention is to provide an antistatic agent for synthetic resins that does not cause any damage.

[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted intensive studies and found that by combining a specific polyglycerin fatty acid ester and a quaternary ammonium compound, extremely high electrostatic charge can be achieved. It is possible to impart a preventive effect to synthetic resins, and its immediate effect and sustainability are extremely high.
! ! ! ! We have discovered an antistatic agent for synthetic resins that does not reduce the heat resistance of fats, and have completed the present invention.

That is, the present invention is based on (A) the following general formula (1) % formula %) (1104 (1) (wherein R is an alkyl group or alkenyl group having 11 to 21 carbon atoms, m is 2 or 3, and n is 1 to 5, R' is a methyl group or an ethyl group); (B) a polyglycerin with a degree of 8 of 2 to 7; and a saturated or unsaturated fatty acid having 12 to 22 carbon atoms. (A): (B)=
It is an antistatic agent for synthetic resins contained in a weight ratio of 10-70:90-30.

Examples of the quaternary ammonium compound used in the present invention include compounds represented by the following general formula (1) % formula % (1), where R has 11 to 11 carbon atoms.
A quaternary ammonium compound in which R has less than 11 carbon atoms in formula 1, which is preferably an alkyl group or an alkenyl group of 21, is undesirable because it causes preacidation when added to the tW fat. Also.

A quaternary ammonium compound in which R has more than 21 carbon atoms has a low antistatic effect and is not practical.

The quaternary ammonium compound represented by the general formula (1) is
For example, it can be synthesized as follows. First, 1 mol of a saturated or unsaturated fatty acid having 12 to 22 carbon atoms or a lower alcohol ester thereof and 08\3 mol of a dialkylaminoalkylamine are subjected to a condensation reaction according to a conventional method to obtain an amide compound. Carbon number 12-2 used here
Examples of the fatty acids No. 2 include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, elaidic acid, linoleic acid, linuric acid, ricinoleic acid, arachidonic acid, eicosapentaenoic acid, and erucic acid. These fatty acids may be used alone or in combination of two or more. Fatty acids that are a mixture of two or more types include fatty acids obtained by decomposing animal and vegetable oils or fats such as hydrogenated hydrogenated oils and fats obtained by hydrogenating these animal and vegetable oils using conventional methods such as high-pressure decomposition or using fat-degrading enzymes. can be mentioned. Examples include the dialkylaminoalkylamine pyramine, diethylaminoethylamine, dimethylaminoethylamine, diethylaminoethylamine, and the like.

1 mol of the above amide compound and alkylene oxide,
An addition reaction is carried out in the presence of water to obtain a quaternary ammonium hydroxide compound, and the compound of general formula (1) is then obtained by neutralization with perchloric acid. Examples of the alkylene oxide include ethylene oxide and propylene oxide, and the number of moles added thereof is preferably 1 to 5 moles.

Examples of the ester (B) used in the present invention include polyglycerin fatty acid esters obtained from polyglycerin and fatty acids. The polyglycerin used here is obtained by dehydration condensation of glycerin, and preferably has a degree of polymerization of 2 to 7. Glycerin fatty acid esters have poor long-lasting effects, and polyglycerin fatty acid esters with a degree of polymerization exceeding 7 are highly effective.

The lack of compatibility with fats causes problems such as stickiness of the film surface, which is undesirable.

Furthermore, the fatty acid used for the ester (B) has 12 carbon atoms.
~22 saturated or unsaturated fatty acids are preferred. Esters of fatty acids with less than 12 carbon atoms lack compatibility with the resin, resulting in problems such as sticky film surfaces, while esters of fatty acids with more than 22 carbon atoms have a reduced antistatic effect. Not practical.

Examples of the fatty acids include the fatty acids listed in the quaternary ammonium compound (A).

Ester (B) can be obtained by carrying out an esterification reaction according to Tsunehiro using the polyglycerin and fatty acid, but in this esterification reaction, a monofatty acid ester and an ester containing two or more fatty acid residues are used. A mixture of esters (
As B), it is preferable to use an ester containing 50% by weight or more of a monofatty acid ester.

The antistatic agent for synthetic resins of the present invention comprises (A):
(B) = 10-70: When contained in a weight ratio of 90-30, a practical antistatic effect with excellent immediate effect and sustainability can be obtained due to the synergistic effect. Immediate effect is recognized when the blending ratio of the quaternary ammonium compound (A) and the ester compound (B) is more than 70% by weight and less than 30% by weight (B). However, the durability is poor, and problems such as coloration of the molded product and stickiness on the surface of the molded product due to excessive bleeding occur, and when (B> exceeds 90% by weight and (A) is less than 10% by weight) However, the immediate effect is poor, and the antistatic effect itself is insufficient, making it impractical.

If necessary, the antistatic agent for synthetic resins of the present invention may contain various additives such as antiblocking agents, antioxidants, ultraviolet absorbers, and lubricants within the range that does not impede the purpose of the present invention. Various conventionally known antistatic agents can also be used in combination.

The antistatic agent for synthetic resins of the present invention can be used as an antistatic agent for films, sheets, molded products, fibers, etc. made of various synthetic resins, but especially for hinyl chloride! ! 1, vinyl chloride-vinyl acetate cobolymer ethylene chloride, vinyl acetate cobolyph, etc. are suitable as antistatic agents.

The antistatic agent for synthetic resins of the present invention can be prepared by a conventionally known method, for example, by mixing the antistatic agent for synthetic resins of the present invention and synthetic resin pellets using a Henschel mixer, a spar mixer, a tumbler, etc., and then using an extruder or injection molding. It can be used by mixing it into a resin using a machine or the like and making it into films, sheets, molded products, fibers, etc.

The amount of the antistatic agent of the present invention added is generally preferably in the range of 0.05 to 5% by weight based on the synthetic resin.

[Example] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Preparation of quaternary ammonium compound 112 g of dimethylaminopropylamine was added to 214 g of lauric acid methyl ester, 0.2 g of sodium methoxide was added as a catalyst, and the amidation reaction was carried out by heating and stirring at 100°C for 5 hours. Excess amine was removed under reduced pressure to obtain 282 g of an amide compound. Next, 50 g of isopropyl alcohol was added to 100 g of this amide compound.
Add 3 g of ethylene oxide and 50 g of water, and add 3 g of ethylene oxide at 20℃.
1 g was subjected to an addition reaction and a quaternization reaction was performed. obtained 4
A 30% aqueous solution of perchloric acid in grade ammonium compound 118
A solution containing a quaternary ammonium compound of formula (1) having an alkyl group having 11 carbon atoms was obtained. This was used as antistatic agents N011-3.5.7-9.12. Also, 298 g of stearic acid methyl ester, 97 g of dimethylaminoethylamine, and 0.0 g of sodium methoxide.
Using 2g, react in the same manner as above to obtain amide compound 354.
Next, 50 g of isopropyl alcohol and 50 g of water were added to 100 g of this amide compound, and 25 g of ethylene oxide was added at 20°C to perform a quaternization reaction. It was neutralized by adding 94 g of an aqueous solution, and had an alkyl group with 17 carbon atoms ([
) prepare a solution containing a quaternary ammonium compound of formula;
This was used as antistatic agent No. 4.6.11.

Preparation of polyglycerin fatty acid ester Add 166 g of polyglycerin with a degree of polymerization of 2 to 166 g of polyglycerin*24
Add 0 g and heat at 230℃ for 1 hour! A step JIy reaction was carried out. The obtained reaction product was subjected to molecular distillation to obtain a fraction containing 96% of monofatty acid ester (hereinafter abbreviated as CM) and 4% of difatty acid ester (hereinafter abbreviated as [D]),
This was used as antistatic agent No. 1.8. Hereinafter, glycerin, polyglycerin with a degree of polymerization of 2.35, and lauric acid,
An esterification reaction was carried out in the same manner as above using stearic acid to prepare an ester having the composition shown in ester (B) in Table 1. Note that the ester (B) using polyglycerin with a degree of polymerization of 3.5 was used as it was without molecular distillation.

Examples 1 to 7, Comparative Examples 1 to 6 A polyglycerin fatty acid ester was added to a hydroalcoholic solution containing a predetermined amount of a quaternary ammonium compound, and water-
Antistatic agent obtained by concentrating and removing alcohol/L (Table 1,
No. 1 to 9.12), antistatic agents obtained by concentrating a water-alcoholic solution containing a quaternary ammonium compound (Table-
1-No. 11), antistatic agent consisting only of fatty acid ester of glycerin or polyglycerin Table 1, N.

10.13> was prepared, and using this, a vinyl chloride resin composition blended in the following weight proportions was supplied to a calender roll heated to 180°C, kneaded, and then molded to a thickness of 0.1 mm by a conventional method. A 5 mm sheet was created.

Polyvinyl chloride resin (P=1050) 100 parts Dioctyl phthalate 2 parts Dibutyltin maleate 1 part Antistatic agent for synthetic resins
Part L: Table 2 shows the evaluation results of the heat resistance of this silt and the results of orally measuring the surface resistivity.

The heat resistance test and the surface resistivity measurement test of the sheet were conducted as follows.

Heat resistance test of sheet Sheet containing antistatic agent for synthetic resin (width 5 mm x
50mm long x 0.5mm thick, 5 sheets for each sample)
The sheet was heated in a gear oven at 30° C., the hue was visually observed over time, and the time (minutes) until the sheet was colored blackish brown was measured.

Measurement test of surface resistivity Sheet containing antistatic agent for synthetic resin (width 50mm
50mm long x 0.5mm thick, 5 sheets for each sample
After leaving it for 3 hours in a constant temperature and humidity room at 0°C, 50% RH, and adjusting the humidity, under the same measurement conditions of 20°C, 50% RH,
Measured according to K-6911. Furthermore, 20℃50%R
It was left standing under the conditions of H, and its performance was measured one week and one year after molding.

Table-1 *(I) means tri or higher fatty acid ester.

[Effects of the Invention] As explained above, the antistatic agent for synthetic resins of the present invention uses a specific quaternary ammonium compound and polyglycerin fatty acid ester in combination, and compared to conventional antistatic agents, It has excellent immediate and long-lasting antistatic effect, can exhibit these effects for a long time, and does not reduce the physical properties such as heat resistance of synthetic resin, so it can be used in any amount in synthetic resin. By blending, the antistatic agent for synthetic resins of the present invention can exhibit an excellent antistatic effect, and when used in products that do not contain pigments or products that are lightly colored even when pigments are added, Compared to antistatic agents, it causes less coloring when administered orally, and has the effect that synthetic resins are less susceptible to deterioration due to heat, especially when used in applications that require heat resistance.

Claims (1)

[Claims] 1. (A) The following general formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼... (I) (However, in the formula, R is an alkyl group or alkenyl having 11 to 21 carbon atoms. group, m is 2 or 3, n is 1 to 5, R' is a methyl group or ethyl group), (B) polyglycerin with a degree of polymerization of 2 to 7, and a carbon number of 12 to 22 saturated or unsaturated fatty acid and the ester obtained from (A):(B)=10-70:90-3
An antistatic agent for synthetic resins, characterized in that it is contained in a weight ratio of 0.