JP2801019B2 - Chlorine-containing resin composition - Google Patents

Description

The present invention relates to a chlorine-containing resin composition obtained by adding an aliphatic dibasic acid polyester and a quaternary ammonium salt compound of perchloric acid. The present invention relates to a chlorine-containing resin composition having an improved antistatic property, in which a plasticizer comprising a polyester of an aliphatic dibasic acid and a glycol and an aliphatic quaternary ammonium salt compound of perchloric acid are added.

[Problems to be solved by conventional technology and invention]

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

These chlorine-containing resins generally have good electrical insulation properties, and are preferable properties in fields requiring electrical insulation such as wire coating materials.However, since they accumulate static electricity by friction, they can be used, for example, in factories and computers. Partition of machine room, IC
When it is used for a case for transportation and protection of a product, or for a packaging film or sheet such as a covering material for electronic communication, it often causes so-called static electricity damage.

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

Furthermore, since chlorine-containing resins have poor affinity for water, when used in food packaging films or containers, agricultural films, etc., water droplets adhere to the surface, causing the fogging, and the chlorine-containing resin has a drawback. It has been desired to prevent this.

In order to eliminate these drawbacks, for example,
Japanese Patent No. 21114 proposes to use an ester of ether alcohol as a plasticizer, but the effect is completely inadequate and not practically satisfactory.

For this reason, in general, attempts have been made to improve or improve the antistatic properties by adding or applying various antistatic agents to the chlorine-containing resin. The fact is that its use has been restricted to significantly reduce its stability.

For example, Japanese 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, a general-purpose plasticizer, Quaternary ammonium halide antistatic agents such as trimethyl dodecylammonium chloride and dimethylhydroxyethyl dodecylammonium bromide can significantly accelerate the thermal decomposition of vinyl chloride resins, and anions of perchloric acid or organic sulfonic acid as anions It is described that a quaternary ammonium salt type antistatic agent using the compound has a small adverse effect, and a compound using an organic sulfonate anion has a very small adverse effect.

However, when a quaternary ammonium salt-type antistatic agent using a perchlorate anion described in the above publication is used, the decrease in thermal stability is not negligible, and compounds using an organic sulfonate anion are not The coloring change due to heating of the chlorine-containing resin was extremely large, and the antistatic effect was insufficient, so that it was not practically satisfactory.

For this reason, it has been proposed to use a nonionic antistatic agent which does not adversely affect thermal stability.For example, Japanese Patent Publication No. 44-22616 discloses an ester of ether alcohol and a nonionic antistatic agent. It is described that the antistatic property is further improved by the combined use, but the effect of improvement is not yet satisfactory, and further improvement has been strongly desired.

[Means for solving the problem]

The present inventors, in view of the current situation, have good antistatic properties, and as a result of intensive studies to obtain a chlorine-containing resin composition having a very low degree of thermal stability reduction,
When a quaternary ammonium salt type antistatic agent of perchloric acid 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,
When a polyester of an aliphatic dibasic acid and a glycol is used in combination with a quaternary ammonium salt type antistatic agent of perchloric acid, not only the antistatic property is improved until satisfactory, but also the thermal stability is reduced. The inventors have found that the amount is extremely small, and have reached the present invention.

That is, the present invention relates to (a)
An aliphatic dibasic acid having 4 to 12 carbon atoms, a glycol having 2 to 4 carbon atoms which may be branched, and 1 to 10 carbon atoms
And 10 to 100 parts by weight of a polyester plasticizer synthesized from a linear alcohol of the formula (I) and (b) 0.01 to 5 parts by weight of a quaternary ammonium salt compound of perchloric acid represented by the following general formula (I). The present invention provides a chlorine-containing resin composition containing no lead-based stabilizer and calcium carbonate.

(Wherein, R ₁ represents an alkyl group having 4 to 22 carbon atoms,
R ₂ , R ₃ and R ₄ each independently represent an alkyl group having 1 to 18 carbon atoms or (BO) _n H, and B represents 2 to 4 carbon atoms.
And n represents 1 to 4. Hereinafter, the chlorine-containing resin composition of the present invention will be described in detail.

The plasticizer as the component (a) used in the present invention is a known compound, for example, a compound represented by the formula HO-CO-A-CO-OH (wherein
A represents an alkylene group having 2 to 10 carbon atoms. A) a linear alcohol represented by the formula R-OH (wherein R represents a linear alkyl group having 1 to 10 carbon atoms); Formula HO
-G-OH (wherein G is a group having 2 to 4 carbon atoms which may be branched)
Represents an alkylene group. Can be easily produced by reacting with the glycol represented by the formula (1).

Examples of the aliphatic dibasic acid represented by the formula HO-CO-A-CO-OH include adipic acid (Ad), pimelic acid (Pm),
Suberic acid (Su), Azelaic acid (Az), Sebacin (S
b) Acids and the like.

The linear alcohol represented by the formula R-OH includes methanol (Me), ethanol (Et), n-propanol (Pro), n-butanol (Bu), and p-pentanol (P
en), n-hexanol (Hex), n-heptanol (H
ep), n-octanol (Oct), n-nonyl alcohol (Non), n-decyl alcohol (Dec) and the like.

Examples of the glycol represented by the formula HO-G-OH include 1,2-propylene glycol (1,2-PG), 1,3-propylene glycol (1,3-PG), and 1,3-butylene glycol. (1,3-BG), 1,4-butylene glycol (1,4-B
G), neopentyl glycol (NPG) and the like.

These aliphatic dibasic acids or their lower alkyl esters, glycols and straight-chain alcohols can be used alone or in combination of two or more.

The blending amount of the aliphatic dibasic acid polyester-based plasticizer can vary widely depending on the purpose, but generally 10 to 100 parts by weight, preferably 15 to 100 parts by weight based on 100 parts by weight of the chlorine-containing resin.
80 parts by weight are blended.

Further, the quaternary ammonium salt type antistatic agent of chloric acid represented by the general formula (I), which is the component (b) used in the present invention, is a known compound, and a commercially available one can be used as it is. If it is not available, it can be easily synthesized, for example, by reacting quaternary ammonium hydroxide with perchloric acid.

Examples of the quaternary ammonium salt of perchloric acid represented by the general formula (I) include dimethyl octyl hydroxyethyl ammonium perchlorate, dimethyl dodecyl hydroxyethyl ammonium perchlorate, and dimethyl stearyl hydroxyethyl ammonium perchlorate. Lolate, trimethyl dodecyl ammonium perchlorate, dimethyl distearyl ammonium perchlorate, dimethyl dipalmityl ammonium perchlorate, methyl dodecyl dihydroxyethyl ammonium perchlorate, methyl stearyl dihydroxyethyl ammonium perchlorate, distearyl dihydroxy Ethyl ammonium perchlorate,
Distearyl dihydroxypropylammonium perchlorate, methyl stearyl dipoly (2-4) oxyethylene ammonium perchlorate and the like can be mentioned.

The amount of the quaternary ammonium salt of perchloric acid is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of the chlorine-containing resin.

In the present invention, an aliphatic dibasic acid polyester-based plasticizer and a quaternary ammonium salt of perchloric acid represented by the general formula (I) are blended in a chlorine-containing resin. It can be added separately at the time of processing the resin, but it is preferable to use a solution in which both are mixed in advance in order to facilitate uniform dispersion in the resin. In this case, of course, the polyester plasticizer and the quaternary ammonium salt of perchloric acid are mixed with the chlorine-containing resin so that the blending amounts thereof become a predetermined amount. The ratio between the polyester plasticizer and the quaternary ammonium salt of perchloric acid can be appropriately changed so as to have the above-mentioned blending amount. The quaternary ammonium salt of the acid 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, a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-ethylene copolymer, a vinyl chloride-acrylate copolymer, and the above-mentioned chlorine-containing resins. Blends of resins with ABS resins, MBS resins, NBR and the like can be given.

In the chlorine-containing resin composition of the present invention, other additives usually blended, for example, Ca, Ba, Mg, Zn, Cd, Sn carboxylate, phenolate, organic acid salts such as organic phosphate salts, Oxides, hydroxides, carbonates, silicates of the above metals,
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, polyols, and organic phosphides Fight compounds, UV absorbers, light stabilizers, pigments, dyes, fillers, foaming agents, lubricants,
Flame retardants, β-diketone compounds, phenol compounds and the like can be appropriately compounded, and other plasticizers can be used together with the polyester plasticizer of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples.

Example 1 The following composition was roll-kneaded at 170 ° C. for 5 minutes, and then pressed at 160 ° C. and 200 kg / cm ² for 50 minutes to obtain a thickness.
A 1mm sheet was created.

[Blending] parts by weight Vinyl chloride resin (GEON 103EP) 100 MARK AC-169 2.5 (Badecorated Argus Chemicals Ba / Zn liquid stabilizer) Epoxidized soybean oil 4.5 Polyester plasticizer (Table 1) 44.5 Dimethyl octyl・ Hydroxyethyl ammonium perchlorate Using this sheet, the volume resistivity (Ωcm) and the surface resistivity (Ω) were measured at 30 ° C. and a relative humidity of 60%.

Using this sheet, the thermal stability (minutes) and the initial coloring property in a gear oven at 175 ° C. were measured.

The epoxidized soybean oil, the polyester plasticizer and the antistatic agent were used by previously dissolving them uniformly.

 Table 1 shows the results.

Example 2 In order to examine the influence of the type of the antistatic agent, a sheet was prepared by the same operation as in Example 1 using the following composition, and a test was performed.

 Table 2 shows the results.

[Blending] Parts by weight Vinyl chloride resin (GEON 103EP) 100 MARK AC-169 2.5 Epoxy fatty acid octyl ester 2.5 (1,2-PG / AD) _n・ Oct 46.5 Antistatic agent (Table 2) 1 Example 3 In order to see 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 formulation, and a test was performed.

 Table 3 shows the results.

[Blending] Parts by weight Vinyl chloride resin (GEON 103EP) 100 MARK AC-169 2.5 Epoxidized linseed oil 2.5 (1,3-BG / AD) _n・ Non 46.5 Dimethyl octyl hydroxy Table-3 Ethyl ammonium perchlorate Example 4 A sheet was prepared in the same manner as in Example 1 with the following composition, and the volume resistivity was measured at 30 ° C. and a relative humidity of 60%.
Further, a thermal stability test was performed in a gear oven at 190 ° C.

 Table 4 shows the results.

[Blending] Parts by weight Vinyl chloride resin (GEON 103EP) 100 MARK AC-2162 (Ba / Zn liquid stabilizer manufactured by Adeka Argus Chemical) MARK RUP-14 0.8 (Ba / Zn powder stabilizer manufactured by Adeka Argus Chemical) ) Dimethyl octyl hydroxyethyl tyl ammonium perchlorate Epoxidized soybean oil 2.5 4,4'-butylidenebis (3-tert-butyl-0.15 4-hydroxy-6-methylphenol) Polyester plasticizer (Table-4) 20 From the results of the above examples, when the combination of the polyester plasticizer and the antistatic agent of the present invention was used, the antistatic ability (volume resistivity and surface resistivity) was remarkably improved. It is understood that the addition of the agent causes little decrease in thermal stability and does not deteriorate initial colorability.

〔The invention's effect〕

INDUSTRIAL APPLICABILITY The chlorine-containing resin composition of the present invention has significantly improved antistatic properties without lowering thermal stability and initial coloring properties.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08K 3/00-13/08 C08L 1/00-101/14

Claims (1)

(57) [Claims] (1) 100 parts by weight of a chlorine-containing resin, (a) an aliphatic dibasic acid having 4 to 12 carbon atoms, a glycol having 2 to 4 carbon atoms which may be branched, and 1 to 10 carbon atoms. Polyester plasticizer synthesized from a linear alcohol of 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 (I) and containing a lead-based stabilizer and calcium carbonate No chlorine-containing resin composition. (Wherein, R ₁ represents an alkyl group having 4 to 22 carbon atoms,
R ₂ , R ₃ and R ₄ each independently represent an alkyl group having 1 to 18 carbon atoms or (BO) _n H, and B represents 2 to 4 carbon atoms.
And n represents 1 to 4. )