JPH0723440B2 - Antistatic vinyl chloride resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition having an antistatic property.

(Prior Art) Vinyl chloride resin is used in large quantities in a wide range of fields because it has excellent strength and electrical insulation properties, but due to its excellent electrical insulation properties, it is easily charged with static electricity. The soft vinyl chloride resin blended with the plasticizer has a lower electric insulation resistance than the hard vinyl chloride resin, but still does not prevent charging.

In order to prevent such electrification of vinyl chloride resin, an antistatic agent is kneaded into the resin or applied to the surface of the product. However, since many antistatic agents have low compatibility with vinyl chloride resin, they tend to seep to the product surface after kneading, and the effect of the coating method diminishes over time.

In recent years, the demand for antistatic vinyl chloride resin has increased, and the advent of plasticizers having antistatic properties as well as plasticity is awaited.

The present inventors have found that a vinyl chloride resin composition having excellent antistatic properties can be obtained by using a specific tartaric acid diester and a benzotriazole compound in combination,
Upon further research, this resin composition had room for improvement in thermal stability.

(Problems to be Solved by the Invention) An object of the present invention is to provide a vinyl chloride resin composition having both plasticity and antistatic property and good heat resistance.

(Means for Solving Problems) The resin composition of the present invention comprises: (R ₁ is an alkyl group having 1 to 13 carbon atoms which are the same or different) or (R ₂ is an alkylene group having 2 or 4 carbon atoms having the same or different carbon atoms, R ₃ is an alkyl group having 1 to 13 carbon atoms having the same or different carbon atoms), a tartaric acid diester, (b) a benzotriazole compound, and (C) An epoxy-based stabilizer is contained.

The ester represented by the general formula (1) or (2) used in the present invention can be easily obtained by, for example, a general method for producing a tartaric acid ester by reacting tartaric acid with an alcohol.

In the case of non-ether alcohol, n-butanol, n-hexanol, i-heptanol, n-octanol, 2-ethylhexanol, i
-Nonanol, i-decanol, n-decanol, i-tridecanol, mixed alcohols having 6 to 11 carbon atoms, and the like. In the case of ether alcohols, ethylene glycol monobutyl ether, ethylene glycol mono-2, etc.
-Ethyl hexyl ether, propylene glycol mono hexyl ether, propylene glycol mono hexyl ether, butylene glycol mono butyl ether.

The tartaric acid diester has two hydroxyl groups having strong hydrophilicity and two carbonyl groups having strong affinity with vinyl chloride resin in the molecule, and the characteristics differ depending on the type of alkyl group bonded.

The plasticizer of the present invention has the general formula above in which R ₁ has 1 carbon atom.
˜13, preferably 4 to 10, R ₂ has 2 to 4 carbon atoms, and R ₃ has 1 to 13 carbon atoms, preferably 4 to 10 carbon atoms. If the carbon number of R ₁ is less than 4, it has a strong hydrophilicity and a low boiling point, so it can be used as a plasticizer, but the vinyl chloride resin product obtained has poor water resistance, volatility resistance, heat resistance, etc. It is easy to become.
On the other hand, when the number of carbon atoms exceeds 13, the compatibility with vinyl chloride resin is poor and the plasticity and chargeability are poor, so that bleeding easily occurs on the surface of resin products, and products that are not sufficiently plasticized and antistatic properties are poor. Only enough products can be obtained. Further, when the carbon number of R ₂ is less than 2, hydrophilicity and volatility are large, and the sustainability of antistatic property is small, and when the carbon number exceeds 4, compatibility is not sufficient and bleeding easily occurs, resulting in transparency and product. Make the appearance of. The carbon number of R ₃ is the water resistance of the obtained vinyl chloride resin,
Since the volatile resistance and heat resistance tend to be poor, 4 or more is preferable. On the other hand, when the carbon number exceeds 13, the compatibility with vinyl chloride resin is poor.

The above tartaric acid diester is usually 30 per 100 parts by weight of resin.
To 100 parts by weight, preferably 40 to 60 parts by weight.

Benzotriazole-based compounds have, for example, the general formula In particular, 1,2,3-benzotriazole, 2-hydroxy-5-methylphenylbenzotriazole, 2-hydroxy-5-octylphenylbenzotriazole, 2
-Hydroxy-3,5-di-t-butylphenylbenzotriazole is preferably used. Benzotriazole compounds are generally known as UV absorbers, and are generally used for various resins in the range of about 0.5 PHR, at most less than 1.0 PHR. Used in. However, in the composition of the present invention, it is generally 0.5
It is used in the range of ˜3 PHR, preferably more than 1.0 PHR and less than 3.0 PHR. As described above, by using a larger amount than the conventional one, it is possible to prevent the initial colorability when the resin composition is commercialized, and to further improve the antistatic property by dusting with the tartaric acid ester. Is.

However, the above two-component system of tartaric acid ester and benzotriazole has room for improvement in heat resistance of the resin composition, and the composition of the present invention further contains an epoxy stabilizer as an essential component.
As the epoxy stabilizer, conventionally known ones can be used, but they are roughly classified into epoxy plasticizers, epichlorohydrin reaction products, and others. As an epoxy plasticizer,
Epoxidized soybean oil, epoxidized linseed oil, epoxy glyceride such as epoxidized cottonseed oil, epoxidized butyl oleate, epoxidized euethylhexyl oleate, (9
・ Epoxy fatty acid monoester such as epoxidized soybean fatty acid butyl, epoxidized soybean fatty acid octyl, etc. The epichlorohydrin reaction product includes a condensate with bisphenol A and a reaction product with salicylic acid. Although the mixing amount is not particularly limited, it is generally 1 to 7 parts by weight, preferably 2 to 5 parts by weight with respect to 100 parts by weight of the resin content.

Since the resin composition of the present invention contains the above-mentioned specific tartaric acid ester, benzotriazole-based compound and epoxy-based stabilizer, it has excellent antistatic properties as well as plasticity, and the initial coloring when commercialized is small and heat stable. Good sex.

Further, the phthalic acid ester of the composition of the present invention can be added and mixed to improve the plasticity.

(A) General formula (R ₁ is an alkyl group having 1 to 13 carbon atoms which are the same or different) or (R ₂ is an alkylene group having 2 to 4 carbon atoms having the same or different carbon atoms, and R ₃ is an alkyl group having 1 to 13 carbon atoms having the same or different carbon atoms), a tartaric acid diester, (b) a benzotriazole-based compound, ( c) an epoxy stabilizer, and (d) a general formula (R ₄ is an alkyl group of _{4 to} 13 having the same or different carbon number) or (R ₅ is an alkylene group having 2 to 4 carbon atoms having the same or different carbon atoms, and R ₆ is a phthalic acid diester represented by an alkyl group having 1 to 13 carbon atoms having the same or different carbon atoms).

The phthalic acid diester is represented by the above general formula, wherein R ₄ has 1 to 13 carbon atoms, preferably 4 to 10 and R ₅ has 2 to 4 carbon atoms.
R ₆ having 1 to 13 carbon atoms, preferably 4 to 10 carbon atoms is used.

The phthalic acid diester can be easily obtained by a general method for producing a phthalic acid ester by reacting phthalic anhydride with an alcohol. As the alcohol used as the raw material, those shown as the raw material of the tartaric acid ester are preferably used.

The mixing ratio of the tartaric acid diester and the phthalic acid ester is not specified, but it is generally used in the range of 1: 9 to 3: 2.
The amount of each ester compounded with respect to the resin content is preferably 10 to 30 PH per 100 parts by weight of resin.
R, Phthalates 30 to 50 parts by weight.

It was expected that a resin composition with increased plasticity was obtained by mixing the phthalate ester,
Surprisingly, a vinyl chloride resin composition having a further excellent antistatic ability was obtained by the synergistic effect with the tartaric acid ester.

In the resin composition of the present invention, in addition to the tartaric acid diester (a), the benzotriazole compound (b), the epoxy stabilizer (c) and the phthalic acid diester (d) optionally added, Other conventionally known plasticizers, stabilizers, antioxidants, coloring agents, filling agents and the like may be contained within a range that can achieve the object of the invention.

(Example) In the following, "parts" means "parts by weight".

Examples 1 to 6 Tartaric acid diester, benzotriazole, epoxy compound and, if necessary, phthalic acid diester were added to 100 parts of vinyl chloride resin (S _X- 13 manufactured by Sumitomo Chemical Co., Ltd.) at a ratio shown in Table 1, and further vinyl chloride was added. 2.5 parts of Ba-Zn-based liquid stabilizer (LTL-272 manufactured by Nissan Ferro Co., Ltd.) was added as a general-purpose stabilizer for resin, and rolled and pressed in accordance with a conventional method to obtain a soft vinyl chloride resin sheet with a thickness of 1 mm. .

The surface of the sheet was not sticky and had excellent transparency.
The surface resistance of the sheet was measured by a surface resistance measuring device (Statco TR-2) manufactured by Tokyo Denshi Co., Ltd.

(30 ° C).

Table 2 shows the results of measuring the initial coloring of the sheet by the 6-step method.
Shown in. Table 2 shows the results of the Congo red test conducted by cutting the sheet into pellets of about 0.5 × 0.5 × 1 mm at 170 ° C. according to JIS K-6723.

Comparative Examples 1 to 5 A soft resin sheet was obtained in the same manner as in the examples from the resin composition comprising the vinyl chloride resin used in the examples and the ester, benzotriazole, and epoxy-based stabilizers having the formulations shown in Table 1. The physical properties are shown in Table 2. Comparative Examples 1 and 2 show conventional phthalic acid diesters, 3 shows Examples 3 and 4, Examples 1 and 5 show comparison with Example 4.

Measurement conditions ・ Tensile strength 20 ℃, dumbbell No.3 ・ Volume loss 100 ℃ × 24 hours ・ Water resistance 50 ℃ × 24 hours, immersion (Effect of the invention) The vinyl chloride resin composition of the present invention has good plasticity and antistatic property. It has a low initial coloring property when it is commercialized and has good thermal stability.

Further, the composition of the present invention containing a phthalic acid diester has more excellent plasticity and antistatic property.

Claims (2)

[Claims] 1. (a) General formula (R ₁ is an alkyl group having 1 to 13 carbon atoms which are the same or different) or (R ₂ is an alkylene group having 2 to 4 carbon atoms having the same or different carbon number, R ₃ is an alkyl group having 1 to 13 carbon atoms having the same or different carbon number), (b) a benzotriazole-based compound, And (c) an epoxy-based stabilizer, which is an antistatic vinyl chloride resin composition. 2. (a) General formula (R ₁ is an alkyl group having 1 to 13 carbon atoms which are the same or different) or (R ₂ is an alkylene group having 2 to 4 carbon atoms having the same or different carbon number, R ₃ is an alkyl group having 1 to 13 carbon atoms having the same or different carbon number), (b) a benzotriazole-based compound, (C) Epoxy stabilizer, and (d) General formula (R ₄ is an alkyl group of _{4 to} 13 having the same or different carbon number) or (R ₅ is an alkylene group having 2 to 4 carbon atoms having the same or different carbon number, and R ₆ is an alkyl group having 1 to 13 carbon atoms having the same or different carbon number). Antistatic vinyl chloride resin composition.