JPH07238197A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To prepare a vinyl chloride resin compsn., contg. a polyester plasticizer, which is less likely to adhere to the surface of a metallic surface of equipment during kneading, molding and fabrication and can offer a long run durability. CONSTITUTION:A vinyl chloride resin compsn. comprises 100 pts.wt. vinyl chloride resin, 20 to 100 pts.wt. polyester plasticizer, and 0.1 to 2 pts.wt. stabilizer contg. at least one metal selected from among potassium, sodium, calcium, and barium, wherein the acid value of the polyester plasticizer is 0.7 to 8mg- KOH/g.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a vinyl chloride resin capable of reducing the contamination of the metal surface of equipment for kneading, molding and processing vinyl chloride resin compositions (collectively referred to as "molding equipment" hereinafter). It relates to a composition. Specifically, it is possible to reduce the generation of deposits during kneading, molding, and processing on the metal surface of molding equipment, etc., thus reducing the frequency of cleaning, enabling stable operation for a long time, and ensuring good quality. The present invention relates to a vinyl chloride resin composition capable of giving a molded product.

[0002]

2. Description of the Related Art Molded articles based on vinyl chloride resin have been widely used because of their easy adjustment of hardness by adjusting the amount of plasticizer, their excellent transparency and their easy coloring. There is. Among them, there are many examples of using trimellitic acid ester or polyester as a plasticizer for applications such as electric wire coatings, housings for electric products, or outdoor sheets, which require durability and non-migratory property. There is.

In molding and processing of these vinyl chloride resins, a vinyl chloride resin, a plasticizer, a stabilizer and, if necessary, a filler, a colorant, etc. are blended and then uniformly mixed. To form a composition, and then kneaded by a kneading machine such as a blender, a Banbury mixer, or a roll mill, and molded / processed by a molding / processing machine such as an extruder, an injection molding machine, or a calender to obtain a molded product having a desired shape. The procedure is general.

In the course of this kneading, molding, and processing, deposits containing components in the composition, such as metal components, fillers, pigments, etc., are formed on the metal surface of the molding equipment that comes into contact with the vinyl chloride resin composition.・ It grows and pollutes the surface, lowers the heat transfer efficiency, and the surface of the molded product may be polluted by peeled deposits, resulting in defective products.Vinyl chloride resin using polyester plasticizer In the kneading, molding, and processing of the composition, an example in which such a phenomenon is particularly noticeable is seen (hereinafter, the phenomenon of deposit formation is referred to as "plate out", and the deposit is referred to as "plate out"). . Therefore, in order to remove this plate-out product, it is necessary to stop the operation, cool the equipment, and then perform the cleaning work, which will significantly impair the productivity of the molded product.Therefore, it is strongly required to prevent plate-out. Has been.

When a stabilizer containing a metal such as potassium, sodium, calcium, barium or the like is used, these metal elements have a high electropositive degree, so that they are compatible with the metal surface of a molding machine or the like. It is said that it is highly prone to plate outs. This measure is generally carried out by adjusting the composition, especially by selecting the stabilizer, but it is necessary to study by trial and error, and it is not always possible to achieve the desired physical properties and thermal stability of the molded product and the prevention of plate-out. Not exclusively.

Japanese Patent Publication No. 2-6776 proposes a method of preventing plate-out in a plastisol composition containing a chemical foaming agent by including a specific solvent in the composition, but it is a countermeasure for non-foaming compounding. Is not mentioned. Further, JP-A-4-24861 discloses a composition containing a specific organic acid metal soap and a glycerin ester in order to improve printability and stickiness of a vinyl chloride resin molded product. This method mainly reduces the squirting of plasticizers and other liquid additives, and there is no teaching about the prevention of the formation of solid plate-outs that contaminate the metal surfaces of molding equipment.

[0007]

In view of the state of the art as described above, the present inventor uses a polyester plasticizer which uses a stabilizer containing at least one metal selected from potassium, sodium, calcium and barium. When kneading, molding, and processing a vinyl chloride resin composition containing the above, a thorough investigation was conducted on a compounding that does not easily cause plate-out to the metal surface of molding equipment, etc., and a polyester plasticizer contained in this composition The present invention has been completed by finding that the plate-out is remarkably reduced by controlling the acid value of ss to a specific range.

That is, the object of the present invention is to reduce the adhesion to the metal surface of molding equipment and the like, thereby reducing the cleaning frequency to improve the productivity and reduce the surface contamination of the obtained product. The present invention aims to provide a vinyl chloride resin composition capable of improving the yield of products.

[0009]

The gist of the present invention is, based on 100 parts by weight of a vinyl chloride resin, 20 to 100 parts by weight of a polyester plasticizer, and a metal selected from the group consisting of potassium, sodium, calcium and barium. In a vinyl chloride resin composition containing 0.1 to 2 parts by weight of a stabilizer containing at least one of the above, the polyester plasticizer used has an acid value of 0.7 to 8 mgKOH / g. A vinyl chloride resin composition.

The present invention will be described in detail below. The vinyl chloride resin in the present invention is a resin containing vinyl chloride as a main constituent unit, such as a homopolymer of vinyl chloride, a copolymer with another copolymerizable comonomer whose main component is vinyl chloride, and the like. Say. As the copolymerizable comonomer, for example, ethylene, propylene, acrylonitrile,
Examples thereof include vinyl acetate, maleic acid or its ester, acrylic acid or its ester, and methacrylic acid or its ester.

The polyester plasticizer used in the present invention has a structure in which a dibasic acid and glycol are polycondensed, and
It is produced by subjecting a dibasic acid and a glycol to an esterification reaction by a conventional method, and its acid value is 0.
7-8 mg KOH / g, preferably 1-3 mg KOH / g
Use what is g. This acid value adjusts the charging ratio of dibasic acid and glycol during the production of polyester,
By adjusting the acid value that determines the end of the reaction,
It can be controlled within a desired range.

When the acid value of the polyester plasticizer is less than 0.7, the effect of preventing plate-out becomes insufficient,
On the other hand, when the acid value exceeds 8, the compatibility between the plasticizer and the vinyl chloride resin becomes insufficient and the plasticizer spouts (“bleed”), and the thermal stability of the composition decreases. To do The polyester plasticizer is used in an amount of 20 to 100 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of the vinyl chloride resin. If the amount used is less than 20 parts by weight, the flexibility expected of the plasticized vinyl chloride resin molded product is insufficient, the plate-out prevention effect is insufficient, and if it exceeds 100 parts by weight, the polyester type used The plasticizer itself tends to squirt out.

The polyester plasticizer preferably has a structure in which a dibasic acid and a glycol having 2 to 9 carbon atoms are polycondensed. As the dibasic acid component of the polyester plasticizer, adipic acid, which is an aliphatic dibasic acid,
Azelaic acid, sebacic acid and the like and aromatic dibasic acids such as phthalic acid, isophthalic acid and terephthalic acid can be exemplified, but among them, compatibility with vinyl chloride resin, availability of raw materials, and obtainable Considering the performance of the polyester-based plasticizer, it is preferable to use an aliphatic dibasic acid, particularly adipic acid.

As the glycol component, an aliphatic dihydric alcohol such as ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, 2, 2-dimethyl-1,3
-Propanediol, 1,6-hexanediol, 3-
Examples include methylpentanediol, octanediol, nonanediol and the like. Glycol has 10 carbon atoms
In the above case, the compatibility of the obtained polyester plasticizer with the vinyl chloride resin tends to decrease.

The polyester type plasticizer is usually end-capped, and the monohydric alcohol or organic acid used for the end capping is, for example, heptanol, 2-ethylhexanol, n-octanol, n-nonanol or mixed butene. Isononyl alcohol produced by oxo reaction of dimer, isodecyl alcohol produced by oxo reaction of propylene trimer, undecanol, and monohydric alcohol such as tridecanol, caprylic acid, lauric acid, palmitic acid, A monovalent carboxylic acid such as stearic acid can be used without any particular limitation, but in view of availability and compatibility with the vinyl chloride resin at the terminal portion, for example, heptanol, 2-ethyl, etc. Hexanol, n-octanol, n-nonanol, isononyl alcohol, etc. Monohydric alcohol, such as lauric acid having a carbon number of 7 to 9 is preferred.

The polyester plasticizer has a molecular weight of 500 to
It is preferably in the range of 5,000, preferably 700 to 3,000. When the molecular weight is less than 500, the non-migration property, which is a characteristic of polyester plasticizers, tends to be insufficient, while 50
When the molecular weight is higher than 00, the viscosity of the plasticizer itself becomes high or becomes solid, so that it tends to be difficult to handle and the compatibility with the vinyl chloride resin tends to decrease.

In the vinyl chloride resin composition of the present invention, a stabilizer containing one or more metals selected from potassium, sodium, calcium and barium is used. The stabilizers containing these metals are excellent in weather resistance and low toxicity, and can be suitably used in combination with the polyester plasticizer. The amount of this stabilizer used is 100% vinyl chloride resin.
0.1 to 2 parts by weight, preferably 0.3 to
It is 1.5 parts by weight. When the amount of the stabilizer is less than 0.1 part by weight, the effect of improving the thermal stability of the composition is insufficient,
Further, even if it is used in an amount of more than 2 parts by weight, the effect of improving the thermal stability does not increase in proportion to the amount added, but also tends to cause spouting and plate out.

Examples of the stabilizer used in the present invention include barium stearate, barium laurate, barium ricinoleate, barium naphthenate, and barium fatty acid salts such as barium 2-ethylhexoate, calcium stearate, calcium laurate, and ricinoleic acid. Fatty acid salts of calcium such as calcium, combinations of these compounds, or one or more of these compounds in combination with salts of fatty acids such as lauric acid and stearic acid such as cadmium and zinc, and if necessary Examples include so-called complex stabilizers such as cadmium-barium-based, barium-zinc-based, and calcium-zinc-based, which are moistened with a liquid substance such as a phosphate ester or a solvent, or dissolved or dispersed in a liquid substance. .

Other types of stabilizers used in the present invention include, for example, sodium tallow, sodium stearate,
Sodium oleate, sodium laurate, potassium tallow, potassium stearate, potassium oleate, one or more sodium or potassium fatty acid salts such as potassium laurate, and sodium or potassium carbonate, carbonic acid as necessary. Hydrogen salt and hydroxide,
Sodium-zinc system, potassium-zinc system, sodium-barium-zinc system, sodium-combination with zinc or barium fatty acid salt, if necessary, moistened as described above, or dissolved or dispersed in a liquid substance. Examples thereof include sodium-based composite stabilizers such as potassium-zinc-based and potassium-based composite stabilizers.

When barium stearate is contained in the stabilizer, plate-out is particularly likely to occur, but the present invention can effectively prevent this. In the present invention, the amount of the polyester plasticizer used per 100 parts by weight of the vinyl chloride resin is P parts by weight (provided that 20 ≦ P ≦ 10.
0), the acid value is A (mgKOH / g) (however, 0.7
≦ A ≦ 8), the amount of the stabilizer containing at least one metal selected from the group consisting of potassium, sodium, calcium and barium is S parts by weight (provided that 0.1 ≦ S ≦
2), when the content of the above metal in the stabilizer is w (% by weight) and the atomic weight of the metal is M, a value obtained from these numerical values by the following formula (1) (hereinafter referred to as “AR value”) But)

[0021]

[Equation 2]

[0022]

## EQU00003 ## 1 ≦ AR, preferably 1.1 ≦ AR (2) and

[0023]

AR ≦ 12, preferably AR ≦ 5 (3)

When the relationship of the above is satisfied, the plate-out prevention effect is particularly remarkable, which is preferable. Formula (1)
In the case where the stabilizer contains two or more kinds of the above-mentioned metals, the content (% by weight) of each metal is represented by w ₁ , w _2.
.. Further, assuming that the respective atomic weights are M ₁ , M _2, ...

[0025]

[Equation 5] Denominator = S × (w ₁ / M ₁ + w ₂ / M ₂ + ...) (4)

In the present invention, the reason why the polyester plasticizer having a specific acid value is effective in preventing plate-out is not clear. For example, potassium, sodium, calcium and barium ions and the polyester plasticizer in the polyester plasticizer may be used. A site showing an acid value, that is, a carboxyl group chemically or electrically forms a weak bond, whereby the stabilizer containing the metal component is stabilized in the vinyl chloride resin matrix and migrates out of the system. It is considered that the carboxyl group in the polyester-based plasticizer is weakly bonded to the metal surface of a molding machine or the like to form a thin film of the polyester-based plasticizer on the surface to prevent the adhesion.

When the AR value is less than 1, the plate-out suppressing effect tends to be insufficient, and when it exceeds 12, the compatibility between the polyester plasticizer and the vinyl chloride resin is insufficient, and the composition The thermal stability of T tends to decrease. The vinyl chloride resin composition of the present invention contains, in addition to the above-mentioned essential components, other plasticizers within a range not exceeding the object of the present invention, and additives usually added to the vinyl chloride resin as necessary. For example, antioxidants, flame retardants, lubricants, fillers, ultraviolet absorbers, colorants such as pigments, surfactants, antistatic agents, etc. may be added.

The composition of the present invention can be manufactured by weighing predetermined amounts of these constituent components, stirring and mixing them. As the mixer, a blender, a super mixer, a mill, a Banbury mixer or the like which is usually used for processing a vinyl chloride resin can be used.

[0029]

EXAMPLES Next, the vinyl chloride resin composition of the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” and “%” indicate “parts by weight” and “% by weight”, respectively, and the pressure display (hPa or mmHg) indicates absolute pressure. <Preparation of polyester plasticizer>

Example 1 (1) Esterification Adipic acid 146 g (1 mol), 1,2-propylene glycol 52.5 g (0.7 mol), 1,3-butanediol 45.0 g (0.5 mol) , And 23.4 g (0.18 mol) of 2-ethylhexanol, a thermometer, a nitrogen introducing pipe (and a pressure reducing nozzle), a stirrer, a Dean-Stark type water divider (hereinafter, simply referred to as “water divider”), And a flask with an internal volume of 1 liter equipped with a reflux condenser and heated while stirring under a nitrogen stream to raise the temperature of the reaction solution to 220 ° C. and continuously generate the produced water by a water separator. Was removed to carry out the reaction. Subsequently, the temperature is kept at 220 ° C. until the distillation of water stops. When the water is no longer distilled off, the pressure inside the system is reduced (about 267 hPa (200 mmHg)), the alcohol is refluxed, and the water is further removed by a water divider. During this operation, a sample was sampled at any time to measure the acid value. When the acid value reached about 15 mgKOH / g, the esterification reaction was terminated and the process proceeded to the next condensation step. Reaction time up to here is about 6
It was time.

(2) Condensation 0.012 g of tetraisopropyl titanate was added to the reaction system after completion of esterification, and the reaction temperature was 220 ° C. for about 7 h.
The pressure is reduced to Pa (5 mmHg), and 2-ethylhexanol and glycols produced by condensation are distilled off. About 3
After reacting for a time, the viscosity is 5000 ± 500 mPa · s (cp
s) (at this time 5000 mPa · s (cps))
The heating was stopped to terminate the reaction, and the acid value was 1.0 (mgKOH /
g), 204 g of a polyester plasticizer having a molecular weight of 2250 was obtained.

Example 2 An esterification reaction and a condensation reaction were carried out in the same manner as in Example 1, but the ester reaction was terminated when the acid value was about 14 mgKOH / g, and then the condensation reaction was conducted to obtain a viscosity of 5020 mPa.
The process was repeated until s (cps) was reached to obtain 205 g of a polyester plasticizer having an acid value of 0.9 (mgKOH / g) and a molecular weight of 2250.

Example 3 The amount of 2-ethylhexanol for end-capping was 26.0 g.
The esterification reaction was carried out in the same manner as in Example 1 except that the amount was adjusted to (0.20 mol) until the acid value reached about 12 mgKOH / g, and then the condensation reaction was carried out at a viscosity of 5170 mPa · s (cps).
Until acid value 0.7 (mgKOH / g), molecular weight 2
203 g of 300 polyester plasticizers were obtained.

Comparative Example 1 The acid value for completing the esterification reaction was set to about 10 mgKOH / g, and the subsequent condensation reaction had a viscosity of 5500 mPa.s (cp).
s) was carried out in the same manner as in Example 3 except that the acid value was 0.6 (mgKOH / g) and the molecular weight was 2450.
200 g of polyester plasticizer of

Comparative Example 2 The acid value for completing the esterification reaction was set to about 8 mgKOH / g,
The reaction was performed in the same manner as in Example 3 except that the subsequent condensation reaction was carried out until the viscosity reached 5400 mPa · s (cps), and 207 g of a polyester plasticizer having an acid value of 0.5 (mgKOH / g) and a molecular weight of 2350. Got

Comparative Example 3 39.0 g of 2-ethylhexanol for end-capping was used.
In the same manner as in Example 1 except that (0.30 mol) was used, the esterification reaction was carried out until the acid value reached about 1 mgKOH / g, and the condensation reaction was carried out until the viscosity reached 5180 mPa · s (cps). Then, 215 g of a polyester plasticizer having an acid value of 0.2 (mgKOH / g) and a molecular weight of 2300 was obtained.

Example 4 103.5 of 1,2-butanediol was used as glycol.
g (1.15 mol) and 19.5 g (0.15 mol) of 2-ethylhexanol for terminal blocking were used, the esterification reaction and condensation reaction were carried out in the same manner as in Example 1 to obtain the acid. When the value is about 15 mgKOH / g, the ester reaction is terminated, and then the condensation reaction is carried out with a viscosity of 5070 mPa · s (cp
s), acid value 1.2 (mgKOH / g), molecular weight 2
220 g of 050 polyester plasticizer was obtained.

Example 5 The acid value for terminating the esterification reaction was set to about 15 mgKOH / g, and the subsequent condensation reaction had a viscosity of 4800 mPa.s (cp).
s) was carried out in the same manner as in Example 4 except that the acid value was 0.9 (mgKOH / g) and the molecular weight was 1900.
218 g of a polyester plasticizer of

Example 6 The acid value for terminating the esterification reaction was set to about 13 mgKOH / g, and the subsequent condensation reaction had a viscosity of 5500 mPa.s (cp).
s) was carried out in the same manner as in Example 4 except that the acid value was 0.7 (mgKOH / g) and the molecular weight was 2200.
218 g of a polyester plasticizer of

Comparative Example 4 26.0 g of 2-ethylhexanol for end-capping was used.
The esterification reaction and the condensation reaction were carried out in the same manner as in Example 4 except that the amount was (0.20 mol), and the acid value was about 10
The ester reaction is terminated at mgKOH / g, and then the condensation reaction is performed until the viscosity reaches 5000 mPa · s (cps),
215 g of a polyester plasticizer having an acid value of 0.5 (mgKOH / g) and a molecular weight of 2050 was obtained.

Comparative Example 5 The acid value for completing the esterification reaction was set to about 3 mgKOH / g,
Reaction was performed in the same manner as in Comparative Example 4 except that the subsequent condensation reaction was carried out until the viscosity reached 5100 mPa · s (cps), and 216 g of polyester plasticizer having an acid value of 0.3 (mgKOH / g) and a molecular weight of 2100. Got

Comparative Example 6 39.0 g of 2-ethylhexanol for end-capping was used.
The esterification reaction was carried out in the same manner as in Comparative Example 4 except that (0.30 mol) was used until the acid value reached about 1 mgKOH / g, and subsequently the condensation reaction was carried out at a viscosity of 5280 mPa.s (cps).
Until acid value 0.1 (mgKOH / g), molecular weight 2
217 g of 100 polyester plasticizers were obtained.

Examples 7 to 18 and Comparative Examples 7 to 16 Polyester-based plasticizers were produced in the same manner as in the above Examples and Comparative Examples with the charging composition and reaction conditions shown in Table 2. The yield of the polyester-based plasticizer and the acid value and molecular weight of the obtained polyester-based plasticizer are shown in Table 2 together. <Evaluation method of polyester plasticizer>

[0044]

[Table 1] (1) Viscosity The viscosity was measured at 25 ° C with an E-type viscometer (manufactured by Tokimec Co., Ltd.). (2) Acid value Based on JIS K6751.

<Plate-Out Evaluation Method> In the test formulation below, each component including the polyester plasticizer of the examples or comparative examples was weighed out, and the formulation was premixed in a beaker to prepare a vinyl chloride system. After the resin composition was prepared, the temperature was adjusted to 160 ° C. by a conventional method, and two mill rolls (gap 0.
2 mm) and kneading for 2 minutes after gelling. After a lapse of a predetermined time, the sheet of the test composition is taken out, the composition of the cleaning composition is added, the mixture is kneaded for 5 minutes under the same conditions, and then the sheet is taken out.

[0046]

<Table 2> <Test formulation> Vinyl chloride resin 100 parts (Central PVC SG-1300 manufactured by Mitsubishi Kasei Vinyl Co., Ltd., average degree of polymerization 1300) Polyester plasticizer 60 Barium stearate (stabilizer) 0.5 Zinc stearate (Stabilizer) 0.3 Titanium white (Pigment) 2

[0047]

[Table 3] <Cleaning formulation> 100 parts of vinyl chloride resin (Central PVC SG-1300 manufactured by Mitsubishi Kasei Vinyl Co., Ltd., average degree of polymerization 1300) DOP 50 Epoxidized soybean oil 3 Phosphite chelator-0.5 hydrotalcite 2 Zinc stearate 0.3

The degree of plate-out is evaluated by visually observing the transparency of the sheet of the cleaning composition thus obtained and the surface condition of the roll after kneading in the test composition. The evaluation results are shown below. ◯: The sheet is transparent and there is no stain on the roll. Δ: The sheet has some cloudiness, but transparency is maintained. X: The sheet is clouded and has almost no transparency. *: The sheet was transparent, but liquid matter adhered to the roll surface. (So-called "bleeding" occurred.) The evaluation results are summarized in Table-1 and Table-2.

[0049]

[Table 4]

[0050]

[Table 5]

<Evaluation of Results> From the above Examples and Comparative Examples, a vinyl chloride resin composition containing a polyester plasticizer having an acid value within a specific range of the present invention was used for kneading. Plate out to the roll surface,
It was found to be significantly less than those outside the scope of the invention.

[0052]

INDUSTRIAL APPLICABILITY The vinyl chloride resin composition containing the polyester plasticizer having a specific acid value according to the present invention causes less plate-out during kneading, molding and processing, and therefore, cleaning frequency of molding equipment etc. It is possible to reduce the number of times, and it is possible to lengthen one continuous operation time, and it is possible to increase the productivity of molded products. In addition, the possibility that the plate-out product will contaminate the surface of the molded product is reduced, and product quality and yield are improved.

Claims (5)

[Claims] 1. To 100 parts by weight of vinyl chloride resin,
Stabilizer containing 20 to 100 parts by weight of polyester plasticizer and at least one metal selected from the group consisting of potassium, sodium, calcium and barium 0.1
In a vinyl chloride resin composition containing 2 parts by weight, the acid value of the polyester plasticizer used is 0.7
A vinyl chloride resin composition, which is 8 mgKOH / g. 2. The acid value of the polyester plasticizer is 1 to 3 m.
The vinyl chloride resin composition according to claim 1, which is gKOH / g. 3. The polyester plasticizer has a structure in which a dibasic acid and a glycol having 2 to 9 carbon atoms are polycondensed, and has a molecular weight of 500 to 5000. Vinyl chloride resin composition. 4. The amount of polyester plasticizer used per 100 parts by weight of vinyl chloride resin is P parts by weight, and the acid value thereof is selected from the group consisting of A (mgKOH / g), potassium, sodium, calcium and barium. When the amount of the stabilizer containing at least one metal is S parts by weight, the content of the above metal in the stabilizer is w (wt%), and the atomic weight of the metal is M, these values are obtained. The vinyl chloride resin composition according to any one of claims 1 to 3, wherein the value of the following formula (hereinafter referred to as "AR value") is in the range of 1 to 12. [Equation 1] 5. The vinyl chloride resin composition according to claim 1, wherein the stabilizer contains barium stearate.