JPS59140261A - Novel halogen-containing resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has improved thermal stability during processing and gives moldings having excellent low-temperature aging properties, by adding a mixed product of a hydrotalcite compd. and perchloric acid to a halogen-contg. resin. CONSTITUTION:The titled stabilized compsn. is obtd. by adding a mixed product obtd. by mixing one mol of a hydrotalcite compd. [MgxAl2(OH)yCO3.zH2O, wherein x is 4-6, y is 12-16 and z is 3-5] with 2-0.001mol of perchloric acid, to a halogen-contg. resin such as PVC. By adding the mixed product, the thermal stability of the halogen-contg. resin during processing can be improved and moldings having excellent low-temperature ageing properties can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a stabilized halogen-containing resin composition.

Specifically, the present invention relates to a new stabilized halogen-containing resin composition C obtained by adding a mixed product of a 71-hydrotalcite compound with perchloric acid to a halogen-containing resin.

Conventional halogen-containing resin 1, for example, vinyl chloride resin (or alone or together with chlorinated polyethylene).

Polymer blends with EVA, MBS, ABS, acrylic resin, etc. are also used as stabilizers.

It contains colorants, fillers, lubricants, etc., and is widely used in various molded products.

However, halogen-containing resin has a processing temperature of 175°C during molding.
It is easy to cause thermal decomposition reactions due to desalinating acid reactions within molecular chains in the vicinity (conventional stabilization of halokene-containing resins has focused on suppressing this decomposition reaction).

However, molded products often undergo thermal deterioration during use.9For example, in the summer, the surface temperature of molded products used outdoors can reach 80°C or more due to the energy of sunlight.
The temperature rises to around 90℃.

In addition, the wire coating material is also continuously exposed to a considerable temperature atmosphere during use, and therefore has a temperature of 90% according to JISC3005.
A deterioration test at temperatures between 120°C and 120°C has been attempted.

Improving the durability of polymeric materials whose main raw material is petroleum is an important issue from the viewpoint of saving resources, saving energy, and ensuring safety.
A comparative study was made of deterioration at around 0°C to 140°C (this is called low-temperature aging, hereafter) and deterioration at around 175°C to 200°C during processing.

We developed a halogen-containing resin composition and completed the present invention.

The present invention is directed to a halogen-containing resin, in which 100 parts by weight of the resin is added to 1 mole of a hydrotalcite compound.

When 0.001 to 100 parts by weight of the mixed product was mixed at a molar ratio of 2 to 0.001 moles of perchloric acid, the thermal stability near the processing temperature was improved.

Although the factors contributing to the effects of the present application are not necessarily clear, the mixed composition of the present invention is characterized by improving the thermal stability during processing of halogen-containing resins and at the same time obtaining molded products with excellent low temperature aging properties. .

When the molar ratio of perchloric acid is 2 or more, the effect is almost the same as that of 2, but the mixing uniformity of the hydrotalcite compound and perchloric acid is not sufficient.

In addition, no effect of the combination is observed when the amount is less than o, ooi mole.

The amount of the mixed product added is 0.00 relative to the halogen-containing resin.
If the amount is less than 1 part by weight, no effect of improving the formulation is observed. Also, 1
00 parts by weight or more, no improvement effect is observed. Also, 1
00 copies or more, an improvement effect can be seen, but it is no longer relevant from an economic standpoint. Furthermore, the combined use of the mixture product of the hydrotalcite compound of the present invention with perchloric acid and a known substance that is normally used as a stable and regular component will not reduce the effects of the present invention in any way. .

These commonly used metal organic salts.

The combination of organic phosphite compounds, UV inhibitors, metal oxides, polyols, N-containing nonmetallic stabilizers, and the composition of the present invention provides synergistic effects on heat aging and prevention of discoloration during low-temperature aging. The present inventors have found that this effect is particularly large. The polyol mentioned here is pentaerythritol.

These include dipentaerythritol, mannitol, sorbitol, glycerin, and polysaccharides. Also.

Examples of N-containing nonmetallic entrainers include urea, melamine, α-phenylindole, and diphenylthiourea.

Tris(2-hydroxyethyl)in cyanurate and the like are used.

The hydrotalcite compounds used in the present invention are Mg
It is a salt of
H) tco-IHO, x: 4-6.
y: Me J 12-16. z: 3-5. It can be synthetic or natural.

As the hydrotalcite compound, when DHT-4A or Kyoward 1100 manufactured by Kyowa Chemical Industry Co., Ltd. is used, the chemical formula is Mg4. fAl, <OH on,
It can be expressed as Co, 3,5HO, and 1 mole is 507°4g. On the other hand, perchloric acid HCI O+1 mole is 10<l
, 5g. HCl02~ per mole of DHT-4H
Based on this figure, a mixture with a ratio of 0.001 mole is
It can be easily obtained by the above mixing method.

Next, the present invention will be explained based on examples. However, the present invention is not limited to the following examples.

Example 1 In order to examine the stabilizing effect of the composition of the present invention, a test sheet was prepared using two rolls with the following formulation.

Thermal stability at 180'C and 120'C in a gear aging tester
We investigated the aging properties of C at low temperatures.

Polyvinyl chloride 100 parts by weight DOP 50 parts by weight Barium stearate 0.5 parts by weight Zinc stearate 1 0.5
Part by weight sample 0. 5 parts by weight The results are shown in Table 1.

Example 2 In order to examine the stabilizing effect of the composition of the present invention, a test sheet was prepared using two rolls with the following formulation.

Thermal stability at 180"C and 120" in a gear aging tester
We investigated the aging properties of G at low temperatures.

Polyvinyl chloride 100 parts by weight AB3 20 parts by weight DOP 30 parts by weight Barium nonylphenate 0.5 weight 1t91S zinc octoate
0.5 parts by weight sample (A) 0.5 parts by weight sample (B) 0.5 parts by weight (A)
Composition of the Invention (B) N-containing nonmetallic stabilizer or polyol The results are shown in Table 2. In Table 2, THECE* used tris(2-hydroxy)ethyl isocyanurate.

Patent applicant: Nissan Ferro Organic Chemical Co., Ltd. Procedural Amendment (
(Spontaneous) March 1980 / Meeting date Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case 1982 Patent Application No. 116892, Title of Invention New Containing...Rogen Resin Composition 5 Amendment Case Relationship with Patent Applicant Address: 1-2-2 Nihonbashi Honmachi, Chuo-ku, Tokyo Contact Telephone Number: 06-245-06614, Claims column and Detailed Description of the Invention column of the specification to be amended.

5. Contents of correction Attachment circular.

Description 1, Title of the Invention Novel halogen-containing resin composition 2, Claims The halogen-containing resin contains 2 moles of perchloric acid to [1001-tongue] per 1 mole of hydrotalcite compound.

A halogen-containing resin composition.

5. Detailed description of the invention The present invention relates to a stabilized halogen-containing resin composition.

Specifically, the present invention relates to a new stable halogen-containing resin composition obtained by adding a mixture of a hydrotalcite compound and perchloric acid to a halogen-containing resin.

Conventional halogen-containing resin 2, for example, vinyl chloride resin.

Chlorinated polyethylene resins and the like are mixed with appropriate plasticizers, stabilizers, colorants, fillers, lubricants, etc., and are commonly used as halogen-containing resin compositions for various molded products.

Halogen-containing resins are also used as polymer blends with EVA, MBS, ABS, acrylic resins, and the like. This blend product is also designated as a halogen-containing resin in a broad sense.

However, the halogen-containing resin composition 1, for example, a vinyl chloride resin composition, tends to undergo a thermal decomposition reaction due to a dehydrochloric acid reaction within the molecular chain in the vicinity at a processing temperature of 175°C during molding, and thus, conventional halogen-containing resin compositions Stabilization efforts have focused on suppressing this decomposition reaction, but this has not always been satisfactory.

Furthermore, molded products often undergo thermal deterioration during use.1 For example, in the summer, the surface temperature of molded products used outdoors can rise to over 980°C due to the energy of sunlight. be. In addition, the wire sheathing material is also continuously exposed to a high temperature atmosphere during use, resulting in
According to Japanese Patent No. 803005, a deterioration test was attempted at 90°C to 120°C, but halogen-containing resin compositions that could meet this test were not necessarily satisfactory.

Improving the durability of polymeric materials whose main raw material is petroleum is an important issue from the viewpoints of resource conservation, energy conservation, and ensuring safety. In order to improve the durability of molded products, the present inventors decided to reduce deterioration in the vicinity of 70"C to 140"C (this is referred to as low-temperature aging, hereinafter the same) and to 175"C to 200"C during processing.
We conducted a comparative study of the deterioration in the vicinity (this is called heat aging, hereinafter the same), and developed a new halogen-containing resin composition.
The present invention has now been completed.

The present invention provides a halogen-containing resin 1 in a halogen-containing resin composition.
A mixed product obtained by mixing 00 parts by weight of perchloric acid in a molar ratio of 2 moles of perchloric acid to 1 mole of perchloric acid to 1 mole of hydrotalcite compound.

The amount added is 0,001 to 100 parts by weight per 100 parts by weight of the resin. The mixed product of the present invention is characterized in that it improves heat aging during processing of a halogen-containing resin composition and at the same time provides a molded article with excellent low temperature aging.

When preparing the mixed product of the present invention, if the molar ratio of perchloric acid to 1 mol of the hydrotalcite compound is 2 or more, the effect is rather reduced.

Moreover, no blending effect is observed below [1001]. If the amount of the mixed product added is less than α001 parts by weight per 100 parts by weight of the halogen-containing resin in the halogen-containing resin composition, no blending improvement effect is observed. Further, if the amount is 100 parts by weight or more, an improvement effect can be seen, but it is no longer relevant from an economic standpoint.

In the present invention, a halogen-containing resin composition is obtained by adding the above-mentioned mixed product, and examples of the halogen-containing resin include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, and polychlorinated resin. Vinylidene, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-
Propylene copolymer, vinyl chloride =~-hethylene copolymer,
Vinyl chloride=--isobutylene styrene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene Copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer.

Vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer Combined.

Examples include internally plasticized polyvinyl chloride.

Furthermore, the mixed product of the hydrotalcite compound of the present invention and perchloric acid may be used in combination with a known substance that is normally used as a stabilizer component.

This does not in any way reduce the effects of the present invention.

These commonly used stabilizers include metal organic acid salts, organic heptatoosphite compounds, and antioxidants.

Examples include ultraviolet absorbers, metal oxides, polyols, and nitrogen-containing nonmetallic compounds. Among these combined stabilizers, polyols and nitrogen-containing nonmetallic compounds are used in combination with the mixed product of the present invention.

The present inventors have discovered that the synergistic effect of preventing coloration during heat aging and low temperature aging is particularly large.

Examples of the polyols mentioned here include pentaerythritol, dipentaerythritol, mannitol, nrubitol, glycerin, polysaccharides, and derivatives thereof. Examples of nitrogen-containing nonmetallic compounds include urea, melamine, α-phenylindole, and tiphenylthiourea.

Tris(2-hydroxyethyl)in cyanurate and the like are used.

The hydrotalcite compound used in the present invention is M
It is a salt of g and At, and has the chemical formula M g X A t 2
(OH)y 00s ・Z Represented by H20, X; 4 ~
6.7; 12-16. z: 3 to 5, which may be a synthetic product or a natural product. Furthermore, baked products such as these may also be used.

Examples of synthetic compounds of hydrotalcite compounds include DHT-4A (hereinafter referred to as DHT-4A) manufactured by Kyowa Chemical Industry Co., Ltd. or Kyoward 1100 (hereinafter referred to as Kyoward 1)
It is written as 100. ), Mg 4
5 A12 (OH) t3. CjOH.

It can be expressed as 3-5H20, and 1 mole is 507.4 f.

The perchloric acid used in the present invention may be a commonly available commercial product or may be used after diluting it with water. In this case, 1 mole of perchloric acid is 1 mole, 10n, converted to 100%.
It will be 5F.

The mixed product according to the invention is then prepared in two, for example, the following three ways.

A. A hydrotalcite compound is placed in a mixing layer equipped with a stirrer, and while stirring, a predetermined amount of perchloric acid aqueous solution is added dropwise and mixed until a uniform state is obtained.

B. Prepared by method A above, and further dried at 100°C or higher.

C6 A predetermined amount of perchloric acid is diluted in a mixed layer equipped with a stirrer and filled with water in advance, and a predetermined amount of hydrotalcite compound is added while stirring. After thorough stirring, take out and filter or dry if necessary.

When the prepared product obtained by the above method is blended into a halogen-containing resin composition, the weight part of the mixed product is calculated in terms of solid content excluding free water from the prepared product.

Next, the effects of the halogen-containing resin composition according to the present invention will be illustrated by examples.

The degree of coloring in the examples was expressed as a linear numerical value.

10 None Color 9-8 light yellow 7-6 Yellow color 5-4 yellowish brown 3-2 reddish brown 1 Black color Moreover, the mixed products of the present invention used in Examples are as follows.

Preparation method A described in the main text of the specification, using perchloric acid at the molar ratio shown in Table 1 below for 1 mole of hydrotalcite compounds,
Among B and O, those prepared according to the following were used as evaluation samples.

Table 1 Example 1 In order to see the effect of the halogen-containing resin composition according to the present invention,
The formulation shown below was mixed with a kneading roll at a roll temperature of 18
A test sheet with a thickness of 0.5 cm was prepared by mixing at 0"C for 5 minutes. Heat aging at 180"C and low temperature aging at 120"C were measured using a gear aging tester. Initial coloration was also examined at the same time.The results are shown in Table 2.The evaluation of heat aging was expressed in terms of the time taken to turn black.

Initial coloration and low-temperature coloring were expressed as numerical values of the degree of coloration. For comparison, similar tests were conducted with and without the DHT-4A iC sample, and the results are also shown in Table 2.

Compounded polyvinyl chloride 100 parts by weight DOP 5ON Barium stearate 0.5 Zinc stearate
[1,2〃 Sample (mixed product of the present invention) Example 2 whose addition amounts are shown in Table 2 When polyols and nitrogen-containing nonmetallic compounds were used in combination with the composition of the present invention, further improvement was achieved. It worked. The effects were investigated in the same manner as in Example 1 using the formulations shown below.

The results are shown in Table 3.

Compounded polyvinyl chloride 100 parts by weight ABS 20
〃DOP
30 #Barium nonylphenate
α5 〃Zinc octoate 0.2
' Sample (mixed product of the present invention) α5N polyols or nitrogen-containing nonmetallic compound (see Table 3) 0.5 #Example 3 In order to see the effect of using chlorine-ratio polyethylene as the halogen-containing resin, the following Tests were conducted in the same manner as in Example 1 using the formulations shown. The results are shown in Table 4.

Compounded chlorinated polyethylene elasthrene 503B*3 100 parts by weight dibutyltin male) 2.0 #dibutyltin laurate 1. OI Rikemar S-200”
1. OI sample (inventive mixed product) 0
．． 5'tr*3 Elasuren 303B manufactured by Showa Denko Chlorinated polyethylene*4 Rikemar S-200 Lubricants manufactured by Riken Vitamin Table 4 Procedure amendment (voluntary) 1 Indication of the case 1988 Patent Application No. 11689 2 Title of the invention New j Halogen-containing resin composition 3 Relationship with the case of the person making the amendment Patent applicant 4 The claims column and the detailed description of the invention column of the specification to be amended.

5 Contents of amendment As per attached sheet.

Description 1, Title of the Invention New halogen-containing resin composition 2, Claims A halogen-containing resin is mixed with a halogen-containing resin at a molar ratio of 2 mol of perchloric acid - 0,001±2 to 1 mol of a hydrotalcite compound. A stabilized halogen-containing resin composition, characterized in that a mixed product is added thereto.

3. Detailed description of the invention The present invention relates to a stabilized halogen-containing resin composition.

Specifically, the present invention relates to a new stabilized halogen-containing resin composition obtained by adding a mixed product of a hydrotalcite compound with perchloric acid to a halogen-containing resin.

Conventional halogen-containing resin 1, for example, vinyl chloride resin alone or together with chlorinated polyethylene.

Polymer blends with EVA, MBS, ABS, acrylic resin, etc. are also made, and stabilizers are added to these.

It contains colorants, fillers, lubricants, etc., and is widely used in various molded products.

However, halogen-containing resin has a processing temperature of 175° during molding.
A thermal decomposition reaction due to a dehydrochlorination reaction within the molecular chain near C tends to occur (and conventional stabilization of halogen-containing resins has focused on suppressing this decomposition reaction).

However, molded products often undergo thermal deterioration during use.2For example, in the summer, the surface temperature of molded products used outdoors can reach 80 degrees Celsius due to the energy of sunlight.
The temperature rises to around 90°C.

In addition, wire coating materials are continuously exposed to a high temperature atmosphere during use, so according to JL, SC3005, a deterioration test at 90°C to 120°C is required from the viewpoint of saving resources and energy and ensuring safety. In order to improve the durability of molded products, the inventors of the present invention
A comparative study was conducted between deterioration at around 40°C (this is called low-temperature aging, hereafter) and deterioration at around 175°C to 200°C during processing.

We developed a halogen-containing resin composition and completed the present invention.

The present invention uses a halogen-containing resin in which 100 parts by weight of the resin is mixed with hydrocruit per mole of the cheek compound.

0.001 to 100 parts by weight, preferably 0.01 to 5.0 parts by weight of the mixed product obtained by mixing perchloric acid at a molar ratio of 2 mol to 0.001 mol are blended.

Although the factors contributing to the effectiveness of the present application are not necessarily clear.

The mixed composition of the present invention is characterized in that it improves the thermal stability of a halogen-containing resin during processing, and at the same time provides a molded article with excellent low-temperature aging properties.

When the molar ratio of perchloric acid is 2 or more, the effect is almost the same as that of 2, but the mixing uniformity of the hydrotalcite compound and perchloric acid is not sufficient.

Also, 0. '001 No mixing effect was observed for 1 at 1 mole or less. The amount of the mixed product added is 0.0% relative to the halogen-containing resin.
If the amount is less than 0.001 parts by weight, no effect of improving the blending is observed. Moreover, if the number of copies exceeds 100, an improvement effect can be seen, but the validity is lost from an economic standpoint.

Further, the combined use of the mixture product of the hydrotalcite compound with perchloric acid of the present invention and a known substance commonly used as a stabilizer component does not reduce the effects of the present invention in any way.

These commonly used metal organic acid salts.

Organic phosphite compounds, antioxidants, ultraviolet absorbers, metal oxides, polyols, N-containing nonmetallic stabilizers, etc., among compositions used in combination with these.

The present inventors have found that the combined use of polyols and N-containing nonmetallic compounds with the composition of the present invention has a particularly great synergistic effect in preventing heat aging and discoloration during low-temperature aging.

Examples of the polyols mentioned here include pentaerythritol, dipentaerythritol, mannitol, sorbitol, glycerin, and polysaccharides. Further, as the N-containing nonmetallic stabilizer, urea, melamine, α-phenylindole, diphenylthiourea, tris(2-hydroxyethyl)isocyanurate, etc. are used.

The hydrotalcite compounds used in the present invention are Mg
It is a salt of and AI, and is represented by the chemical formula MgAl (2 0H)y C0i-2H ○, x r 4
~6, yr12~16. z: 3 to 5, which may be a synthetic product or a natural product.

To produce a mixture of hydrotalcite compounds and perchloric acid, put the hydrotalcite compounds in a mixing tank equipped with a stirrer, and add perchloric acid dropwise at room temperature while stirring. This can be obtained by continuing stirring for 30 minutes.

Hydrotarsai 1-IJ? As a compound, DHT-4A or Kyoward 1100 manufactured by Kyowa Chemical Industry Co., Ltd.
When using the chemical formula TeMg, AI□(OHλ, CO
,・3. It can be expressed as 5 HLO, and 1 mole is 507°4g. In contrast, 100.5 g of perchloric acid HCl0I mole is used. H per mole of DHT-4A
A mixture with a ratio of Cl042 mol to 0.001 mol is
Based on this value, it can be easily obtained by the above mixing method.

Next, the present invention will be explained based on examples. However, the present invention is not limited to the following examples.

1) In order to examine the stabilizing effect of the composition of the present invention, a test sheet was prepared using two rolls using the combination of the ingredients.

Thermal stability at 180”C and 12
The aging properties at low temperatures of 0°C were investigated.

Bored vinyl chloride 100 parts by weight DOP
50 parts by weight barium stearate 0.
5 parts by weight Zinc stearate 0.5 parts by weight
The results are shown in Table 1.

Example 2 In order to examine the stabilizing effect of the composition of the present invention, a test sheet was prepared using two rolls using the following composition.

Thermal stability at 180”C and 12
The aging properties at low temperatures of 0°C were investigated.

Table 2 Polyvinyl chloride 100 parts by weight AB3 20 parts by weight DOP 30 parts by weight Barium nonylphenate 0.5 parts by weight Zinc octoate 0.
2 parts by weight sample (A) 0.5 parts by weight sample
(B) 0.5 parts by weight (A)
; Composition (B) of the present invention; N-containing nonmetallic stabilizer or polyols The results are shown in Table 2.

Note that for THEIC* in Table 1, tris(2-hydroxy)ethyl isocyanurate was used.

Claims (1)

[Claims] A stabilized product characterized by coating a mixed product when mixed with a halogen-containing resin at a molar ratio of 2 moles of perchloric acid to 1 mole of perchloric acid to 1 mole of a hydrotalcite compound. Taconino\Rogen Toh Monthly Thread and Composition.