JPH08157422A - Ester composition - Google Patents

Abstract

PURPOSE: To provide a phthalic acid ester composition giving a resin having excellent heat-resistance, cold-resistance and moldability when used as a plasticizer for vinyl chloride resin. CONSTITUTION: This ester composition is composed of phthalic acid diesters of a mixture of 9, 10 and 11C aliphatic alcohols at weight ratios (9C alcohol/10C alcohol/11C alcohol) of (5-20)/(85-50)/(10-30). The 10C alcohol in the above mixture is preferably a 10C aliphatic alcohol mixture composed mainly of 2- propylheptanol (2PH) and 4-methyl-2-propylhexanol (MPH) at a weight ratio (2PH/MPH) of (88-70)/(12-30). The ester composition is compounded in an amount of 10-200 pts.wt. to 100 pts.wt. of a vinyl chloride resin. A resin composition produced by compounding 100 pts.wt. of a vinyl chloride resin with 30-100 pts.wt. of the ester composition, 0.1-10 pts.wt. of a stabilizer and 0.1-2 pts.wt. of a lubricant has excellent cold-resistance and thermal aging resistance and good volume resistivity and is suitable for the coating of an electric wire.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a phthalic acid ester composition for vinyl chloride resin, which is excellent in heat resistance, cold resistance, and processability, and a vinyl chloride resin mixed with this as a plasticizer. The present invention relates to a vinyl chloride resin composition.

[0002]

Various compounds such as phthalic acid diesters, aliphatic dibasic acid diesters, polyesters, phosphoric acid esters and epoxy plasticizers have been used as plasticizers for vinyl chloride resins. These plasticizers are used alone or in combination of two or more depending on the purpose. Among them, phthalic acid diesters, especially phthalic acid di-2
-Ethylhexyl (hereinafter referred to as "DOP") has various physical properties such as plasticization efficiency, heat stability, and cold resistance in a suitable range,
Many are used.

With the expansion and sophistication of the range of use of soft vinyl chloride resin molded products, it is becoming more and more desirable to have better durability. As the wire becomes thinner, the coating layer is becoming thinner. Therefore, the coating layer is required to have higher durability than before, that is, heat aging resistance and low volatility, and high volume resistivity so that sufficient insulation can be achieved even with a thin coating layer.

As such a plasticizer having improved heat aging resistance, diisononyl phthalate (hereinafter referred to as "DiNP"), which is less volatile than DOP, diisodecyl phthalate (hereinafter referred to as "DiDP"), and phthalate are used. Diundecyl acid (hereinafter referred to as "DUP") is used. Also,
A diester of 2-propylheptanol and phthalic acid (hereinafter referred to as “DPHP”) is used as a plasticizer having improved strength and cold resistance of the obtained soft vinyl chloride resin sheet.
For example, it is proposed in Japanese Patent Laid-Open No. 4-106146.

[0005]

However, the DiNP and D
iDP or DUP has a problem in cold resistance or strength of a molded product, and D which has been proposed as an improved product.
Since PHP has insufficient moldability such as absorbability to a vinyl chloride resin and gelation rate of the compound, there is a possibility that productivity during processing may decrease. Therefore, it has been desired to develop an ester for a plasticizer, which has heat aging resistance and cold resistance comparable to those of DPHP, has excellent moldability, and has a high volume resistivity.

[0006]

In view of the state of the art as described above, the present inventor has conducted extensive studies to find a plasticizer having excellent cold resistance and good moldability, and as a result, the number of carbon atoms has been increased. We have found that phthalic acid diesters of mixed alcohols in which 9, 10 and 11 aliphatic alcohols are mixed in specific composition ratios give good results and completed the present invention.

That is, the gist of the present invention is that the carbon number is 9, 10
And a mixture of 11 aliphatic alcohols (hereinafter referred to as “C _9-11 alcohol”, and each component is an aliphatic alcohol having 9 carbon atoms, an aliphatic alcohol having 10 carbon atoms,
And an aliphatic alcohol having 11 carbon atoms, respectively, "C
₉ alcohol ”,“ C ₁₀ alcohol ”and“ C ₁₁ alcohol ”), and the weight composition ratio of C ₉ alcohol, C ₁₀ alcohol and C ₁₁ alcohol in the mixture (C ₉ alcohol / C ₁₀ alcohol / C). ₁₁ alcohol,
Hereinafter, referred to as "C _9-11 alcohol composition ratio") is (5-20) / (85-85), where 100 is the total amount of the mixed alcohol.
50) / (10 to 30), wherein the ester composition is characterized by comprising a phthalic acid diester.

The present invention will be described in detail below. Departure
The bright ester composition is the above C_9-11Alcohol and anhydrous
Esterification reaction with thallic acid or phthalic acid by a conventional method
You can get it. Production of the ester composition of the present invention
C used for manufacturing_9-11Alcohol is the C ₉Al
Cole, C_TenAlcohol and C₁₁Weight composition of alcohol
Ratio (C_9-11Alcohol composition ratio) is the total amount of mixed alcohol
As 100, (5 to 20) / (85 to 50) / (1
Those in the range of 0 to 30) are used.

If the C _9-11 alcohol composition ratio is out of the above specified range, the following problems will occur. If the amount of C ₉ alcohol is too small, the processability tends to deteriorate, and if it is too large, the heat aging resistance tends to deteriorate. Contrary to the above, when the amount of C ₁₁ alcohol is too small, the heat aging resistance tends to be insufficient, and when it is too large, the moldability tends to deteriorate.

When the amount of C ₁₀ alcohol deviates from the above specified range, at least one of the C ₉ alcohol and the C ₁₁ alcohol will be out of the above preferred range, and it will be affected thereby. The C ₁₀ alcohol used in the present invention is an aliphatic alcohol having 10 carbon atoms, for example, so-called isodecanol obtained by hydrogenating an aldehyde having 10 carbon atoms produced by the oxo reaction of a propylene trimer, particularly, Although it can be used without limitation, 2-propylheptanol (hereinafter referred to as "2PH"), which is produced by hydrogenating an aldol condensation product of a C5 aldehyde obtained by subjecting butene to an oxo reaction, and 4-methyl-2-
A mixed alcohol containing propylhexanol (hereinafter referred to as "MPH") as a main component is preferable, and particularly, a weight ratio of 2PH and MPH in the mixed alcohol (hereinafter referred to as "2PH").
/ MPH composition ratio ") is (88 to 70) / (12
~ 30), preferably (85-75) / (15-25)
It is preferable to use a resin having the range of 10 because the processability, cold resistance and heat aging resistance are all satisfied.

When the 2PH / MPH composition ratio is less than 2PH than 70/30, volatility and cold resistance tend to be deteriorated. Further, the 2PH / MPH composition ratio is 8
When 2PH is more than 8/12, the moldability tends to be low, and the volume resistivity of the obtained sheet tends to be low. As the C ₉ alcohol used in the present invention, various linear or branched C ₉ alcohols can be used, but typically, a dimer of isobutene or mixed butene is subjected to an oxo reaction, The so-called isononyl alcohol obtained by subsequent hydrogenation can be exemplified.

Similarly, the type of the C ₁₁ alcohol is not particularly limited, but for example, a higher alcohol obtained by subjecting an α-olefin having 6 to 12 carbon atoms obtained by low polymerization of ethylene to an oxo reaction and then hydrogenating the same. An alcohol having 11 carbon atoms obtained by distilling and separating an alcohol mixture can be mentioned. In this case, distillation may be carried out at the stage of α-olefin to obtain decene-1 in advance, and then oxo reaction and hydrogenation may be carried out to obtain C ₁₁ alcohol.

The ester composition of the present invention is usually used as a plasticizer in an amount of 10 to 2 per 100 parts by weight of vinyl chloride resin.
00 parts by weight, preferably 15 to 150 parts by weight,
Used as a vinyl chloride resin composition. If the compounding ratio of the ester composition is less than 10 parts by weight, the effects such as cold resistance and improvement of molding processability are not exhibited, and if it exceeds 200 parts by weight, the bleeding phenomenon (a phenomenon in which the plasticizer seeps out to the surface of the molded product) Tends to occur, and stickiness or adhesion of dirt often occurs.

The above vinyl chloride resin composition is prepared by adding and mixing the vinyl chloride resin with the ester composition of the present invention and, if necessary, a plasticizer and various additives other than the ester composition of the present invention. Can be obtained. As the mixer, a blender, a super mixer, a mill, a Banbury mixer or the like which is usually used for processing vinyl chloride resin is used.

The above vinyl chloride resin contains vinyl chloride as a main constituent unit such as a homopolymer of vinyl chloride and a copolymer with other copolymerizable comonomer whose main component is vinyl chloride. Refers to resin. The copolymerizable comonomer is not particularly limited, and examples thereof include ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid or its ester, acrylic acid or its ester,
Methacrylic acid or its ester may, for example, be mentioned.

When the ester composition of the present invention is blended with a vinyl chloride resin as a plasticizer to produce a vinyl chloride resin composition and a soft resin product, the object of the present invention is to the extent that the object of the present invention is not impaired. A plasticizer other than the ester composition may be used in combination, and additives usually added to vinyl chloride resins, such as stabilizers, antioxidants, flame retardants, lubricants, fillers, ultraviolet absorbers, colorants, You may add surfactant, an antistatic agent, etc.

Further, 30 to 100 parts by weight of the ester composition of the present invention is added to 100 parts by weight of vinyl chloride resin,
Further, 0.1 to 10 parts by weight of stabilizer and 0.1 to 10 parts of lubricant are used.
The vinyl chloride resin composition containing 2 parts by weight has excellent cold resistance and heat aging resistance, and also has good volume resistivity,
It is particularly suitable for wire coating applications. The stabilizer used here is not particularly limited as long as it is a stabilizer for vinyl chloride resin, and examples thereof include tribasic lead sulfate, dibasic lead phthalate, lead orthosilicate-silica gel coprecipitate, and dibasic base. Lead stearate, cadmium-barium stabilizer, barium-zinc stabilizer, calcium-zinc stabilizer, tin stabilizer, and stabilizers mainly composed of inorganic salts such as magnesium, aluminum and silicon. Can be mentioned. The amount of the stabilizer used is 0.1 to 1 per 100 parts by weight of the vinyl chloride resin.
A range of 0 parts by weight, preferably 1 to 5 parts by weight is suitable.

As the lubricant, higher fatty acids or metal salts thereof, various paraffins, higher alcohols, natural waxes, polyethylene wax, fatty acid esters,
Alternatively, a fatty acid amide or the like can be used, and the amount thereof is preferably 0.1 to 2 parts by weight per 100 parts by weight of the vinyl chloride resin. This electric wire coating vinyl chloride resin composition may be used in combination with a plasticizer other than the ester composition of the present invention within a range that does not impair the object of the present invention, and usually other than the above-mentioned essential components. Additives used for vinyl chloride resins, such as flame retardants, antioxidants, UV absorbers,
You may use a filler, a coloring agent, a mold release agent, etc. Furthermore, a chelator, a cross-linking agent, and a cross-linking aid may be added if necessary. Examples of the filler include calcium carbonate, clay, talc, silica-based fine powder, aluminum hydroxide, and the like, and examples of the flame retardant include antimony trioxide, barium borate, zinc borate, zinc oxide, and Examples include chlorinated polyethylene and other halogen-based flame retardants.

The vinyl chloride resin composition for coating electric wires of the present invention can be produced by adding and mixing the above-mentioned essential compounding ingredients to the vinyl chloride resin and, if necessary, the above-mentioned various additives. it can. As the mixer, a blender, a super mixer, a mill, a Banbury mixer or the like which is usually used for processing vinyl chloride resin is used. The thus-produced vinyl chloride resin composition for electric wire coating of the present invention is coated by coating an uncoated electric wire such as a copper wire or an already-covered electric wire by extrusion coating with an extruder. Electric wires can be manufactured.

[0020]

EXAMPLES The embodiments of the present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples and comparative examples, "part" and "%" mean "part by weight" and "% by weight", respectively.

<Preparation of Ester> Example 1 148 g (1 mol) of phthalic anhydride, and as C _9-11 alcohol, the C ₁₀ alcohol component was 2PH 243.3 g.
(1.540 mol) and MPH33.2 g (0.210 mol) (2PH / MPH composition ratio: 88/12), decanol, C ₉ alcohol component isononyl alcohol (obtained from mixed butene as a raw material, The same applies hereinafter) 3
6.0 g (0.250 mol), and C ₁₁ alcohol component is undecanol (decene-1 which is the ethylene pentamer).
86.0 g (0.500)
A total of 398.5 g (C) of mixed alcohols such that
_9-11 alcohol composition ratio 10/70/20), 0.30 g of tetraisopropyl titanate as an esterification catalyst
(0.2% / phthalic anhydride) with a thermometer, nitrogen inlet tube, stirrer, Dean-Stark type water divider (hereinafter simply referred to as "water divider"), and a reflux condenser with an internal volume of 2 liters The flask was charged into a flask and heated under a nitrogen stream while stirring, and the reaction liquid temperature was raised to 210 ° C. to start the reaction. Subsequently, the produced water was continuously removed from the system by a water separator, and the reaction was continued until the acid value of the reaction solution became 5 mgKOH / g or less.
After completion of the reaction, the system was depressurized to recover unreacted C _9-11 alcohol, which was then neutralized, washed with water and dehydrated under reduced pressure by a conventional method.
448 g of phthalic acid diester of _9-11 alcohol was obtained.

The obtained ester was colorless and oily in appearance, and had a hue of 25APHA, an acid value of 0.1 mgKOH / g and an ester value of 250 mgKOH / g. Gas chromatographic analysis of saponification products (hereinafter referred to as "GLC") Retention time was the same as that of isononyl alcohol, 2PH, MPH, and undecanol.

Example 2 As a C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 295.5 g (1.870 mol) and MPH 40.3
g (0.255 mol) (2PH / MPH composition ratio: 88/1
2) decanol, C ₉ alcohol component is isononyl alcohol 18.0 g (0.125 mol), and C ₁₁
The alcohol component is undecanol 43.0 g (0.25
A total of 396.8 g of mixed alcohols such that
Except for using (C _9-11 alcohol composition ratio 5/85/10) performs reaction and post-treatment as in Example 1, C _9-11
446 g of phthalic acid diester of alcohol are obtained. The obtained ester is a colorless transparent oil with an appearance of 25 AP.
HA, acid value 0.1 mgKOH / g, ester value 251 mgKOH / g
The retention time of the saponification product on GLC was the same as that of isononyl alcohol, 2PH, MPH, and undecanol.

Example 3 As a C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 208.6 g (1.320 mol) and MPH 28.4
g (0.180 mol) (2PH / MPH composition ratio: 88/1
2) decanol, the C ₉ alcohol component is isononyl alcohol 54.0 g (0.375 mol), and C ₁₁
The alcohol component is undecanol 107.5 g (0.6
A total of 398.5 g of mixed alcohols such as
Reaction and post-treatment were carried out in the same manner as in Example 1 except that (C _9-11 alcohol composition ratio 15/60/25) was used.
_9-11 phthalic acid diester 446 g was obtained.
The obtained ester is a colorless transparent oily appearance and has a hue of 3
0APHA, acid value 0.1mgKOH / g, ester value 250mgKO
At H / g, the retention times on the GLC of saponification products were consistent with isononyl alcohol, 2PH, MPH, and undecanol, respectively.

Example 4 As a C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 207.4 g (1.313 mol) and MPH 69.1
g (0.438 mol) (2PH / MPH composition ratio: 75/2
5) decanol, the C ₉ alcohol component is isononyl alcohol 36.0 g (0.250 mol), and C ₁₁
The alcohol component is 86.0 g (0.50 g) of undecanol.
08.5 mol) mixed alcohol total of 398.5 g
Reaction and post-treatment were carried out in the same manner as in Example 1 except that (C _9-11 alcohol composition ratio 10/70/20) was used.
447 g of phthalic acid diester of _9-11 alcohol was obtained.
The obtained ester is a colorless transparent oily appearance and has a hue of 3
0APHA, acid value 0.1mgKOH / g, ester value 250mgKO
At H / g, the retention times on the GLC of saponification products were consistent with isononyl alcohol, 2PH, MPH, and undecanol, respectively.

Comparative Example 1 Only C ₁₀ alcohol as C _9-11 alcohol, that is, 2P
H347.6g (2.200mol) and MPH47.4g
(0.300 mol) (2PH / MPH composition ratio: 88/1
395 g (2.500 mol) of decanol consisting of 2) (C
_The reaction and post-treatment were carried out in the same manner as in Example 1 except that _9-11 alcohol composition ratio: 0/100/0) was used to obtain 433 g of a phthalic acid diester of C ₁₀ alcohol. The resulting ester is colorless and oily in appearance and has a hue of 25 APHA.
The acid value is 0.1 mgKOH / g, the ester value is 251 mgKOH / g,
The retention time of the saponified degradation product by GLC is 2 PH each.
And MPH.

Comparative Example 2 As C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 295.5 g (1.870 mol) and MPH 40.3
g (0.255 mol) (2PH / MPH composition ratio: 88/1
2) decanol, C ₉ alcohol component is isononyl alcohol 36.0 g (0.250 mol), and C ₁₁
The alcohol component is undecanol 21.5 g (0.12
Mixed alcohols such that the total amount is 393.3 g.
Except for using (C _9-11 alcohol composition ratio 10/85/5) performs reaction and post-treatment as in Example 1, C _9-11
443 g of phthalic acid diester of alcohol was obtained. The obtained ester is a colorless transparent oil with an appearance of 25 AP.
HA, acid value 0.1 mgKOH / g, ester value 250 mgKOH / g
The retention time of the saponification product on GLC was in agreement with that of isononyl alcohol, 2PH, MPH, and undecanol, respectively.

Comparative Example 3 As C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 271.8 g (1.720 mol) and MPH 37.0
g (0.234 mol) (2PH / MPH composition ratio: 88/1
2) decanol, the C ₉ alcohol component is isononyl alcohol 7.2 g (0.050 mol), and the C ₁₁ alcohol component is undecanol 86.0 g (0.500).
402.0 g (C
_The reaction and post-treatment were carried out in the same manner as in Example 1 except that the composition ratio of _9-11 alcohol was 2/78/20), and 449 g of phthalic acid diester of C _9-11 alcohol was obtained. The obtained ester is a colorless transparent oily appearance, and has a hue of 30APHA,
The acid value is 0.1mgKOH / g, the ester value is 249mgKOH / g,
The retention times of the saponified products by GLC were consistent with isononyl alcohol, 2PH, MPH, and undecanol, respectively.

Comparative Example 4 As C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 191.2 g (1.210 mol) and MPH26.1
g (0.165 mol) (2PH / MPH composition ratio: 88/1
2) decanol, C ₉ alcohol component is isononyl alcohol 90.0 g (0.625 mol), and C ₁₁
The alcohol component is 86.0 g (0.50 g) of undecanol.
Mixed alcohols such that the total amount of mixed alcohols is 0.
Reaction and post-treatment were carried out in the same manner as in Example 1 except that (C _9-11 alcohol composition ratio: 25/55/20) was used.
442 g of phthalic acid diester of _9-11 alcohol was obtained.
The obtained ester is a colorless transparent oily appearance and has a hue of 3
0APHA, acid value 0.1mgKOH / g, ester value 253mgKO
At H / g, the retention times on the GLC of saponification products were consistent with isononyl alcohol, 2PH, MPH, undecanol, respectively.

Comparative Example 5 As C _9-11 alcohol, the C ₁₀ alcohol component was 2
PH 191.2 g (1.210 mol) and MPH26.1
g (0.165 mol) (2PH / MPH composition ratio: 88/1
2) decanol, C ₉ alcohol component is isononyl alcohol 36.0 g (0.250 mol), and C ₁₁
The alcohol component is undecanol 150.5 g (0.8
A total of 403.8 g of mixed alcohols such that
Reaction and post-treatment were carried out in the same manner as in Example 1 except that (C _9-11 alcohol composition ratio: 10/55/35) was used.
450 g of phthalic acid diester of _9-11 alcohol was obtained.
The obtained ester is a colorless transparent oily appearance and has a hue of 3
0APHA, acid value 0.1mgKOH / g, ester value 248mgKO
At H / g, the retention times on the GLC of saponification products were consistent with isononyl alcohol, 2PH, MPH, undecanol, respectively.

Comparative Example 6 Instead of C _9-11 alcohol, isononyl alcohol, the above C ₁₀ alcohol (2PH / MPH composition ratio: 88/1
2) and undecanol alone (2.5 moles per 1 mole phthalic anhydride), Example 1
The esterification reaction was carried out in the same manner as in, to synthesize diisononyl phthalate, diisodecyl phthalate and diundecyl phthalate, respectively. 41.8 g, 312.2 g, and 94.8 g of these phthalic acid esters (C _9-11 alcohol composition ratio in terms of alcohol: 10/70)
/ 20) was used to prepare a phthalate ester mixture.

<Evaluation Method of Ester Composition> (1) Appearance The transparency and presence / absence of impurities are visually evaluated. (2) Hue Based on JIS K6751. (3) Acid value Based on JIS K6751. (4) Ester value Based on JIS K6751.

<Physical Property Evaluation Method> (1) Processability Evaluation The phthalic acid diesters of Examples and Comparative Examples were mixed in the following formulation, and Brabender Plastograph (Brabender) was used.
(Plastic coder PLV151 type, mechanical torque detection method manufactured by K.K.), cell temperature 160 ° C, rotation speed 80rp
The mixture was kneaded at m 2, and the time required to reach the maximum torque value (expressed as "gelling time") was measured. It was determined that the shorter the gelation time, the better the workability.
The evaluation results are shown in Table-1.

[0034]

[Table 1] (Compounding) Vinyl chloride resin 100 parts (Mitsubishi Kasei Vinyl Co., Ltd., trade name Vinica (trademark) 37L, average degree of polymerization 1050) Phthalic acid diester 50 Cd-Ba stabilizer 1

(2) Physical Properties of Sheet (Transparent Blending Test) Using the phthalic acid diesters of Examples and Comparative Examples as a plasticizer, a vinyl chloride resin composition was prepared with the following formulation.

[0036]

[Table 2] (Compounding) Vinyl chloride resin 100 parts (Mitsubishi Kasei Vinyl Co., Ltd., trade name Vinica (registered trademark) 37H, average degree of polymerization 1300) Phthalic acid diester 67 Barium-zinc liquid stabilizer 3

The above blends were premixed in a beaker, thoroughly mixed on a two-mill roll whose temperature was adjusted to 170 ° C. by a conventional method (5 minutes), and then pressed to a predetermined thickness. (Temperature: 175 ° C, preheat: 1.96
2 minutes at MPa (20kg / cm ² ), less: 19.6MPa (200kg / cm 2
² ) for 5 minutes). Using the obtained sheet, the physical properties were measured by the following methods, and the performance of these esters as a plasticizer was evaluated. The results are also shown in Table-1.

Tensile test JIS K67
23. Hardness Based on JIS K6301. Volatilization Loss ASTM D1203-52
Compliant with T. Oil resistance (kerosene extraction amount) A sample having a diameter of 5 cm is weighed, immersed in petroleum (kerosene) at 23 ° C. for 24 hours, and then taken out. The taken-out sample is dried in an air circulation oven at 80 ° C. for 4 hours to remove absorbed petroleum, and then cooled to room temperature in a desiccator. The sample after cooling is re-weighed to determine the amount of loss of plasticizer extracted by petroleum (% by weight). Cold resistance (low temperature flexible temperature) ASTM D1043-51
Compliant with. Water resistance (water absorption) Based on ASTM D570-42. (Weight Loss) Based on ASTM D1239-52T. However, as the sample, a circular flat plate with a diameter of 5 cm was used instead of a square plate with a square of 2 inches.

Soap water extractability In the above oil resistance (kerosene extraction amount), the same as the evaluation of the kerosene extraction amount except that 1% soap water was used in place of petroleum (kerosene) and immersed at a temperature of 50 ° C. for 4 days. Was tested. Compatibility (loop method) Prepare two sheets with a width of 1 cm, a length of 4 cm, and a thickness of 1 mm.
Set in a bending test jig in a letter shape. 23 ° C, 50%
It was placed in the RH room and taken out after 4 hours, 1 day, and 1 week, and the exudation state of the plasticizer at the fold portion (inside) was observed.

The evaluation results are displayed as follows, and it is judged that the ones up to "S" after one week are normally usable. (Judgment) C (compatible): Completely compatible VVS (very, very slightly incompatible): Very slightly incompatible VS (very slightly incompatible): Very slightly incompatible S (slightly incompatible): Slightly incompatible Compatibility

[0041]

[Table 3]

(3) Sheet Physical Properties (Filler Blending Test) Using the phthalic acid diesters of Examples and Comparative Examples as plasticizers, vinyl chloride resin compositions were prepared with the following blending.

[0043]

[Table 4] (Compounding) Vinyl chloride resin 100 parts (manufactured by Mitsubishi Kasei Vinyl Co., Ltd., trade name Vinica (registered trademark) 37H, average degree of polymerization 1300) Phthalic acid diester 50 Calcium carbonate (manufactured by Bihoku Powder Co., Ltd., Trade name Softon 1200) 10 Lubricant (barium stearate) 0.5 Lead-based stabilizer (Shinagawa Kako Co., Ltd., trade name TS-GM) 5

The above blends were premixed in a beaker, thoroughly mixed on a two-mill roll whose temperature was adjusted to 170 ° C. by a conventional method (5 minutes), and then pressed to a predetermined thickness. (Temperature: 175 ° C, preheat: 1.96
2 minutes at MPa (20kg / cm ² ), less: 19.6MPa (200kg / cm 2
² ) for 5 minutes). The obtained sheet was used to measure the physical properties by the following methods to evaluate the performance of these esters as plasticizers. Table 2 shows the results.

Tensile test JIS K67
23. Post-heating tensile test According to JIS K6723. Oil resistance test According to JIS K6723. Cold resistance (brittleness temperature) According to JIS K6723. Volume resistivity Based on JIS K6723. <Evaluation of Results> From the above examples, the following points are recognized in the vinyl chloride resin composition obtained by using the ester composition of the present invention as a plasticizer and the molded article (sheet) obtained from the vinyl chloride resin composition.

Processability: As shown in Table 1, the gelation is faster and the processability is better than those of didecyl phthalate (Comparative Example 1) and those containing a large amount of C ₁₁ alcohol (Comparative Examples 3 and 5). Heat resistance: Didecyl phthalate alone (Comparative Example 1), a large amount of C ₉ alcohol (Comparative Example 4), C _{11 in} both the volatilization loss in Table 1 and the heat resistance test (tensile test after heating) in Table 2 Compared with the one with a small amount of alcohol (Comparative Example 2) and the ester mixture (Comparative Example 6), both volatilization weight loss and weight loss are low and heat resistance is good.

Oil resistance: In the oil resistance test of Table-2, the weight loss is smaller than that of the C ₁₁ alcohol excess (Comparative Example 5). Cold resistance: From Tables 1 and 2, the cold resistance is better than that of didecyl phthalate (Comparative Example 1). Volume resistivity: As shown in Table 2, the volume resistivity is higher than that of C ₁₁ alcohol in excess (Comparative Example 5).

From these results, it is clear that the ester composition of the present invention has a good balance of volatility resistance, heat resistance, cold resistance and workability as a plasticizer for vinyl chloride resin. Also, since the volatilization loss is low and the volume resistivity is high,
It can be said that the vinyl chloride resin composition is particularly suitable for coating electric wires.

[0049]

By blending the ester composition of the present invention with a vinyl chloride resin, it is possible to produce a soft resin product having an excellent balance of physical properties such as processability and cold resistance, and improved heat aging resistance. You can In particular, the composition obtained by blending the ester composition of the present invention as a plasticizer with a stabilizer and a lubricant in a vinyl chloride resin has low volatility and high volume resistivity, and thus is suitable for electric wire coating applications. .

[0050]

[Table 5]

Claims (4)

[Claims] 1. A mixture of aliphatic alcohols having 9, 10 and 11 carbon atoms (hereinafter referred to as "C _9-11 alcohol", and an aliphatic alcohol having 9 carbon atoms, which is an individual component, having 10 carbon atoms. Aliphatic alcohols and aliphatic alcohols having 11 carbon atoms are respectively referred to as “C ₉ alcohol” and “C
₁₀ alcohol ”and“ C ₁₁ alcohol ”), and the composition ratio of C ₉ alcohol, C ₁₀ alcohol and C ₁₁ alcohol in the mixture (total amount of the mixture is 100,
Displayed as the weight composition ratio of C ₉ alcohol / C ₁₀ alcohol / C ₁₁ alcohol, hereinafter "C _9-11 alcohol composition ratio"
Is called (5-20) / (85-50) / (10
An ester composition comprising a phthalic acid diester in the range of 30). 2. The C ₁₀ alcohol in the C _9-11 alcohol is mainly 2-propylheptanol (hereinafter referred to as “2PH”) and 4-methyl-2-propylhexanol (hereinafter referred to as “MPH”). A mixture of aliphatic alcohols having 10 carbon atoms as a component, wherein 2PH is contained in the mixture.
And the weight ratio of MPH (2PH / MPH) is (88-7
0) / (12-30), The ester composition according to claim 1. 3. The ester composition 10 according to claim 1, with respect to a vinyl chloride resin and 100 parts by weight of the resin.
A vinyl chloride resin composition containing about 200 parts by weight of the vinyl chloride resin composition. 4. The ester composition 30 according to claim 1, with respect to a vinyl chloride resin and 100 parts by weight of the resin.
A vinyl chloride resin composition for electric wire coating, which comprises 0.1 to 100 parts by weight, a stabilizer of 0.1 to 10 parts by weight, and a lubricant of 0.1 to 2 parts by weight.