JPH03182541A - Antistatic chlorinated vinyl chloride resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention relates to antistatic chlorinated vinyl chloride resins. In particular, the present invention relates to a chlorinated vinyl chloride resin that has good band-it prevention properties while retaining the excellent heat resistance of the chlorinated vinyl chloride resin.

(Prior Art) Chlorinated vinyl chloride resin (hereinafter referred to as CPVC) is produced by chlorinating vinyl tetrachloride resin (hereinafter referred to as PvC). CPVC is widely used in place of PvC as it retains the excellent weather resistance, chemical resistance, flame resistance, dimensional stability, etc. of PvC, and improves the low heat resistance, which is said to be a drawback of PvC. I am trying to do.

For example, packaging members and transport members for IC components such as IC cases and carrier cases have been made from PvC. However, since PvC has poor heat resistance, it sometimes deforms during storage or transportation.

Therefore, packaging members and transport members for these IC parts have come to be made using CPVC instead of PvC.

By the way, when packaging members for IC parts and the like are made using CPVC, the chargeability of CPVC has once again become a problem. This is a drawback in that CPVC has a high electrical insulation property, so it is easily charged with static electricity, and therefore dust is likely to adhere to it. To prevent static electricity, there is a method of applying an antistatic agent to the surface of a packaging member, etc., but this method is not reliable because the antistatic effect is limited to the surface only. Therefore, it has been desired to create a CPVC composition having antistatic properties by incorporating an antistatic agent into CPVC.

Not limited to CPVC, but generally when kneading a chemical agent into synthetic resin, the chemical agent is synthetic 4! It often lowers the softening point of r-fat. For this reason, when chemical agents are mixed in, the heat resistance of the synthetic resin decreases.

Although CPVC is characterized by good heat resistance, it was necessary to avoid a decrease in heat resistance at all costs. Therefore, while maintaining the heat resistance of CPVC,
There was a desire for a CPVC composition with antistatic properties.

(Problems to be Solved by the Invention) The present invention has been made with the object of providing a CPVC composition that has excellent antistatic properties without impairing the good heat resistance of CPVC. .

(Means for Solving the Problems) In order to solve the above problems, the inventor kneaded various antistatic agents into CPVC, and the obtained CPVC [
The chargeability of the power was tested. As a result, when various cationic antistatic agents were mixed into CPVC, the resulting CPV
It has been found that the C composition has excellent antistatic properties. This invention was made based on such knowledge.
This relates to an antistatic (pvcpAt product) obtained by adding 1 to 4 parts by weight of a compound represented by the formula as an antistatic agent to -33 parts by weight.

Cocote, in the formula R1 is an alkyl group having 4-10 carbon atoms,
R,, R3 and R1 represent an alkyl group or a hydroxyalkyl group having 1-4 carbon atoms.

The CPVC used in this invention is not particularly limited in its manufacturing method.

As mentioned above, CPVC is produced by chlorinating PvC, and in that case, PvC can be chlorinated by various methods such as a gas phase method, a solution method, and a suspension method. The CPVC used in this invention may be chlorinated by any of these methods. In addition, PvC in this case is not only a homopolymer of vinyl chloride, but also α-olefins such as ethylene and propylene, vinyl monomers such as vinyl acetate, and acrylates such as 2-ethylhexyl acrylate and butyl methacrylate. It may also be a copolymer of a vinyl chloride monomer, such as vinylidene chloride, and vinyl chloride. Also, CPV
There is no particular restriction on the chlorine content of C. However, cp
As vc, one containing #1!1 outside 62-70 weight is preferable.

There are no particular limitations on the manufacturing method for PvC, which may be mixed into CPVC if necessary. That is, Pvc is the suspension method;
Those produced by either the bulk method or the emulsion polymerization method can be used. In addition, PvC can be used not only for vinyl chloride homopolymers, but also for α-olefins such as ethylene and propylene, vinyl monomers such as vinyl acetate and vinyl stearate, and 2-ethylhexyl acrylate and butyl methacrylate. Acrylic and methacrylic monomers,
A copolymer of vinylidene chloride or the like and vinyl chloride, a graft polymer obtained by grafting vinyl chloride onto ethylene/vinyl acetate or polyurethane may also be used.

In this invention, P for 100-67 parts by weight of CPVC.
Mix o-33 parts by weight of VC. In this case, the total amount is 100 parts by weight. The reason why Pvc is limited to 0-33 parts by weight is that when Pvc exceeds 83 parts by weight, cpv
Not only does it impair the performance of the band 1, which is the original purpose of this invention! However, the prevention performance and heat resistance cannot be exhibited.

In this invention, it is necessary to add 1 to 4 parts by weight of a compound represented by the general formula as an antistatic agent to 100 parts by weight of CPVC or PVC. Here, R1 is an alkyl group having 4 to 10 carbon atoms, and R2, R3 and R4 are an alkyl group or a hydroxyalkyl group having 1 to 4 carbon atoms. R,
, R, , R, and R4 are limited to the above ranges because:
If the number of carbon atoms in R1 is 3 or less, there is a problem in manufacturing and stability. If R1 has 11 or more carbon atoms, or if R, R, and R4 have 5 or more carbon atoms, This is because the antistatic properties are low.

Further, the reason why the amount of the antistatic agent represented by formula 1 is limited to 1-4 parts by weight is that if it is less than 1 part by weight, the antistatic effect will not be sufficiently exhibited, whereas if it exceeds 4 parts by weight, Thermal stability deteriorates, resulting in coloring, and CPV
This is because it will impair the performance of C.

When processing the composition according to this invention, generally CPV
Various chemical agents added during the processing of C may be added as necessary. For example, lubricants, stabilizers,
Processing aids, reinforcing agents, plasticizers, antioxidants, UV absorbers, pigments, fillers, etc. can be added.

As the lubricant, those commonly used for processing CPVC and PVC can be used.

For example, stearic acid, oleic acid, lysyllic acid, hydroxystearic acid, etc. Acids, their metal salts such as magnesium, aluminum, calcium, lead, zinc, and barium, higher alcohols such as stearyl alcohol and oleyl alcohol, and these alcohols and the above organic acid tonoesters, halaffin wax, polyethylene wax, etc. waxes can be used.

As the stabilizer, generally a stabilizer for CPVC or PVC can be used. For example, tin-based stabilizers such as diptyltin malate, dioctyltin malate polymer, diptyltin laurate, monomethyltin bis(in-octylmercaptoacetate), lead-based stabilizers such as tribasic lead sulfate, dibasic phosphite, etc. , epoxy stabilizers, phosphate ester stabilizers, calcium/zinc stabilizers, barium/zinc stabilizers, etc. can be used.

Processing aids and reinforcing agents include methyl methacrylate/styrene copolymer (MBS) and acrylonitrile.

Butadiene-styrene copolymer (ABS), chlorinated polyethylene, copolymer of methyl methacrylate and nistert acrylate, ethylene-vinyl acetate (EVA), acrylonitrile-butadiene copolymer (NBR), etc. can be used. . The amount of these used is preferably 10 parts by weight or less per 100 parts by weight of the resin.

Examples of plasticizers include 7tal I! such as dioctyl phthalate and diisodecyl phthalate. , 1%,) limellitic acid type,
Polyester, chlorinated paraffin, etc. can be used. However, since these plasticizers reduce the heat resistance of CPVC, the amount used is 5 parts by weight or less per 100 parts by weight of the resin.

As the antioxidant, either phenol type or thio type can be used, but hindered phenol type is particularly effective in improving thermal stability, and it is preferable to use 5-2 parts by weight of Q.

Calcium carbonate, clay, talc, mica, etc. can be used as the filler, but since these deteriorate the physical properties of the composition, it is better not to use them unless particularly necessary.

(Effects of the Invention) The composition according to the present invention has 1 to 4 parts by weight of the compound represented by formula 1 added to 100 to 67 parts by weight of CPVC, so it has antistatic properties without reducing the heat resistance of CPVC. It has become a thing with.

Therefore, when a molded article is made from this composition, the resulting molded article not only has the excellent weather resistance, chemical resistance, and flame retardancy inherent to CPVC, but also has high heat resistance and is difficult to charge. It is difficult to adsorb dust, etc., and is therefore suitable for making containers for IC parts and the like. Moreover, since this molded product is made from a composition and the compound of formula 1 is uniformly kneaded into the CPVC, it retains its non-static property for a long time, unlike products where only the surface is subjected to charging treatment. It is excellent.

Furthermore, since we decided to add 0 to 33 parts by weight of PVC as necessary, without significantly impairing the characteristics of CPVC,
The bottom shape of the composition can be easily formed and the price can be reduced. In this way, the present invention provides a cp with antistatic properties.
This is a great benefit in that it can provide a VC set of precepts.

(Example) The reasons why the composition according to the present invention is excellent will be specifically explained with reference to Examples and comparative examples. In the following, parts simply mean parts by weight.

Example 1 CPVC with a chlorine content of 65% by weight (manufactured by Tokuyama Tanezuisha) 1
00 parts, 1.5 parts of dioctyltin mercaft (manufactured by Nitto Kasei Co., Ltd., TVS #8831) as a stabilizer, and dioctyltin malate polymer (manufactured by Nitto Kasei Co., Ltd., TVS #8).
813) 0.5 part and stearic acid monoglyceride (
1.5 parts of Monogly MB (manufactured by Nihon Yushi Co., Ltd.) and stearic acid (manufactured by Yoken Fine Chemicals Co., Ltd., F-3) as a lubricant.
) 1.0 part and a hindered phenolic antioxidant (
1 part of Irganox 1076 (manufactured by Ciba Geigy), 15 parts of MBS resin (manufactured by Kane Ace B-31, manufactured by Kanebuchi Chemical Co., Ltd.) as a processing aid, and 3 parts of a compound represented by the molecular formula as an antistatic agent, It was made into a mixture.

After roll kneading this mixture at 200℃, 190℃
A plate-shaped molded product was obtained by pressing for 7 minutes.

Regarding this plate-shaped molded product, the surface resistivity value was measured at 20°C and 50% relative humidity, and the Kratschberg softness temperature was measured to determine the temperature that indicates heat resistance. The yellowness difference ΔE with respect to a standard white plate was measured using a color difference meter manufactured by Co., Ltd., and was defined as the initial coloring property. The surface resistivity value is 2X10! ;), and the heat resistance is 87°C,
Initial colorability was 42. Therefore, this composition has C
It was recognized that it has antistatic properties while maintaining the properties of PVC.

Example 2 Completely the same as Example 1 except that the amount of CPVC used in Example 1 was reduced to 80 parts, PVC was used 20 parts, and the amount of antistatic agent was increased to 4 parts. A plate-shaped molded product was obtained.

The physical properties of this molded article were measured in exactly the same manner as in Example 1.

The surface resistivity of the molded article was 1X10,Q, the heat resistance was 83°C, and the initial colorability was 35.

Therefore, it was recognized that it had good antistatic properties without impairing the properties of CPVC.

Example 3 In Example 1, except that CPVC with a chlorine content of 68% by weight was used, Example f! A molded article was obtained by processing in exactly the same manner as g1, and its physical properties were further measured.

The surface specific refraction value of the molded product is 3X10. 2, heat resistance was 95°C, and initial colorability was 48. Therefore, it was recognized that O had good antistatic properties while maintaining the characteristics of CPVC.Example 4 In Example 1, the antistatic agent was changed to molecule CH.

CH.

A molded article was obtained by processing in exactly the same manner as in Example 1, except that 3 parts of the compound represented by was used, and its physical properties were further measured.

The surface specific resistance value of the molded article was 3×10 2 , Q, the heat resistance was 86° C., and the initial colorability was 40.

Therefore, it was recognized that it had good antistatic properties while maintaining the characteristics of CPVC.

Comparative Example 1 A molded article was obtained by processing in exactly the same manner as in Example 1, except that no antistatic agent was used, and its physical properties were further measured.

The surface specific resistance value of the molded article was 3×10 ff, the heat resistance was 87° C., and the initial colorability was 38.

Therefore, it was recognized that although the properties of CPVC were maintained, the antistatic properties were insufficient.

Comparative Example 2 In Example 1, the amount of antistatic agent used was reduced to 0.
A molded article was obtained by processing in exactly the same manner as in Example 1, except that the amount was changed to 5 parts, and its physical properties were further measured.

The surface resistivity value of the molded product is 2X10. 17, heat resistance was 87°C, and initial colorability was 40.

Therefore, it was recognized that although the properties of CPVC were maintained, the antistatic properties were insufficient.

Ratio 1 Example 3 In Example 1, the antistatic agent was changed, and in formula 1 of the general formula of the antistatic agent, R1 was CI2 R25,
R2, R, and Toha both have CH2F, and R4 has C, H, and T.
Cf(.

A molded article was obtained by processing in exactly the same manner as in Example 1, except that 3 parts of the compound represented by was used, and its physical properties were further measured.

The surface resistivity value of the molded article was lXl0.2, the heat resistance was 81° C., and the initial colorability was 42.

Therefore, it was recognized that both heat resistance and antistatic properties were inferior.

Comparative Example 4 In Example 1, the antistatic agent was changed, and in formula 1, R1, R2 and R8 are all C, H, A, and R
A molded article was obtained in exactly the same manner as in Example 1, except that 3 parts of a compound where 2 was C2H, that is, a compound represented by the formula % was used, and its physical properties were measured.

The molded article had a surface resistivity of 8×10 g, a heat resistance of 79° C., and an initial colorability of 43.

Therefore, it was recognized that the heat resistance was poor and the antistatic property was also poor.

Comparative Example 5 In Example 1, CPVC was not used and PVC was used instead.
A molded article was obtained by processing in exactly the same manner as in Example 1, except that 100 parts of VC was used, and its physical properties were further measured.

The surface resistivity value of the molded product is 5X10! 2, heat resistance was 63° C., and initial colorability was 24.

Therefore, it was recognized that not only the heat resistance was poor, but also the antistatic property was poor.

Comparative Example 6 In Example 1, the amount of CPVC used was reduced to 50 parts, and 50 parts of PvC was used instead to reduce the total resin to 10 parts.
A molded article was obtained by processing in exactly the same manner as in Example 1, except that the amount was 0 parts, and its physical properties were further measured.

The surface specific resistance value of the molded article was 1X10.0, the heat resistance was 75° C., and the initial colorability was 88.

Therefore, it was recognized that not only the heat resistance was poor, but also the antistatic property was poor.

Comparative Example 7 A molded article was obtained in the same manner as in Example 1, except that the amount of antistatic agent used was increased to 6 parts, and its physical properties were measured. .

The surface specific resistance value of the molded article was 7×10 2 , Q, the heat resistance was 84° C., and the initial colorability was 63.

Therefore, although the heat resistance and antistatic properties were good, it was recognized that the thermal stability was poor.

Claims (1)

[Claims] 100-67 parts by weight of chlorinated vinyl chloride resin and 0-33 parts by weight of vinyl chloride resin, as an antistatic agent represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ An antistatic chlorinated vinyl chloride resin composition containing 1 to 4 parts by weight of a compound. However, in the formula R_1
represents an alkyl group having 4-10 carbon atoms, and R_2, R_3 and R_4 represent an alkyl group or hydroxyalkyl group having 1-4 carbon atoms.