JPH0696659B2 - Chlorinated vinyl chloride resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chlorinated vinyl chloride resin composition. An object of the present invention is to obtain a chlorinated vinyl chloride resin which is stable to heat and has little coloring due to decomposition when heated and melted.

Chlorinated vinyl chloride resin (hereinafter referred to as CPVC)
Is made by chlorinating vinyl chloride resin (hereinafter referred to as PVC). CPVC is expected to have a wide range of uses because it maintains the good properties of PVC as it is and improves the major drawbacks of PVC. Specifically, CPVC has the same excellent weather resistance, fire resistance and chemical resistance that PVC has. On the other hand, PVC has a low heat distortion temperature, so 60-70 ℃
Although it has a major drawback that it cannot be used under the above conditions, CPVC has a heat distortion temperature that is 20-40 ° C higher than that of PVC, which is why it has improved heat resistance of PVC. Therefore, CPVC is opening up a wider range of applications than PVC.

However, the conventional CPVC was not suitable for new applications. This is because when the conventional CPVC is heated to mold it, it is already colored from yellow to brown at the beginning of heating and cannot be colorless and transparent. In other words, the new application to open is
Although it is necessary to be colorless and transparent like electronic parts cases and display boards, conventional CPVC can not be made colorless and transparent because it is already colored yellow only by heating and melting for molding. This is because the. Therefore, in order to aim for new applications, there is no initial coloring during heating and melting,
It was necessary to make a CPVC that produced a clear colorless melt.

This inventor was
Extensive research was conducted to find a way to prevent the division of VC and stabilize CPVC against heat. Generally, stabilization of CPVC is PV
Although it is likely to be considered similar to the stabilization of C, the research result of the present inventor revealed that stabilization of CPVC is significantly different from stabilization of PVC. For example, stabilization of PVC can be achieved by adding basic lead carbonate or metal soaps, but stabilization of CPVC cannot be achieved only by adding these. Therefore, as a result of further research, the present inventor found that an oxypolycarboxylic acid such as tartaric acid was effective in preventing coloration of CPVC during heating and melting, and filed a patent application based thereon. This time, we also discovered that the ester of oxypolycarboxylic acid is effective in preventing coloration of CPVC during heating and melting.

Among the oxypolycarboxylic acids, tartaric acid and malic acid are described in JP-B-53-18227, in which the alkali metal salts thereof have the effect of stabilizing PVC. However, tartaric acid and malic acid alkali metal salts make CPVC opaque and are not suitable for the purpose of making it transparent. However, it was found that when tartaric acid or malic acid is not made into an alkali metal salt and is added in the form of an ester, it is possible to prevent coloration during heating and melting of CPVC, and to make the melting of CPVC transparent. It was

Further, it is disclosed in JP-A-55-164239 that a mixture of a tartaric acid ester and an organic carboxylate acts as a heat stabilizer for PVC.
It is described in Japanese Patent Publication No.

However, it is not mentioned therein that the mixture serves as a heat stabilizer for CPVC. Further, it is described in JP-A-59-142234 that oxypolycarboxylic acid, its partial ester and its salt widely facilitate the processing of polymer materials. It is described therein that those acids, partial esters and salts work effectively for a wide range of olefin-based, urethane-based, butadiene-based and vinyl chloride-based polymer materials. Among them, to see examples of vinyl chloride polymer materials that are explained to work effectively, polyvinyl chloride, ethylene / vinyl chloride copolymer, urethane / vinyl chloride copolymer, vinyl chloride / vinyl acetate copolymer , Ethylene / vinyl acetate / vinyl chloride copolymer, etc., and polyvinylidene chloride, chlorinated polyethylene, and chlorinated polyethylene / acrylonitrolyl / styrene copolymer as the resin containing chlorine. The polymer materials included are comprehensively illustrated, but CPVC is not included therein. Therefore, this publication also fails to teach the improvement of processability for CPVC.

Esters of higher fatty acids are used as a lubricant for PVC by mixing and mixing with PVC. This ester of higher fatty acid is also used as a lubricant for CPVC. However, esters of higher fatty acids have not been used as heat stabilizers. Further, the higher fatty acid constituting the ester as the lubricant does not have a hydroxyl group and is neither an oxycarboxylic acid nor a polycarboxylic acid. Therefore, it is entirely novel that oxycarboic acid and polycarboxylic acid ester are used as heat stabilizers.

The present invention relates to a CPVC composition obtained by adding 0.01-5 parts by weight of an ester of oxycarboxylic acid to 100 parts by weight of CPVC.

In this invention, the stabilizer used is an ester of oxypolycarboxylic acid (hereinafter referred to as HOPE).
Is. The oxypolycarboxylic acid in this case (hereinafter referred to as CA) is a compound having at least one hydroxyl group in the molecule and two or more carboxyl groups. Preferred examples of CA include tartaric acid, tartronic acid, malic acid, α-methylmalic acid, tetrahydroxysuccinic acid, citric acid, 1,2-dihydroxy-1,1,2′-ethanetricarboxylic acid and the like. . HOPE has two or more carboxyl groups, and at least one of them should be esterified. That is, HOPE may contain an unesterified one of the two carboxyl groups. Further, HOPE may be one in which the carboxyl group therein is not esterified, but instead the hydroxyl group is esterified with another carboxylic acid.

Various alcohols can be used as the alcohol for esterifying CA. Among them, preferred chain-type alcohols. Alcohol is monovalent,
It may be divalent or polyhydric alcohol having 3 or more valences. Suitable examples of alcohols include chain monohydric alcohols such as methanol, ethanol, butanol, heptanol, octanol, decanol and stearyl alcohol, polyhydric alcohols such as ethylene glycol, butadiol, glycerol and pentaerythritol, erythritol, sorbitol and mannitol. The sugar alcohol and the like.

When CA has two or more hydroxyl groups, some of them may be esterified with another carboxylic acid.
Other carboxylic acids for esterifying CA are formic acid, acetic acid, propionic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, behenic acid, oxalic acid, succinic acid, sebacic acid, maleic acid and the like.

In the present invention, examples of suitable HOPE include: Tartrate ester of glycerin monostearate represented by Is a monostearate ester of tartaric acid represented by It is a citric acid ester of glycerin monostearate represented by.

In this invention, CPVC 100 parts by weight (hereinafter simply referred to as "part")
0.01 to 5 parts of HOPE is used. Of these, preferred is 0.1 to 1.0 part of HOPE. HOPE need only be added to the CPVC and mixed. The addition time may be any time from when the CPVC is chlorinated to remove the residual chlorine and the by-produced hydrochloric acid in a slurry state until immediately before the molding process. The most suitable time to add CP is just before molding.
It is time to mix various things into VC.

The composition of the present invention contains HOPE 0.01-5 per 100 parts by weight of CPVC.
Since it is made by adding parts by weight, when it is heated and melted, it is stable to heat and produces a transparent melt without coloration, and thus a colorless and transparent molded product. You can Also, since this composition is stable to heat,
When this is heated, it takes a long time until it is divided and blackened. Therefore, it is possible to produce various molded products of good quality by sufficient heating. The composition of the present invention has the advantages described above.

It is impossible to prevent the composition of the present invention from being added with other additives which are usually added in the molding process of CPVC. Other additives are stabilizers, lubricants, processing aids, reinforcing agents, antioxidants, ultraviolet absorbers, plasticizers, dyes, pigments and the like.

Examples and Comparative Examples will be given below to clarify that the resin composition according to the present invention is excellent in that the initial coloring during processing is small and that the blackening time is long.

Example 1 A tartaric acid ester of glycerin monostearate represented by the formula (I) was used as the oxypolycarboxylic acid ester, and 0.5 part of the above ester was added to 100 parts of dry CPVC having a chlorine content of 65% by weight and mixed well, Dioctyltin sulfur-containing stabilizer (TVS # 8831 manufactured by Nippon Kasei) 2 parts, processing aid (METATABLEN P551 manufactured by Mitsubishi Rayon Co., Ltd.) L5 part, lubricant (Hiwax 4202E manufactured by Mitsui Petrochemical Co., Ltd.) 1.0 part, reinforced Add 5 parts of the agent (Kureha BTA IIIN)
After mixing well, use a 6 inch roll for 5 minutes at 180 ℃
After kneading for a minute, a roll sheet was obtained. This roll sheet was cut, laminated and pressed at 180 ° C. for 10 minutes to obtain a pressed plate. The press plate obtained was almost colorless and transparent.

With respect to this breath plate, the difference in yellowness ΔN from the standard plate was measured using a color difference meter manufactured by Nippon Denshoku Industries Co., Ltd.
ΔN was 69. The above-mentioned roll sheet was heated in a gear open at 190 ° C., and the blackening time until the sheet became black was measured. The blackening time was 170 minutes.

Example 2 Instead of the tartaric acid ester of glycerin monostearate used in Example 1, 0.5 part of the monostearic acid ester of tartaric acid represented by color (II) was used.
A roll sheet and a press plate were obtained in exactly the same manner as.

The blackening time of this roll sheet was 170 minutes, and the ΔN of the press plate was 68.

Example 3 The same as Example 1 except that 0.5 part of the citrate ester of glycerin monostearate represented by the formula (III) was used in place of the tartaric acid ester of glycerin monostearate used in Example 1. It processed and obtained the roll sheet and the press plate. The blackening time of this roll sheet is 170
Minutes and ΔN was 71.

Example 4 The same process as in Example 1 was carried out except that the addition timing of the tartaric acid ester of glycerin monostearate represented by the formula (I) was changed. That is, in Example 4, CPVC was made into an aqueous slurry state, the above ester was added thereto, and then dehydrated and dried CPVC was obtained, which was treated in exactly the same manner as in Example 1 to obtain a roll sheet and a press plate. The blackening time was 160 minutes and the ΔN was 66.

Comparative Example 1 A roll sheet and a press plate were obtained in the same manner as in Example 1, except that the tartaric acid ester of glycerin monostearate represented by the formula (I) was not used. Blackening time is 140 minutes, △ N is 81
However, it was confirmed that the thermal stability was inferior to that of any of the examples.

Comparative Example 2 Treatment was carried out in the same manner as in Example 1 except that 0.5 part of glycerin monostearate was simply added instead of the tartaric acid ester of glycerin monostearate represented by the formula (I). Then, a roll sheet and a press plate were obtained. In other words, the comparative example 2 is the comparative example 1
It was carried out by adding 0.5 part of glycerin monostearate to the mixture. Blackening time is 140 minutes, △ N
Was 80.

In Comparative Example 2, the effect of lubrication was slightly recognized as compared with Comparative Example 1, and the thermal stability was not changed at all.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-55-164239 (JP, A) JP-A-59-142234 (JP, A) JP-B-44-7540 (JP, B1) JP-B-51- 17593 (JP, B2) JP-B-52-41785 (JP, B2)

Claims (1)

[Claims] 1. A chlorinated vinyl chloride resin composition obtained by adding 0.01-5 parts by weight of an oxypolycarboxylic acid ester to 100 parts by weight of a chlorinated vinyl chloride resin.