CN107099105A - Vinyl chloride resin composition and insulated electric conductor and the manufacture method of insulated electric conductor using it - Google Patents

Vinyl chloride resin composition and insulated electric conductor and the manufacture method of insulated electric conductor using it Download PDF

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CN107099105A
CN107099105A CN201710432525.6A CN201710432525A CN107099105A CN 107099105 A CN107099105 A CN 107099105A CN 201710432525 A CN201710432525 A CN 201710432525A CN 107099105 A CN107099105 A CN 107099105A
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vinyl chloride
chloride resin
resin composition
coated
insulated electric
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CN107099105B (en
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菊池龙太郎
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Proterial Ltd
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Hitachi Metals Ltd
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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
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • 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
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H01B13/145—Pretreatment or after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H01B7/0275—Disposition of insulation comprising one or more extruded layers of insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

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Abstract

The present invention provides vinyl chloride resin composition and insulated electric conductor and the manufacture method of insulated electric conductor using it.The vinyl chloride resin composition is anti-flammability and electrical characteristics, heat endurance, cold resistance and molding processibility all excellent vinyl chloride resin compositions.The vinyl chloride resin composition contains vinyl chloride resin, plasticizer, amorphous silicon di-oxide, hydrotalcite and burns till clay, does not contain metal hydroxides.

Description

Vinyl chloride resin composition and the manufacture using its insulated electric conductor and insulated electric conductor Method
The application be original application, the applying date be on May 13rd, 2015, Application No. 201510242240.7, denomination of invention For " vinyl chloride resin composition and using its insulated electric conductor and insulated electric conductor manufacture method " Chinese patent application point Case application.
Technical field
The manufacture method of insulated electric conductor and insulated electric conductor the present invention relates to vinyl chloride resin composition and using it.
Background technology
Insulated electric conductor is used in the inside distribution of e-machine class.Insulated electric conductor has conductor and is arranged to coated conductor Periphery it is insulation-coated so that conductor is electrically insulated with extraneous formed.
For the insulated electric conductor requirement anti-flammability used in the inside distribution of e-machine class so that when e-machine hair During raw firing accident etc., conductance isolation electric wire and flame is not extended.For example, for insulated electric conductor requirement relative to the U.S. The qualified high flame retardant of the testing vertical flammabilities (VW-1 experiments) of UL758 standards.
Such insulated electric conductor it is insulation-coated in, as formed material, widely use the vinyl chloride containing vinyl chloride Resin combination.Vinyl chloride resin contains the chlorine as halogen, excellent in flame retardance in chemical constitution.
In general vinyl chloride resin is hard, thus as the insulation-coated formation material for requiring flexibility In use, in order that its softening and plasticizer is largely added to use.But, plasticizer is flammable, can reduce chloroethene The anti-flammability of olefine resin composition.Therefore, the vinyl chloride resin composition containing substantial amounts of plasticizer is difficult to obtain vinyl chloride tree The anti-flammability that fat had originally.
Herein, in order to improve the anti-flammability that have dropped caused by the plasticizer, in the vinyl chloride containing plasticizer Fire retardant is added in resin combination.Antimonial was used as fire retardant in the past, but antimonial has not to environment, human body Good influence, and have the tendency of because rare price rising, therefore its use is restricted.Thus, as The fire retardant of antimonial is substituted, the metal hydroxides such as aluminium hydroxide, magnesium hydroxide is gradually used in recent years.
For example, as the vinyl chloride resin composition for not containing harmful antimonial, disclosing relative to 100 mass parts Vinyl chloride resin adds the aluminium hydroxide of 8~22 mass parts and/or the technical scheme (example of magnesium hydroxide and non-lead system stabilizer As with reference to patent document 1).
Prior art literature
Patent document
Patent document 1：JP 2011-26427 publications
The content of the invention
The problem to be solved in the present invention
But, according to the cognition of the present inventor, although metal hydroxides improves the anti-flammability of vinyl chloride resin composition, But there is the worry for reducing its electrical characteristics, heat endurance, cold resistance and molding processibility.Particularly, it is big as in patent document 1 When amount ground contains metal hydroxides (8~22 mass parts), have that each characteristic of vinyl chloride resin composition declines to a great extent asks Topic.
The present invention in view of so the problem of the invention that completes, its object is to provide anti-flammability and electrical characteristics, heat Stability, cold resistance and molding processibility all excellent vinyl chloride resin compositions and use its insulated electric conductor.
The method solved the problems, such as
According to the 1st mode of the present invention there is provided a kind of vinyl chloride resin composition, contain vinyl chloride resin, plasticizer, non- Crystalline silicon dioxide, at least one selected from hydrotalcite and in burning till clay and metal hydroxides.
According to the 2nd mode of the present invention there is provided the vinyl chloride resin composition of the 1st mode, the metal hydroxides Content is below 7 mass parts relative to vinyl chloride resin described in 100 mass parts.
According to the 3rd mode of the present invention there is provided the vinyl chloride resin composition of the 1st mode or the 2nd mode, contain the water Talcum and described burn till both clays.
According to the 4th mode of the present invention there is provided the vinyl chloride resin composition of any one of the 1st~the 3rd mode, the gold The average grain diameter for belonging to hydroxide is less than 2 μm, and is not surface treated.
According to the 5th mode of the present invention there is provided the vinyl chloride resin composition of any one of the 1st~the 4th mode, the gold Category hydroxide is aluminium hydroxide.
According to the 6th mode of the present invention there is provided a kind of vinyl chloride resin composition, contain vinyl chloride resin, plasticizer, non- Crystalline silicon dioxide, hydrotalcite and clay is burnt till, but do not contain metal hydroxides.
According to the 7th mode of the present invention there is provided a kind of insulated electric conductor, by the 1st with conductor and on the conductor periphery It is insulation-coated that the vinyl chloride resin composition of any one of~the 6 mode is formed.
It is described insulation-coated to be crosslinked according to the 8th mode of the present invention there is provided the insulated electric conductor of the 7th mode.
According to the 9th mode of the present invention there is provided a kind of manufacture method of insulated electric conductor, with the extrusion on the periphery of conductor The vinyl chloride resin composition of any one of the 1st~the 6th mode is coated to form insulation-coated process.
According to the 10th mode of the present invention there is provided the manufacture method of the insulated electric conductor of the 9th mode, further with crosslinking institute State insulation-coated process.
Invention effect
According to the present invention it is possible to obtain anti-flammability and electrical characteristics, heat endurance, cold resistance and molding processibility are all excellent Vinyl chloride resin composition and use its insulated electric conductor.
Brief description of the drawings
Fig. 1 is the sectional view of the insulated electric conductor involved by an embodiment of the invention.
Symbol description
1 insulated electric conductor
10 conductors
11 is insulation-coated
Embodiment
The opinion that the present inventor is obtained
Before explanation an embodiment of the invention, first illustrate the opinion obtained by the present inventor.
As described above, the metal hydroxides such as aluminium hydroxide, magnesium hydroxide can improve the resistance of vinyl chloride resin composition Combustion property.But, electrical characteristics, heat endurance, cold resistance and the shaping that metal hydroxides has reduction vinyl chloride resin composition add The worry of work.Therefore, by the vinyl chloride resin composition containing metal hydroxides in large quantities formed it is insulation-coated in, The problem of following (1)~(4) can be produced so.
(1) aluminium hydroxide due to its volume intrinsic resistance value it is low, the volume that can reduce vinyl chloride resin composition is inherently electric Resistance, reduces insulation-coated electrical characteristics (electrical insulating property).Magnesium hydroxide is by hydrolyzing increasing contained in vinyl chloride resin combination Agent is moulded, insulation-coated electrical characteristics are reduced in the same manner as aluminium hydroxide.
(2) because aluminium hydroxide reduces the heat endurance of vinyl chloride resin composition, so that becoming prone to heat deteriorates insulation It is coated.
(3) metal hydroxides such as aluminium hydroxide is due to reducing the cold resistance of vinyl chloride resin composition, thus insulation quilt When covering exposed to low temperature, become prone to brittle and produce cracking.
(4) metal hydroxides such as aluminium hydroxide is extruded while being cut to vinyl chloride resin composition When processing and forming is insulation-coated, the key factor of foaming is produced as the cutting heating for promoting resin and in resin.If tree Fat foams, and can deteriorate the insulation-coated outward appearance after processing and forming.In addition, aluminium hydroxide etc. is extruding vinyl chloride tree by mould Oil/fat composition processing and forming into it is insulation-coated when, as mould outlet produce mould residue (ダ イ ス カ ス) it is important because Element.If producing mould residue, the insulation-coated thickness after processing and forming is caused to produce uneven (produce so-called outer sometimes Footpath deviation).The speed (extruded velocity) of extrusion vinyl chloride resin composition gets over high speed, and the foaming of such resin, mould are residual The generation of slag is then more obvious.Such aluminium hydroxide etc., due to reducing the molding processibility of vinyl chloride resin composition, can be caused Insulation-coated bad order, outside diameter tolerance.
For the decline of the characteristic that suppresses the above-mentioned vinyl chloride resin composition caused by metal hydroxides, it is contemplated that Reduce the content of metal hydroxides.Here, in order to maintain relative to VW-1 pass the tests high flame retardant while drop The amount of low contained metal hydroxides, for vinyl chloride resin composition, the present inventor is to that can make up because of the content Reduction caused by anti-flammability decline, other compounds with anti-flammability are studied.As a result, being found that amorphous State silica and hydrotalcite and burn till such opinion that at least one combination selected in clay has been.Due to these changes Compound has anti-flammability respectively, metal hydroxides can be replaced to use.Moreover, the combination of these compounds, can be replaced Part or all of metal hydroxides.I.e., it is possible to reduce the content of metal hydroxides, or even it is allowed to as 0.Thus, may be used While with the anti-flammability equal when maintaining with only largely using metal hydroxides, it can suppress because of metal hydroxides institute Caused electrical characteristics, heat endurance, the decline of cold resistance and molding processibility.
The present invention is namely based on above-mentioned opinion and completed.
The first embodiment of the present invention
In the present invention, as described above, by amorphous silicon di-oxide and hydrotalcite and any one of clay is burnt till, can To replace some or all of metal hydroxides.In present embodiment, the part to replacing metal hydroxides Situation is illustrated.Specifically, to containing metal hydroxides, amorphous silicon di-oxide, hydrotalcite and burning till in clay At least one situation is illustrated.In addition, to metal hydroxides, amorphous silicon di-oxide, hydrotalcite and burning till viscous below Soil burns till clay to be said respectively as (A) metal hydroxides, (B) amorphous silicon di-oxide, (C1) hydrotalcite with (C2) It is bright.
Vinyl chloride resin composition
The vinyl chloride resin composition of present embodiment contains vinyl chloride resin, plasticizer, (A) metal hydroxides, (B) Amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till any of clay.
Hereinafter, each composition is specifically described.
Vinyl chloride resin
Vinyl chloride resin is base resin.It is not particularly limited as vinyl chloride resin, can outside the homopolymer of vinyl chloride With using the copolymer of vinyl chloride and other polymerizable monomers, such as vinyl chloride-vinyl acetate copolymer.In addition, at this In a little resins, it can be used as needed with mixed ethylene-acetate ethylene copolymer, haloflex etc..Vinyl chloride resin Average degree of polymerization from the angle preferably less than more than 1,300 2500 of heat endurance, cold resistance and molding processibility, more Preferably less than more than 1,500 2000.
Plasticizer
It is not particularly limited as plasticizer, known plasticizer can be used.In plasticizer, preferably use partially Benzenetricarboxylic acid system plasticizer, for example, can use tri trimellitate 2- ethylhexyls, tri trimellitate nalka base ester, tri trimellitate Isodecyl base ester etc..From heat endurance, the angle of cold resistance, more preferably tri trimellitate nalka base ester.Tri trimellitate Nalka base ester contains the alkyl of carbon number 8 preferably as principal component, can the alkyl containing carbon number 10 as accessory ingredient.
The content of plasticizer, can moderately change according to insulation-coated required flexibility.If simply plasticizer Content it is very few, when vinyl chloride resin composition is formed into insulation-coated, have the load ftractureed because fragility is insulation-coated The heart.On the other hand, if the content of plasticizer is excessive, due to plasticizer, the dissolution from vinyl chloride resin composition, insulation-coated It is tacky, thus have the worry of operability decline.Therefore, the content of plasticizer, can be with relative to 100 mass parts vinyl chloride resins Below more than 35 mass parts 60 mass parts, more than preferably 40 mass parts below 55 mass parts.
(A) metal hydroxides
(A) metal hydroxides improves the anti-flammability of vinyl chloride resin composition.(A) metal hydroxides can be because of heating Dehydration, the temperature (endothermic reaction) of vinyl chloride resin is reduced by the moisture discharged, suppresses its burning.
It is not particularly limited as (A) metal hydroxides, such as can use aluminium hydroxide, magnesium hydroxide.Can be with One kind in these is used alone, two or more can also be used in combination.Magnesium hydroxide is compared with aluminium hydroxide, although dehydration temperaturre Height, but cause in vinyl chloride resin composition the hydrolysis of plasticizer, coloring sometimes.Therefore, as (A) metal hydroxide Thing, aluminium hydroxide is only used preferably without using magnesium hydroxide.Thus, it is possible to improve the electrical characteristics of vinyl chloride resin composition, Molding processibility.
(A) average grain diameter of metal hydroxides is not particularly limited, from preferably 2 μm of the angle of dispersiveness with Under.Furthermore it is preferred that (A) metal hydroxides is without surface treatment.
(B) amorphous silicon di-oxide
(B) amorphous silicon di-oxide is amorphous state particulate silica.Amorphous state particulate silica for example passes through Silica is reduced in gas, is aoxidized to obtain in its vapor phase.Amorphous state particulate silica, such as one Secondary shape of particle is substantially spherical, and average grain diameter is less than more than 0.1 μm 0.2 μm.In addition, amorphous state particulate silica Active hydrogen-based on surface is few.Therefore, amorphous state particulate silica is compared with conventional particulate silica, it is easy to point Dissipate in vinyl chloride resin composition.Amorphous state particulate silica, can be with by being distributed in vinyl chloride resin composition Improve its anti-flammability.For this point, it is described as follows.
The not aggegation in vinyl chloride resin composition of amorphous state particulate silica, can be with dispersed.Work as chloroethene Olefine resin composition starts during burning (burning initial stage), and amorphous state particulate silica is evenly distributed in the resin surface, shape Into hard cured layer (so-called to burn).Oxygen is blocked by cured layer, thus the burning of vinyl chloride polymer resin can be suppressed.And And, amorphous state particulate silica is in vinyl chloride resin composition, by making the gasification using silica as starting point foam Diameter microminiaturization, can suppress the diffusion of comburant, suppress spreading for burning.Thus, based on amorphous state particulate silica, Vinyl chloride resin composition can be assigned with the anti-flammability with nano silicon on an equal basis above.
It should be noted that, the situation of amorphous state particulate silica high filling in vinyl chloride resin composition, The decline of the decline of the molding processibility of vinyl chloride resin composition, insulation-coated extensibility etc. is also few caused by aggegation.
(C1) hydrotalcite
(C1) hydrotalcite is for example with composition formula Mg6Al2(OH)16CO3·4H2There is the layer containing magnesium and aluminium represented by O Shape structure, in interlayer contain carbanion (CO3 2-) compound.(C1) hydrotalcite in acidic region because having anion friendship It is transsexual, so as to improve the anti-flammability and heat endurance of vinyl chloride resin composition.On this point, saying in detail below It is bright.
(C1) hydrotalcite passes through the carbanion (CO in chemical constitution3 2-) replace in the heat deterioration of vinyl chloride resin Chlorion (Cl in the hydrogen chloride of generation-) (ion exchange), chlorion can be captured in crystal structure.By such Ion exchange, (C1) hydrotalcite turns into the hydrotalcite-based compound of chlorion type.The compound has in the temperature up to about 400 DEG C Spend and chlorion is caught in chemical constitution without the property that disengages it from.Therefore, (C1) hydrotalcite can be by catching from chloroethene The hydrogen chloride departed from the chemical constitution of olefine resin, suppresses its heat deterioration, to improve the heat endurance of vinyl chloride resin.Moreover, (C1) hydrotalcite improves the initial temperature of the heat deterioration of vinyl chloride resin while heat endurance is improved, and promotes its (charcoal that is carbonized Scorification), so as to improve the anti-flammability of vinyl chloride resin.
(C2) clay is burnt till
(C2) burn till clay and assign electrical characteristics and anti-flammability to vinyl chloride resin composition.(C2) it is to for example to burn till clay It is used as a kind of wet type kaolin (chemical formula of kaolinton：Al2O3·2SiO2·2H2O obtained from) being burnt till.(C2) Burn till in clay, the crystallization water is discharged by burning till, destroy original crystal structure.By the way that with the structure, (C2) burns till viscous Soil is high compared to the activity of other kaolin (wet type kaolin, dry type kaolin etc.), it is easy to the fixed dissociated ion of absorption.Cause This, the electrical characteristics (electrical insulating property) of vinyl chloride resin can further be improved by burning till clay by (C2).Further, since (C2) burns There is the structure of Porous into clay, low molecular organic principle is absorbed, the anti-flammability of vinyl chloride resin is also assigned.
The proportioning of each composition
As described above, in vinyl chloride resin composition, obtained using only (A) metal hydroxides for example relative to In the case of the high flame retardant of above-mentioned VW-1 pass the tests, its content is at least needed to be more than 8 mass parts.But, this feelings Under condition, due to substantial amounts of metal hydroxides, each characteristic of vinyl chloride resin composition can be reduced.On the other hand, this embodiment party In formula, burn till at least one of clay to replace (A) metal with (C2) by (B) amorphous silicon di-oxide, (C1) hydrotalcite The content of (A) metal hydroxides, can be reduced to less than 8 mass parts by a part for hydroxide.Particularly, according to this hair The opinion of a person of good sense, the content of metal hydroxides if 7 mass parts below, the chlorine caused by metal hydroxides can be suppressed The decline of each characteristic of acetate resin composition.For the combination of above-mentioned (A) composition~(C2) composition, there are three kinds of following feelings Condition.
(1)：(A) metal hydroxides+(B) amorphous silicon di-oxide+(C1) hydrotalcite
(2)：(A) metal hydroxides+(B) amorphous silicon di-oxide+(C2) burns till clay
(3)：(A) metal hydroxides+(B) amorphous silicon di-oxide+(C1) hydrotalcite+(C2) burns till clay
Here, when above-mentioned (1)~(3), the proportioning of each composition is illustrated respectively.It should be noted that, this embodiment party In formula, it can suitably change proportioning (content of each composition), the following is one example.
In the case of (1), this 3 kinds of (A) metal hydroxides, (B) amorphous silicon di-oxide and (C1) hydrotalcite are used Composition.In this case, the content of (B) amorphous silicon di-oxide and (C1) hydrotalcite is relative to 100 mass parts vinyl chloride resins, It can be following scope.It should be noted that, the scope of "~" expression " more than defined numerical value, below defined numerical value ".
(B) amorphous silicon di-oxide：The mass parts of 4 mass parts~15, the mass parts of preferably 4 mass parts~10
(C1) hydrotalcite：The mass parts of 5 mass parts~30, the mass parts of preferably 5 mass parts~25
, can be by (A) metal by making the content of (B) amorphous silicon di-oxide and (C1) hydrotalcite in above-mentioned scope The content of hydroxide is reduced to below 7 mass parts.It is preferred that the content of (A) metal hydroxides can be more than 0.1 mass parts 6 Below mass parts.It should be noted that, as (A) metal hydroxides and when using two or more, above-mentioned model is added up to using it Enclose.
In the case of (2), use (A) metal hydroxides, (B) amorphous silicon di-oxide and (C2) burn till clay this three Individual composition.In this case, (B) amorphous silicon di-oxide and (C2) burn till the content of clay relative to 100 mass parts vinyl chloride Resin, can be following scope.
(B) amorphous silicon di-oxide：The mass parts of 4 mass parts~15, the mass parts of preferably 4 mass parts~10
(C2) clay is burnt till：The mass parts of 4 mass parts~15, the mass parts of preferably 5 mass parts~10
By making (B) amorphous silicon di-oxide and (C2) burns till the content of clay in above-mentioned scope, can will (A) it is golden The content of category hydroxide is reduced to below 7 mass parts.It is preferred that the content of (A) metal hydroxides can for 0.1 mass parts with Below upper 6 mass parts.It should be noted that, in the case of (2), and if burnt till with (B) amorphous silicon di-oxide and (C2) viscous Soil, then because synergistic effect is compared with being used alone respective situation, further improve anti-flammability.Therefore, even in reduction by 3 kinds into In the case of the content divided, desired anti-flammability can be also obtained.
In the case of (3), (A) metal hydroxides, (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) are used Burn till clay this 4 kinds of compositions.In this case, (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till the content of clay Can be following scope relative to 100 mass parts vinyl chloride resins.
(B) amorphous silicon di-oxide：The mass parts of 4 mass parts~15, the mass parts of preferably 4 mass parts~10
(C1) hydrotalcite：The mass parts of 5 mass parts~30, the mass parts of preferably 5 mass parts~25
(C2) clay is burnt till：The mass parts of 4 mass parts~15, the mass parts of preferably 5 mass parts~10
By making (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burns till the content of clay in above-mentioned scope, The content of (A) metal hydroxides can be reduced to below 7 mass parts.It is preferred that the content of (A) metal hydroxides can be More than 0.1 mass parts below 6 mass parts.It should be noted that, in the case of (3), due to being used in combination in the same manner as the situation of (2) (B) amorphous silicon di-oxide and (C2) burn till clay, because respective synergistic effect can further improve vinyl chloride resin combination The anti-flammability of thing.Therefore, in the case of the content of 4 kinds of compositions is reduced, desired anti-flammability can also be obtained.For example, It can be adjusted by reducing the content of any condition so that the content of (C1) hydrotalcite of the high cost of reduction.
In this way, according to present embodiment, being burnt till by using (B) amorphous silicon di-oxide and (C1) hydrotalcite and (C2) viscous Any one in soil, can reduce the content of (A) metal hydroxides
Other additives
In present embodiment, in addition to mentioned component, stabilizer can also be further contained as needed.Stabilizer is only If the non-lead system stabilizer for not containing lead is not just limited.
Further, it is also possible to further use inorganic filler.As inorganic filler, such as calcium carbonate, cunning can be used Stone etc..
In addition, when to insulation-coated be crosslinked, crosslinking agent and crosslinking coagent can also be used., can as crosslinking agent To use organic peroxide, silane compound etc..In addition, as crosslinking coagent, trimethylol propane trimethyl can be used Acrylate, dipentaerythritol acrylate etc..The content of crosslinking coagent is not particularly limited, if crossing crosslinking at least becomes It is insufficient, at most it is crosslinked if crossed in processing and forming, therefore, the content of crosslinking coagent is relative to 100 mass parts chloroethenes Olefine resin can be for more than 2 mass parts 20 mass parts below.It is if the content as above-mentioned, then insulation-coated when can make crosslinking The degree of cross linking less than more than 40% 65%, preferably less than more than 49% 60% are calculated as with gel fraction.
In addition, as needed can also containing one or more kinds of ultra-violet absorbers, light stabilizer, lubricant, Colouring agent, processability modifying agent, other modifying agent etc..These can use known additive, and its content can also root Suitably change according to purposes.
It should be noted that the vinyl chloride resin composition of present embodiment can be by by above-mentioned vinyl chloride resin, increasing Modeling agent, (A) metal hydroxides, (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till at least one of clay with And other additives of crosslinking coagent as needed etc. are mixed, kneaded to obtain while heating.For mixed The condition of refining, the order of addition of each composition are not particularly limited, can be identical with known method.In addition, mixing can be with Using mixing roll, Banbury, uniaxially or biaxially extruder etc. carry out.In addition, heating-up temperature during mixing is, for example, Less than more than 170 DEG C 200 DEG C.
Insulated electric conductor
Hereinafter, the insulated electric conductor in an embodiment of the invention is illustrated using Fig. 1.The one of Fig. 1 display present invention The sectional view of insulated electric conductor 1 involved by individual embodiment.
As shown in figure 1, insulated electric conductor 1 has insulation-coated the 11 of conductor 10 and the periphery for being arranged to coated conductor 10.Absolutely Edge coated 11 is formed by above-mentioned vinyl chloride resin composition.
As conductor 10, it is not particularly limited, usually used metal wire can be used, such as except copper cash, copper alloy Aluminum steel, gold thread, silver wire outside line etc..Further, it is also possible to implement leading for the metal-plateds such as tin, nickel using in the periphery of metal wire Body.Further, it is possible to be twisted together conductor using the twisted set for having metal wire.Do not limited especially for the conductor diameter of conductor 10 It is fixed, for example can be more than 0.15mm below 7mm.
Insulation-coated 11 are formed by extruding coated above-mentioned vinyl chloride resin composition in the periphery of conductor 10.Insulate quilt The thickness for covering 11 is not particularly limited, for example, can be more than 0.1mm below 3mm.In addition, insulation-coated 11 from improve mechanicalness The angle of energy, which is set out, to be preferably crosslinked.It is not particularly limited for the cross-linking method, for example, can uses organic peroxy The known methods such as thing crosslinking, crosslinked with silicane, radioactive ray crosslinking.Wherein, consider from chain of command, cost face, preferably use The radioactive ray crosslinking of electron beam.
The manufacture method of insulated electric conductor
Above-mentioned insulated electric conductor 1 can be manufactured by known method.The manufacture method of insulated electric conductor 1, for example, have Have and above-mentioned vinyl chloride resin composition extrusion is coated on the periphery of conductor 10 process that forms insulation-coated 11 and right Insulation-coated 11 implement the process of crosslinking.Specifically, make conductor 10 with defined linear speed (for example：It is 400m/min) mobile When, by extruding coated vinyl chloride resin composition on their outer circumference, to form insulation-coated 11.Afterwards, by insulation quilt Cover the cross linked insulations such as 11 irradiating electron beams coated 11.Thus the insulated electric conductor 1 of present embodiment is obtained.In present embodiment, by In having used the vinyl chloride resin composition that content is few, molding processibility is excellent of (A) metal hydroxides, thus it can suppress Foaming, the generation of mould residue caused by cutting heating, can be with high speed extrusion.I.e., it is possible to improve the production effect of insulated electric conductor 1 Rate.
It should be noted that, in present embodiment, to directly extruding coated vinyl chloride resin composition shape in the periphery of conductor It is illustrated into the insulation-coated situation as insulating barrier, but the invention is not restricted to this.Can also be for example common exhausted Extrude and be coated on the periphery of edge electric wire, formation is used as the insulation-coated of sheath.In addition, showing that conductor 10 is single in Fig. 1 The situation of line, but twisted thread the invention is not restricted to this or multicore.In addition, the cross sectional shape of conductor 10 is not limited to circular shape Shape or flat pattern.
The effect of embodiments of the present invention
According to present embodiment, one or more effects as shown below are realized.
(a) according to present embodiment, vinyl chloride resin composition contains vinyl chloride resin, plasticizer, (A) metal hydroxide Thing, (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till at least one of clay.(B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till clay and assign vinyl chloride resin composition respectively with anti-flammability, thus can replace (A) metal Hydroxide is used.Moreover, by the combination of these compounds, the part even in displacement (A) metal hydroxides is come In the case of reducing the content of (A) metal hydroxides, the situation with only a large amount of use (A) metal hydroxides can also be maintained Equal anti-flammability.Thus, for example it is insulation-coated to become to close with the testing vertical flammability (VW-1 experiments) for UL758 standards The high flame retardant of lattice.
(b) according to present embodiment, by reducing the content of (A) metal hydroxides, vinyl chloride resin group can be suppressed The reduction of the electrical characteristics of compound.Thus, for example the insulation-coated A-stage before heat deterioration has more than 15kV high destruction Voltage.
(c) according to present embodiment, by reducing the content of (A) metal hydroxides, vinyl chloride resin group can be suppressed The reduction of the heat endurance of compound.Thus, it is possible to suppress electrical characteristics, stretching caused by the heat deterioration of vinyl chloride resin composition Decline.For example, the destruction voltage A of A-stage before insulation-coated heat deterioration with placed 168 hours at 136 DEG C after it is broken Bad voltage B ratio B/A is more than 0.9, it is suppressed that the decline of the electrical characteristics caused by heat deterioration.In addition, insulation-coated 150 DEG C hot environment under exposure 500 hours when stretching absolute value rate of descent be less than 50%, it is suppressed that because heat deterioration is drawn The decline of the stretching risen.
(d) according to present embodiment, by reducing the content of (A) metal hydroxides, vinyl chloride resin group can be suppressed The decline of the cold resistance of compound.Thus, for example even in will it is insulation-coated in the environment of -35 DEG C exposure 1 hour in the case of, Also it is difficult to embrittlement, it is difficult to crack.
(e) according to present embodiment, by reducing the content of (A) metal hydroxides, vinyl chloride resin group can be improved The molding processibility of compound.Therefore, vinyl chloride resin composition can be with high speed extrusion.That is, even in using such as linear speed as 400m/ In the case of min carries out high speed extrusion vinyl chloride resin composition, the foaming in vinyl chloride resin composition can also be suppressed, obtained To the insulation-coated of good outward appearance.And then, due to the generation of the mould residue in vinyl chloride resin composition, energy can be suppressed Access few insulation-coated of uneven thickness (outside diameter tolerance).
(f) according to present embodiment, preferably the content of (A) metal hydroxides is relative to 100 mass parts vinyl chloride resins Below 7 mass parts.Thus, it is possible to further suppress each caused by (A) metal hydroxides in vinyl chloride resin composition The decline of characteristic.
(g) according to present embodiment, preferably comprise (C1) hydrotalcite and (C2) burns till both clays.Thus, it is possible to enter One step improves the anti-flammability of vinyl chloride resin composition.
(h) according to present embodiment, vinyl chloride resin composition substance does not contain harmful antimonial and lead system is steady Determine agent.Thus, it is possible to reduce environmental pressure.
(i) according to present embodiment, using the formation of above-mentioned vinyl chloride resin composition for example with the composition shown in Fig. 1 Insulation-coated the 11 of insulated electric conductor 1.According to such insulated electric conductor, due to the insulation with the effect for possessing above-mentioned (a)~(h) It is coated, it can be used for matching somebody with somebody for the high-temperature portion such as dryer, electric cooker, lead-out wire, ligthing paraphernalia, air-conditioning in electric equipment Line.
(j) according to present embodiment, preferably cross linked insulation is coated to 11.According to crosslinking, it can further improve insulation-coated Mechanical property.
(k) according to present embodiment, due to vinyl chloride resin composition, its molding processibility is excellent, it is thus possible to squeeze at a high speed Go out.As a result, insulation-coated 11 formation high speed, improves the productivity of insulated electric conductor 1.
The 2nd embodiment of the present invention
Next, the 2nd embodiment to the present invention is illustrated.But only illustrate and above-mentioned 1st embodiment here Difference.
In above-mentioned 1st embodiment, it is illustrated for replacing the situation of a part of (A) metal hydroxides, But the invention is not restricted to this.In the present invention, clay can be burnt till by (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) To replace the whole of (A) metal hydroxides.That is, can also without using (A) metal hydroxides in vinyl chloride resin composition Obtain anti-flammability equal during with using only (A) metal hydroxides.It is additionally, since without using (A) metal hydroxides, can be with Prevent the decline of each characteristic caused by (A) metal hydroxides.Thus, it is possible to maintain the fire-retardant of vinyl chloride resin composition Property, while further improving electrical characteristics, heat endurance, cold resistance and molding processibility.
It should be noted that, (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till containing for clay in present embodiment Amount, can be following scope relative to 100 mass parts vinyl chloride resins.
(B) amorphous silicon di-oxide：The mass parts of 4 mass parts~15, the mass parts of preferably 4 mass parts~10
(C1) hydrotalcite：The mass parts of 5 mass parts~30, the mass parts of preferably 5 mass parts~25
(C2) clay is burnt till：The mass parts of 4 mass parts~15, the mass parts of preferably 5 mass parts~10
Embodiment
Hereinafter, embodiments of the invention are illustrated.
(1) material
Material used in embodiment and comparative example is as described below.
As vinyl chloride resin, use " TH-1700 " (degree of polymerization 1700) of ocean vinyl chloride Co. Ltd. system.
As plasticizer, tri trimellitate nalka base ester (hereinafter referred to as n-TOTM) (Kao Corp's system is used “TRIMEX No8”)。
As (A) metal hydroxides, following 4 kinds are used.
(a1) aluminium hydroxide：Showa Denko K. K's system " HIGILITEH-42M " (1 μm of average grain diameter)
(a2) aluminium hydroxide：Showa Denko K. K's system " HIGILITEH-43M " (0.75 μm of average grain diameter)
(a3) aluminium hydroxide：Showa Denko K. K's system " HIGILITEH-32 " (8 μm of average grain diameter)
(a4) aluminium hydroxide：Showa Denko K. K's system " HIGILITEH-42S " (1 μm of average grain diameter, at surface Reason)
As (B) amorphous silicon di-oxide, (Elkem) Co. Ltd. system " SIDISTAR 120U " are agreed using angstrom.
As (C1) hydrotalcite, Sakai KCC system " HT-1 " is used.
Clay is burnt till as (C2), is used " SP#33 " of BASF Co. Ltd. systems.
In addition, as other additives, using following material.
Non- lead stabilizer：Marshy land KCC system " NL-HT7 "
Crosslinking coagent：Trimethylolpropane trimethacrylate (KCC of Xin Zhong villages system " NK Ester H-200 ")
Calcium carbonate：Three powder Co. Ltd. systems " SCP#2010 " processed altogether
Antimony trioxide：Chinese occasion state Co. Ltd. system " NANO-200 "
(2) modulation of vinyl chloride resin composition
In embodiment 1~5, modulated using (B) amorphous silicon di-oxide, (C1) hydrotalcite and (A) metal hydroxides Vinyl chloride resin composition.
In embodiment 1, the n-TOTM as plasticizer, 4 matter of 44 mass parts are added in 100 mass parts vinyl chloride resins Measure part (B) amorphous silicon di-oxide, 7 mass parts (C1) hydrotalcite, 5 mass parts (a1) hydrogen-oxygen as (A) metal hydroxides Change aluminium, as the non-lead stabilizer of 4 mass parts of other additives, 4 mass parts crosslinking coagents, mixed.The mixture is existed It is heated to kneading in 140 DEG C of mill.Mixture is cooled into graininess afterwards, so as to be modulated into the chloroethene of embodiment 1 Olefine resin composition.Modulation condition is shown in table 1 below
In addition, in embodiment 2~5, except changing (A) metal hydroxides, (B) amorphous silicon di-oxide, (C1) neatly Beyond the addition of stone, the species of other additives, addition, the vinyl chloride of embodiment 2~5 is modulated similarly to Example 1 Resin combination.
Table 1
In embodiment 6~9, except using (A) metal hydroxides, (B) amorphous silicon di-oxide and (C2) to burn till clay Outside, vinyl chloride resin composition is modulated similarly to Example 1.Modulation condition is shown in table 2 below.
Table 2
In embodiment 10~15, except use (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till clay it Outside, vinyl chloride resin composition is modulated similarly to Example 1.Modulation condition is shown in table 3 below.
Table 3
In embodiment 16~22, except use (A) metal hydroxides, (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) burn till outside clay, vinyl chloride resin composition is modulated similarly to Example 1.Modulation condition is shown in table 4 below.
Table 4
In comparative example 1~7, except appropriately combined antimony trioxide, (A) metal hydroxides, (C2) burn till clay and use Outside, vinyl chloride resin composition is modulated similarly to Example 1.Modulation condition is shown in table 5 below.
Table 5
(3) manufacture of insulated electric conductor
Then, using the embodiment 1~22 and the vinyl chloride resin composition of comparative example 1~7 of above-mentioned modulation, manufacture insulation Electric wire.Specifically, in the twisted twisted conductor (external diameter of the tin annealed copper wire by 26 external diameter 0.16mm as conductor On periphery 0.94mm), by extrusion by melting to be coated to the vinyl chloride resin composition of the coated modulation of thickness 0.5mm extrusions, Form the insulation-coated of thickness 0.5mm.Afterwards, electron beam crosslinking is passed through with line amount 3.5Mrad irradiating electron beams to insulation-coated To manufacture insulated electric conductor.
(4) evaluation method
Then, for resulting insulated electric conductor, anti-flammability, electrical characteristics, heat endurance, cold resistance and processing and forming are evaluated Property.Illustrate evaluation method below.
Anti-flammability
For anti-flammability, tested based on VW-1 specified in UL1581, carry out Vertical Flame Test.In the present embodiment, to 5 Root insulated electric conductor is tested, and 5 are designated as "○" when all qualified, as long as 1 unqualified is just designated as "×".
Electrical characteristics
As electrical characteristics, insulated electric conductor for A-stage and 168 hours hot bad is placed in the environment of 136 DEG C Insulated electric conductor after change, carries out following two experiments, each single item experiment is designated as "○" when qualified, is not so based on UL758 Shi Jiwei "×".
(i) plug 6 that the respective insulated electric conductor after A-stage and heat deterioration is wound up into diameter 5mm is enclosed, in water Apply assigned voltage, determine the destruction voltage until insulation breakdown.Moreover, being remembered with the destruction voltage of the insulated electric conductor of A-stage For A, the destruction voltage of the insulated electric conductor after heat deterioration is designated as B, and it is qualified to be designated as when A is more than 15kV and B/A is more than 0.9.
(ii) coiled metal paper tinsel on respective insulated electric conductor in the early stage after state and heat deterioration, 105 DEG C of rated condition/ 2000V charges 1 minute.For the insulated electric conductor after A-stage and heat deterioration, it is qualified to be designated as when each without short circuit.
Heat endurance
As heat endurance, following two experiments are carried out, each experiment is designated as "○" when qualified, is designated as when being not such “×”。
(i) insulated electric conductor is subjected to heat deterioration at 150 DEG C, the absolute value for determining the insulation-coated stretching after heat deterioration is arrived Up to time when 50%, it is qualified that the time is designated as when being more than 500 hours, is designated as during less than 500 hours unqualified.
(ii) be coated with the wax specified on insulated electric conductor in CSA experiments, 105 DEG C of dryings 30 minutes, afterwards 150 DEG C, Harden wax within 20 hours.It winds on diameter 1mm plug to 6 circles, it is insulation-coated in be designated as when not cracking it is qualified.
Cold resistance
As cold resistance, insulated electric conductor is placed 1 hour in the environment of -35 DEG C, it is rolled up on diameter 1mm plug Around 6 weeks, it is insulation-coated in be designated as "○" when not cracking, "×" is designated as when cracking.
Molding processibility
As molding processibility, following two experiments are carried out, each experiment is designated as "○" when qualified, remembers when being not such For "×".
(i) using 40mm extruder, with the coated vinyl chloride resin composition of linear speed 400m/min extrusions, it be not derived from The spark-over of vinyl chloride resin composition or because remembering caused by the generation of raised (U Block) mould residue during outside diameter tolerance To be qualified, it is designated as during generation unqualified.
(ii) choose extrusion initial stage sample and extrusion it is coated carried out the sample after 1 hour, do not confirming insulation Coated outward appearance is coarse, be designated as with light microscope with 100 times of multiplying power observations when also not confirming foaming in insulation-coated It is qualified.
(5) evaluation result
In embodiment 1~5, by using (B) amorphous silicon di-oxide and (C1) hydrotalcite, even in by (A) metallic hydrogen The content of oxide is reduced to below 7 mass parts, also confirms to be able to maintain that desired anti-flammability.It is additionally, since (A) gold The content of category hydroxide is reduced to below 7 mass parts, it is suppressed that electrical characteristics, heat endurance, cold resistance and molding processibility Decline, it is thus identified that these characteristics can be improved.
In embodiment 6~9, clay is burnt till by using (B) amorphous silicon di-oxide and (C2), it is same with embodiment 1~5 Ground confirms while anti-flammability is maintained, it is possible to increase electrical characteristics, heat endurance, cold resistance and molding processibility.
In embodiment 10~15, clay is burnt till by using (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2), really Accept and also obtained desired anti-flammability without using (A) metal hydroxides.It should be noted that embodiment 10~15 is with making Compared with the embodiment 1~9 of (A) metal hydroxides, it is thus identified that can further improve insulation-coated electrical characteristics, thermally-stabilised Property, cold resistance and molding processibility.
In embodiment 16~22, by making together with burning till clay with (B) amorphous silicon di-oxide, (C1) hydrotalcite and (C2) With (A) metal hydroxides below 7 mass parts, it is thus identified that together with anti-flammability, improve electrical characteristics, heat endurance, resist cold Property and molding processibility.It should be noted that in embodiment 16~22, it is viscous due to being burnt till by using (C1) hydrotalcite and (C2) Content that is native and adding flame-retardant composition, compared with embodiment 1~9, it is thus identified that can further improve insulation-coated anti-flammability.
It should be noted that, in embodiment 4,9 etc., by using calcium carbonate, while each characteristic is maintained, it can reduce Cost.
Comparative example 1 is to have used antimony trioxide and (C2) to burn till the example of clay.In comparative example 1, due to antimony trioxide Content is few, confirms that insulation-coated anti-flammability is low.Specifically, in VW-1 experiments, there are 3 generations in 5 insulated electric conductors Burning.It should be noted that, in comparative example 1, due to containing antimony trioxide, cost is high and carrying capacity of environment is big.
Comparative example 2 is to burn till the example that clay is used together 15 mass parts (a4) aluminium hydroxide with (C2).Comparative example 2 In, because the content of (A) metal hydroxides is more than 7 mass parts, the raising of insulation-coated anti-flammability is can confirm that, but heat is steady Qualitative and molding processibility step-down.Specifically, insulation-coated in 150 DEG C of heat deteriorations because heat endurance declines, insulate quilt The extensibility covered for 50% time less than 350 hours, in addition, when being wound experiment, it is insulation-coated in crack.This Outside, because molding processibility declines, in processing and forming, mould residue is produced, because being attached to for mould residue is insulation-coated Upper generation outside diameter tolerance.
Comparative example 3 is (a4) aluminium hydroxide (surface for using the species of (A) metal hydroxides in comparative example 2 Managed) it is changed to the example of (a1) aluminium hydroxide (not being surface-treated).It is same with comparative example 2 in comparative example 3, confirm insulation Coated heat endurance and molding processibility step-down.It follows that (A) metal hydroxides is regardless of whether surface treated, effect Fruit is without difference.It should be noted that, confirm to generate mould residue in comparative example 3, insulation-coated thickness also produces inequality.
Comparative example 4 be (A) metal hydroxides content it is more more than comparative example 3 be 22 mass parts example.Comparative example 4 In, because the content of (A) metal hydroxides further increases compared with comparative example 3, thus except heat endurance and molding processibility Outside, electrical characteristics and cold resistance step-down.In comparative example 4, confirm to generate mould residue in the same manner as comparative example 3.
Comparative example 5 is example of the content of (A) metal hydroxides than comparative example 3 less for 8 mass parts.In comparative example 5, Because flame-retardant composition is few, confirm not obtain the anti-flammability of VW-1 pass the tests.Further, since non-lead stabiliser content is high, In vinyl chloride resin composition, because exterior active has played more multiaction, confirm that molding processibility is poor.
Comparative example 6 is (a1) aluminium hydroxide for using the species of (A) metal hydroxides in comparative example 5 (through surface Processing) it is changed to the example of big (a3) aluminium hydroxide of particle diameter.Comparative example 6 and the same anti-flammability of comparative example 5 are low, or due to hydrogen The particle diameter of aluminum oxide becomes big, and cold resistance further declines.
Comparative example 7 is the example that antimony trioxide is further added in comparative example 5.In comparative example 7, because flame-retardant composition contains Amount is few, confirms the result same with comparative example 5.

Claims (5)

1. a kind of vinyl chloride resin composition, it is characterised in that contain vinyl chloride resin, plasticizer, amorphous silicon di-oxide, water Talcum and clay is burnt till, do not contain metal hydroxides.
2. a kind of insulated electric conductor, it is characterised in that as the chloroethene described in claim 1 with conductor and on the conductor periphery It is insulation-coated that olefine resin composition is formed.
3. insulated electric conductor according to claim 2, wherein, it is described insulation-coated to be crosslinked.
4. a kind of manufacture method of insulated electric conductor, it is characterised in that be coated to claim 1 institute with being extruded on the periphery of conductor The vinyl chloride resin composition stated forms insulation-coated process.
5. the manufacture method of insulated electric conductor according to claim 4, wherein, it is further described insulation-coated with being crosslinked Process.
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JPH08120140A (en) * 1994-10-19 1996-05-14 Mitsubishi Chem Mkv Co Flame-retardant resin composition and coated electrical wire
CN103865191A (en) * 2012-12-13 2014-06-18 日立金属株式会社 Polyvinyl chloride resin composition and insulated wire using polyvinyl chloride resin composition
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