CN107686592A - Fire retardant resin composition and insulated electric conductor - Google Patents
Fire retardant resin composition and insulated electric conductor Download PDFInfo
- Publication number
- CN107686592A CN107686592A CN201710597255.4A CN201710597255A CN107686592A CN 107686592 A CN107686592 A CN 107686592A CN 201710597255 A CN201710597255 A CN 201710597255A CN 107686592 A CN107686592 A CN 107686592A
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- Prior art keywords
- magnesium hydroxide
- resin composition
- fire retardant
- retardant resin
- mass parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
-
- 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
- H01B3/448—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 other vinyl compounds
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a kind of fire retardant resin composition and insulated electric conductor, even if the use level of magnesium hydroxide is not high, can also improve anti-flammability.More than the mass parts of silane compound 1 that the fire retardant resin composition contains the mass parts of ethylene acrylate copolymer 100, is represented more than the mass parts of magnesium hydroxide 25 and below 120 mass parts and by following formula (1) and below 10 mass parts.In formula (1), Ra、X1、X2、X3It is each independently carbon number aliphatic alkyl below 3, the n in formula (1) is more than 1 and less than 5 real number.[changing 1]
Description
Technical field
The present invention relates to fire retardant resin composition and insulated electric conductor.
Background technology
In the past, fire retardant resin composition is used in insulated electric conductor, insulated cable etc..As fire retardant resin composition,
There is halogen-free resin composition.Such halogen-free resin composition refers to that metal hydroxides is added in polyolefin-based resins to be formed
Resin combination.As metal hydroxides, the magnesium hydroxide being surface-treated, not surface treated hydrogen can be enumerated
Magnesia (with reference to patent document 1,2).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2000-2418126 publications
Patent document 2：Japanese Unexamined Patent Publication 6-306215 publications
The content of the invention
Invent problem to be solved
In order to improve the mechanical property of fire retardant resin composition, electrical characteristics, the cooperation of metal hydroxides is preferably reduced
Amount.But if reducing the use level of metal hydroxides, it can typically reduce the anti-flammability of fire retardant resin composition.
The purpose of one aspect of the present invention is, there is provided a kind of use level that need not increase metal hydroxides can also make
Anti-flammability high fire retardant resin composition and insulated electric conductor.
For solving the method for problem
An embodiment of the invention is fire retardant resin composition, and it contains the matter of vinyl-acrylate copolymer 100
More than amount part, the mass parts of magnesium hydroxide 25 and below 120 mass parts and as the mass of silane compound 1 shown in following formula (1)
More than part and below 10 mass parts.
[changing 1]
In formula (1), Ra、X1、X2、X3Be each independently carbon number aliphatic alkyl below 3, the n in formula (1) for 1 with
It is upper and less than 5 real number.
The fire retardant resin composition of the present invention, even if not improving the use level of magnesium hydroxide, can also improve its anti-flammability.
Another embodiment of the invention is a kind of insulated electric conductor, and it has conductor and covers above-mentioned conductive surface extremely
At least part of insulating barrier, above-mentioned insulating barrier contain above-mentioned fire retardant resin composition.
The fire retardant resin composition of the insulated electric conductor of the present invention is formed, even if the use level of magnesium hydroxide is not high, it hinders
Combustion property is also high.Therefore, the anti-flammability of insulated electric conductor is also improved.
Brief description of the drawings
Fig. 1 is the sectional view for the structure for representing insulated electric conductor 1.
Symbol description
1：Insulated electric conductor, 3：Conductor, 5：Insulating barrier.
Embodiment
Embodiments of the present invention are illustrated.
1. vinyl-acrylate copolymer
Vinyl-acrylate copolymer is, for example, the base polymer of fire retardant resin composition.Ethylene-acrylate is total to
The melt flow rate (MFR) (MFR) of polymers is preferably more than 0.1 and less than 3.0.When MFR is in such scope, in terms of processability
It is outstanding.
The carbon number of ester group in vinyl-acrylate copolymer is preferably more than 1 and less than 4.The carbon atom of ester group
It is heat resistance, outstanding with the miscibility of additive aspect when number is in such scope.
In vinyl-acrylate copolymer, the polymerization amount of acrylate is preferably with respect to vinyl-acrylate copolymer
More than 10 mass % and below 20 mass %.When the polymerization amount of acrylate is in such scope, with metal hydrate, organic
It is outstanding in terms of the miscibility of silicon.
2. magnesium hydroxide
When the use level of vinyl-acrylate copolymer is 100 mass parts, the use level of magnesium hydroxide for 25 mass parts with
Below upper and 120 mass parts.More than for 25 mass parts, it is improved so as to the anti-flammability of fire retardant resin composition.It is logical
Cross below 120 mass parts, to be improved so as to mechanical property, the electrical characteristics of fire retardant resin composition.
Magnesium hydroxide is for example including magnesium hydroxide and is incorporated in the silane coupler on its surface.Magnesium hydroxide can be carried out
The magnesium hydroxide of surface treatment can also be the magnesium hydroxide not being surface-treated, but especially not surface treated hydrogen
Magnesia, due to good with the compatibility of organosilicon, it is favorably improved anti-flammability.
Silane coupler can be with (below, being otherwise referred to as " silicon by the aftermentioned organo-silicon compound represented by formula (1)
Hydride compounds ") identical compound or different compounds.
It is incorporated in 0.1 matter of the quality of the silane coupler on the surface of magnesium hydroxide, the preferably quality of magnesium hydroxide
Measure more than % and below 1.0 mass %.If integrated into the surface of magnesium hydroxide silane coupler quality in such model
It is in enclosing, then outstanding in terms of hygroscopicity, processability.
3. organo-silicon compound
Organo-silicon compound are that silane compound is represented by following formula (1).
[changing 1]
In formula (1), Ra、X1、X2、X3It is each independently aliphatic alkyl of the carbon number below 3, the n in formula (1) is 1
Above and less than 5 real number.
When the use level of vinyl-acrylate copolymer is set into 100 mass parts, the use level of silane compound is 1 matter
Measure more than part and below 10 mass parts, preferably more than 1.2 mass parts and below 5 mass parts.
Use level by silane compound is more than 1 mass parts, preferably more than 1.2 mass parts, so as to anti-flammability tree
The anti-flammability of oil/fat composition is improved.In addition, the use level for passing through silane compound is preferably 5 matter below 10 mass parts
Measure below part, so as to which processability aspect is outstanding.
As the R in formula (1), can enumerate such as alkyl, phenyl, amino, vinyl.As the X in formula (1)1、X2、
X3, can enumerate such as alkyl.
4. other compositions
Except vinyl-acrylate copolymer, magnesium hydroxide and the silane represented by formula (1) in fire retardant resin composition
Outside compound, it can also suitably contain other known compositions.
5. the characteristic of fire retardant resin composition
The oxygen index (OI) of the JIS K7201-2 defineds of the fire retardant resin composition of the present invention, for example, more than 30, preferably
For more than 33.Oxygen index (OI) is the index for representing anti-flammability.
The reasons why oxygen index (OI) of the fire retardant resin composition of the present invention is high, can estimate as follows.Silane compound disperses
In fire retardant resin composition, organo-silicon compound react with each other and form network structure.The network structure, which plays, hinders resistance
The effect that oxygen in combustion property resin combination passes through.And then the hydroxyl on magnesium hydroxide surface and the alkoxy of organo-silicon compound
Condensation reaction occurs in material mixing, so as to which the network of magnesium hydroxide and organo-silicon compound can be formed in resin, is firing
Suppress the motion of resin during burning, and then suppress oxygen and pass through, thus can further improve anti-flammability.
6. the manufacture method of fire retardant resin composition
The fire retardant resin composition of the present invention, such as can be manufactured by following method.
Manufacture method 1：Fire retardant resin composition for example can by will contain vinyl-acrylate copolymer, without
Each composition of the magnesium hydroxide of surface treatment and the silane compound represented by formula (1) is kneaded to manufacture in predetermined temperature.
Mixing can be carried out by known method, it is, for example, possible to use double-roll rolling mill etc..
Manufacture method 2：Fire retardant resin composition will be for example by that will contain vinyl-acrylate copolymer, by surface
Each composition of the magnesium hydroxide of processing and the silane compound represented by formula (1) is kneaded to manufacture in set point of temperature.It is kneaded
It can be carried out by known method, it is, for example, possible to use double-roll rolling mill etc..
When using manufacture method 1, during mixing, the silane compound that is represented by formula (1) is attached to not surface treated
The surface of magnesium hydroxide, generate surface treated magnesium hydroxide.When using manufacture method 1, preferably make silane compound
Use level has more the silane compound on the surface for being attached to not surface treated magnesium hydroxide compared with the situation of manufacture method 2
Amount.
It should be noted that it is less than 5 by the n in the silane compound that is represented by formula (1), so as to which silane compound is easy to
It is incorporated into the surface of magnesium hydroxide, and scattered in resin becomes good.
7. insulated electric conductor
Insulated electric conductor 1 is for example as shown in figure 1, at least one of insulating barrier 5 including conductor 3 and covering conductor 3 surface.
Insulating barrier 5 includes the fire retardant resin composition of the present invention.Fig. 1 is the sectional view with axially vertical section of insulated electric conductor 1.
Insulating barrier 5 can cover the whole on the surface of conductor 3, can also cover a part.Can be by the fire-retardant of the present invention
Property resin combination formed insulating barrier 5 whole or by the present invention fire retardant resin composition form insulating barrier 5
A part.Insulated electric conductor 1 can also be the multi-layer insulated electrical wire for also having in addition to insulating barrier 5 other layers.Other layers are for example
It can be arranged between conductor 3 and insulating barrier 5, or be arranged on the outside of insulating barrier 5.
As the method for forming insulating barrier 5, known method can be suitably selected, such as the coated method of extrusion can be used
Deng.
Embodiment
(1) manufacture of fire retardant resin composition
By each composition being kneaded described in table 1, so as to manufacture embodiment 1~4, the flame retardant resin group of comparative example 1~6
Compound.The unit of use level in table 1 is mass parts.
Table 1
As the vinyl-acrylate copolymer in table 1, the ethylene ethyl acrylate of three well Du Ponts has been used
A1150.Polymer based on A1150.The polymerization amount of acrylate in A1150 is 15 mass % of A1150 gross mass.
A1150 MFR is 0.8g/min.The carbon number of ester group in A1150 is 2.
As the low density polyethylene (LDPE) in table 1, the MIRASON 3530 (registration mark) of three well Du Ponts has been used.Should
MIRASON 3530 MFR is 0.23g/min.Polymer based on MIRASON 3530.
Magnesium hydroxide in table 1 is not surface treated magnesium hydroxide.As the magnesium hydroxide in table 1, association has been used
With the Kisuma 5 (trade name) of chemical industry.
Surface treated magnesium hydroxide in table 1 is silane treatment magnesium hydroxide, uses Liao Shen islands chemical industry
Magseeds S45 (trade name).In Magseeds S4, the quality for being incorporated in the silane coupler on magnesium hydroxide surface is hydrogen-oxygen
Change 0.3 mass % of the quality of magnesium.
As the organic silicon solution in table 1, the 11-100Additive (registration mark) of the beautiful DOW CORNING in east is used.It is organic
Silicon solution corresponds to organo-silicon compound.11-100Additive is using propyl trimethoxy silicane as principal component.Propyl group trimethoxy
Base silane corresponds to as the silane compound shown in formula (1).The use level of 11-100Additive in table 1 is expressed as propyl group three
The use level (being scaled solid constituent) of methoxy silane.
As the organic silica gel in table 1, the X-21-3043 (registration mark) of SHIN-ETSU HANTOTAI's organosilicon company system is used.X-21-
3043 be the organic silica gel of HMW.
(2) evaluation of fire retardant resin composition
For embodiment 1~4, the fire retardant resin composition of comparative example 1~6, JIS K 7201-2 are determined respectively and are advised
Fixed oxygen index (OI).The results are shown in above-mentioned table 1.Oxygen index (OI) in embodiment 1~4 is more than 33, is significantly high value.With this
Relatively, the oxygen index (OI) in comparative example 1~6 is respectively less than 30, is relatively low value.
In addition, not surface treated magnesium hydroxide is coordinated in embodiment 4, with having used surface treated hydroxide
The embodiment 1~3 of magnesium is compared, and has obtained the higher result of oxygen index (OI).Such result, it is believed that be because by magnesium hydroxide surface
Hydroxyl and organo-silicon compound alkoxy condensation reaction caused by flame retardant effect and bring.
Other embodiment
More than, embodiments of the present invention are illustrated, but the invention is not restricted to above-mentioned embodiment, can carry out
Various modifications are implemented.
(1) function possessed by an inscape in the respective embodiments described above can be shared in multiple inscapes,
Or function possessed by multiple inscapes can be played by an inscape.In addition it is also possible to omit above-mentioned each implementation
A part for the composition of mode.In addition it is also possible to relative to the composition of other above-mentioned embodiments by the respective embodiments described above
At least a portion of composition be added, replace.It should be noted that limited by the word described in claim
Whole embodiments included in technical concept, all it is embodiments of the present invention.
(2), can be by using the fire retardant resin composition to be formed in addition to above-mentioned fire retardant resin composition
The various embodiments such as the product of key element, the manufacture method of fire retardant resin composition, the manufacture method of insulated electric conductor are realized
The present invention.
Claims (6)
1. a kind of fire retardant resin composition, it contains the mass parts of vinyl-acrylate copolymer 100, the mass of magnesium hydroxide 25
Part more than and 120 mass parts below and by following formula (1) represent the mass parts of silane compound 1 more than and 10 mass parts with
Under,
[changing 1]
Formula (1)
In formula (1), Ra、X1、X2、X3It is each independently carbon number aliphatic alkyl below 3, the n in formula (1) is more than 1 and 5
Following real number.
2. fire retardant resin composition as claimed in claim 1, the magnesium hydroxide is not surface treated magnesium hydroxide.
3. fire retardant resin composition as claimed in claim 1, the magnesium hydroxide is surface treated magnesium hydroxide.
4. fire retardant resin composition as claimed in claim 1, the magnesium hydroxide contains magnesium hydroxide and is incorporated in its table
The silane coupler in face, the quality of the silane coupler are more than the 0.1 mass % and 1.0 matter of the quality of the magnesium hydroxide
Measure below %.
5. fire retardant resin composition as claimed in claim 3, the surface treated magnesium hydroxide contains magnesium hydroxide
With the silane coupler for being incorporated in its surface, the quality of the silane coupler is 0.1 matter of the quality of the magnesium hydroxide
Measure more than % and below 1.0 mass %.
6. a kind of insulated electric conductor, it has conductor and covers at least one of insulating barrier on the surface of the conductor, described exhausted
Edge layer contains the fire retardant resin composition any one of claim 1 to 5.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016154787 | 2016-08-05 | ||
| JP2016-154787 | 2016-08-05 | ||
| JP2016-215984 | 2016-11-04 | ||
| JP2016215984A JP2018024813A (en) | 2016-08-05 | 2016-11-04 | Flame-retardant resin composition and insulated wire |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107686592A true CN107686592A (en) | 2018-02-13 |
Family
ID=61152930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710597255.4A Pending CN107686592A (en) | 2016-08-05 | 2017-07-20 | Fire retardant resin composition and insulated electric conductor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107686592A (en) |
-
2017
- 2017-07-20 CN CN201710597255.4A patent/CN107686592A/en active Pending
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| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180213 |