JPH02155942A - Vinyl chloride resin composition - Google Patents

Abstract

PURPOSE:To make it possible to improve remarkadly heat resistance without spoiling flexibility, processability, oil resistance and other characteristics by compounding a vinyl chloride resin with a lead silicate stabilizer and a specified polyester plasticizer at a specified ratio. CONSTITUTION:This vinyl chloride resin compsn. contains 100pts.wt. vinyl chloride resin, 0.1-20pts.wt. lead silicate stabilizer and 10-200pts.wt. polyester plasticizer of formula I or II contg. at least 97wt.% component with n=1 or larger and a viscosity of 100-20,000cps at 25 deg.C. In formulas I and II, A is a residue of a monohydric alcohol and a group obtd. by removing a hydroxyl group from a monohydric alcohol; D is a residue of a dibasic acid and a group obtd. by removing carboxyl groups from a dibasic acid; G is a residue of a dihydric alcohol and a group obtd. by removing hydroxyl groups from a dihydric alcohol; L is a residue of a monobasic acid and a group obtd. by removing a carboxyl group from a monobasic acid; n is a number of 0 or 1 or larger; A and D, D and G, and L and G are each bound through an ester bond (-coo-).

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a vinyl chloride resin composition.

Specifically, the present invention relates to a soft vinyl chloride resin composition having excellent heat resistance.

(Prior art) Vinyl chloride resins are used in a wide range of applications, but especially when applied to the fields of wire coatings, sheets, and hoses that require a high degree of heat resistance, tribasic resins are used as stabilizers. Lead-based heat-resistant stabilizers such as lead sulfate, dibasic lead phthalate, and dibasic lead phosphite are used, and as a plasticizer, diisodecyl phthalate CDI is used in areas with moderate heat resistance.
Phthalate esters such as DP), diundecyl phthalate (DtJP), and ditridecyl phthalate (DTDP) are used, and in fields where a high degree of heat resistance is required, trioctyl trimethy) (TOTM), Monomeric plasticizers such as tetraoctyl bilomerite (TOPM) are used.

On the other hand, polyester plasticizers are used in applications that require durability such as oil resistance and migration resistance, but the higher the molecular weight of these plasticizers, the better they are in terms of heat resistance. On the other hand, it has the drawback of poor flexibility, high viscosity, and difficulty in handling, and when used in combination with the lead-based heat-resistant stabilizer, it is easily decomposed and loses its high molecular weight characteristics.

Composite stabilizers such as barium-zinc stabilizers and cadmium-barium stabilizers are effective in suppressing the decomposition of plasticizers, but sufficient heat resistance cannot be obtained in these cases.

Furthermore, in order to suppress the decomposition of polyester plasticizers, it is known that basic lead silicate is used as a stabilizer.
However, sufficiently satisfactory heat resistance has not been obtained.

(Problems to be Solved by the Invention) The object of the present invention is to obtain a vinyl chloride resin composition that has excellent heat resistance without impairing flexibility, processability, oil resistance, and other properties. It is.

(!J::Means for Solving the Problem) The present inventors have solved the above-mentioned drawbacks of the prior art, and as a result of studies aimed at improving the heat resistance of vinyl chloride resin 4 (1). , polyester plasticizers generally have a wide molecular weight distribution, of which low molecular weight components are
Based on this knowledge, we focused on the fact that this was the cause of the p-property being inhibited, and by using a specific polyester plasticizer and stabilizer at a specific m ratio, we were able to achieve the above objective. The present invention has been completed to achieve this. That is, the gist of the present invention is that vinyl chloride resin +00
0.1 to 20 parts by weight of a lead silicate stabilizer to m part of silica, and the general formula [11 or [2] A - D + G - D to A ---- [13L ”
G + D CE±L ----- [2] [In the formula, A is a residue of a monohydric alcohol and a group obtained by removing a hydroxyl group from a monohydric alcohol, and D is a residue of a dibasic acid and a group obtained by removing a hydroxyl group from a dibasic acid. Carbo A is a group from which the syl group has been removed, G is a residue of a dihydric alcohol and is a group from which the hydroxyl group has been removed from the dihydric alcohol,
1, represents a group obtained by removing a carboxyl group from a monobasic acid as a residue of a basic acid, n represents a number of 0 or 1 or more, and A
In addition, D and G, and L and G are all ester bonds (-C
oo-), and n=
Contains at least 97% of one or more ingredients, and 2
The present invention relates to a vinyl chloride resin composition containing 10 to 200 parts by weight of a polyester plasticizer having a viscosity of 100 to 20.000 cps at 5°C.

The present invention will be explained in detail below.

In addition to polyvinyl chloride resins, the vinyl chloride resin in the present invention includes copolymers of vinyl chloride and other monomers containing vinyl chloride as a predominant component, or mixtures thereof. Moreover, regardless of the polymerization method, suspension polymerization products, emulsion polymerization products, and bulk polymerization products can all be applied. Examples of copolymerizable monomers include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, acrylic acid, methacrylic acid, maleic ester, acrylic ester, and methacrylic ester.

The lead silicate stabilizer used in the present invention includes PbO/
It is desirable that the weight ratio of 5i02 is in the range of 9575 to 30/To, such as lead metasilicate, lead orthosilicate,
51 with silica gel co-precipitated lead silicate, basic lead silicate or Pbo
It can be used alone or in a mixture of two or more, such as a mixture with 02. Among these, one prepared by firing and pulverizing a mixture of Pbo and 5102 within the above range is particularly recommended.

Next, the polyester plasticizer used in the present invention is not particularly different from known polyester plasticizers in terms of its constituent components, as will be described later.
Contains at least 97% by weight of components having a value of n in formula 1F and [21], and has a viscosity of 1 at 25°C.
00 to 20,000 cps, and this point is a major feature of the present invention.

In general, polyester plasticizers are prepared using dibasic acids and dihydric alcohols, alcohol as a molecular weight regulator, or -
The polyester plasticizer obtained in this way has a wide molecular weight distribution, with the minimum molecular weight component being a substance in which n is O in formulas [1 and 21]. It consists of a mixture of substances, and in some cases also contains raw dibasic acids and dihydric alcohols, -hydric alcohols or -basic acids, and the presence of these low molecular weight components in the plasticizer As a result, it becomes a cause of inhibiting the heat resistance of vinyl chloride resin.

The plasticizer of the present invention was selected based on the above-mentioned findings. That is, in the plasticizers represented by formulas [1] and [2], when the content of the component where n is 1 or more is less than 97% by weight, chloride having a high degree of heat resistance is used as shown in the examples below. Vinyl resin cannot be obtained. Also 25℃
Even in the case of an ungrooved plasticizer with a viscosity of 100 cps, a vinyl chloride resin with excellent heat resistance cannot be obtained. On the other hand, if the plasticizer has a viscosity higher than 20,000 cps at 25°C, the flexibility and processability of the vinyl chloride resin will be impaired. A particularly preferred viscosity at 25°C is 20
0 to 10,000 cps.

Dibasic acid component in the polyester plasticizer of the present invention (
As component D), various well-known aliphatic, aromatic, and alicyclic dibasic acids or anhydrides thereof are used. Specific examples include adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof, and one type or a mixture of two or more of these may be used.

In addition, as the dihydric alcohol component (G component), well-known diols such as ethylene glycol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 , 2-dimethyl-1,3-propanediol, 1,6-hexanediol, and the like.

Furthermore, m alcohols (A component) and -basic acid (L component)
2 to 2 carbon atoms, which are well known as molecular weight regulators, respectively.
2 preferably 6 to 18 m alcohols and -basic acids are used. - Examples of alcohols include hexanol, heptatool, n-octatool, 2-ethylhexanol, nonanol, decanol, undecanol,
Tridecanol, stearyl alcohol, etc., and examples of basic acids include caproic acid, caprylic acid, lauric acid, myristic acid, stearic acid, coconut oil fatty acid, etc.

The ratio of dibasic acid and dihydric alcohol used in producing the polyester plasticizer of the present invention varies greatly depending on whether monobasic acid or dihydric alcohol is used as the molecular weight regulator, but It is usually desirable to use 0.1 to 4 equivalents of dibasic acid per equivalent of dihydric alcohol. In addition, the amount of m alcohols used as a molecular weight regulator is 0.02 to 6 m alcohols per equivalent of dihydric alcohol.
The amount of -basic acid used is preferably 0.02 to 4 equivalents per equivalent of dihydric alcohol.

More specifically, for example, when m alcohols are used as molecular weight regulators, the molar ratio of dihydric alcohols is 20 to 49, the molar ratio of dibasic acids is 40 to 50, and the -hydric alcohols are 40 to 49 molar ratios.
A molar ratio of 40 to 2 is suitable, and when a basic acid is used as a molecular weight regulator, a dihydric alcohol of 40 to
50 molar ratio, dibasic acid 20-49 molar ratio, -basic acid 40
The molar ratio is preferably in the range of 2 to 2 molar ratios.

In order to produce the polyester plasticizer of the present invention, first, the above-mentioned dibasic acid or its anhydride is directly condensed with a dihydric alcohol, or a lower alkyl ester of the above-mentioned dibasic acid and A conventional polyester plasticizer is produced by reacting it with a dihydric alcohol.

For example, the above-mentioned dibasic acid and dihydric alcohol, and the monobasic acid or m alcohol as a molecular weight regulator,
The reaction is carried out in the presence or absence of a catalyst, if necessary by heating in a nitrogen atmosphere, and at a temperature above the boiling point (azeotropic point) of the reaction mixture while removing water produced by the reaction. After the reaction has progressed to a certain extent, the pressure in the system is reduced, and while gradually increasing the degree of vacuum, excess alcohol, molecular ffi regulator, etc. are removed. The temperature at the end of the reaction is usually about 200°C
, the pressure is 1-10 mm11g. In addition, in the early stage of the reaction, only the dibasic acid and the dihydric alcohol are reacted, if necessary, using a solvent that is azeotropic with water but not compatible, such as toluene or xylene, to maintain a certain acid value or hydroxyl value. Once obtained, a molecular weight regulator can be added to continue the reaction.

As the catalyst, well-known catalysts such as sulfuric acid, phosphoric acid, p-
) Acid catalysts such as luenesulfonic acid, titanium compounds such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate, tetrabutyl titanate, diethyltin dilaurate, dibutyltin oxide, dibutyltin diacetate,
Examples include combinations of tin compounds such as tin oxide, acetates of magnesium, calcium, zinc, etc., and antimony oxide or the above-mentioned titanium compounds.

The polyester plasticizer obtained by the well-known method described above is composed of a mixture of substances having a wide molecular weight distribution, with the minimum molecular weight component being a substance in which n is 0 in formulas [1] and [2]. In some cases, it also contains dibasic acids and dihydric alcohols as raw materials, -hydric alcohols, or -basic acids. contains at least 97% by weight of one or more components, and has a viscosity of 1 at 25°C.
00 to 20,000 cps.

As a purification means, for example, a method of distillation using a molecular distillation apparatus is advantageous. Molecular distillation equipment includes batch type,
Although any type such as a falling film type or a centrifugal type may be used, the falling 711 membrane type or centrifugal type is usually used industrially. In the case of the falling thin film type, the evaporation area is 0.5 to 112, and the number of revolutions is 2.
In the case of a centrifugal type, an evaporation area of 0.1 to 0.8 m2 and a rotation speed of about 100° rpm are used. In addition, the operating temperature during distillation is 100-3
The temperature is 00°C, preferably 130 to 240°C, and the operating pressure during distillation is about 10 to +01 torr.

The vinyl chloride resin composition of the present invention contains 0.1 to 20 parts by weight of a lead silicate stabilizer and 10 to 200 parts by weight of the above polyester plasticizer per 100 parts by weight of the vinyl chloride resin. It is what it is. The amount of lead silicate stabilizer is 0.
If it is less than 1 part by weight, heat resistance will not be sufficient, and if it exceeds 20 parts by weight, the specific gravity will increase and the cost of the product will increase, which is not preferable. Furthermore, if the amount of the polyester plasticizer is less than 10 parts by weight, the plasticizing effect will not be sufficient, and if the amount exceeds 200 parts by weight. This causes plasticizer to ooze out, making it impossible to obtain a desirable product.

In the vinyl chloride resin composition of the present invention, in addition to the above-mentioned lead silicate stabilizer and polyester plasticizer, other additives are used in the field of processing vinyl chloride resins to the extent that the purpose of the present invention is not impaired. Other well-known plasticizers, heat-resistant stabilizers may be used in combination, and well-known ultraviolet stabilizers, antioxidants,
Flame retardants, lubricants, fillers, colorants, etc. can be added.

The vinyl chloride resin composition of the present invention is prepared by adding predetermined amounts of the lead silicate stabilizer and polyester plasticizer to the vinyl chloride resin, and further adding the above additives if necessary.
It is prepared by uniformly mixing or kneading and is used for various purposes such as films, sheets, containers, flooring materials, and wall materials.

(Examples) The present invention will be described in more detail below with reference to Examples and Reference Examples, but the present invention is not limited to these unless it exceeds the gist thereof.

The acid value of the polyester plasticizer in the reference example was measured in accordance with JISK 0070, and the viscosity was measured at 25° C. using an E-type viscometer.

In addition, the composition of the polyester plasticizer was measured by gel permeation chromatography (GPC), and the content of n = 1 or more! (%) was determined from the area ratio of peaks with n=o and n=1 or more. Furthermore, in Examples and Comparative Examples, "parts" means "parts by weight" unless otherwise specified.

Reference Example 1 (Preparation of polyester plasticizer) 146 g of adipic acid and 1 1.2-butanediol were placed in a reaction vessel equipped with a thermometer, a fractionating tube, a nitrogen introduction tube, a stirrer, a reflux condenser, etc.
088 and 2-ethylhexanol (molecular weight regulator) 3
Add 2g and heat while stirring under a nitrogen stream to 22
The temperature was raised to 0°C. Next, 0.05 m of tetraisopropyl titanate (catalyst) was added and the reaction was carried out at the same temperature, and the water produced during this time was continuously distilled out of the system from the fractionating tube until the acid value of the reaction liquid was 1 mg. The reaction was continued until the temperature dropped below KOH/g. Thereafter, the pressure inside the system was reduced to 5 mm Hg or less, and the reaction was carried out at 220° C. for 3 hours to obtain a polyester plasticizer (referred to as undistilled plasticizer A). The content of components with n=1 or more in this substance was 96.3%, and the viscosity at 25°C was 3,000 cps.

This undistilled plasticizer A was evaporated using a falling thin film type molecular distillation apparatus [Shibata Molecular Distillation Apparatus MS (special) type], with an evaporation area of 0.5
m+2, rotation speed 150 rpm, operating temperature 180°C, operating pressure 2X 101 torr, the content of components n = 1 or more is 98.8%, and the viscosity at 25°C is 3,500 cps. (referred to as refined plasticizer A)
I got it.

Reference Example 2 (Preparation of polyester plasticizer) Instead of 108 g of 1,2-butanediol used in Reference Example 1, 1
, 3-butanediol and 1,4-butanediol (50:50) was used, and 52 g of undecyl alcohol was used instead of 32 g of 2-ethylhexanol. A polyester plasticizer (referred to as undistilled plasticizer B) was obtained by reacting under similar conditions. The content of components with n=1 or more in this substance was 95.5%, and the viscosity at 25°C was 800 cps.

This undistilled plasticizer was evaporated using the falling film type molecular distillation apparatus in Example 1, with an evaporation area of 0.5 m2 and a rotation speed of 150.
rpm operating temperature 180℃, operating pressure 2X 1O-2t
orr, and the component content of n=1 or more is 97.
A plasticizer (referred to as purified plasticizer B) with a viscosity of 1,400 cps at 25° C. was obtained.

Example 1 Polyvinyl chloride resin (Mitsubishi Kasei Vinyl Co., Ltd. U 5G130
0, a homopolymer with a degree of polymerization of 1300), 50 parts of the purified plasticizer A obtained in Reference Example 1 and a lead silicate stabilizer (
Mizusawa Chemical Co., Ltd. BALS-5, PbO/5i02:85/
15 mixed calcined product), and further calcium carbonate (
Filler), lead stearate (lubricant), and bisphenol A (monidation inhibitor) were added, kneaded using a mill roll, and then pressed to a thickness of 0.5 mm. The obtained sheet was inserted into a gear oven and heated at 136°C for 7 days.
After being held at 158°C for 3 days and 14 days at 158°C, it was taken out.

Measure the weight of the sheet before and after inserting it into the oven,
Table 1 shows the percentage (%) of the difference in weight between the two, divided by the weight before insertion into the oven, as the weight loss.

Example 2 A polyvinyl chloride resin sheet was prepared in the same manner as in Example 1, except that 50 parts of purified plasticizer B obtained in Reference Example 2 was used instead of purified plasticizer A used in Example 1. The weight loss measured by the same test method as in Example 1 is shown in Table 1.

Comparative Example 1 A polyvinyl chloride resin sheet was produced in the same manner as in Example 1, except that 50 parts of the undistilled plasticizer A obtained in Reference Example 1 was used instead of the purified plasticizer A used in Example 1. The weight losses prepared and measured by the same test method as in Example 1 are shown in Table 1.

Comparative Example 2 A polyvinyl chloride resin sheet was produced in the same manner as in Example 1, except that 50 parts of undistilled plasticizer B obtained in Reference Example 2 was used instead of the purified plasticizer used in Example 1. SF! ! ! Table 1 shows the weight loss measured by the same test method as in Example 1.

Comparative Example 3 Polysalt 1 hibinyl resin was prepared in the same manner as in Example 1, except that 5 parts of tribasic lead sulfate (3Pbo-PbS04.+120) was used instead of the lead silicate stabilizer used in Example 1. A sheet was prepared and the heavy ffi loss measured by the same test method as in Example 1 is shown in Table 1.

Comparative Example 4 In place of the purified plasticizer A used in Example 1, 50 parts of the undistilled plasticizer obtained in Reference Example 1 was used, and in place of the lead silicate stabilizer used in Comparative Example 3. A polyvinyl chloride resin sheet was prepared in the same manner as in Example 1 except for using 5 parts of tribasic lead sulfate, and the weight loss measured by the same test method as in Example 1 is shown in Table 1.

Comparative Example 5 50 parts of trioctyl trimate (TOTM) was used instead of the purified plasticizer A used in Example 1, and the tribasic lead sulfate used in Comparative Example 3 was used instead of the lead silicate stabilizer. A polyvinyl chloride resin sheet was prepared using 5 parts by the same method as in Example 1, and the heavy ffi loss measured by the same test method as in Example 1 is shown in Table 1.

(Note) Lead silicate stabilizer: f'bQ/5iOt45/
+5 mixed compound tribasic W lead: 3PbO-PbSO
a・1120-0 "[i Nitrioctyltrimethate (Effects of the Invention)] As shown in Table 1, the vinyl chloride resin composition of the present invention contains the above-mentioned specific polyester plasticizer and lead silicate stabilizer. By using it in a specific amount ratio, there is less weight loss due to high temperature treatment, and it can be applied to the fields of electric wire coatings, sheets, and hoses that require a high degree of heat resistance, and its practical use. The value above is great.

Claims (1)

[Claims] (1) 100 parts by weight of vinyl chloride resin, 0.1 to 20 parts by weight of lead silicate stabilizer, and the following general formula [1] or [2] ▲There are mathematical formulas, chemical formulas, tables, etc.▼...・[1] ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [2] [In the formula, A is the residue of a monohydric alcohol and is the group obtained by removing the hydroxyl group from the monohydric alcohol, and D is a dibasic acid. G is a residue of a dihydric alcohol and is a group obtained by removing a hydroxyl group from a dihydric alcohol, and L is a residue of a monobasic acid and is a group obtained by removing a hydroxyl group from a dibasic acid. Each represents a group excluding a carboxyl group, n represents a number of 0 or 1 or more, and A and D, D and G, and L and G are all bonded by an ester bond (-COO-)] and contains at least 97% by weight of a component with n=1 or more, and has a viscosity of 100 to 20 at 25°C.
,000cps polyester plasticizer 10-20
0 parts by weight of a vinyl chloride resin composition.