JPS5819692B2 - Antistatic agent for synthetic polymer materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antistatic agent for synthetic polymeric materials.

More specifically, the present invention relates to one or two selected from alkali metal or alkaline earth metal salts of sulfonate compounds having free carboxyl groups, and salts obtained by neutralizing the free carboxyl groups of the sulfonate compounds with amine compounds. This invention relates to an antistatic agent for synthetic polymer materials consisting of at least one type of sulfonate compound, and a synthetic polymer comprising one or more types selected from the salts of the sulfonate compounds and a specific organic oligomer or polymer. This invention relates to antistatic agents for materials.

Synthetic polymer materials are usually characterized by high hydrophobicity;
As a result, the tendency to be easily charged poses a major obstacle in the manufacturing process of these materials and in the use of their products.

In other words, in the manufacturing process of plastic molded products, films, and synthetic fibers that use synthetic polymer materials, static electricity generated by contact friction between synthetic polymer materials and friction between synthetic polymer materials and manufacturing equipment can interfere with smooth operation. In extreme cases, this can lead to product quality deterioration.

In addition, undesirable phenomena such as dust adhesion and electrostatic shock are unavoidable during use and storage of the above-mentioned products made of synthetic polymer materials, and depending on the application, they may easily become electrostatically charged or may cause fatal defects. There are also many.

Various methods have been proposed in the past to reduce the problems caused by the chargeability of synthetic polymer materials.

One of these methods is to add antistatic substances, mainly surfactants, to the surface of synthetic polymer materials, but although this method is simple, it has the disadvantage that the effect is only temporary. .

In addition, in order to improve this shortcoming, there is a method of fixing a polymeric substance to the surface or using a considerable amount of a reactive compound, but in this method, the amount used is generally also This tends to damage the good surface properties and physical properties inherent in synthetic polymer materials.

Another method, which has been proposed extensively, is to improve the properties of synthetic polymer materials by incorporating substances with antistatic properties into them.

Although this method is superior to the above-mentioned method of applying it to the surface in terms of the durability of the effect, when using it in combination,
Since it is already included as part of the synthetic polymer material in the process of manufacturing molded products, films, and synthetic fibers, additives blended as antistatic agents need to satisfy more advanced required characteristics. .

For example, in this method, coloration of the material due to heating during the manufacturing process, reduction of mechanical properties such as strength and hardness of the material due to mixing, lack of compatibility between additives and synthetic polymer materials, and additives that are mixed Problems such as a decrease in transparency due to the particle size and increased stickiness on the surface of the polymer material due to additive bleed-out may occur, and the excellent characteristics of the original synthetic polymer material may be adversely affected. Prone.

The main additives proposed for this method are:
Nonionic surfactants and anionic, cationic,
Amphoteric type ionic surfactants are known.

Nonionic surfactants generally have better compatibility with synthetic polymer materials or less antistatic properties than ionic surfactants, and must be blended in large amounts to obtain sufficient effects. It becomes necessary.

This is undesirable because it causes deterioration in the physical properties inherent in the synthetic polymer material and troubles in the manufacturing process.

On the other hand, ionic surfactants generally have poor compatibility with synthetic polymeric materials and are difficult to uniformly disperse in synthetic polymeric materials.

In addition, ionic surfactants, especially cationic and amphoteric surfactants that contain quaternary nitrogen in their molecules, have low thermal stability; Because it easily absorbs moisture, when actually using it,
There are many difficulties in terms of production methods, equipment, workability, etc., and the reality is that there is currently no product that is sufficiently satisfactory for actual industrial production.

In view of the above-mentioned circumstances, the present inventors have conducted intensive studies to obtain an antistatic agent for synthetic polymer materials that has excellent antistatic properties and has improved the various other drawbacks mentioned above, and as a result, they have arrived at the present invention. It is something.

The second invention is an alkali metal or alkaline earth metal salt of a sulfonate compound having a free carboxyl group represented by the following general formula (1), and a free carboxyl group of the sulfonate compound represented by the general formula (1). This article relates to an antistatic agent for synthetic polymeric materials consisting of one or more salts selected from salts in which a group is neutralized with an amine compound represented by the following general formula (It) or (m). The second invention is an alkali metal or alkaline earth metal salt of a sulfonate compound having a free carboxyl group represented by the following general formula (I), and a free carboxyl group of a sulfonate compound represented by the general formula (1). One or more salts selected from the salts neutralized with amine compounds represented by the following general formula (1) or the symbol, and further have a number average molecular weight of 350 or more and a melting point or softening point of 180°
The present invention relates to an antistatic agent for synthetic polymer materials containing one or more organic oligomers or polymers having a molecular weight of C or higher.

General formula ・R is alkyl with carbon number b to 20 ・M is alkali metal or alkaline earth metal ・n is metal M
The valence number is 1 or 2, R1 and R2 are H1 alkyl having 1 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, HOCmH2m (OCmH2m) or R1゜R2 combined via nitrogen, It is also possible to form 0 and 11.

・R3 is alkyl having 1 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, HOCmH2m(OCmH2m)l-2・
R4C0NT (R5-, R4 is alkyl or alkenyl having 7 to 17 carbon atoms, R5 is alkylene having 2 to 4 carbon atoms, l is 0 to 10, m is an integer of 2 to 4, R6- is H or 1 carbon number ~4 alkyl・RIO is alkylene having 2 to 4 carbon atoms・X is 1 to 4 y is O or 1 In the second invention, the sulfonate compound represented by the general formula (I), the general formula (1 ) and the general formula (II) or (III)
An excellent antistatic effect can be achieved by incorporating one or more salts selected from the salts with amine compounds represented by into a synthetic polymer material. By adding an organic oligomer or polymer having a number average molecular weight of 350 or more and a melting point or softening point of 180°C or less to the synthetic polymer material together with the sulfonate compound described above, the sulfonate compound and the synthetic polymer can be combined. compatibility with materials,
Since the dispersibility is improved, even more remarkable effects can be exhibited.

General formula (I
) α-sulfolauric acid salts include α-sulfolauric acid sodium salt, α-sulfolauric acid potassium salt, α-sulfolauric acid calcium salt, α-sulfopalmitic acid potassium salt, α-sulfostearic acid sodium salt. etc.

Further, as the monoamis compound represented by the general formula (1) used in the present invention, butylamine, octylamine, dibutylamine, dilaurylamine, triethylamine,
Addition of ethylene oxide and propylene oxide to alkylamines such as tributylamine and dimethyllaurylamine, alkanolamines such as monoethanolamine, jetanolamine, triethanolamine, and triisopropanolamine, and monoamine compounds having these active hydrogens. and heterocyclic derivatives such as idoamine derivatives and laurylmorpholine.

Examples of the polyamine compound represented by the general formula (III) used in the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, N, N, N',
Examples include, but are not limited to, N'-tetramethylethylenediamine, methylimidobisprolamine, and the like.

The organic oligomer or polymer used in the second invention is selected from those having a number average molecular weight of 350 or more and a melting point or softening point of 180° C. or less.

There are a wide variety of organic oligomers or polymers that can be used, but representative examples include polymers and copolymers of olefins such as ethylene and propylene, or unsaturated hydrocarbon compounds such as styrene, ethylene oxide, and propylene oxide. Examples include polymers, copolymers and derivatives thereof of alkylene oxide compounds, mesh type polymers such as polyesters and polyamides, paraffins which are long chain hydrocarbons, paraffin waxes and their oxides, but the present invention is not limited to these representative examples.

When using these in the present invention, one or more of these are appropriately selected depending on the type and purpose of the synthetic polymer material used, taking into consideration the type, molecular weight, melting point, softening point, etc.

These organic oligomers and polymers have the disadvantage that if the molecular weight is too low, the mechanical properties of the polymer material may be reduced, or a synergistic effect with the sulfonate compound may not be exhibited and the durability of the effect may be insufficient. Usually, a number average molecular weight of 350 or more is required.

However, if the molecular weight is too high, the viscosity may be too high or the affinity with the sulfonate compound may be insufficient.

However, the upper limit of the molecular weight that can be used varies greatly depending on the type of organic oligomer or polymer and is also related to its melting point and softening point.

When carrying out the present invention, there are no particular limitations on the timing and method of adding the important components of the present invention. Regarding the timing of addition, it may be added at the time of the polymerization reaction, or at the time of melting the polymer or at various steps thereafter. It is possible.

In addition, it is possible to add the sulfonate compound in various processes and in various combinations, or to add it to the polymer material after uniformly dispersing the sulfonate compound and the organic oligomer or polymer. good dispersion into
This is the best method in terms of ease of operation, manufacturing cost, etc.

In carrying out the present invention, the amount of the component of the present invention to be used may be approximately 0.0% based on the polymer material when the sulfonate compound is used alone.
．． The content is preferably 2 to 4% by weight, more preferably 0.3 to 2% by weight.

In addition, when the sulfonate compound and an organic oligomer or polymer are used, the sulfonate compound is in the range of 0.1 to 3% by weight, preferably 0.2 to 2% by weight based on the polymer material, and the organic oligomer Alternatively, the content of the polymer is in the range of 0.3 to 10% by weight, preferably 0.5 to 6% by weight based on the polymeric material.

Further, when the weight ratio of the sulfonate compound of the present invention and the organic oligomer or polymer is 5:95 to 60:40, preferably 10290 to 50:50, a remarkable effect can be exhibited.

When carrying out the present invention, other components may be added for other purposes within a range that does not impair the effects of the present invention.

For example, stabilizers such as antioxidants and ultraviolet absorbers, or surfactants to improve dispersibility may be added, as well as many other additives used in polymeric materials used in plastic molded products, films, and synthetic fibers. Examples include the addition of inorganic compounds.

The polymeric material to which the present invention is applied is not particularly limited, and may be effectively used such as polyethylene, polypropylene, polystyrene, polyester, polyamide, polycarbonate, and the like.

Furthermore, the usage form of the polymeric material to which the present invention is applied is not particularly limited, and the present invention can be effectively used for any polymeric material that ultimately takes the form of plastic molded products, films, fibers, etc. obtain.

Examples of the present invention will be described below, and the effects thereof will be described.
The present invention is not limited to these.

Example 1 100 parts by weight of the slurry of the compound shown in Example 1 (water content 30%) was mixed with 150 parts by weight of styrene oligomer (softening point 75°C, number average molecular weight 400) and 150 parts by weight of isopropyl alcohol.
After heating to 80°C with parts by weight and mixing uniformly,
Water and isopropyl alcohol were distilled off under reduced pressure, and the contents were rapidly solidified to obtain uniformly dispersed pellets (Additive 1).

12.0 parts by weight of the above additives were mixed with 98 parts by weight of polypropylene resin, and 220
Sheet A with a thickness of 0.3 mm was kneaded at ~2300C.
It was created.

100 parts by weight of the slurry of the compound shown in Example 2 (water content 20%) was mixed with 180 parts by weight of polyethylene glycol (melting point 53°C, number average molecular weight 4000) and 1 part by weight of isopropyl alcohol.
After heating and uniformly mixing with 20 parts by weight at 80° C., water and isopropyl alcohol were distilled off under reduced pressure, and the contents were rapidly solidified to obtain uniformly dispersed pellets (additive ①).

Add 1 part of the above additive (■) to 98.5 parts by weight of polypropylene resin.
．． Sheet B was obtained in the same manner as in Example 1 by mixing 5 parts by weight.

50 parts by weight of the slurry of the compound shown in Example 3 (moisture 25%) was heated to 80°C and mixed uniformly with 70 parts by weight of paraffin wax (melting point 49°C) and 80 parts by weight of xylene, and then mixed uniformly under reduced pressure. After water and xylene were distilled off, the mixture was rapidly cooled and solidified to obtain uniformly dispersed pellets (Additive ■).

Sheet C was obtained by mixing 98 parts by weight of the polypropylene resin and 120 parts by weight of the above additive, and extruding the mixture in the same manner as in Example 1.

Sheet D was obtained in the same manner as in Example 1 using 0.6 parts by weight of the compound (dehydrated product) shown in Example 4 and 99.4 parts by weight of polypropylene resin.

Example 5 12.0 parts by weight of the additive obtained in Example 1 and 98.0 parts by weight of low density polyethylene resin were mixed in 25 m5. Sheet E was obtained by kneading at 150 to 160°C using an extruder.

Example 6 1.5 parts by weight of the additive ■ obtained in Example 2 and 98.5 parts by weight of polyester resin were mixed into 270 parts by weight using a 25 mm $ extruder.
Sheet F was obtained by kneading at ~280°C.

Example 7 0.3 parts by weight of the compound (dehydrated product), 10 parts by weight of polyethylene glycol (molecular weight 2000) distearate (melting point 50°C), and 98.7 parts by weight of polystyrene resin were mixed, and the mixture was mixed with a 25 mm $ extruder. 200~210°
C) was kneaded to obtain C)G.

0.3 parts by weight of the compound (dehydrate) represented by, propylene oligomer (melting point 150°C, number average molecular weight 4000) 0
．． Sheet H was obtained by kneading 6 parts by weight and 99.1 parts by weight of low density polyethylene resin at 150 to 160°C using a 25 mm 96 extruder.

0.3 parts by weight of the compound shown in Example 9 (dehydrate), propylene oligomer (melting point 150°C, number average molecular weight 4000) 0
．． Sheet I was obtained by kneading 6 parts by weight of low density polyethylene resin and 99.1 parts by weight of low density polyethylene resin at 150 to 160°C using a 25 mm $ extruder.

Comparative Examples 1 to 4 For comparison, sheets of polypropylene, polyethylene, polyester, and polystyrene resins containing no additives were prepared as blank sheets in the same manner as in the examples, and sheet J,
Then, L and M were obtained.

0.3 parts by weight of the compound represented by and polypropylene resin 9
Sheet N was obtained under the same conditions as in Example 1 using 9.7 parts by weight.

0.3 parts by weight of the compound shown in Comparative Example 6 and polypropylene resin 9
A sheet P was obtained under the same conditions as in Example 1 using 9.7 parts by weight.

Comparative Example 7 Sheet Q was obtained under the same conditions as Example 1 using 0.3 parts by weight of triisopropanolamine, 0.7 parts by weight of propylene oligomer, and 99 parts by weight of polypropylene resin.

The performance of Examples 1 to 9 and Comparative Examples 1 to 7 was measured and the results were as shown in the following table.

The measurement method for the measured values in the table is as follows.

Generated electricity: Measured using the Kyoto University Kaken 2 Rotary Static Tester, load 200 g, rotation speed 300 rp [l11] Measured using the same sheet under conditions of temperature 20° C. and humidity 60%.

Half-life: A sample was charged in a high electric field (10,000 volts), and the time from immediately after the electric field was removed until the charging voltage became half of the initial charging voltage was measured.

Coloration: Observe the coloring status of the sample with the naked eye.

1 part by weight of the compound represented by and polyethylene glycol (
4.0 parts by weight of an additive uniformly mixed with 3.0 parts by weight of distearate (molecular weight 2,000), 9 parts by weight of polystyrene resin
6.0 parts by weight was mixed, and sheet R was prepared in the same manner as in Example 7.
I got it.

6.5 parts by weight of an additive made by uniformly mixing 1.5 parts by weight of the compound shown by 5 parts by weight of propylene oligomer (melting point 150°C, number average molecular weight 4,000), and 93.5 parts by weight low density polyethylene resin. Sheet S was obtained in the same manner as in Example 8 by mixing.

2.5 parts by weight of the compound shown by and styrene oligomer (
7.5 parts by weight of an additive uniformly mixed with 5 parts by weight (softening point: 75°C, number average molecular weight: 400), polypropylene resin (9 parts by weight)
A sheet T was obtained in the same manner as in Example 1 by mixing 2.5 parts by weight.

In addition, the softening point and melting point in the examples are determined by the ring and ball method and the D
This is a value based on the TA method.

The performance of the sheets obtained in Examples 10 to 12 was measured and the results were as shown in the following table.

The measurement method was the same as in the previous table.

The following procedure was carried out under the same conditions as in Example 1, using 0.3 parts by weight of C) and 99.7 parts by weight of a low-density polyethylene resin to obtain C) U.

The performance of the obtained sheet was measured in the same manner as in the other Examples, and the results were as follows.

The above results show that the generated electricity and half-life values of the synthetic resin sheet to which the antistatic agent for polymeric materials of the present invention has been added are blank (sheet made only of synthetic resin) and the conventional antistatic agent for synthetic resins. This result shows that the value is significantly smaller than that of the synthetic resin sheet to which the amine compound is added, and this result clearly demonstrates the excellent effects of the present invention.

Claims (1)

[Scope of Claims] 1. An alkali metal or alkaline earth metal salt of a sulfonate compound having a free carboxyl group represented by the following general formula (1), and a free carboxyl group of the sulfonate compound represented by the general formula (1). An antistatic agent for synthetic polymer materials consisting of one or more salts selected from salts in which groups are neutralized with amine compounds represented by the following general formula (Ill).General formula: R is the number of carbon atoms 6-20 alkyl・M is alkali metal or alkaline earth metal・n is metal M
1 or 2 in the valence number of R,, R2 is H1 alkyl having 1 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, ・R3 is alkyl having 1 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, HOCmH2m(OCmH2tT1)L. R4C0NHR5゜・R4 is alkyl or alkenyl having 7 to 17 carbon atoms, ・R5 is alkylene having 2 to 4 carbon atoms, 1 is 0 to 10, m is an integer of 2 to 4, and R6-R9 is H or 1 to 4 carbon atoms. Alkyl Rlo
is an alkylene having 2 to 4 carbon atoms, One or more salts selected from the salts obtained by neutralizing the free carboxyl group of the sulfonate compound represented by formula (I) with an amine compound represented by the following general formula or (III), and further a number average An antistatic agent for synthetic polymer materials, which is made by adding one or more organic oligomers or polymers having a molecular weight of 350 or more and a melting point or softening point of 180°C or less.General formula: R is 6 to 6 carbon atoms 20 alkyl・M is alkali metal or alkaline earth metal・n is metal M
1 or 2 in valence number ・R1, R2 is H1 alkyl having 1 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, ・R3 is alkyl having 1 to 18 carbon atoms, alkenyl having 8 to 18 carbon atoms, HOCmH2m (OCmH2m)lR4C
ONHR6, -R4 is alkyl or alkenyl having 7 to 17 carbon atoms, -R6 is alkylene having 2 to 4 carbon atoms, l is 0 to 10, m is an integer of 2 to 4, and R6-R9 are H or carbon atoms 1 to 4. Alkyl Rlo
is alkylene having 2 to 4 carbon atoms, X is 1 to 4, and y is 0 or 1