JPH11116753A - Stabilizing agent composition for armoring cable - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a molding composition which can prevent deterioration of electric resistivity caused by the action of humidity for a long period of time by compounding a halogen-containing polymer with a natural or synthetic hydrotalcite with its surface optically modified and a calcium-aluminum-hydroxy compound. SOLUTION: As a hydroxy compound is employed a basic calcium-aluminum- hydroxy phosphite represented by formula I and/or a basic calcium-aluminum- hydroxy carboxylate represented by formula II. In the formulae, 2<=x<=12; (2x+5)/2>y>0; 0<=m<=12 (provided that when 2<=x<=8, y=1); 1<=n<=8; and A<n> represents a 1-22C aliphatic mono- or polyfunctional carboxylate anion or a 6-20C aromatic or heteroaromatic mono- or polyfunctional carboxylate anion. Preferably 1-12 pts.wt. of a hydrotalcite and 0.5-10 pts.wt. of the hydroxy compound are compounded with 100 pts.wt. of a halogen-containing polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the use of molding compositions based on halogen-containing polymers, in particular polyvinyl chloride, and containing stabilizer compositions, that is to say the electrical resistance values caused by the action of moisture over a long period. To use in cable manufacturing to prevent degradation in

[0002]

2. Description of the Related Art
Stabilizers based on basic lead compounds, such as tribasic lead sulfate, dibasic lead stearate or dibasic lead phthalate, are used in thermoplastic processing of polyvinyl chloride to prevent polymer degradation during processing. It is usually used for. Such stabilizers containing heavy metals are preferably used together with other organic and inorganic co-stabilizers in applications where high long-term requirements are made for thermal and climatic stability. In addition, when the cable sheath is stabilized, the electrical values required by various standards must be observed.
High electrical resistance is very important to prevent short circuits. Particularly critical here are, for example, the long-term electrical resistance properties under the action of moisture, such as when having outdoor applications. Currently used lead stabilizers meet all the requirements made on them. Since lead compounds are classified as toxic, attempts have been made for some time to find alternatives to them. Heavy metal-free stabilizers, in particular all stabilizers based on calcium and zinc compounds, so-called calcium-zinc stabilizers, have been used for some time for stabilizing cables, but these stabilizers In terms of long-term stability, it shows a much lower electrical resistance than standard lead stabilizers.

[0003] For example, FR-A-2403326 describes the stabilization of plasticized polyvinyl chloride for cable insulation with a mixture of calcium and zinc fatty acids, sorbitol and β-diketone. US Patent 5,451,6
No. 28 describes the use of "mixed metal" stabilizers with hydrotalcite and antimony trioxide to increase thermal stability.

[0004] Although the demands made on thermal and aging stability can in part be solved by these lead-free systems, the values measured for electrical resistance are, without exception, the long-term moisture content. Is lower than that of conventional lead stabilizers.

[0005] DE-A-384 43 581 discloses a thermoplastic system comprising, as stabilizer system, a combination of zinc soap, ethylene vinyl acetate copolymer hydrolysate, hydrotalcite and, optionally, basic calcium-aluminum-hydroxy-phosphite. A PVC molding composition is described. The electrical resistance properties of these molding compositions have not, however, been investigated since these molding compositions have not been used for cable sheathing.

It is an object of the present invention to use molding compositions based on halogen-containing polymers for cable sheathing, which meet the requirements made on thermal stability and aging stability.

[0007]

According to the present invention, there is provided at least one halogen-containing polymer comprising:
At least one optically surface modified natural or synthetic hydrotalcite, and (b)
At least one selected from (b1) and / or (b2)
Two calcium-aluminum-hydroxy compounds (b1) Basic calcium-aluminum-hydroxy-phosphite Ca _x Al ₂ (OH) _{2 (x + 3-y)} (HPO ₃ ) y ² represented by the general formula (I) ^- · MH ₂ O (I) where 2 ≦ x ≦ 12

[0008]

(Equation 3)

0 ≦ m ≦ 12 However, when 2 ≦ x ≦ 8, y = 1; (b2) Basic calcium-aluminum-hydroxy-carboxylate Ca _x Al ₂ (OH) represented by the general formula (II) _{) [(2x + 6) -y} ] A y / n n- · mH 2 O (II) wherein 2 ≦ x ≦ 12

[0010]

(Equation 4)

0.ltoreq.m.ltoreq.12, 1.ltoreq.n.ltoreq.8, and A ^n- is an aliphatic saturated, unsaturated, linear or branched mono- or polyfunctional carboxylic acid anion having 1 to 22 carbon atoms. Or 6
Represents an aromatic or heteroaromatic mono- or polyfunctional carboxylic acid anion having from 20 to 20 carbon atoms, or a combination thereof.

However, when 2 ≦ x ≦ 8, it is achieved by using a molding composition containing a stabilizer composition comprising y = 1 for cable sheathing.

The stabilizers used according to the invention preferably comprise, as another component, at least one liquid or solid, organic or inorganic zinc salt.

A cable sheath having a resistance corresponding to that of a PVC cable sheath with a standard lead stabilizer, even after prolonged moisture action, is obtained by the inventive use of the molding composition described above.

Hydrotalcite is, for example, DE-A-4
425266, EP-A-0189899, DE-A-38
43581, US-A-4,883,533, EP-A-0
407139, DE-A-4031818, DE-A-41
10835, DE-A-4117034, EP-A-052
2810, DE-A-4439934 and US-A-5,3
52,723. The compounds represented by the general formula (I) are described, for example, in DE-A-4106411, and the compounds represented by the general formula (II) are known, for example, from DE-A-4106404.

The carboxylate anion A ^n- contained in the general formula (II) is, for example, malonic acid, succinic acid, adipic acid,
Fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, pyridine acid, benzoic acid, salicylic acid, tartronic acid, malic acid
cid), tartaric acid, acetonedicarboxylic acid, oxaloacetic acid,
It is selected from aconitic acid, citric acid and anions of amino acids. Anions of fumaric and phthalic acids are preferred. Fumarates are used in particular.

Component (a), the hydrotalcite, preferably comprises 1 part by weight based on 100 parts by weight of the halogen-containing polymer.
It is used in an amount of up to 12 parts by weight, in particular in an amount of 2 to 8 parts by weight.

The amount of component (b) depends on the amount of the halogen-containing polymer.
Preferably 0.5 to 10 parts by weight, especially 1 to 100 parts by weight
To 3 parts by weight.

Calcium used in the prior art
In zinc stabilizers, large amounts of zinc components are required to ensure the desired properties. As described in the examples below, 0.8 parts by weight of lead laurate is used, for example, in formulation V2 according to the prior art, whereas in compositions B1 and B2 according to the invention 0.45 and 0.55 of zinc laurate are used. 0.3
Only parts by weight are required in each case. Prior art formulations V4 and V5 contain 1.05 and 1.6 parts by weight of zinc stearate, while compositions B3 and B4 of the present invention require only 0.35 and 0.40 parts by weight of zinc stearate. As can be seen from the examples given in the present invention below, the amount of zinc, here in the form of zinc laurate and zinc stearate, is each reduced to 25% of the amount previously required in the prior art. Can be done.

Liquid or solid, inorganic or organic zinc salts are used in the amounts required to achieve the desired properties according to the invention. This amount is preferably in the range from 0.1 to 12 parts by weight, especially from 0.5 to 7 parts by weight, based on 100 parts by weight of the halogen-containing polymer. An amount of 0.5 to 2 parts by weight of the zinc salt is particularly preferred, based on 100 parts by weight of the halogen-containing polymer.

The zinc salts used according to the invention include, for example, zinc oxide, zinc sulfide, zinc caprylate, zinc laurate, zinc stearate, zinc behenate, zinc acetylacetonate, zinc arachinate, zinc borate, stannic acid. It is selected from zinc and zinc hydroxystannate. Zinc caprate, zinc laurate, zinc stearate, zinc arachiate and zinc behenate are preferably used. Zinc laurate and zinc stearate are used in a particularly preferred embodiment.

Polyvinyl chloride is preferably used according to the invention as halogen-containing polymer.

The term polyvinyl chloride as used in the present invention includes standard vinyl chloride homopolymers or copolymers, as well as mixtures of such vinyl chloride compounds with other polymeric compounds. Such polymers may be prepared in any desired manner, for example by suspension, emulsion or block polymerization. Their K values are, for example, 50 to
It can be in the range of 100.

The stabilizer composition used in the present invention can be combined with other heat stabilizers, light stabilizers and antioxidants. Such compounds commonly used as additives for chlorine-containing polymers are, for example, oxides and / or hydroxides of metals such as calcium hydroxide or zinc oxide, zeolites or tin-containing stabilizers. In addition, organic stabilizers such as 1,3-diketones or metal salts thereof, polyols, isocyanurates, dihydropyridines, epoxides and phosphites and / or inorganic stabilizers such as garnets, modified hydrotalcite or other layer compounds. Stabilizers can be used.

According to the invention, the molding compositions used for the cable sheathing are composed of commonly used additives such as fillers (eg chalk, kaolinite), pigments (such as titanium dioxide), flame retardants ( It may contain magnesium hydroxide, aluminum hydroxide, such as antimony trioxide), reinforcing agents (eg, glass fiber, talcum) and plasticizers (phthalate, phosphate, polymeric plasticizer, chlorinated paraffin).

To set the rheological requirements, lubricants such as paraffin waxes, low molecular weight polyolefins, ester lubricants of monohydric or polyhydric alcohols with mono- or dicarboxylic acids or amide waxes are added to the halogen-containing polymer. obtain. In addition, other additives such as antioxidants, UV and light stabilizers such as sterically hindered amines, optical brighteners and sulfur-containing compounds, especially sulfur-containing organic compounds used to make tin-containing stabilizers, are chlorine-containing. It can be added to the containing polymer.

The following example will illustrate the invention. Unless otherwise specified, information given in parts or percentages relates to weight.

[0028]

EXAMPLES The composition indicated by "B" relates to a stabilizer composition used according to the invention, while the composition indicated by "V" relates to a stabilizer not constituted according to the invention. A composition.

Example 1 100 parts of S-polyvinyl chloride having a K value of 70, 50 parts of dioctyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 0.4 part of lead stearate, 3.4 parts of 4 basic lead sulfate, 0.3 part of calcium stearate And 0.2 parts of paraffin wax were mixed for composition V1. A cable having an outer diameter of 2.92 mm and a conductor diameter of 1.3 mm was extruded from the composition V1 by a screw laboratory extruder according to standard preparation methods. A piece of the cable having a length of 5 m was stored at 70 ° C. in a water bath to determine the long-term stability of the electrical resistance. Electrical resistance was determined before the start of underwater storage and one year after underwater storage.

Example 2 100 parts of S-polyvinyl chloride having a K value of 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A,
0.1 part of calcium stearate, hydrotalcite (Al
2.9 parts of kamizer 1, 0.8 parts of zinc laurate and 0.2 parts of paraffin wax were mixed for composition V2. The processability of the composition V2 corresponds to the composition V1. Composition V2 under the same conditions as the cable indicated in Example 1
Was extruded. This cable was stored exactly as the cable of composition V1 in a water bath having a temperature of 70 ° C., and the electrical resistance was measured before the start of storage in water and one year after storage in water.

Example 3 Composition B1 according to the invention is an S-polyvinyl chloride having a K value of 70
100 parts, diisodecyl phthalate 50 parts, coated chalk 50 parts,
Bisphenol A 0.1 part, hydrotalcite (Alkami
zer, trade name) 3.0 parts, basic calcium-aluminum-hydroxy-phosphite 1.0 parts, lead laurate 0.45
And 0.2 parts of paraffin wax. Also in this case, the processability is consistent with that of composition V1. According to the invention, a cable having the same dimensions as described for V1 is also extruded from composition B1,
Water storage in ° C. The electric resistance was measured according to Examples 1 and 2.

Example 4 Composition B2 of the present invention comprises 100 parts of polyvinyl chloride having a K value of 70,
From 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 2.0 parts of hydrotalcite (Alkamizer, trade name), 2.0 parts of basic calcium-aluminum-hydroxy-fumarate, 0.3 parts of lead laurate and 0.2 parts of paraffin wax Was prepared. Cable extrusion and underwater storage and electrical resistance measurements were performed under the same conditions as described in Examples 1-3.

The results of the measurement of the electrical resistance at the start of underwater storage and one year after storage in water are summarized in Table 1.

[0034]

[Table 1]

1) The electric resistance constant K [MΩkm] is calculated as follows:

[0036]

(Equation 5)

Where D = diameter of the cable [mm] d = diameter of the conductor [mm] l = length of the cable [m] R = resistance of the cable [MΩ] Comparison of the compositions V1 and V2 shows the effect of moisture. Composition V comprising a calcium-zinc stabilizer as far as the lower long-term properties are concerned
2 is significantly inferior in its electrical resistance to composition V1 with lead stabilizer after one year of storage in water at 70 ° C. In contrast, after one year of storage in water having a temperature of 70 ° C., the cables made from the compositions B1 and B2 according to the invention show, when the electrical resistance is measured, above the value of the composition V1 with lead stabilizer. Even shows a certain value. Thus, these mixtures can be used advantageously under conditions as required, after long periods of high electrical resistance, especially under the action of moisture.

EXAMPLE 5 As described in Example 1, the cable was made of polyvinyl chloride (K value 7
0) 100 parts, TOTM (trioctyl trimellitate) 45
Of a cable V extruded from a composition V3 consisting of 20 parts of calcined kaolin, 6 parts of dibasic lead phthalate, 0.5 parts of calcium stearate, 0.3 parts of bisphenol A and 3 parts of antimony trioxide and having a length of 5 m. 70 pieces
Subjected to underwater storage at 0 ° C. Electrical resistance was measured at the start of underwater storage and one year after storage in water at 70 ° C.

EXAMPLE 6 Composition V4 was prepared by using hydrotalcite (Alkamize) instead of 6 parts of lead phthalate and 0.5 part of calcium stearate.
r 1, trade name) except that 4 parts, zinc stearate 1.05 parts and calcium stearate 0.9 parts were used
Prepared as in Example 5. Cables were extruded from this mixture and then subjected to underwater storage at 70 ° C. as described in Example 1. Electrical resistance was measured at the beginning and after one year of storage in water at 70 ° C.

Example 7 The following ingredients were used for composition V5: 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined kaolin, 3 parts of antimony oxide, 1 part of hydrotalcite (Alkamizer1, trade name) , Bisphenol A 0.6 parts, zinc stearate
1.6 parts, 1.61 parts of dipentaerythritol and 0.8 parts of calcium laurate. Cables were extruded from this mixture as described in Example 1 and then subjected to underwater storage at 70 ° C. Electrical resistance was measured at the beginning and after one year of storage in water at 70 ° C.

Example 8 Composition B3 according to the invention is constituted as follows: 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined kaolin, 0.3 parts of bisphenol A, hydrotalcite (Alkamizer 1,
(Trade name) 3.1 parts, calcium-aluminum-hydroxy-phosphite 1.2 parts, zinc stearate 0.35 part, and antimony trioxide 3 parts. As described in Example 1, a cable was also extruded from this mixture and then subjected to underwater storage at 70 ° C. Electrical resistance was measured at the beginning and after one year of storage in water at 70 ° C.

Example 9 100 parts of polyvinyl chloride, 45 parts of TOTM, calcined kaolin 20
Part B and the composition B of the present invention in addition to 3 parts of antimony trioxide
4 is 0.3 parts of bisphenol A, hydrotalcite (Alk
amizer 1, trade name) 3.3 parts, calcium-aluminum-hydroxy-fumarate 0.8 parts and zinc stearate
0.4 parts. As described in Example 1, a cable was also extruded from this mixture and then subjected to underwater storage at 70 ° C. Electrical resistance was measured at the beginning and after one year of storage in water at 70 ° C.

The electrical resistance of the cables extruded from the compositions V3, V4, V5, B3 and B4 was measured in water at 70 ° C. 1
Determined years later. The electrical resistance results before storage and one year after storage in water are summarized in Table 2.

[0044]

[Table 2]

All examples give comparable results in terms of stabilizing properties and can only be used in this regard.
Apart from the known and currently widely used lead stabilizers based on lead phthalate, it is only possible with permanent compositions that a sufficiently high electrical resistance can be achieved in a permanent manner. Disclosed is only the measurement of electrical resistance after storage in water at 70 ° C. for an extended period. First after production
In this phase, calcium-zinc stabilizers which have hitherto been commonly used give rise to an electrical resistance comparable to that of lead stabilizers, but in the action of moisture this resistance drops rapidly over time.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H01B 3/44 H01B 3/44 P (72) Inventor Stephen Forster 85221 Dachau, Germany, Sillerstrasse 32

Claims (5)

[Claims] 1. At least one halogen-containing polymer, (a) at least one optically surface-modified natural or synthetic hydrotalcite, and (b) (b1) and / or (b2) (B1) Basic calcium-aluminum-hydroxy-phosphite Ca _x Al ₂ (OH) _{2 (x + 3-y} ) represented by the general formula (I) ₎ (HPO ₃ ) y ² -mH ₂ O (I) where 2 ≦ x ≦ 12 0 ≦ m ≦ 12, where y = 1 when 2 ≦ x ≦ 8; (b2) Basic calcium-aluminum-hydroxy-carboxylate Ca _x Al ₂ (OH) _{[( 2x + 6) -y]} A _{y / n} ^n- · mH ₂ O (II) where 2 ≦ x ≦ 12 0 ≦ m ≦ 12, 1 ≦ n ≦ 8, and A ^n- is an aliphatic saturated with 1 to 22 carbon atoms, unsaturated, straight-chain or branched-chain mono- or poly-functional carboxylic acid anion or 6 to Represents an aromatic or heteroaromatic mono- or polyfunctional carboxylic acid anion having 20 carbon atoms, or a combination thereof. However, 2
The use of a molding composition comprising a stabilizer composition wherein y = 1 when ≦ x ≦ 8 for cable sheathing. 2. The use according to claim 1, wherein the stabilizer composition further comprises at least one liquid or solid, organic or inorganic zinc salt. 3. Component (a) is contained in the molding composition in an amount of 1 to 12 parts by weight based on 100 parts by weight of the halogen-containing polymer, and component (b1) and / or (b2) is contained in the molding composition. 3. Use according to claim 1 or 2, characterized in that it is present in the composition in a total amount of 0.5 to 10 parts by weight. 4. Component (a) is contained in the molding composition in an amount of 2 to 8 parts by weight based on 100 parts by weight of the halogen-containing polymer, and components (b1) and / or (b2) are contained in the molding composition. 4. Use according to claim 3, characterized in that it is contained in the product in an amount of from 1 to 3 parts by weight. 5. Use according to claim 1, wherein said halogen-containing polymer is polyvinyl chloride.