DE1569403B2 - ANTISTATICS FOR RESINS - Google Patents

Description

It is known to impart antistatic properties to synthetic resins by adding various cationic properties surfactants, nonionic surfactants such as alkylene oxide adducts and Fatty acid esters of polyhydric alcohols, various ampholytic surfactants and their Salts with organic amines or with metals, anionic surface-active agents such as phosphates or sulfonates, etc. are incorporated into these resins.

Some conventional antistatic agents among them, e.g. B. cationic and ampholytic surfactants Medium, have a good antistatic effect. Their poor heat resistance forms however, a great disadvantage for their practical use. One wants such antistatic means too To add synthetic resins, the means must withstand the high temperatures in the manufacture of objects can withstand. However, the above antistatic agents are so sensitive to a heating that at such high temperatures they are rapidly decomposed, with the result that not only the antistatic property of the synthetic resins is impaired, but the synthetic resins too discolor (or yellow).

Other conventional antistatic agents such as anionic and nonionic surfactants have good heat resistance. However, their antistatic effect is insufficient.

The subject of the invention is the use of a mixture or a compound with an ionic bond from 0.2 to 4.0 parts (A) of at least one surface-active Substance with at least one quaternary basic nitrogen atom, the at least one the organic radicals alkyl-, acyloxyalkyl, alkoxyalkyl, alkylaryloxyalkyl, N-acylaminoalkyl, alkylpolyoxyalkylene and alkylaryl polyoxyalkylene having at least 10 carbon atoms in direct association containing the quaternary basic nitrogen atom, and 1.0 part of (B) at least one anionic Surface-active phosphate with at least one alkyl polyoxyalkylene, alkenyl polyoxyalkylene or Alkylarylpolyoxyalkylene radical each having at least 10 carbon atoms as an internal antistatic agent for organic polymeric plastics or rubber in amounts of 0.05 to 5.0 percent by weight on the weight of the polymers.

It has been found that synthetic resins are given such excellent antistatic properties as without compromising the various physical properties of the resins for practical purposes.

The use of the mixture according to the invention

or connection offers surprising advantages. First of all, it should be pointed out that the mixture or compound can be used as an internal antistatic for plastics, ie. she can do that. Plastic is added before processing and is permanently bound by the homogeneous distribution in the plastic, so that abrasion, etc. does not reduce the antistatic properties once given. So far known, structurally comparable chemical compounds are inferior to the compounds or mixtures used according to the invention by a factor of about 10 ³ , as are known, only superficially applied surface-active substances, which also contain phosphorus-containing surface-active substances, but with different chemical bond ratios on the phosphorus atom, the ones in the Inferior mixtures or compounds used in the invention. Furthermore, a limited mixing ratio of the two components A and B is necessary to achieve the desired effect. It can therefore be stated that the selection of the compounds used according to the invention, in particular the phosphorus-containing surface-active component B from a large number of known, phosphorus-containing surface-active substances, makes the use according to the invention quite inventive

is. ■.; .

The antistatic properties became various antistatic agents according to the present invention as well as antistatic agents which are structurally similar to these. Specifically, the compounds labeled I to XI were used, wherein the compounds I to IV are antistatic agents according to the invention.

The antistatic agents V to XI correspond to the compounds listed in the following patents :

V, VI U.S. Patent 2,653,113,

VII British patent specification 700 356,

VIII, IX German Auslegeschrift 1 034 849,

X, XI German interpretation document 1091 978.

The molar ratio of monoester to diester is in the compounds I to IV, VIII and IX the list about 1: 1.

. Antistatic N-containing surfactants C ₁₂ H ₂₅ l i — CH ₃ · CH ₃ SO ₄ - I — CH ₃ · CH ₃ SO ₄ - ^ CH ₂ CH ₂ 0H weight Anionic surfactants weight middle formula : CH ₃ > ■. CH ₃ 10.2 formula 7.0 • ι O ONa
II /
Q ₂ H ₂₅ O (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ O-P '. 'N- (
C ₁₁ H ₂₃ C
■ \ H *
¹ - ■ ■ '■■ ■■''"N ( ONa : h ₂
• CH ₃ SO ₄ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ OO
PONa CH ₃ ■. · .- · ■ .. ■ IN ■. - - viii. - ■ _
· ■ · ■ -. ■. ·: ■ : ■, ■■: ■ / \ ■ ■■; · ■ -
\\ % CH ₃ CH ₂ CH ₂ OH Q ₂ H ₂₅ 0 (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ 0 j Q ₂ H ₂₅ -? : CH ₂ CH ₂ OH
'/. Vf-CH ₂ CH ₂ OH ■ CH ₃ SO ₄ - ■ ', .- NH _; ... 10.2 the same 7.0 II CH ₃ : CH ₃ V C ₁₁ H ₂₃ CONH (CHa) ₃ -l 12.7 the same 7.0 III O ONa
/ Λ II /
C ₉ H ₁₉ ^ f VO (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ OP
ONa
C ₉ H ₁₉ - / ~ 0 (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ OO
P-ONa
C ₉ H ₁₉ - ^ XO (CH ₂ CH ₂ O) ₉ CH ₂ CH ₂ O 11.8 OC ₁₂ H ₂₅ 11.0 IV O = P-OH
\ \
OH 10.5 27.6 ■ .: ' ^v v, ..-

N-containing surfactants CH _{3 Sequel:} Anionic surfactants OC ₂ H ₅ weight Antistatic ■ '. formula C ₁₈ H ₃₇ -N-CH ₃ CH ₃ SO ₄ - formula P-OC ₂ H ₅ ' 27.6 middle CH ₂ CH ₂ OH
CH ₃ -N CH ₃ weight OC ₁₂ H ₂₅
O = P-OH
\ NHC ₁₈ H ₃₇ -; ■ VI CH ₂ CH ₂ OH 11.9 \
OH OC ₂ H ₅ 28.8 CH ₂ CH ₂ OH
ν N-CH ₂ CH ₂ OH
CH ₂ CH ₂ OH C ₁₂ H ₂₅ OSO ₃ Na O = P-NHC ₁₈ H ₃₇₁ VII (
+
QHi ₇ ί
( 14.9 7.4 : h ₃
i - CH ₃ -Cl "-
: h ₃ O ONa
II /
C ₁₂ H ₂₅ OP
ONa
C ₁₂ H ₂₅ OO
\ ll
P-ONa NHC ₁₈ H ₃₇ VIII 6.2 C ₁₂ H ₂₅ O 7.4 the same DC 12.7 X ■. "■. ■ XI

Cn CJ) CD

In the following comparative tests, the antistatic agents or their starting materials shown in the table were used. Agent I was prepared by mixing 7.0 parts by weight Natriumdecaoxyäthylenglykollauryläther - phosphates (molar ratio of mono- to di = 1: 1) with 10.2 parts by weight Lauryltrimethylarrimoniummethylsulfat at 60 to 70 ⁰ C.

The antistatic agents II to VII were also prepared by appropriately mixing the two components in the amounts given in the list at a temperature of 60 to 70 ° C. ^;

The antistatic agents VIII and DC were made by mixing the 50% solution of the compounds in isopropanol at 60 to 70 ° C and distilling off the Solvent produced by reduced pressure.

1.5 parts by weight each of the antistatic agents I to XI, 1.0 part by weight of dibutyltin dilaurate and 100 parts by weight of a powder of vinyl chloride / vinyl acetate copolymer (the vinyl acetate content was about 13 percent by weight of the total amount, the average specific viscosity about 0.25 and the average degree of polymerization about 450) were placed in a ball mill for uniformity. After the mixture was allowed to stand 12 hours at about 40 ⁰ C, it was extruded into films of 0.5 mm thickness at a molding temperature of 14O ⁰ C. The copolymer films containing no antistatic agents were prepared in the same manner as above.

Furthermore, 1.5 parts by weight of the antistatic agents I to XI were added to 100 parts by weight of ABS pellets (acrylonitrile - butadiene - styrene - synthetic resin, Rockwell hardness = 112, density = 1.06 g / cm ³ ). After combining, the mixture was ground evenly and injection molded to give sheets 2.0 mm thick at a die head temperature of 210 ^{° C.} The ABS panels containing no antistatic agent were made in the same manner. The films and plates produced in this way were cut into test samples with a size of 2.5 cm × 3 cm. Each sample was then stored for 24 hours at 20 ° C and a relative humidity of 65%.

The electrical surface resistance was determined under the above-mentioned environmental conditions using a "Super Megohmmeter Model SM-10" (manufacturer TOA ELECTRONICS, LTD) . >'' ^: ■ ''·; · ■■ - '' · ■ ■ '■'' ^:;

- The results are shown in the following table :: "■ - ^> - _: ■ '-' ■ ■■ '·· ■ - ^ -'- ■ " -

continuation

Surface electrical resistance (Ohm)

.7.,. I; -Anti-,. ··· '.
static
", .Medium vinyl
chloride/
Vinyl-
acetate-
Copoly-
merisat SECTION : '".'"''-'I/■'.-'' ■■: ■ ■ ■ ■ '
Remarks I.
-II
/ III
IV 8 IO ¹⁰
6-10 ¹⁰
2 -W ⁰
4 ■ l & ° 9.TlO ¹⁰
8-10 ¹⁰
4-1O ¹⁰
7 · 10 ¹⁰

55

60

Anti
static
middle vinyl
chloride/
Vinyl-
acetate-
Copoly-
merisat SECTION Remarks V 2 · 10 ¹³ 9-1O ¹³ low thermal stability VI 3 ■ IO ¹³ 7 · 10 ¹³ VII 4-10 ¹⁴ 8 · 10 ¹⁴ low thermal stability
and compatibility VIII 1 -1O ¹² 2 ■ IO ¹² low tolerance IX 2-1O ¹² 7 - IO ¹² low tolerance X 1-10 ¹⁴ 5 ■ IO ¹⁴ XI. 3 ■ 10 ' ⁴ 8-10 ¹⁴ Control. 1 10 ¹⁵ 5 IO ¹⁵

From the table above it is clear it can be seen that the antistatic agents according to the invention, namely compounds I to IV, are more effective than conventional means are.

As a surface-active agent (A) according to the In the invention, any of the conventional surfactants within the scope of the claim are used will. They can be divided into cationic and ampholytic surfactants. Carbon numbers of the organic radicals from 12 to 26 have proven to be particularly suitable.

Illustrative examples of cationic surfactants are salts of quaternary ammonium, e.g. B. alkyltrimethylammonium salts, Diälkyldiäthylammoniumsalze, Alkyldimethylbehzylammoniümsalze, alkyl-zS-hydrokyathyldimethylammoniumsalze, alkyltri - (/ S-hydroxyethyl) -ammoniümsalze, AIkoxyalkyltriäthylammoriiumsalze, Älkbxyalkyltrirhe-, thylammoniumsalze, Alkoxyalkyldi - (/ S-hydroxyethyl) -methylammoniumsalze, ⁷ N-Acyiärhinoalkyldiäthylbenzylammoniumsalze, · ■ N ^ acyläminöalkyltrimethylammoniumsalze, N-acylamirioalkyldiäthylmethylam- moniurhsalze ■ "■" ■ Alkylpolyoxyalkylentriäthylammohiumsalze and _{Alkylarylpölyöxyalkylentrimethylammo:} niümsälze: [beispielswöise with deri-counter Anibnen hydroxyl;. ! Halide - (GT, Βτ ~% t- CH ₃ OSO ^ V CH ₃ CH ₂ OSO ₃ -, CH ₃ C ₆ H ₄ SO ₃ -, NO ₃ - '- and ClO ₄ -G, and the heterocyclic compounds, such as N -alky! pyridinium salts, 1-methyl-1-hydroxyethyl-2-alkylimidazolinium salts, N-alkylmethylpiperizinium salts ^: and N - "- alkylmethylmorpholium salts [for example with the counter-anions hydroxyl, halide (Cl", Br "); CH ₃ OSO ₃ -, CH ₃ CH ₂ OSO ₃ -, CH ₃ C ₆ H ₄ SO ₃ -, NO ₃ - and ClO ₄ ]; - ^; i _; C

Illustrative examples of hemolytic surfactants that can be used in accordance with the invention ^; are compounds with at least one quaternary nitrogen atom; these can be classified into compounds with a carboxy, sulfo, phosphono, etc. radical: '; . ■

Examples of compounds with carboxy radicals are alkyldimethylbetaine, Al-

309 522/508

kyldi - (/? - hydroxyethyl) betaines, N-acylaminoalkyldimethyl betaines, N - acylaminoalkyldi - (ji - hydroxyethyl) betaines, dialkyl - ^ - hydroxyethyl betaines, alkoxyalkyl diethyl betaines, bis- (alkylaryl) -hydroxyethyl betaines, alkylaryl compounds and l-hydroxyethyl-l-carboxymethyl-2-alkylimidazolines. As examples of compounds having Sulforadikalen be mentioned alkyl dimethyl-y-sulfopropylammoniumverbindungen, alkyl di - (/ J-hydroxyethyl) - γ - sulfopropylammoniumverbindungen, Dialkylmethyl - β - sulfoäthylammoniumverbindungen, Acyloxyalkyldimethyl - γ - sulfopropylammoniumverbindungen, N - Acylaminoalkyldimethyl - γ - sulfopropylammonium compounds and 1- Hydroxyethyl -1 - γ - sulfopropyl - 2 - alkylimidazolinium compounds.

Furthermore, the salts of the aforementioned ampholytic surface-active agents can also be used will.

Examples of anionic surface-active phosphates (B) are mono- and dialkyl polyoxyalkylene phosphates, Mono- and dialkenyl polyoxyalkylene phosphates, mono- and dialkylaryl polyoxyalkylene phosphates.

Illustrative examples of cationic counter ions are hydrogen ions, ammonium ions derived from amines, and metal ions such as Na ⁺ , K ⁺ , Ca ⁺⁺ , Mg ⁺⁺ , Ba ⁺⁺ , Zn ⁺⁺ , Sn ⁺⁺ , Sn ^{++ + +} and Al ⁺ " ¹ " ⁺ , with Na ⁺ and K ^{+ being} the most suitable. . . ■

Alkyl phosphates having 10 to 22 carbon atoms are particularly suitable for the purposes of the invention in the alkyl radical al.

The antistatic agent of the invention can be manufactured in various ways. It is however, it is usually advantageous to combine one of the aforementioned surfactants with the other Mix and melt the mixture by heating. Solvents such as ethanol can be used will. The by-produced salt can be removed if desired.

With regard to the synergistic effect between two surfactants as described above is generally believed to be used to form a strong or loose ionic bond when the two surface-active substances are mixed, a certain reaction must occur between them.

Some of the antistatic agents of the invention can be prepared by mixing an acidic anionic surfactant with a primary, secondary or tertiary amine and reacting the amine salt with alkylene oxides (finally, quaternary ammonium compounds are obtained). _r

There are various methods of imparting antistatic properties to synthetic resins according to the invention. For example, the antistatic property can be given to synthetic resins by either

1. the antistatic prepared in the above-mentioned manner Means yourself or

2. each component of the antistatic agent separately to the resins or their raw materials in any manufacturing process of the resins clogs.

In either case, however, it is necessary that the two types of surfactants be uniform are mixed into the synthetic resins.

As the preferred concrete operation in the above-mentioned Method 1, one method is adopted after which the antistatic agent is used in the manufacture of various items such as Form-i, bodies, fibers or films are added to the powder or pearls of the synthetic resins. Solvent like Methanol, ethanol, isopropanol, acetone, benzene and toluene can be used to create a homogeneous To facilitate mixing of the antistatic agent and the synthetic resins. These solvents can also can be used in method 2 mentioned above. Conventional additives such as resin stabilizers, Mold lubricants and pigments can be used in the antistatic agent of the present invention or in the surface active agents Substances that make up its components are incorporated.

The present invention can be advantageously applied to synthetic resins used for developing a electrostatic charge on their surfaces,

z. B. polyethylenes, polypropylenes, polystyrenes, polyamides, polyvinyl chlorides, ABS resins and synthetic resins Types of rubber, as well as natural rubber, to reduce the electrostatic charge to the Surfaces of moldings, fibers, films and other objects made from these materials to prevent.

, Examples

The antistatic agent according to the invention imparts the synergistically good antistatic property to synthetic resins and is thermally stable. The results of experiments are shown in Tables 1 to 3, and the Experimental methods were as follows:

1. Measurement of static electricity

The synthetic resin to which the antistatic agent was incorporated became sheets (0.2 mm or 0.1 mm thick), bottles (wall thickness 1 mm) or threads. Sheets and bottles became test pieces cut with a size of 2x3 cm. Each sample was then stored for 24 hours at the temperature and relative humidity indicated in each table conditioned.

The static electricity was measured by placing the test piece or the combed threads under the above condition against a clean cotton cloth using the Rotary Static Tester KOA SHOKAT CO., LTD., Was used. The number of frictional revolutions of the apparatus drum was 800 per minute. .

2. Measurement of the specific resistance

Using a super megohmmeter model SM-IO of the company TOA ELECTRONICS LTD. the specific electrical resistance (surface and / or volume resistance) of the test piece under the same conditions as measured before.

3. Cigarette ash test

A test piece was rubbed 30 times with a clean cotton cloth and rubbed 1 cm above the fresh one Cigarette ash was held, and it was observed whether there was any under the same condition as above showed electrostatic attraction or not.

Table 1
Polypropylene resin

No. Antistatic agents Conc. Frictional
electricity (V) Speci
Wide
surface
(Ohm) isher
rstand
volume
(Ohm / cm) Cigarettes
ash test temperature
and relative
humidity Discoloration compatibility shape De-
mingling
tem-
temperature
( ⁰ C) 1 Stearyl di (^ - hydroxyethyl) betaine _; (A) 5 x 10 " * not pale yellow Well foil
(0.2 mm) Sodium diethylene glycol stearyl ether
phosphate (B) 1.2 4 · 10 ¹² weak 20 ⁰ C
65% colorless bad the same (A) I (B) = 7: 3
heated and mixed at 80 to 90 ⁰ C. 7.5-10 ¹⁰ not colorless Well the same N-CH ₂ (C) 500 to 700 nearly pale yellow Well the same Q7H35- C.
I.
/
HIGH ₂ CH ₂ not 2. +
sT-C
: h ₂ c 3000 to 4000 . weak 20 ⁰ C
65% pale yellow satisfactory foil
(0.2 mm) 250 ITT
IH ₂ CH ₂ SO ₃ - 1.0 1500 to 2000 weak colorless bad Di - (/ 3-hydroxyethyl) stearylamine (D) 100 to 200 not colorless satisfactory the same 3 Sodium decaethylene glycol lauryl
, ätherphpsphat: (E),:.:,., 0 10,000 <10 ¹⁶ <10 ¹⁶ strong 20 ⁰ C
65% colorless - the same 250 (C): (D): (E) = 5: 3: 2
mixed and heated to 80 to 90 ° C control

Table 2
Polyethylene resin

No. Antistatic agents Cone. Frictional
I electricity (V) Spec
Wide
surface
(Ohm) isher
was standing
volume
(Ohm / cm) Cigarettes
ash test temperature
and relative
humidity Discoloration compatibility shape De-
mingling
tem-
temperature
("C) 4th Lauryltriimethylammonium methosulfate (F) 300 to 500 7 · 10 ¹¹ weak pale yellow Well foil Sodium triethylene glycol cetyl ether
phosphate (G) 1.0 1000 to 1500 4 · 10 ¹² weak 20 ° C
• 50% colorless bad foil 210 (F) :( G) = 4: 6 ' 15 to 40 5.2 x 10 ° not colorless Well foil (F): (G) = 6: 4,
heated and mixed at 80 to 9O ⁰ C 30 to 40 5.5 ■ 10 " not almost colorless Well foil 5 Monobehenin (H) 500 to 600 strong colorless satisfactory thread Potassium pentadecaethylene glycol behenyl
ether phosphate (I) 800 to 1200 weak colorless bad thread 1.5 200 to 300 nearly
not 10 ⁰ C
60% pale yellow Well thread 210 N-CH ₂ (J) 70 to 100 not colorless Well thread 6th C17H35-C.,
; ^{v :: i: i} --- N ^ c
_ ,,,.,; - _; ^CI ? 3. ⁽ 0 10,000 < 10 ¹⁵ < strong 20 ° C
50% colorless foil 210 : h ₂
: h ₂ ch ₂ oh (H): a): (J) "= 7: 1: 2
heated and mixed at 80 to 9O ⁰ C control

r--, 1

Table 3
PVC resin

No. Antistatic agents + (K) middle Cone.
% Frictional
electricity (V) Speci
Wide
surface
(Ohm) isher
rstand
volume
(Ohm / cm) Cigarettes
ash test temperature
and relative
humidity Discoloration compatibility shape De-
mingling
tem-
temperature
(° Q ClO ₄ - Potassium penta ethylene glycol lauryl ether
phosphate (L) 7th (K): (L) = 7.5: 2.5 2.5 · 10 ¹² 2 · 10 ^U not pale yellow Well foil CH ₂ CH ₂ OH " control 1.0 25 ° C
65% QeH ₃₇ -I
( Conventional anti-static
for PVC 3 · 10 ¹⁴ 3.5 ¹⁰ strong colorless bad foil 150 T-CH ₂ COOH
: h ₂ ch ₂ oh 1.5-1O ¹² 6.5 · 10 ¹⁰ not colorless Well foil 8th O 4500 to 5000 4.0-10 ¹⁴ 5 · 10 ¹⁴ strong 20 ⁰ C
65% colorless foil 150 9 1.0 1 · 10 ¹² 8 ■ 10 ¹⁰ " not 20 ⁰ C
65% Brown Well foil 150

Tables 1 b _; Figure 3 shows that the synthetic resins to which antistatic property has been given according to the invention have a lower static electricity or a lower specific resistance than the same synthetic resins when they were treated with only one of the surfactants. A synergistic antistatic property can therefore be found.

Furthermore, Tables 1 to 3 show that the antistatic agents according to the invention have good thermal stability in the synthetic resins.

The antistatic agents according to the invention show good compatibility with the synthetic resins and are free from an excessive tendency to bloom, what is due to the combination of the two types of surfactants as components.

For the examples in Table 3, 0.75 part of the salt of an ampholytic surfactant (K), 0.25 part of potassium pentaethylene glycol lauryl ether phosphate were used (L), 50 parts of dioctyl phthalate, 2.0 parts of dibutyl tin dilaurate, 0.6 part of cadmium stearate and 0.4 part of barium stearate to 100 parts of polyvinyl chloride powder added. After uniformly blending in, the mixture was ground and formed into sheets 1 mm thick. They were also made from the same polymer Films produced as above, each containing the components, i.e. the surface-active substances (K) and (L). The antistatic and thermal properties of these films are shown in Table ^ (No. 7).

Claims (1)

Claim: Use of a mixture or a compound having an ionic bond of 0.2 to 4.0 parts (A) at least one surfactant with at least one quaternary basic nitrogen atom, the at least one of the organic radicals alkyl, acyloxyalkyl, alkoxyalkyl, alkylaryloxyalkyl, N-acylaminoalkyl, alkyl polyoxyalkylene and alkylaryl polyoxyalkylene having at least 10 carbon atoms in direct association with the quaternary basic nitrogen atom erit- holds, and 1.0 parts of (B) at least one anionic phosphate surfactant with at least an alkyl polyoxyalkylene, alkenyl polyoxyalkylene or alkylaryl polyoxyalkylene radical with at least 10 carbon atoms each as an internal antistatic agent for organic polymers Plastics or rubber in amounts of 0.05 to 5.0 percent by weight based on weight of the polymers.