JPH0730223B2 - Chlorine-containing resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chlorine-containing resin composition obtained by adding an aliphatic dibasic acid diester and a quaternary ammonium salt compound of perchloric acid. The present invention relates to a chlorine-containing resin composition having an improved antistatic property, which is obtained by adding a plasticizer composed of an ester of an aliphatic dibasic acid and an ether alcohol and an aliphatic quaternary ammonium salt compound of perchloric acid.

[Conventional technology and its problems]

Chlorine-containing resins such as polyvinyl chloride resin are various packaging films or containers, agricultural films, sheets, as soft products to which a plasticizer is added in a relatively large amount or so-called semi-rigid products in which a plasticizer is added to a relatively small amount. Widely used for flooring and wall materials.

These chlorine-containing resins generally have good electrical insulation properties, which is a desirable property in fields requiring electrical insulation properties such as wire coating materials, but since they accumulate static electricity due to friction, they can be used, for example, in factories and computers. Partitions for rooms, IC
When it is used as a case for transporting / protecting, or as a packaging film or sheet such as a covering material for telecommunications, so-called electrostatic damage is often caused.

Further, even when a chlorine-containing resin is used as a flooring material, there is a disadvantage that the dirt is adsorbed by static electricity and the appearance is impaired.

Further, since chlorine-containing resin has a poor affinity with water, when used in food packaging films or containers, agricultural films, etc., there is a drawback that water droplets adhere to the surface and cause clouding. It has been desired to prevent this.

In order to eliminate these drawbacks, for example, Japanese Patent Publication No. 39-21
Japanese Patent Laid-Open No. 114 has proposed the use of an ester of ether alcohol as a plasticizer, but the effect is completely unsatisfactory and it is not satisfactory in practice.

Therefore, it has been generally attempted to add or apply various antistatic agents to the chlorine-containing resin to improve the antistatic property. However, most of these antistatic agents have thermal stability of the chlorine-containing resin. The fact is that its use was restricted because it markedly deteriorates sex.

For example, Japanese Examined Patent Publication No. 40-7366 describes in detail the effect of adding a quaternary ammonium salt type antistatic agent to a vinyl chloride resin containing dioctyl phthalate, which is a general-purpose plasticizer. , Trimethyl dodecyl ammonium chloride, dimethyl hydroxyethyl dodecyl ammonium bromide and other quaternary ammonium halide antistatic agents significantly accelerate the thermal decomposition of vinyl chloride resin, and perchloric acid or organic sulfonic acid as an anion. It is described that the quaternary ammonium salt type antistatic agent using the above anion has a small adverse effect, and particularly the compound using the organic sulfonate anion has a very small adverse effect.

However, when the quaternary ammonium salt type antistatic agent using the perchlorate anion described in the above publication is used, the decrease in thermal stability is not negligible, and the compound using the organic sulfonate anion is not negligible. However, the coloring change of the chlorine-containing resin due to heating was extremely large, and the antistatic effect was insufficient, which was not actually satisfactory.

Therefore, it is also proposed to use a nonionic antistatic agent that does not adversely affect the thermal stability, for example,
JP-B-44-22616 discloses a combination of an ether alcohol ester and a nonionic antistatic agent.
Although it is described that the antistatic property is further improved, the improvement effect is not yet satisfactory, and further improvement has been strongly desired.

[Means for solving problems]

In view of the above situation, the present inventors have conducted extensive studies to obtain a chlorine-containing resin composition that has good antistatic properties and has a very low degree of decrease in thermal stability. When a quaternary ammonium salt type antistatic agent and an ester of an aromatic carboxylic acid are used in combination, not only the antistatic effect is insufficient but also the thermal stability is significantly reduced,
An ester of an aliphatic dibasic acid and an ether alcohol,
It has been found that when a quaternary ammonium salt type antistatic agent of perchloric acid is used in combination, not only the antistatic property is improved to a satisfactory level, but also the thermal stability is not significantly reduced.

The present invention has been made on the basis of the above-mentioned findings, and in 100 parts by weight of a chlorine-containing resin, (a) an aliphatic dibasic acid ester plasticizer represented by the following general formula (I) is used.
The present invention provides a chlorine-containing resin composition comprising 100 parts by weight and (b) 0.01 to 5 parts by weight of a quaternary ammonium salt compound of perchloric acid represented by the following general formula (II).

R [CO (O-A) nO- R 1 ] ₂ (I) (In the formula, R represents a group of the formula _{-R 2 (CO-O-G} -O-CO-R 2) m, R 2 represents an alkylene group having 2 to 10 carbon atoms, G is It represents an alkylene group having 2 to 8 carbon atoms which may have an ether bond, and m represents 0 to 2. R ₁
Represents an alkyl group having 1 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n represents 1 to 8.

R ₃ represents an alkyl group having 6 to 22 carbon atoms, R ₄ , R ₅ and
R ₆ represents an alkyl group or (A-O) nH having 1 to 18 carbon atoms independently. ) Hereinafter, the chlorine-containing resin composition of the present invention will be described in detail.

Plasticizer represented by general formula (I) is a known compound, for example, aliphatic dibasic acid or its lower alkyl ester represented by the formula _{HO-CO-R 2 -CO-} OH, wherein R ₁ -O
It can be easily produced by reacting an ether alcohol represented by (A-O) nH and a glycol represented by HO-G-OH, if necessary.

Examples of the aliphatic dibasic acid of the formula _{HO-CO-R 2 -CO-} OH, for example, succinic acid, glutaric acid, methyl succinic acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Examples include sebacic acid and dodecanedioic acid.

Examples of the ether alcohol represented by the formula R ₁ —O (A—O) nH include methoxyethanol, methoxypropanol, ethoxyethanol, propoxyethanol,
Butoxyethanol, octoxyethanol, decyloxyethanol, dodecyloxyethanol, octadecyloxyethanol, methoxyethoxyethanol, ethoxyethoxyethanol, butoxyethoxyethanol,
Examples include octoxyethoxyethanol, poly (3-8) oxyethylene monoethyl ether, poly (3-8) oxyethylene monobutyl ether, poly (3-8) oxypropylene monobutyl ether, and the like.

As the glycol represented by the formula HO-G-OH, for example,
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-
Butylene glycol, neopentyl glycol, 1,6-
Hexanediol and the like can be mentioned.

Therefore, typical examples of the plasticizer represented by the general formula (I) used in the present invention include bis (butoxyethyl) succinate, bis (butoxyethyl) glutarate, bis (methoxyethyl) adipate, and bis (ethoxyethyl). ) Adipate, bis (butoxyethyl) adipate,
Bis (butoxyethyl) azelate, bis (butoxyethyl) sebacate, bis (butoxyethyl) dodecanedioate, bis (butoxyethoxyethyl) succinate, bis (butoxyethoxyethyl) adipate, bis (butoxyethoxyethyl) sebacate, bis (butoxy) Ethoxyethyl) dodecanedioate, bis (tetraethylene glycol monoethyl ether) adipate,
Bis (tetraethylene glycol monobutyl ether)
Adipate, ethylene glycol bis (butoxyethyl adipate), 1,2-propylene glycol bis (butoxyethyl adipate), 1,3-butylene glycol bis (butoxyethyl adipate), 1,3-butylene glycol bis (butoxyethoxyethyl adipate) , Neopentyl glycol bis (butoxyethyl adipate), diethylene glycol bis (butoxyethyl adipate), dipropylene glycol bis (methoxyethoxyethyl adipate) and the like.

The amount of the aliphatic dibasic acid ether alcohol ester-based plasticizer can be varied over a wide range depending on the purpose, but generally 10 to 100 parts by weight, particularly 100 parts by weight of the chlorine-containing resin,
15 to 80 parts by weight are blended.

The quaternary ammonium salt compound of perchloric acid represented by the general formula (II) (antistatic agent) is a known compound,
Although commercially available products can be used as they are, if they are not available, they can be easily synthesized by reacting, for example, a quaternary ammonium hydroxide with perchloric acid.

Examples of the perchloric acid quaternary ammonium salt compound represented by the general formula (II) include dimethyl octyl hydroxyethyl ammonium perchlorate, dimethyl dodecyl hydroxyethyl ammonium perchlorate,
Dimethyl stearyl hydroxyethyl ammonium perchlorate, trimethyl dodecyl ammonium perchlorate, dimethyl distearyl ammonium perchlorate, dimethyl dipalmityl ammonium perchlorate, methyl dodecyl dihydroxyethyl ammonium perchlorate, methyl stearyl dihydroxy ethyl Ammonium perchlorate, distearyl dihydroxyethyl ammonium perchlorate, distearyl dihydroxypropyl ammonium perchlorate, methyl stearyl dipoly (2 to
4) Oxyethylene ammonium perchlorate and the like.

The compounding amount of the above quaternary ammonium salt compound of perchloric acid is 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the chlorine-containing resin.

In the present invention, the aliphatic dibasic acid ester plasticizer represented by the general formula (I) and the quaternary ammonium salt compound of perchloric acid represented by the general formula (II) are used as a chlorine-containing resin. Although they may be added, they may be added separately at the time of compounding the chlorine-containing resin, but in order to facilitate uniform dispersion in the resin, it is preferable to use them as a mixed solution in advance. In this case, as a matter of course, the plasticizer and the quaternary ammonium salt compound of perchloric acid with respect to the chlorine-containing resin are mixed so as to have a predetermined amount. The ratio of the plasticizer and the quaternary ammonium salt compound of perchloric acid can be appropriately changed so as to have the above-mentioned compounding amount, but generally, the ratio of the perchloric acid to the compounding amount is 100 parts by weight of the perchloric acid. The quaternary ammonium salt compound is mixed in a ratio of 0.5 to 10 parts by weight.

Examples of the chlorine-containing resin used in the present invention include polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-
Examples thereof include acrylic acid ester copolymers or blends of the above chlorine-containing resins with ABS resins, MBS resins, NBR and the like.

The chlorine-containing resin composition of the present invention, other additives usually added, for example, Ca, Ba, Mg, Zn, Cd, Sn, Pb carboxylates, phenolates, organic acids such as organic phosphate salts. Salts, oxides of the above metals, hydroxides, carbonates, silicates,
Inorganic metal compounds such as phosphates, phosphites, aluminates or double salts thereof, general-purpose heat stabilizers such as organic tin compounds, epoxidized soybean oil, epoxy compounds such as epoxy resins, organic phosphite compounds , UV absorber, light stabilizer, pigment, dye, filler, foaming agent, lubricant, flame retardant, β-
A diketone compound, a phenol compound or the like can be added, and a plasticizer can be used together with the plasticizer of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples.
The invention is not limited by the examples below.

Example 1 The following formulation was roll kneaded at 170 ° C for 5 minutes and then 1
1mm thick by press working at 60 ℃, 200kg / cm ² for 50 minutes
Created a sheet of.

[Blending] Vinyl chloride resin (GEON 103EP) 100 MARK AC-169 2.5 (Ba / Zn liquid stabilizer made by Adeka Argus Chemical) Epoxidized soybean oil 2.5 Plasticizer (Table-1) 46.5 Dimethyl octyl hydroxy Ethyl ammonium perchlorate 1 Using this sheet, the volume specific resistance (Ωcm) and the surface specific resistance (Ω) were measured under the conditions of 30 ° C. and relative humidity of 60%.

Further, this sheet was used to measure the thermal stability (minutes) and the initial colorability in a gear oven at 175 ° C.

The epoxidized soybean oil, the plasticizer, and the antistatic agent (dimethyl octyl hydroxyethylammonium perchlorate) were uniformly dissolved and used.

The results of the above measurements are shown in Table 1 below.

Example 2 To examine the effect of the type of antistatic agent, a sheet was prepared in the same manner as in Example 1 using the following formulation,
The test was conducted.

The results are shown in Table 2 below.

[Composition] Parts by weight Vinyl chloride resin (GEON 103EP) 100 MARK AC-169 2.5 Epoxidized soybean oil 2.5 Bis (butoxyethyl) adipate 46.5 Antistatic agent (Table-2) 1 Example 3 In order to examine the effect of changing the amount of the antistatic agent, a sheet was prepared by the same operation as in Example 1 using the following formulations, and the test was conducted.

The results are shown in Table 3 below.

[Composition] Parts by weight Vinyl chloride resin (GEON 103EP) 100 MARK AC-169 2.5 Epoxidized soybean oil 2.5 Bis (butoxyethyl) adipate 46.5 Dimethyl octyl hydroxyethyl ammonium perchlorate Table-3 Example 4 A sheet was prepared by the same operation as in Example 1 with the following composition, and the volume resistivity was measured at 30 ° C. and a relative humidity of 60%, and a thermal stability test in a gear oven at 190 ° C. was performed. went.

The results are shown in Table 4 below.

[Blending] Vinyl chloride resin (GEON 103EP) 100 MARK AC-216 2 (Ba / Zn type liquid stabilizer made by Adeka Argus Chemical) MARK RUP-14 0.8 (Ba / Zn type powder stabilizer made by Adeka Argus Chemical) ) Dimethyl octyl hydroxyethyl ammonium perchlorate 1 Epoxidized soybean oil 2.5 4,4'-butylidene bis (3-tert-butyl-4-hydroxy-6-methylphenol) 0.15 Plasticizer (Table-4) 20 From the results of the above respective examples, when the combination of the plasticizer of the present invention and the antistatic agent was used, the antistatic ability (volume specific resistance and surface specific resistance) was remarkably improved, and the antistatic agent It is understood that the addition does not significantly lower the thermal stability and does not deteriorate the initial colorability.

〔The invention's effect〕

The chlorine-containing resin composition of the present invention has improved antistatic properties, has very little deterioration in thermal stability due to the addition of antistatic agents, and has good initial colorability.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 101/00

Claims (1)

[Claims] 1. An aliphatic dibasic acid ester plasticizer represented by the following general formula (I) in 100 parts by weight of a chlorine-containing resin:
A chlorine-containing resin composition obtained by adding 10 to 100 parts by weight and (b) 0.01 to 5 parts by weight of a quaternary ammonium salt compound of perchloric acid represented by the following general formula (II). R [CO (O-A) nO- R 1 ] ₂ (I) [In the formula, R represents a group of the formula _{-R 2 (CO-O-G} -O-CO-R 2) m, R 2 represents an alkylene group having 2 to 10 carbon atoms, G is It represents an alkylene group having 2 to 8 carbon atoms which may have an ether bond, and m represents 0 to 2. R ₁
Represents an alkyl group having 1 to 18 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n represents 1 to 8. R ₃ represents an alkyl group having ₄ to 22 carbon atoms, and R ₄ , R ₅ and
R ₆ represents an alkyl group or (A-O) nH having 1 to 18 carbon atoms independently. )