CA2218792C - Stabilizer composition for cable sheathings - Google Patents
Stabilizer composition for cable sheathings Download PDFInfo
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- CA2218792C CA2218792C CA002218792A CA2218792A CA2218792C CA 2218792 C CA2218792 C CA 2218792C CA 002218792 A CA002218792 A CA 002218792A CA 2218792 A CA2218792 A CA 2218792A CA 2218792 C CA2218792 C CA 2218792C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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Abstract
The present invention relates to the use of a molding composition, containing halogen-containing polymers, in particular polyvinyl chloride, and a special stabilizer composition for cable sheathings. Thanks to the stabilizer composition which contains at least one optionally surface-modified hydrotalcite, at least one basic calcium-aluminum-hydroxy-phosphite and/or at least one basic calcium-aluminum-hydroxy-carboxylate, and optionally at least one liquid or solid, organic or inorganic zinc salt, the high electrical resistance value of the molding composition remains constant over a long period of time, also under the action of moisture, as is required for cable sheathings.
Description
Stabilizer comPosition for Cable Sheathinqs The present invention relates to the use of molding compositions which are based on halogen-containing polymers, particularly polyvinyl chloride, and contain a stabilizer composition, namely in the production of cables in order to prevent any drop in the electrical resistance value caused by the long-term action of moisture.
At the moment, stabilizers based on basic lead compounds, such as tribasic lead sulfate, dibasic lead stearate or dibasic lead phthalate, are normally used for the thermoplastic processing of polyvinyl chloride to prevent polymer from decomposing during processing. Such stabilizers which contain heavy metals are preferably used together with further organic and inorganic co-stabilizers in applications where high long-temm demands are made on heat and weather stability. In addition, when cable sheathings are stabilized, the electrical values required by various standards must be observed. A high electrical resistance is very important for preventing short-circuiting.
Particularly critical are here the long-term electrical-resistance characteristics under the action of moisture, which is, for instance, the case with outdoor applications. The lead stabilizers which are presently used meet all of the demands made on them.
Since lead compounds are classified as toxic, attempts have been made since quite some time to find a substitute therefor. Stabilizers which are free from heavy metals, above all stabilizers based on calcium and zinc compounds, so-called calcium-zinc stabilizers, have been used for the stabilization of cables since some time, but these stabilizers exhibit an electrical resistance that is considerably inferior to that of standard lead stabilizers with respect to long-term stability.
FR-A-24 03 326, for instance, describes the stabilization of plasticized polyvinyl chloride for cable insulations with a mixture of fatty acids of calcium and zinc, of ~_ 2 sorbite and of a 13-diketone. US-A-5,451,628 describes the use of a "mixed-metal"
stabilizer with hydrotalcite and antimony trioxide for enhancing thermostability.
Although the demands made on thermostability and aging stability can, in part, be met with these lead-free systems, the values measured for the electrical resistance are, without exception, lower than those of conventional lead stabilizers after a prolonged moisture action.
DE-A-3843581 describes thermoplastic PVC molding compositions which contain, as the stabilizer system, a combination consisting of a zinc soap, an ethylene vinylacetate copolymer hydrolysate, a hydrotalcite and, optionally, a basic calcium-aluminum-hydroxy-phosphite. The electrical resistance characteristics of these molding compositions have, however, not been examined, since these molding compositions are not used for cable sheathings.
It is the object of the present invention to use molding compositions based on halogen-containing polymers for cable sheatings, which satisfy the demands made on thermostability and aging stability.
This object is achieved according to the invention by the use of a molding composition, containing at least one halogen-containing polymer and a stabilizercomposition, comprising (a) at least one natural or synthetic hydrotalcite which is optionally surface-modified, and (b) at least one basic calcium-aluminum-hydroxy compound, selected from (b1 ) basic calcium-aluminum-hydroxy-phosphites represented by the general formula (I) _ 3 CaxAl2(0H)2~x+3y~(HPO3)y2- mH20 (1) wherein 2 <x< 12, 2x~5>y>0, and O~mc12 except for y=1, when 2 < x < 8;
and/or (b2) basic calcium-aluminum-hydroxy-carboxylates represented by the general formula (Il)*
CaxAl2(oH)~(2x+6~ ylAylnn mH20 (Il) wherein 2 < x < 1 2 2x~5>y~0 o < m c 12, 1 <n<8,and ~_ 4 An is an aliphatic saturated, unsaturated, straight-chain or branched mono- or polyfunctional carboxylic acid anion having 1 to 22 carbon atoms or an aromatic or heteroaromatic mono- or polyfunctional carboxylic acid anion having 6 to 20 carbon atoms or combinations thereof, except for y=1 when 2 < x ~ 8, for cable sheathings.
The stabilizer composition used according to the invention preferably comprises at least one liquid or solid, organic or inorganic zinc salt as a further component.
Cable sheatings which even after the prolonged action of moisture have resistance values corresponding to those of PVC cable sheatings having standard lead stabilizers are obtained by the inventive use of the above-mentioned molding composition.
Hydrotalcites are, for instance, described in DE-A-4425266, EP-A-0189899, DE-A-3843581, US-A4,883,533, EP-A-0407139, DE-A-4031818, DE-A4110835, DE-A-4117034, EP-A-0522810, DE-A-4439934, and US-A-5,352,723; compounds represented by the general formula (I) are, e.g., described in DE-A4106411, and compounds represented by the general fommula (Il) are, for instance, known from DE-A4106404.
The carboxylic acid anion An- contained in the general formula (Il) can, for instance, be selected from anions of malonic acid, succinic acid, adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, pyridinic acid, benzoic acid, salicylic acid, tartronic acid, malic acid, tartaric acid, acetonedicarboxylic acid, oxalacetic acid, aconitic acid, citric acid and amino acid. The anions of fumaric acid and phthalic acid are preferred. Fumarates are particularly used.
_ 5 Component (a), i.e. hydrotalcite, is preferably used in an amount of from 1 to 12 parts by weight, in particular in an amount of from 2 to 8 parts by weight, based on 100 parts by weight of the halogen-containing polymer.
The amount of component (b) is preferably 0.5 to 10 parts by weight, in particular 1 to 3 parts by weight, based on 100 parts by weight of the halogen-containing polymers.
In the calcium-zinc stabilizers used in the prior art, a large amount of zinc component is needed for guaranteeing the desired characteristics. As documented in the following examples, 0.8 part by weight of zinc laurate is, for instance, used in formulation V2 according to the prior art, whilst in the inventive compositions B1 and B2 only 0.45 and 0.3 parts by weight of zinc laurate are, respectively, needed. Formulations V4 and V5 according to the prior art contain 1.05 and 1.6 parts by weight of zinc stearate, whereas the inventive compositions B3 and B4 only require 0.35 and 0.40 parts byweight of zinc stearate. As follows from the examples which are given in the present invention, the amount of zinc, here in the form of zinc laurate and zinc stearate, respectively, can be reduced to 25% of the amount which has so far been needed in the prior art.
The liquid or solid, inorganic or organic zinc salt is used according to the invention in an amount which is needed for achieving the desired characteristics. This amountpreferably ranges from 0.1 to 12 parts by weight, in particular 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 zinc salt, based on 100 parts by weight of the halogen-containing polymer, is particularly preferred.
The zinc salt which is used according to the invention is, for instance, selected from zinc oxide, zinc sulfide, zinc caprylate, zinc laurate, zinc stearate, zinc behenate, zinc acetylacetonate, zinc arachinate, zinc borates, zinc stannates, and zinc ~_ 6 hydroxystannates. Zinc caprylate, zinc laurate, zinc stearate, zinc arachinate and zinc behenate are preferably used; zinc laurate and zinc stearate are used in a particularly preferred manner.
Polyvinyl chloride is preferably used according to the invention as the halogen-containing polymer.
The term polyvinyl chloride as used in the present invention covers standard homopolymers or copolymers of vinyl chloride as well as mixtures of such polyvinyl chloride compounds with other polymer compounds. Such polymers may have been prepared in any desired ways, e.g., by suspension, emulsion or block polymerization.
Their K value may, for instance, range from 50 to 100.
The stabilizer compositions used according to the invention may be combined withfurther heat stabilizers, light stabilizers and antioxidants. Such compounds, which are normally used as additives for chlorine-containing polymers, are, for instance, oxides and/or hydroxides of metals, such as calcium hydroxide or zinc oxide; zeolites or tin-containing stabilizers. Furthermore, organic stabilizers, such as 1 ,3-diketones or the metal salts thereof, polyols, isocyanurates, dihydropyridines, epoxides and phosphites and/or inorganic stabilizers such as garnets, modified hydrotalcites or other layer compounds, may be used.
According to the invention the molding compositions which are used for cable sheathings may contain additives that are normally used, for instance fillers (e.g.
chalk, kaolinite), pigments (such as titanium dioxide), flameproofing agents (such as magnesium hydroxide, aluminum hydroxide, antimony trioxide), reinforcing agents (e.g. glass fibers, talcum) and plasticizers (phthalate, phosphate, polymer plasticizers, chlorinated paraffins).
_ 7 For setting the rheogical requirements, lubricants such as paraffin waxes, low-molecular polyolefins, ester lubricants of mono- or polyvalent alcohols and mono- or dicarboxylic acids or amide waxes may be added to the halogen-containing polymers.
Moreover, further additives, such as antioxidants, UV and light stabilizers, such as sterically hindered amines, optical brightening agents and sulfur-containing compounds, in particular the sulfur-containing organic compounds used for producing tin-containing stabilizers, may be added to the chlorine-containing polymers.
The following examples will explain the invention. Unless otherwise specified, information which is given in parts or percentage refers to the weight.
The compositions which are designated by "8" relate to stabilizer compositions used according to the invention, whereas the compositions designated by"V" are stabilizer compositions which are not composed in accordance with the present invention.
Example 1 100 parts of S-polyvinyl chloride, K value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 0.4 part of lead stearate, 3.4 parts of tetrabasic lead sulfate, 0.3 part of calcium stearate and 0.2 part 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 with a single-screw laboratory extruder from said composition V1 in accordance with standard preparation methods.
A piece of said cable with a length of 5 m was stored in a water bath at 70~C tomeasure the long-time stability of the electrical resistance. The electrical resistance was determined before the beginning of water storage and after one year of waterstorage.
~_ 8 Example 2 100 parts of S-polyvinyl chloride, K value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 0.1 part of calcium stearate, 2.9 parts of hydrotalcite (Alkamizer 1, trade name), 0.8 part of zinc laurate and 0.2 part of paraffin wax were mixed for composition V2. The processability of composition V2 corresponds to composition V1. A cable was extruded with composition V2 under the same conditions as indicated in Example 1. This cable was stored in exactly the same manner as the cable of composition V1 in a water bath having a temperature of 70~C, and the electrical resistance was measured prior to the beginning of water storage and after one year of water storage.
Example 3 Composition B1 according to the invention was prepared from 100 parts of S-polyvinyl chloride, K value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 3.0 parts of hydrotalcite (Alkamizer 1, trade name), 1.0 part of basic calcium-aluminum-hydroxy-phosphite, 0.45 part of zinc laurate and 0.2 part of paraffin wax. In this instance, too, the processing properties correspond to those of composition V1. According to the invention, a cable with the same dimensions as described for V1 was also extruded from composition B1 and subsequently subjected to water storage at 70~C. The electrical resistance was measured by analogy withExamples 1 and 2.
Example 4 Composition B2 of the invention was prepared from 100 parts of polyvinyl chloride, K
value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of _ 9 bisphenol A, 2.0 parts of hydrotalcite (Alkamizer 1, trade name), 2.0 parts of basic calcium-aluminum-hydroxy-fumarate, 0.3 part of zinc laurate and 0.2 part of paraffin wax. Extrusion of the cable as well as water storage and measurement of the electrical resistance were performed under the same conditions as described in Examples 1 to 3.
The measurement results for the electrical resistance at the beginning of water storage and after one year of water storage are summarized in Table 1.
Table 1 Example K value [MQkm] at 70~C ') directly after extrusion after one year of water storage at 70~C
3.102 2.803 2 2.984 0 540 3 3.187 3.019 4 3.177 3.124 ') The electrical resistance constant K [MQkm] is calculated as follows:
I R
K = 1000 log10 (D/d) wherein D = diameter [mm] of the cable d = diameter [mm] of the conductor I = length [m] of the cable R = resistance [MQ] of the cable.
A comparison of composition V1 and V2 shows that, as far as long-term characteristics under the action of moisture are concemed, composition V2 which contains the calcium-zinc stabilizer is considerably inferior, in its electrical resistance, to composition V1 having a lead stabilizer after one year of water storage at 70~C. By contrast, after one year of storage in water having a temperature of 70~C, the cables which are made from compositions B1 and B2 of the invention exhibit a value that is even above the value of composition V1 with the lead stabilizer when the electrical resistance is measured. Hence, these mixtures can advantageously be used under conditions where a high electrical resistance value is also required after a long time, in particular under the action of moisture.
Example 5 As described in Example 1, a cable was extruded from the composition V3 consisting of 100 parts of polyvinyl chloride (K value 70), 45 parts of TOTM (trioctyl trimellitate), 20 parts of calcined kaoline, 6 parts of dibasic lead phthalate, 0.5 part of calcium stearate, 0.3 part of bisphenol A and 3 parts of antimony trioxide, and a piece of said cable having a length of 5 m was subjected to water storage at 70~C. The electrical resistance was measured at the beginning of water storage and onè year after water storage at 70~C.
Example 6 Composition V4 was prepared as in Example 5, except for the measure that instead of 6 parts of lead phthalate and 0.5 part of calcium stearate, 4 parts of hydrotalcite (Alkamizer 1, trade name), 1.05 parts of zinc stearate and 0.9 part of calcium stearate were used. A cable was also extruded from this mixture for subsequent water storage at 70~C, as described in Example 1. The electrical resistance was measured at the beginning and one year after water storage at 70~C.
Example 7 The following components were used for composition V5: 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined kaoline, 3 parts of antimony trioxide, 1 part of hydrotalcite (Alkamizer 1, trade name), 0.6 part of bisphenol A, 1.6 parts of zinc stearate, 1.61 parts of dipentaerythritol, and 0.8 part of calcium laurate. As described in Example 1, a cable was extruded from this mixture for subsequent water storage at 70~C. The electrical resistance was measured at the beginning and one year afterwater storage at 70~C.
Example 8 The inventive composition B3 is composed as follows 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined kaoline, 0.3 part of bisphenol A, 3.1 parts of hydrotalcite (Alkamizer 1, trade name), 1.2 parts of calcium-aluminum-hydroxy-phosphite, 0.35 part of zinc stearate and 3 parts of antimony trioxide. As described in Example 1, a cable was also extruded from this mixture for subsequent water storage at 70~C. The electrical resistance was measured at the beginning and one year after water storage at 70~C.
Example 9 Apart from 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined clay and 3 parts of antimony trioxide, the inventive composition B4 contained 0.3 part of bisphenol A, 3.3 parts of hydrotalcite (Alkamizer 1, trade name), 0.8 part of calcium-aluminum-hydroxy-fumarate and 0.4 parts of zinc stearate. As described in Example 1, a cable was also extruded from this mixture for subsequent water storage at 70~C.
The electrical resistance was measured at the beginning and one year after waterstorage at 70~C.
_ 12 The electrical resistance values of the cables extruded from compositions V3, V4, V5, B3 and B4 were determined after one year of water storage at 70~C. The results of the electrical resistance prior to storage and after one year of water storage are summarized in Table 2.
Table 2 Example K value [MQkm] at 70~C
directly after extrusion after one year of water storage at 70~C
At the moment, stabilizers based on basic lead compounds, such as tribasic lead sulfate, dibasic lead stearate or dibasic lead phthalate, are normally used for the thermoplastic processing of polyvinyl chloride to prevent polymer from decomposing during processing. Such stabilizers which contain heavy metals are preferably used together with further organic and inorganic co-stabilizers in applications where high long-temm demands are made on heat and weather stability. In addition, when cable sheathings are stabilized, the electrical values required by various standards must be observed. A high electrical resistance is very important for preventing short-circuiting.
Particularly critical are here the long-term electrical-resistance characteristics under the action of moisture, which is, for instance, the case with outdoor applications. The lead stabilizers which are presently used meet all of the demands made on them.
Since lead compounds are classified as toxic, attempts have been made since quite some time to find a substitute therefor. Stabilizers which are free from heavy metals, above all stabilizers based on calcium and zinc compounds, so-called calcium-zinc stabilizers, have been used for the stabilization of cables since some time, but these stabilizers exhibit an electrical resistance that is considerably inferior to that of standard lead stabilizers with respect to long-term stability.
FR-A-24 03 326, for instance, describes the stabilization of plasticized polyvinyl chloride for cable insulations with a mixture of fatty acids of calcium and zinc, of ~_ 2 sorbite and of a 13-diketone. US-A-5,451,628 describes the use of a "mixed-metal"
stabilizer with hydrotalcite and antimony trioxide for enhancing thermostability.
Although the demands made on thermostability and aging stability can, in part, be met with these lead-free systems, the values measured for the electrical resistance are, without exception, lower than those of conventional lead stabilizers after a prolonged moisture action.
DE-A-3843581 describes thermoplastic PVC molding compositions which contain, as the stabilizer system, a combination consisting of a zinc soap, an ethylene vinylacetate copolymer hydrolysate, a hydrotalcite and, optionally, a basic calcium-aluminum-hydroxy-phosphite. The electrical resistance characteristics of these molding compositions have, however, not been examined, since these molding compositions are not used for cable sheathings.
It is the object of the present invention to use molding compositions based on halogen-containing polymers for cable sheatings, which satisfy the demands made on thermostability and aging stability.
This object is achieved according to the invention by the use of a molding composition, containing at least one halogen-containing polymer and a stabilizercomposition, comprising (a) at least one natural or synthetic hydrotalcite which is optionally surface-modified, and (b) at least one basic calcium-aluminum-hydroxy compound, selected from (b1 ) basic calcium-aluminum-hydroxy-phosphites represented by the general formula (I) _ 3 CaxAl2(0H)2~x+3y~(HPO3)y2- mH20 (1) wherein 2 <x< 12, 2x~5>y>0, and O~mc12 except for y=1, when 2 < x < 8;
and/or (b2) basic calcium-aluminum-hydroxy-carboxylates represented by the general formula (Il)*
CaxAl2(oH)~(2x+6~ ylAylnn mH20 (Il) wherein 2 < x < 1 2 2x~5>y~0 o < m c 12, 1 <n<8,and ~_ 4 An is an aliphatic saturated, unsaturated, straight-chain or branched mono- or polyfunctional carboxylic acid anion having 1 to 22 carbon atoms or an aromatic or heteroaromatic mono- or polyfunctional carboxylic acid anion having 6 to 20 carbon atoms or combinations thereof, except for y=1 when 2 < x ~ 8, for cable sheathings.
The stabilizer composition used according to the invention preferably comprises at least one liquid or solid, organic or inorganic zinc salt as a further component.
Cable sheatings which even after the prolonged action of moisture have resistance values corresponding to those of PVC cable sheatings having standard lead stabilizers are obtained by the inventive use of the above-mentioned molding composition.
Hydrotalcites are, for instance, described in DE-A-4425266, EP-A-0189899, DE-A-3843581, US-A4,883,533, EP-A-0407139, DE-A-4031818, DE-A4110835, DE-A-4117034, EP-A-0522810, DE-A-4439934, and US-A-5,352,723; compounds represented by the general formula (I) are, e.g., described in DE-A4106411, and compounds represented by the general fommula (Il) are, for instance, known from DE-A4106404.
The carboxylic acid anion An- contained in the general formula (Il) can, for instance, be selected from anions of malonic acid, succinic acid, adipic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, pyridinic acid, benzoic acid, salicylic acid, tartronic acid, malic acid, tartaric acid, acetonedicarboxylic acid, oxalacetic acid, aconitic acid, citric acid and amino acid. The anions of fumaric acid and phthalic acid are preferred. Fumarates are particularly used.
_ 5 Component (a), i.e. hydrotalcite, is preferably used in an amount of from 1 to 12 parts by weight, in particular in an amount of from 2 to 8 parts by weight, based on 100 parts by weight of the halogen-containing polymer.
The amount of component (b) is preferably 0.5 to 10 parts by weight, in particular 1 to 3 parts by weight, based on 100 parts by weight of the halogen-containing polymers.
In the calcium-zinc stabilizers used in the prior art, a large amount of zinc component is needed for guaranteeing the desired characteristics. As documented in the following examples, 0.8 part by weight of zinc laurate is, for instance, used in formulation V2 according to the prior art, whilst in the inventive compositions B1 and B2 only 0.45 and 0.3 parts by weight of zinc laurate are, respectively, needed. Formulations V4 and V5 according to the prior art contain 1.05 and 1.6 parts by weight of zinc stearate, whereas the inventive compositions B3 and B4 only require 0.35 and 0.40 parts byweight of zinc stearate. As follows from the examples which are given in the present invention, the amount of zinc, here in the form of zinc laurate and zinc stearate, respectively, can be reduced to 25% of the amount which has so far been needed in the prior art.
The liquid or solid, inorganic or organic zinc salt is used according to the invention in an amount which is needed for achieving the desired characteristics. This amountpreferably ranges from 0.1 to 12 parts by weight, in particular 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 zinc salt, based on 100 parts by weight of the halogen-containing polymer, is particularly preferred.
The zinc salt which is used according to the invention is, for instance, selected from zinc oxide, zinc sulfide, zinc caprylate, zinc laurate, zinc stearate, zinc behenate, zinc acetylacetonate, zinc arachinate, zinc borates, zinc stannates, and zinc ~_ 6 hydroxystannates. Zinc caprylate, zinc laurate, zinc stearate, zinc arachinate and zinc behenate are preferably used; zinc laurate and zinc stearate are used in a particularly preferred manner.
Polyvinyl chloride is preferably used according to the invention as the halogen-containing polymer.
The term polyvinyl chloride as used in the present invention covers standard homopolymers or copolymers of vinyl chloride as well as mixtures of such polyvinyl chloride compounds with other polymer compounds. Such polymers may have been prepared in any desired ways, e.g., by suspension, emulsion or block polymerization.
Their K value may, for instance, range from 50 to 100.
The stabilizer compositions used according to the invention may be combined withfurther heat stabilizers, light stabilizers and antioxidants. Such compounds, which are normally used as additives for chlorine-containing polymers, are, for instance, oxides and/or hydroxides of metals, such as calcium hydroxide or zinc oxide; zeolites or tin-containing stabilizers. Furthermore, organic stabilizers, such as 1 ,3-diketones or the metal salts thereof, polyols, isocyanurates, dihydropyridines, epoxides and phosphites and/or inorganic stabilizers such as garnets, modified hydrotalcites or other layer compounds, may be used.
According to the invention the molding compositions which are used for cable sheathings may contain additives that are normally used, for instance fillers (e.g.
chalk, kaolinite), pigments (such as titanium dioxide), flameproofing agents (such as magnesium hydroxide, aluminum hydroxide, antimony trioxide), reinforcing agents (e.g. glass fibers, talcum) and plasticizers (phthalate, phosphate, polymer plasticizers, chlorinated paraffins).
_ 7 For setting the rheogical requirements, lubricants such as paraffin waxes, low-molecular polyolefins, ester lubricants of mono- or polyvalent alcohols and mono- or dicarboxylic acids or amide waxes may be added to the halogen-containing polymers.
Moreover, further additives, such as antioxidants, UV and light stabilizers, such as sterically hindered amines, optical brightening agents and sulfur-containing compounds, in particular the sulfur-containing organic compounds used for producing tin-containing stabilizers, may be added to the chlorine-containing polymers.
The following examples will explain the invention. Unless otherwise specified, information which is given in parts or percentage refers to the weight.
The compositions which are designated by "8" relate to stabilizer compositions used according to the invention, whereas the compositions designated by"V" are stabilizer compositions which are not composed in accordance with the present invention.
Example 1 100 parts of S-polyvinyl chloride, K value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 0.4 part of lead stearate, 3.4 parts of tetrabasic lead sulfate, 0.3 part of calcium stearate and 0.2 part 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 with a single-screw laboratory extruder from said composition V1 in accordance with standard preparation methods.
A piece of said cable with a length of 5 m was stored in a water bath at 70~C tomeasure the long-time stability of the electrical resistance. The electrical resistance was determined before the beginning of water storage and after one year of waterstorage.
~_ 8 Example 2 100 parts of S-polyvinyl chloride, K value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 0.1 part of calcium stearate, 2.9 parts of hydrotalcite (Alkamizer 1, trade name), 0.8 part of zinc laurate and 0.2 part of paraffin wax were mixed for composition V2. The processability of composition V2 corresponds to composition V1. A cable was extruded with composition V2 under the same conditions as indicated in Example 1. This cable was stored in exactly the same manner as the cable of composition V1 in a water bath having a temperature of 70~C, and the electrical resistance was measured prior to the beginning of water storage and after one year of water storage.
Example 3 Composition B1 according to the invention was prepared from 100 parts of S-polyvinyl chloride, K value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of bisphenol A, 3.0 parts of hydrotalcite (Alkamizer 1, trade name), 1.0 part of basic calcium-aluminum-hydroxy-phosphite, 0.45 part of zinc laurate and 0.2 part of paraffin wax. In this instance, too, the processing properties correspond to those of composition V1. According to the invention, a cable with the same dimensions as described for V1 was also extruded from composition B1 and subsequently subjected to water storage at 70~C. The electrical resistance was measured by analogy withExamples 1 and 2.
Example 4 Composition B2 of the invention was prepared from 100 parts of polyvinyl chloride, K
value 70, 50 parts of diisodecyl phthalate, 50 parts of coated chalk, 0.1 part of _ 9 bisphenol A, 2.0 parts of hydrotalcite (Alkamizer 1, trade name), 2.0 parts of basic calcium-aluminum-hydroxy-fumarate, 0.3 part of zinc laurate and 0.2 part of paraffin wax. Extrusion of the cable as well as water storage and measurement of the electrical resistance were performed under the same conditions as described in Examples 1 to 3.
The measurement results for the electrical resistance at the beginning of water storage and after one year of water storage are summarized in Table 1.
Table 1 Example K value [MQkm] at 70~C ') directly after extrusion after one year of water storage at 70~C
3.102 2.803 2 2.984 0 540 3 3.187 3.019 4 3.177 3.124 ') The electrical resistance constant K [MQkm] is calculated as follows:
I R
K = 1000 log10 (D/d) wherein D = diameter [mm] of the cable d = diameter [mm] of the conductor I = length [m] of the cable R = resistance [MQ] of the cable.
A comparison of composition V1 and V2 shows that, as far as long-term characteristics under the action of moisture are concemed, composition V2 which contains the calcium-zinc stabilizer is considerably inferior, in its electrical resistance, to composition V1 having a lead stabilizer after one year of water storage at 70~C. By contrast, after one year of storage in water having a temperature of 70~C, the cables which are made from compositions B1 and B2 of the invention exhibit a value that is even above the value of composition V1 with the lead stabilizer when the electrical resistance is measured. Hence, these mixtures can advantageously be used under conditions where a high electrical resistance value is also required after a long time, in particular under the action of moisture.
Example 5 As described in Example 1, a cable was extruded from the composition V3 consisting of 100 parts of polyvinyl chloride (K value 70), 45 parts of TOTM (trioctyl trimellitate), 20 parts of calcined kaoline, 6 parts of dibasic lead phthalate, 0.5 part of calcium stearate, 0.3 part of bisphenol A and 3 parts of antimony trioxide, and a piece of said cable having a length of 5 m was subjected to water storage at 70~C. The electrical resistance was measured at the beginning of water storage and onè year after water storage at 70~C.
Example 6 Composition V4 was prepared as in Example 5, except for the measure that instead of 6 parts of lead phthalate and 0.5 part of calcium stearate, 4 parts of hydrotalcite (Alkamizer 1, trade name), 1.05 parts of zinc stearate and 0.9 part of calcium stearate were used. A cable was also extruded from this mixture for subsequent water storage at 70~C, as described in Example 1. The electrical resistance was measured at the beginning and one year after water storage at 70~C.
Example 7 The following components were used for composition V5: 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined kaoline, 3 parts of antimony trioxide, 1 part of hydrotalcite (Alkamizer 1, trade name), 0.6 part of bisphenol A, 1.6 parts of zinc stearate, 1.61 parts of dipentaerythritol, and 0.8 part of calcium laurate. As described in Example 1, a cable was extruded from this mixture for subsequent water storage at 70~C. The electrical resistance was measured at the beginning and one year afterwater storage at 70~C.
Example 8 The inventive composition B3 is composed as follows 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined kaoline, 0.3 part of bisphenol A, 3.1 parts of hydrotalcite (Alkamizer 1, trade name), 1.2 parts of calcium-aluminum-hydroxy-phosphite, 0.35 part of zinc stearate and 3 parts of antimony trioxide. As described in Example 1, a cable was also extruded from this mixture for subsequent water storage at 70~C. The electrical resistance was measured at the beginning and one year after water storage at 70~C.
Example 9 Apart from 100 parts of polyvinyl chloride, 45 parts of TOTM, 20 parts of calcined clay and 3 parts of antimony trioxide, the inventive composition B4 contained 0.3 part of bisphenol A, 3.3 parts of hydrotalcite (Alkamizer 1, trade name), 0.8 part of calcium-aluminum-hydroxy-fumarate and 0.4 parts of zinc stearate. As described in Example 1, a cable was also extruded from this mixture for subsequent water storage at 70~C.
The electrical resistance was measured at the beginning and one year after waterstorage at 70~C.
_ 12 The electrical resistance values of the cables extruded from compositions V3, V4, V5, B3 and B4 were determined after one year of water storage at 70~C. The results of the electrical resistance prior to storage and after one year of water storage are summarized in Table 2.
Table 2 Example K value [MQkm] at 70~C
directly after extrusion after one year of water storage at 70~C
5.438 S.342 6 5.254 0.784 7 5.371 0.367 8 5.211 5.195 9 5.562 5.422 All examples yield comparable values with respect to the stabilizing characteristics and would also be usable under this aspect alone. It is only a measurement of the electrical resistance after prolonged water storage at 70~C which reveals that apart from the known and presently wide-spread lead stabilizers based on lead phthalate it is only with the stabilizer compositions used according to the invention that a sumciently high electrical resistance can be achieved in a permanent manner. In the first phase after preparation, calcium-zinc stabilizers which have so far been in common use yield an electrical resistance which is comparable to that of lead stabilizers, but upon the action of moisture this resistance drastically drops in the course of time.
Claims (5)
1. Use of a molding composition containing at least one halogen-containing polymer and a stabilizer composition, comprising (a) at least one natural or synthetic hydrotalcite which is optionally surface-modified, and (b) at least one basic calcium-aluminum-hydroxy compound selected from (b1) basic calcium-aluminum-hydroxy-phosphites represented by the general formula (I) CaxAl2(OH)2(x+3-y)(HPO3)y2-mH2O (I) wherein
2 ~ x ~ 12 0 ~ m ~ 12, except for y=1 when 2 ~ x ~ 8;
and/or (b2) basic calcium-aluminum-hydroxy-carboxylates represented by the general formula (II) CaxAl2(OH)[(2x+6)y]Ay/nn-mH2O (II) wherein 2 ~ x ~ 12, 0 ~ m ~ 12, 1 ~ n ~ 8, and An- represents an aliphatic saturated, unsaturated, straight-chain or branched mono- or polyfunctional carboxylic acid anion having 1 to 22 carbon atoms or an aromatic or heteroaromatic mono- or polyfunctional carboxylic acid anion having 6 to 20 carbon atoms, or combinations thereof, except for y=1, when 2 ~ x ~ 8 for cable sheathings.
2. Use according to claim 1, characterized in that said stabilizer composition further contains at least one liquid or solid, organic or inorganic zinc salt.
and/or (b2) basic calcium-aluminum-hydroxy-carboxylates represented by the general formula (II) CaxAl2(OH)[(2x+6)y]Ay/nn-mH2O (II) wherein 2 ~ x ~ 12, 0 ~ m ~ 12, 1 ~ n ~ 8, and An- represents an aliphatic saturated, unsaturated, straight-chain or branched mono- or polyfunctional carboxylic acid anion having 1 to 22 carbon atoms or an aromatic or heteroaromatic mono- or polyfunctional carboxylic acid anion having 6 to 20 carbon atoms, or combinations thereof, except for y=1, when 2 ~ x ~ 8 for cable sheathings.
2. Use according to claim 1, characterized in that said stabilizer composition further contains at least one liquid or solid, organic or inorganic zinc salt.
3. Use according to claim 1 or 2, characterized in that said component (a) is contained in said molding composition in an amount of from 1 to 12 parts by weight and component (b1) and/or (b2) is/are jointly contained in said molding composition in an amount of from 0.5 to 10 parts by weight, based on 100 parts by weight of halogen-containing polymer.
4. Use according to claim 3, characterized in that component (a) is contained insaid molding composition in an amount of from 2 to 8 parts by weight and component (b1) and/or (b1) is/are jointly contained in said molding composition in an amount of from 1 to 3 parts by weight, based on 100 parts by weight of halogen-containing polymer.
5. Use according to any one of claims 1 to 4, characterized in that said halogen-containing polymer is polyvinyl chloride.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19644128.5 | 1996-10-23 | ||
| DE19644128A DE19644128C2 (en) | 1996-10-23 | 1996-10-23 | Stabilizer combination for cable sheathing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2218792A1 CA2218792A1 (en) | 1998-04-23 |
| CA2218792C true CA2218792C (en) | 2001-12-25 |
Family
ID=7809814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002218792A Expired - Fee Related CA2218792C (en) | 1996-10-23 | 1997-10-21 | Stabilizer composition for cable sheathings |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0838493B1 (en) |
| JP (1) | JPH11162257A (en) |
| AR (1) | AR004446A1 (en) |
| AT (1) | ATE204008T1 (en) |
| AU (1) | AU694394B2 (en) |
| BR (1) | BR9705114A (en) |
| CA (1) | CA2218792C (en) |
| DE (2) | DE19644128C2 (en) |
| DK (1) | DK0838493T3 (en) |
| ES (1) | ES2163699T3 (en) |
| GR (1) | GR3037051T3 (en) |
| TW (1) | TW334460B (en) |
| ZA (1) | ZA979292B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364305A (en) * | 2011-12-05 | 2015-02-18 | 科莱恩金融(Bvi)有限公司 | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
| US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100584167B1 (en) | 1999-02-05 | 2006-05-26 | 토다 고교 가부시끼가이샤 | Mg-Al-Based hydrotalcite type particles, chlorine-containing resin composition and process for producing the particles |
| FR2797088B1 (en) * | 1999-07-26 | 2002-01-18 | Sagem | INSULATED ELECTRIC CABLE AND METHOD FOR MANUFACTURING SUCH A CABLE |
| JP4756737B2 (en) * | 2000-12-18 | 2011-08-24 | 株式会社Ａｄｅｋａ | Coil material composition for coil wire |
| EP2072567B1 (en) | 2007-12-18 | 2016-02-24 | Bene_fit Systems GmbH & Co. KG | Compound for stabilising polymers containing halogens, method for manufacture and use |
| DE102009039125A1 (en) | 2009-08-27 | 2011-03-03 | Baerlocher Gmbh | Process for the preparation of stabilizer melts, moldings produced therefrom and their use |
| US8354462B2 (en) | 2009-11-30 | 2013-01-15 | Chemson Polymer Additives AG | Heat stabilizers containing hydrotalcite particles with specific zeta potentials that demonstrate improved processing and performance in molded vinyl compounds |
| DE102011120218A1 (en) * | 2011-12-05 | 2013-06-06 | Clariant International Ltd. | Alkali-aluminum mixed phosphites, process for their preparation and their use |
| DE102011120192A1 (en) * | 2011-12-05 | 2013-06-06 | Clariant International Ltd. | Aluminum hydrogen phosphites, a process for their preparation and their use |
| DE102011120190A1 (en) | 2011-12-05 | 2013-06-06 | Clariant International Limited | Mixtures of aluminum hydrogen phosphites with aluminum salts, process for their preparation and their use |
| DE102011120191A1 (en) | 2011-12-05 | 2013-06-06 | Clariant International Ltd. | Mixtures of aluminum phosphite with sparingly soluble aluminum salts and foreign ions, process for their preparation and their use |
| JP5716653B2 (en) * | 2011-12-21 | 2015-05-13 | 日立金属株式会社 | Polyvinyl chloride resin composition, electric wire and cable using the same |
| JP2017075335A (en) * | 2017-01-20 | 2017-04-20 | 日立金属株式会社 | Polyvinyl chloride resin composition and insulated wire prepared therewith, and method for producing insulated wire |
| JP6256787B2 (en) * | 2017-04-19 | 2018-01-10 | 日立金属株式会社 | Flame-retardant vinyl chloride resin composition, insulated wire using the same, and method for producing insulated wire |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2097577A5 (en) * | 1970-07-10 | 1972-03-03 | Peugeot & Renault | |
| JPH0639560B2 (en) * | 1986-08-14 | 1994-05-25 | 協和化学工業株式会社 | Stabilized composition of polyvinyl chloride resin |
| DE3941902C1 (en) * | 1989-12-19 | 1991-02-28 | Chemische Werke Muenchen Otto Baerlocher Gmbh, 8000 Muenchen, De | |
| DE4106411C2 (en) * | 1991-02-28 | 1994-09-01 | Baerlocher Gmbh | Basic calcium aluminum hydroxy phosphites, process for their preparation and their use |
| DE4106404C2 (en) * | 1991-02-28 | 1995-05-18 | Baerlocher Gmbh | Calcium aluminum hydroxide dicarboxylates, process for their preparation and their use |
| JPH0570649A (en) * | 1991-09-11 | 1993-03-23 | Sakai Chem Ind Co Ltd | Vinyl chloride resin composition |
| DE4134325C2 (en) * | 1991-10-17 | 1997-12-18 | Henkel Kgaa | Process for the stabilization of polymers of vinyl chloride and means for carrying out the process |
| US5451628A (en) * | 1994-06-01 | 1995-09-19 | Synthetic Products Company | Heat stabilization of PVC compositions containing a mixed metal stabilizer and antimony trioxide |
-
1996
- 1996-10-23 DE DE19644128A patent/DE19644128C2/en not_active Expired - Fee Related
-
1997
- 1997-10-16 ZA ZA9709292A patent/ZA979292B/en unknown
- 1997-10-20 DK DK97118196T patent/DK0838493T3/en active
- 1997-10-20 AT AT97118196T patent/ATE204008T1/en not_active IP Right Cessation
- 1997-10-20 DE DE59704232T patent/DE59704232D1/en not_active Expired - Fee Related
- 1997-10-20 AU AU42720/97A patent/AU694394B2/en not_active Ceased
- 1997-10-20 ES ES97118196T patent/ES2163699T3/en not_active Expired - Lifetime
- 1997-10-20 EP EP97118196A patent/EP0838493B1/en not_active Expired - Lifetime
- 1997-10-21 CA CA002218792A patent/CA2218792C/en not_active Expired - Fee Related
- 1997-10-22 TW TW086115638A patent/TW334460B/en active
- 1997-10-22 AR ARP970104887A patent/AR004446A1/en unknown
- 1997-10-22 JP JP9288983A patent/JPH11162257A/en active Pending
- 1997-10-22 BR BR9705114A patent/BR9705114A/en active Search and Examination
-
2001
- 2001-10-30 GR GR20010401923T patent/GR3037051T3/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104364305A (en) * | 2011-12-05 | 2015-02-18 | 科莱恩金融(Bvi)有限公司 | Mixtures of flame protection means containing flame protection means and aluminium phosphites, method for production and use thereof |
| CN104364305B (en) * | 2011-12-05 | 2016-10-26 | 科莱恩金融(Bvi)有限公司 | Comprise the flame-retardant mixture of fire retardant and aluminium phosphite, Its Preparation Method And Use |
| US10508238B2 (en) | 2014-01-29 | 2019-12-17 | Clariant International Ltd. | Halogen-free solid flame retardant mixture and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE19644128A1 (en) | 1998-04-30 |
| DE19644128C2 (en) | 1999-07-22 |
| EP0838493B1 (en) | 2001-08-08 |
| TW334460B (en) | 1998-06-21 |
| GR3037051T3 (en) | 2002-01-31 |
| AU4272097A (en) | 1998-05-21 |
| ZA979292B (en) | 1998-05-11 |
| BR9705114A (en) | 1998-09-15 |
| CA2218792A1 (en) | 1998-04-23 |
| JPH11162257A (en) | 1999-06-18 |
| EP0838493A1 (en) | 1998-04-29 |
| AR004446A1 (en) | 1998-12-16 |
| ATE204008T1 (en) | 2001-08-15 |
| DE59704232D1 (en) | 2001-09-13 |
| AU694394B2 (en) | 1998-07-16 |
| DK0838493T3 (en) | 2001-10-01 |
| ES2163699T3 (en) | 2002-02-01 |
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