CN101186728A - Arc extinguishing resin molding articles and breaker using the same - Google Patents
Arc extinguishing resin molding articles and breaker using the same Download PDFInfo
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- CN101186728A CN101186728A CNA2007101934348A CN200710193434A CN101186728A CN 101186728 A CN101186728 A CN 101186728A CN A2007101934348 A CNA2007101934348 A CN A2007101934348A CN 200710193434 A CN200710193434 A CN 200710193434A CN 101186728 A CN101186728 A CN 101186728A
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H9/00—Details of switching devices, not covered by groups H01H1/00 - H01H7/00
- H01H9/30—Means for extinguishing or preventing arc between current-carrying parts
- H01H9/302—Means for extinguishing or preventing arc between current-carrying parts wherein arc-extinguishing gas is evolved from stationary parts
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/06—Copolymers of allyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H9/00—Details of switching devices, not covered by groups H01H1/00 - H01H7/00
- H01H9/30—Means for extinguishing or preventing arc between current-carrying parts
- H01H9/34—Stationary parts for restricting or subdividing the arc, e.g. barrier plate
Abstract
The invention provides an arc extinguishing resin moulding product and a breaker using the resin moulding product. The thermal-decomposition gas generated by the resin moulding product has little contribution to raise the pressure of the arc extinguishing device and kills the electric arc generated during the current OFF process, with good thermal durability bearing the rising of the temperature, good pressure durability bearing the rising of pressure during the circuit OFF process, excellent flame-retardant property. The breaker comprises a fixed contact part having a fixed contact sheet, a movable contact part having a movable contact sheet so as to be contacted with the fixed contact part and to open or close the fixed contact part, and an arc extinguishing device for extinguishing the electric arc during the opening and closing operation between the fixed contact part and the movable contact part, wherein, the arc extinguishing device utilizes the arc extinguishing resin moulding product having the resin composition which includes POF resin. In the POF resin, one part of the hydrogen atom in a methylene chain is replaced by hydroxyl, and the content of the hydroxyl is controlled with 0.2 to 0.7mol relative to 1mol of methylene. The resin composition also includes a reactive organic phosphor flame-retardant agent including unsaturated terminal linkage. The resin moulding product is irradiated after being molded for cross-linking.
Description
Technical field
The present invention relates to a kind of arc extinguishing resin molding goods with flame-retardant nature, these goods are used for eliminating the electric arc that produces from contactor segment when device current interruptions such as isolating switch, also relate to the isolating switch that uses this arc extinguishing resin molding goods.
Background of invention
When contactor segment because of overcurrent or rated current therefrom when opening, between the contactor segment of the removable contact part of isolating switch and contactor segment that fixed contact divides, produce electric arc.In order to eliminate electric arc, generally there are arc extinguishing device, this device to have on the isolating switch and producing the spark chamber that arc position is made of the arc extinguishing parts on every side.The arc extinguishing parts can decompose by arc heat, eliminate electric arc by the pyrolysated gas that this arc extinguishing parts produce.
The matrix resin of the initial arc extinguishing parts that use comprises thermosetting resin, as unsaturated polyester resin (patent documentation 1) and melamine resin (patent documentation 2), thermoplastic resin is as polyolefin resin, polyamide resin and polyacetal resin (patent documentation 3).
Yet there is following problem in thermosetting resin, and thermosetting resin is because mold flashing takes place in moulding process easily, and its molding character specific heat plastic resin is poor.In the arc extinguishing process, the thermolysis gas that is produced by the arc extinguishing parts raises the pressure in the arc extinguishing device.The compressive strength of thermosetting resin is poor, breaks easily, and has high relatively hardness, is difficult to make the arc extinguishing device to reach miniaturization.
On the other hand, though mold flashing takes place thermoplastic resin hardly, its intensity, resistance to pressure and thermotolerance are all relatively poor, therefore, and the easily deformable over time or downgrade of this arc extinguishing parts.The thermoplastic resin that contains a large amount of aromatic rings as aromatic polyamide resin, has good intensity, resistance to pressure and thermotolerance, and still, this resinoid easily discharges uncombined carbon in burning.As a result, the arc extinguishing device may be polluted by these uncombined carbons, and its electric insulating quality descends.
For intensity, resistance to pressure and the thermotolerance of improving thermoplastic resin and thermosetting resin, once attempted in resin, to comprise mineral filler, as fortifying fibre (patent documentation 1 to 4).But the content that increases mineral filler can reduce the growing amount of thermolysis gas, causes the problem of arc extinction performance variation.
Patent documentation 5 discloses a kind of isolating switch, and this isolating switch uses thermoplastic resin such as polyester and polymeric amide are carried out the molded resin that electron irradiation obtains.
Recently, more and more higher to the requirement of the flame retardant level of the resin material that uses in the isolating switch.For meeting this requirement, can contemplate, flame retardant resin is used for the matrix resin of arc quenching material.Known halogen-containing compound as bromine can reach effective flame retardant properties in resin, and the resin that contains the additive of halogen compounds has been used for the flame-retarded resin of conventional purpose.Yet the flame retardant resin that contains a large amount of halogen compounds may produce dioxin under some combustion conditions.From the viewpoint of environment protection, require to use the not flame-retarded resin of the non-halogen of halogen contained compound in recent years.
[patent documentation 1]
Japanese Patent No.3098042 and at the patent families of foreign country: United States Patent (USP) 6,046,258, German patent DE 69717433 and European patent EP 089 7955
[patent documentation 2]
Japanese unexamined patent communique No.H02-256110
[patent documentation 3]
Japanese unexamined patent communique No.H07-302535 and at the patent families of foreign country: United States Patent (USP) 5,841,088, european patent application communique No.0 694 940 and Chinese patent application communique No.CN 1,124 402
[patent documentation 4]
Japanese unexamined patent communique No.H08-171847, and at the patent families of foreign country: U.S. Patent No. 6,361,848, German patent DE 69532063, European patent EP 071 8356 and Chinese patent CN 1 169 866
[patent documentation 5]
International patent application communique WO 2003-044818, and at the patent families of foreign country: european patent application communique EP 1 475 817 and Chinese patent CN 1 255 839
Summary of the invention
The problem that the present invention solves
By thermoplastic resin is carried out crosslinking Treatment, though can observe some improvement aspect intensity, thermotolerance and resistance to pressure, arc extinction performance does not improve.In addition, be difficult to suppress raise, and the arc extinguishing device because of raising, pressure in the arc extinguishing process is easy to break because of the thermolysis gas that produces in the arc extinguishing process makes the pressure in the arc extinguishing device.In addition, flame retardant resistance also is an open question always.
Therefore, the purpose of this invention is to provide a kind of arc extinguishing resin molding goods, these goods produce the thermolysis gas that pressure slightly raises, and can eliminate the electric arc that produces when opening circuit efficiently, these goods have the resistance to pressure of tolerance thermotolerance that temperature raises in the process that opens circuit and pressure rising, and excellent flame-retardant performance.Another object of the present invention provides the isolating switch that uses this arc extinguishing resin molding goods.
The mode of dealing with problems
For achieving the above object, arc extinguishing resin molding goods of the present invention comprise a kind of resin combination, said composition contains polyolefin resin (A), in this resin, the part of the hydrogen atom in the methene chain is replaced by hydroxyl, and the content of hydroxyl is in the 0.2-0.7mol scope with respect to the 1mol methylene radical, this resin combination also comprises reactive organophosphorous fire retardant (B), this fire retardant has unsaturated end key, and this molded resin carries out irradiation after moulding, and is crosslinked to carry out.
In the above-mentioned arc extinguishing molded resin of the present invention, by following assisting of irradiation, the chemical reaction that carries out between the unsaturated end key of reactive organophosphorous fire retardant (B) and the polyolefin resin (A) forms the crosslinked of tridimensional network.As a result, flame retardant compositions stably is combined in the resin.Therefore, bleed (breed out) can take place in fire retardant hardly, and can keep flame-retardant nature for a long time.Owing in polyolefin resin (A), form the crosslinked of tridimensional network, therefore, also improved intensity, thermotolerance and resistance to pressure.
Polyolefin resin (A) has the OH group at its side chain, and it dissociates by pyrolysis easily, produces to contain high concentration hydrogen, H
2O, O
2With the thermolysis gas of O, therefore electric arc can be eliminated at once.Polyolefin resin (A) contains a kind of component of lower concentration, and as tar, this component is very little to the effect of arc extinguishing sexual function, but the pressure in the control arc extinguishing device raises.In addition, carbon can adhere on the parts of arc extinguishing device in the arc extinguishing process hardly.Therefore, guaranteed electrical insulating property in the arc extinguishing device.
The resin combination of arc extinguishing resin molding goods of the present invention preferably contains polyacetal resin (C), and with respect to 100 weight part polyolefin resines (A), its content is in 5-90 weight part scope.Described polyacetal resin (C) contains the repeating unit that is derived from formaldehyde of 75-100mol%.Though polyacetal resin can produce the thermolysis gas of efficient arc extinguishing usually, find to adopt melt-kneaded to be difficult to it is carried out mould molding, that is, molding capability is poor.Because polyacetal resin produces a large amount of thermolysis gases, can cause pressure that relatively large rising is arranged, and the pressure in the arc extinguishing device is risen.Yet the present invention uses polyolefin resin (A) and polyacetal resin (C) combination at this on the one hand, has therefore improved arc extinction performance, does not damage the molded performance of resin combination again.
The resin combination of arc extinguishing resin molding goods of the present invention preferably contains the mineral filler that is selected from one or more following types (D) of 1-70 weight %: glass fibre, barium titanate must be brilliant, aerosil particles, boehmite, talcum, magnesiumcarbonate and metal hydroxides.By this one side of the present invention, improved the intensity and the resistance to pressure of molded resin.
Polyolefin resin (A) better has the decomposition latent heat of 30cal/g at least in the arc extinguishing resin molding goods of the present invention.
Polyolefin resin (A) ethylene-vinyl alcohol copolymer preferably in the arc extinguishing resin molding goods of the present invention.
By these aspects of the present invention, produce the good thermolysis gas of arc extinguishing, make and can eliminate electric arc at once.Therefore, arc voltage is kept.
In arc extinguishing molded resin of the present invention, reactive organophosphorous fire retardant (B) is that the content of this fire retardant is in 0.5-20 weight % scope in the resin combination by the organo phosphorous compounds of following chemical formula (I) and/or chemical formula (II) expression preferably.
In the formula, R
1To R
4Represent CH separately
2=CY
1-Y
2-, or contain heteroatomic simple function aromatic hydrocarbon group, R
5Expression contains heteroatomic difunctionality aromatic hydrocarbon group;
X
1To X
4Separately the expression be selected from following group :-O-,-NH-,-(CH
2=CY
1-Y
2) N-, and X
1To X
4In at least one group contain-NH-or-(CH
2=CY
1-Y
2) N-;
R
1To R
4And X
1To X
4In at least one group contain CH
2=CY
1-Y
2-;
Y
1Expression hydrogen atom or methyl; With
Y
2The expression carbon number be 1-5 alkylidene group or-COO-Y
3-, Y wherein
3The expression carbon number is the alkylidene group of 1-5.
In the formula, in a molecule, comprise at least one P-C key;
Ar
1And Ar
2Represent that separately carbon number mostly is 20 and do not contain the difunctionality aromatic hydrocarbon group of the hydrogen that flows most, n is 0,1 or 2 integer; R
6To R
10Expression is selected from following group :-NHCH separately
2CH=CH
2,-N (CH
2CH=CH
2)
2,-OCH
2CH=CH
2,-CH
2CH=CH
2,-CH
2CH
2OCH=CH
2,-(C
6H
4)-CH=CH
2,-O (C
6H
4)-CH=CH
2,-CH
2(C
6H
4)-CH=CH
2,-NH (C
6H
4)-CH=CH
2,-N (CH
2CH=CH
2)-(C
6H
4)-CH=CH
2,-O-R-OOC-C (R ')=CH
2,-NH-R-NHCO-C (R ')=CH
2Mostly be most 12 aryl with carbon number, wherein R represents that carbon number is the alkylidene group of 2-5, R ' expression hydrogen atom or methyl;
R
6To R
10In at least one group contain-CH=CH
2Group or-C (CH
3)=CH
2Group.
Reactive organophosphorous fire retardant (B) is stable in its energy state, resin is mediated with molded process in evaporation hardly, in addition, hardly can be because of being heated and shearing and decompose.Therefore, molded character is not produced detrimentally affect.
Preferably formaldehyde-acetaldehyde (oxyethylene) multipolymer or yuban of polyacetal resin (C) in the arc extinguishing resin molding goods of the present invention.By this one side of the present invention, produce the good thermolysis gas of arc extinguishing, make and can eliminate electric arc at once.Therefore, arc voltage is kept.
In arc extinguishing resin molding goods of the present invention, polyacetal resin (C) better is dispersed in the polyolefin resin (A), forms micro phase separation structure.By this one side of the present invention, pyrolysis takes place in polyacetal resin in the thermal decomposition process of arc extinguishing resin molding goods (C) easily, and disperses the thermolysis gas with high arc extinction performance.Therefore, arc energy is eliminated at once.
Isolating switch of the present invention comprises the fixed contact part with fixed contact piece; Removable contact part has removable contactor segment and contacts to reach with the fixed contact part, and the closure and the opening action of guiding and fixed contact part; And the arc extinguishing device, it is used for eliminating the electric arc that open and close when action between fixed contact part and removable contact part produces; Wherein, the arc extinguishing device do not include not in before the arc extinguishing resin molding goods of uniqueness.Can reach electric arc that effective elimination produces between contactor segment in the current interruptions process and the pressure in the control arc extinguishing device in isolating switch of the present invention raises.Therefore, this isolating switch is small-sized, has at circuit to disconnect process, comprises the premium properties when overload disconnection and short circuit disconnect.
The invention effect
Arc extinguishing resin molding goods of the present invention have satisfied intensity, resistance to pressure, thermotolerance, flame retardant resistance and mould-forming character.In addition, molded resin can discharge the thermolysis gas with high arc extinction performance.As a result, can effectively eliminate the electric arc that when current interruptions, forms between the contactor segment, and can be with the pressure-controlling in the arc extinguishing device low-level.The present invention uses the isolating switch of arc extinguishing resin molding goods can miniaturization, and has good circuit and disconnect, and comprises that overload disconnects and short circuit disconnection performance.
The accompanying drawing summary
Fig. 1 is the skeleton view of the embodiment of isolating switch of the present invention, and partial cross section is shown;
Fig. 2 is the skeleton view of the spark chamber that uses in the isolating switch of the present invention;
Fig. 3 is the sectional view of the arc extinguishing device that uses in the isolating switch of the present invention.
The explanation of Reference numeral
1: removable contact part
2: grid
4: the power supply side
5: the fixed contact part
Embodiment
Arc extinguishing resin molding goods of the present invention comprise a kind of resin combination, and said composition comprises polyolefin resin (A), and in this resin, (OH) replace, the content of hydroxyl is with respect to 1mol methylene radical (CH to the part of the hydrogen atom in methene chain by hydroxyl
2-) in the 0.2-0.7mol scope, this resin combination also comprises the reactive organophosphorous fire retardant (B) with unsaturated end key.This molded resin carries out cross-linking radiation after moulding handles.
The hydroxy radical content of polyolefin resin (A) is with respect to the 1mol methylene radical, at 0.2-0.7mol scope, more preferably 0.2-0.65mol.If hydroxy radical content then is difficult to produce the thermolysis gas with good arc extinction performance in thermal decomposition process less than 0.2 in Ding Yi the part in the above, the result can not eliminate electric arc at once.In addition, the pressure of arc extinguishing device in the arc extinguishing process can become higher.Simultaneously, the uncombined carbon that is increased of arc extinguishing device pollutes.Then the electrical insulating property of arc extinguishing device descends.If the hydroxy radical content of polyolefin resin (A) surpasses 0.7mol, intermolecular HYDROGEN BOND INTENSITY is less than or equal to the situation of 0.7mol greater than hydroxy radical content.Hydrogen bond is strong more, and the fusing point of polyolefin resin (A) is more near degradation temperature.Then, moulding process becomes difficult because of the thermolysis in the melt kneading process.
The decomposition latent heat that polyolefin resin (A) has is preferably 30cal/g at least, more preferably 40cal/g at least.The decomposition latent heat of polyolefin resin (A) can improve by the hydroxy radical content that increases in the resin.Wherein a part of hydrogen atom in the methene chain replaced by hydroxyl and hydroxy radical content with respect to the 1mol methylene radical at the decomposition latent heat of the polyolefin resin of 0.2-0.7mol scope in the 30-50cal/g scope.The decomposition latent heat of resin can be measured by thermal degradation sample resins in inert atmosphere.
Preferred polyolefin resin is an ethylene-vinyl alcohol copolymer, and this multipolymer is because its good arc extinguishing character and particularly advantageous.And polyethylene shows the arc extinction performance of difference, and poly-(vinyl alcohol) can use mould-forming method with good conditionsi.
Reactive organophosphorous fire retardant (B) is the organo phosphorous compounds with unsaturated end key, preferably the compound of being represented by following chemical formula (I) or chemical formula (II).
In the formula, R
1To R
4Represent CH separately
2=CY
1-Y
2-, or contain heteroatomic simple function aromatic hydrocarbon group, R
5Expression contains heteroatomic difunctionality aromatic hydrocarbon group;
X
1To X
4Separately the expression be selected from following group :-O-,-NH-,-(CH
2=CY
1-Y
2) N-, and X
1To X
4In at least one group contain-NH-or-(CH
2=CY
1-Y
2) N-;
R
1To R
4And X
1To X
4In at least one group contain CH
2=CY
1-Y
2-;
Y
1Expression hydrogen atom or methyl; With
Y
2The expression carbon number be 1-5 alkylidene group or-COO-Y
3-, Y wherein
3The expression carbon number is the alkylidene group of 1-5.
In the formula, in a molecule, comprise at least one P-C key;
Ar
1And Ar
2Represent that separately carbon number mostly is 20 and do not contain the difunctionality aromatic hydrocarbon group of the hydrogen that flows most, n is 0,1 or 2 integer;
R
6To R
10Expression is selected from following group :-NHCH separately
2CH=CH
2,-N (CH
2CH=CH
2)
2,-OCH
2CH=CH
2,-CH
2CH=CH
2,-CH
2CH
2OCH=CH
2,-(C
6H
4)-CH=CH
2,-O (C
6H
4)-CH=CH
2,-CH
2(C
6H
4)-CH=CH
2,-NH (C
6H
4)-CH=CH
2,-N (CH
2CH=CH
2)-(C
6H
4)-CH=CH
2,-O-R-OOC-C (R ')=CH
2,-NH-R-NHCO-C (R ')=CH
2Mostly be most 12 aryl with carbon number, wherein R represents that carbon number is the alkylidene group of 2-5, R ' expression hydrogen atom or methyl;
R
6To R
10In at least one group contain-CH=CH
2Group or-C (CH
3)=CH
2Group.
Organo phosphorous compounds contains-CH=CH
2Or-C (CH
3)=CH
2In at least one group, be unsaturated end key.This functional group combines with polyolefin resin (A) by the irradiation radioactive ray.Preferably in a molecule, contain two or more unsaturated end keys.
CH in chemical formula (I) compound
2=CY
1-Y
2-concrete example is as can be CH
2=CH-CH
2-, CH
2=CH-CH
2CH
2CH
2-, CH
2=C (CH
3)-CH
2-, CH
2=CHCOO-CH
2CH
2-and CH
2=C (CH
3) COO-CH
2CH
2-.
At R
1To R
4In contain heteroatomic simple function aromatic hydrocarbon group preferably carbon number be the aromatic hydrocarbon group of 6-14.Particularly, this class group comprises-C
6H
5(phenyl) ,-C
6H
5OH (hydroxy phenyl), C
6H
5-C
6H
5OH (Hydroxybiphenyl) ,-CH
2C
6H
5(benzyl) ,-α-C
10H
7(Alpha-Naphthyl) and-β-C
10-H
7(betanaphthyl).
Contain R
5Heteroatomic difunctionality aromatic hydrocarbon group preferably carbon number is the aromatic hydrocarbon group of 10-14.Particularly, this group comprises :-p-C
6H
4-p-C
6H
4-,-p-C
6H
4-CH
2-p-C
6H
4-,-p-C
6H
4-C (CH
3)
3-p-C
6H
4,-p-C
6H
4-C (=O)-p-C
6H
4-,-p-C
6H
4-SO
2-p-C
6H
4-and 2,6-C
10H
6＜(2, the 6-naphthylidene).
The aromatic hydrocarbon group of in specification sheets of the present invention and claims, quoting not only comprise aromatic hydrocarbon group such as phenyl and-p-C
6H
4-p-C
6H
4-, also comprise the heteroatomic aromatic hydrocarbon group that contains oxygen or sulphur, as hydroxy phenyl and-p-C
6H
4-SO
2-p-C
6H
4-.
By the object lesson of the organo phosphorous compounds of chemical formula (I) expression can be compound by following structural formula (I-1) to (I-18) expression.
The compound that illustrates above can adopt the method described in the WO 2005/012415 synthetic.For example, the compound of formula (I-1) can obtain in the following manner, adds phosphorus oxychloride in N,N-DIMETHYLACETAMIDE (DMAc), in this solution, drip and contain dissolved 4, the pure and mild triethylamine of 4 '-xenyl reacts to each other them, and the mixing solutions with allyl amine and triethylamine reacts then.
In the compound by chemical formula (II) expression, the object lesson that carbon number mostly is 12 aryl most can be-C
6H
5(phenyl) ,-C
6H
5OH (hydroxy phenyl) ,-C
6H
5-C
6H
5OH (Hydroxybiphenyl) ,-α-C
10H
7(Alpha-Naphthyl) and-β-C
10H
7(betanaphthyl).
Do not contain Ar
1And Ar
2In the object lesson that the carbon number of hydrogen mostly is 20 difunctionality aromatic hydrocarbon group most that flows can be-p-C
6H
4-,-p-C
6H
4-O-,-O-p-C
6H
4-O-,-p-C
6H
4-p-C
6H
4-,-p-C
6H
4-CH
2-p-C
6H
4-,-p-C
6H
4-C (CH
3)
2-p-C
6H
4-,-p-C
6H
4-C (=O)-p-C
6H
4-,-p-C
6H
4-SO
2-p-C
6H
4-and 2,6-C
10H
6＜(2, the 6-naphthylidene).Mobile hydrogen refer to as OH (hydroxyl) ,-NHCO-(amido linkage) or-functional group of NHCOO-(amino-formate bond) in contained hyperergy hydrogen, this hydrogen forms hydrogen bond easily, at room temperature reacts generation hydrogen easily with sodium Metal 99.5 and sodium hydride.
The object lesson of the organo phosphorous compounds of formula (II) expression comprises by the compound of structural formula (II-1) to structural formula (II-23) expression.In these compounds, the compound of formula (II-1) to (II-12) is the example of n=0,, contains the example of two phosphorus atom in a molecule that is.The compound of formula (II-13) to (II-20) is the example of n=1,, contains the example of three phosphorus atom in molecule that is.The compound of formula (II-21) to (II-23) is n=2, contains the example of four phosphorus atom in molecule.
The compound that illustrates above can adopt among the WO 2005-087852 disclosed method synthetic.Formula (II-1) compound for example can obtain in the following manner, and 4,4 '-DCBP raw material and phosphorus oxychloride reaction with the allyl bromide 98 reaction, are introduced unsaturated group then endways.
The content of reactive organophosphorous fire retardant (B) is preferably in 0.5-20 weight % scope, more preferably in 4-12 weight % scope in the resin combination.If the content of reactive organophosphorous fire retardant (B) is less than 0.5 weight %, flame-retardant nature is difficult to be improved, and in addition, because the lower crosslink density of resin combination, intensity, resistance to pressure and stable on heating physical properties almost are not improved.If this content surpasses 20 weight %, reactive organophosphorous fire retardant is excessive, therefore have the decomposition gas of unreacted monomer and reactive organophosphorous fire retardant, and oligomeric material may ooze out (breed out).
Be used for arc extinguishing resin molding goods resin combination of the present invention and better also contain polyacetal resin (C).
Though polyacetal resin generally can produce the thermolysis gas of efficient arc extinguishing, find that it is difficult to adopt the method for melt-kneaded to be shaped, and promptly shows the molding capability of difference in mould.Because polyacetal resin produces a large amount of thermolysis gases, can cause pressure that relatively large rising is arranged, and the pressure in the arc extinguishing device is risen.By being used in combination polyacetal resin and polyolefin resin (A), can improve arc extinction performance, do not damage the mould-forming ability of resin combination again.In addition, can also suppress the pressure of arc extinguishing device in the arc extinguishing process raises.
Polyacetal resin (C) contains the repeating unit that is derived from formaldehyde, and its ratio is preferably in the 75-100mol% scope, more preferably in the 80-100mol% scope.If the content of described repeating unit is less than 75mol%, then arc extinction performance is poor, and can not carry out quick arc extinguishing.
A kind of preferred polyacetal resin is formaldehyde-acetaldehyde (oxyethylene) multipolymer or yuban, and preferably these multipolymers or polymkeric substance are because their good arc extinguishing character.And the arc extinction performance of metaldehyde is poor.
The content of polyacetal resin (C) is preferably the 5-90 weight part, more preferably the 7-88 weight part with respect to 100 weight part polyolefin resines (A).If less than 5 weight parts, expection is very little by the effect that polyacetal resin (C) produces according to ratio defined above for the content of polyacetal resin (C), arc extinction performance does not almost improve.If this content surpasses 90 weight parts, the thermolysis gas volume increases, and the pressure in the arc extinguishing device raises.
The resin combination that is used for arc extinguishing resin molding goods of the present invention comprises the resin except that above-mentioned resin; The thermoplastic resin that for example, can contain conventional purpose.The content of this resin is preferably the 0-15 weight part with respect to the polyolefin resin (A) of 100 weight parts, more preferably in 0-12 weight part scope.
The resin combination that is used for arc extinguishing resin molding goods of the present invention also comprises radiation crosslinker (D).The radiation crosslinker that comprises is by irradiation radioactive ray and resin Chemical bond, thereby cross-linked resin is tridimensional network and improves cross-linking density.Therefore, improved the physical properties that comprises intensity, thermotolerance, resistance to pressure.
Spendable radiation crosslinker comprises the compound that does not contain aromatic ring and be easy to generate hydrogen, this compounds be two official's degree can or the melamine compound with reactive functional groups of high functionality more, comprising: the vinylformic acid front three is for allyl ester, vinylformic acid triallyl and isocyano-three (methyl) acrylate.More specifically, radiation crosslinker can be selected from following material: triallyl isocyanurate, isocyanuric acid front three for allyl ester, the oligomeric acquisition oligopolymer of free radical, trimellitic acid triallyl, trimellitic acid front three by these isocyanuric acid esters for allyl ester, pyromellitic acid tetraene propyl ester, pyromellitic acid tetramethyl for allyl ester, N, N, N ', N '; N ", N " and-six allyl group trimeric cyanamides, N, N; N '; N ', N ", N "-pregnancy is for allyl group trimeric cyanamide etc.
The content of radiation crosslinker is preferably in 0.5-20 weight % scope, more preferably in 1-12 weight % scope in the resin combination.If the content of radiation crosslinker is less than 0.5 weight %, then the crosslinked of resin combination almost do not improve; If this content surpasses 20 weight %, the bleed that radiation crosslinker causes may take place.
The resin combination that is used for arc extinguishing resin molding goods of the present invention preferably contains the mineral filler (D) that is selected from one or more following types: fortifying fibre, barium titanate palpus crystalline substance, aerosil particles, boehmite, talcum, magnesiumcarbonate and metal hydroxides.Contain dimensional stability and density, resistance to pressure and thermotolerance that mineral filler can improve the arc extinguishing resin molding goods.
Fortifying fibre can be selected from for example glass fibre, carbon fiber and steel fiber, wherein, preferred glass fibers, reason be glass fibre intensity and with the binding property of resin and inorganic filling material.Can use independent a kind of fortifying fibre, perhaps two or more type combination are used.In addition, fiber can be handled with known surface treatment agent such as silane coupling agent.Glass fibre preferably carries out surface treatment, and further covering resin.This measure also further improved with resin combination in the binding property of resin.
Metal hydroxides preferably is dispersed in the polyolefin resin (A), because this resin has the ability that pressure raises that suppresses.Preferred metal hydroxides comprises aluminium hydroxide, boehmite and magnesium hydroxide, and its particle diameter is at the 1-10 mu m range.
The content of mineral filler in the resin combination (D) is preferably in 1-70 weight % scope, more preferably in 20-70 weight % scope.If the content of mineral filler (D) less than 1 weight %, then almost can not reach the effect of mineral filler, if this content surpasses 70 weight %, then the thermolysis gas volume reduces, and has reduced the arc extinguishing ability.
The resin combination of arc extinguishing resin molding goods of the present invention can also comprise the typical additives except top described material, as long as these additives can obviously not impair the character of purpose of the present invention, promptly impair thermotolerance, resistance to pressure, arc extinguishing ability, intensity and flame-retardant nature.Additive for example comprises, nucleus agent (crystallizing nucleus agent), tinting material, antioxidant, releasing agent, softening agent, thermo-stabilizer, slip(ping)agent, uv-absorbing agent etc.
Arc extinguishing resin molding goods of the present invention are made by the resin combination irradiation radioactive ray to mould-forming.
The mould-forming of resin combination can adopt known method to carry out.For example, behind resin combination melt kneading formation pellet, adopt currently known methodss such as injection moulding, extrusion moulding, vacuum forming, blowing to carry out molded.Melt kneading can be used kneader device commonly used, carries out as single screw rod or twin screw extruder, banbury mixers, kneader, mixing roll etc.Kneading operation preferably carries out 170-230 ℃ of temperature range.If temperature is lower than 170 ℃, melt kneading almost can not be carried out; If temperature surpasses 230 ℃, the hydroxyl in the resin combination dissociates, and reduces the arc extinguishing ability.Particularly, following process is favourable in the present invention.The resin combination of polyolefin-containing resin (A) and polyacetal resin (C) carries out melt kneading and moulding under 180-220 ℃ of temperature in inert atmosphere, be cooled to 40-60 ℃ then.By this moulding process, can obtain to have the molded resin of micro phase separation structure, wherein, for the polyacetal resin (C) of the submicron-scale of the 0.1-0.9 μ m configuration with island, hexagon cylinder or thin slice is dispersed in the polyolefin resin (A).By forming micro phase separation structure, polyacetal resin (C) is decomposed easily, send thermolysis gas with high arc extinction performance, eliminate electric arc fast.Also do not begin in this stage owing to crosslinked, remaining spool part (spool portion) can circulate in the molded process.
On thus obtained molded resin, the irradiation radioactive ray obtains arc extinguishing resin molding goods of the present invention.Crosslinked fix of micro phase separation structure by implementing by this irradiation.
The radiation of irradiation molded resin can be α-ray, gamma-radiation, X-ray or uv-radiation, wherein preferred gamma-radiation, and reason is that gamma-radiation has strong penetrance, and can carry out even irradiation.
Irradiation dose preferably is at least 10kGy, more preferably in the 10-45kGy scope.By the irradiation of this scope dosage, can by described irradiation reach crosslinked, obtain to have the arc extinguishing resin molding goods of above-mentioned advantageous property.If irradiation dose is inhomogeneous by the tridimensional network that is cross-linked to form less than 10kGy, unreacted linking agent may bleed.If this dosage surpasses 45kGy, irradiation stays internal strain because of the oxygenolysis product in molded resin, and these strain meetings cause distortion and shrink
The arc extinguishing resin molding goods that obtain according to the present invention have good intensity, resistance to pressure, thermotolerance, arc extinction performance and flame-retardant nature, therefore, can be advantageously used in the arc extinguishing device in the isolating switch.
Below, isolating switch of the present invention is described.
Isolating switch of the present invention comprises: the fixed contact part with fixed contact piece; Removable contact part has removable contactor segment and contacts to reach with the fixed contact part, and carries out closure and opening action with the fixed contact part; And the arc extinguishing device, the electric arc that produces when being used for eliminating the open and close action between fixed contact part and removable contact part; Wherein, the arc extinguishing device is included in foregoing arc extinguishing resin molding goods.
An object lesson of this isolating switch is shown among Fig. 1 to Fig. 3, and Fig. 1 is the skeleton view that partial cross section is shown, and Fig. 2 is the skeleton view of arc extinguishing device, and Fig. 3 is the sectional view of isolating switch.
Referring to Fig. 1, shown in isolating switch comprise fixed contact part 5 with en-block construction, at the one end power source side terminal 4 is arranged, have U-shape bool at the other end along removable contact part 1; And removable contact part 1, this part has removable contactor segment 6, contacts with the fixed contact piece 7 that reaches on the U-bool 5a top with the fixed contact part.Arcuate angle 9 links to each other with fixed contact part 5, and the electric arc that guiding produces between removable contactor segment 6 and fixed contact piece 7 extends towards the arc extinguishing device.
The arc extinguishing device is made up of grid 2 and spark chamber 13.Grid 2 comprises and a plurality ofly is stacked on plate (being five plates in the accompanying drawing) on the isolator 12 with predetermined space.Removable contact part 1 disconnects and closing motion between the open position that the make-position that is marked by thick line and dotted line mark, by the V-shape recess 2a that forms in grid 2.Spark chamber 13 is formed by arc extinguishing resin molding goods of the present invention, and between removable contact part 1 and grid 2.
Isolator 12 shown in Fig. 1 and Fig. 3 is included in the pair of sidewalls 12a on the left side and the right side, and the interconnecting piece 12b and the 12c of the sidewall of the top of connecting wall and bottom.Isolator is formed by monoblock trimeric cyanamide moulding resin, and this resin can anti-electric-arc.Form the groove 14 of many square-sections on the opposite face of pair of sidewalls 12a, these grooves tilt to rise from loading side (right-hand end of Fig. 3).Each grid sheet 2 pressurization is assembled to groove 14, and forms bridge joint between left side wall and right side wall 12a.
Spark chamber 13 comprises that a pair of left side wall is connected the arcuate front 13b at the top of left side wall and right side wall 13a with right side wall 13a, along the V-shape recess 2a in the grid 2.Spark chamber 13 also comprises partition wall 15, with the arc extinguishing device with open-closing device separates, and also comprises insulating cover 16, it covers above the fixed contact part 5, partition wall and insulating cover form monoblock in spark chamber.The slit 15a that forms along the opening of removable contact part-closing motion path is arranged on the partition wall 15.One window 16a is arranged, to expose fixed contact piece 7 on the insulating cover 16.Spark chamber 13 is in isolator 12, and from right side and partition wall 15 assemblings of Fig. 3, this partition wall 15 contacts with the right side of the sidewall 12a of isolator 12.Spark chamber 13 is bearing on the fixed contact part 5 by insulating cover 16, and the compacting of the body cover (not shown) by this isolating switch and fixing.At this assembled state, the sidewall 13a of spark chamber 13 covers the shank (parts in the both sides of V-shape recess) of grid 2, and grid 2 is positioned at the both sides of removable contact part, and antetheca 13b is positioned at the back of V-shape recess 2a of the top board of grid 2, as shown in Figure 3.
In said structure, in the current interruptions process, electric arc is formed between removable contactor segment 6 and the fixed contact piece 7, and electric arc moves in the grid 2, is eliminated in grid.Because dividing, two shanks of grid 2 all covered internally by two sidewall 13a of spark chamber 13, and with the current interruptions process in arc shield, fusion and scattering take place in these parts that prevent grid because of electric arc, in addition, thermolysis gas produces and sends from sidewall 13a near electric arc, promote the electric arc cooling, with quick elimination electric arc.
Embodiment
Referring to some preferred implementations, describe the present invention in detail.But, the invention is not restricted to these embodiment.
Embodiment 1
At first, melting mixing 67 weight part polyolefin resines (" EVAL-L104B ", Kuraray Co., product) and 25 weight part polyoxymethylene-acetaldehyde copolymers (" Tenac-C 4520 " Ltd., Asahi Kasei Corporation product), described polyolefin resin contains the 0.58mol hydroxyl with respect to the 1mol methylene radical, and described polyoxymethylene-acetaldehyde copolymer contains the repeating unit that is derived from formaldehyde of 90mol%.Then, add 8 weight part formula (I-14) compounds as reactive organophosphorous fire retardant.The mixture that produces uses side-flow type twin screw extruder (by Japan Steel Works, Ltd. makes) to mediate the acquisition resin granular material in 220 ℃.Resin granular material in 80 ℃ of dryings 7 hours, is used injection moulding machine (α 50C type is made by FANUC Ltd.) then, is 215 ℃ at resin temperature, and die head temperature is to carry out molding under 50 ℃ the condition.With the cross section of the goods after the SEM observation moulding, determine micro phase separation structure, show spherulitic texture with thin layer configuration and even island structure.
Then, the goods after the moulding are used from the gamma-radiation of cobalt 60 source and are carried out irradiation with the dosage of 25kGy.Obtain the arc extinguishing resin molding goods of embodiment 1 like this.Observe the cross section of these arc extinguishing resin molding goods with SEM, determine micro phase separation structure, show to have the thin layer configuration and the even spherulitic texture of island structure.
At first, melting mixing 50 weight part polyolefin resines (" EVAL-L104B ", Kuraray Co., product) and 20 weight part polyoxymethylene-acetaldehyde copolymers (" Tenac-C 4520 " Ltd., Asahi Kasei Corporation product), described polyolefin resin contains the 0.58mol hydroxyl with respect to the 1mol methylene radical, and described polyoxymethylene-acetaldehyde copolymer contains the repeating unit that is derived from formaldehyde of 90mol%.Then, add 10 weight part boehmites (" BMT-10 ", Kawai Lime Co., product) and the glass fibre (" 03.JAFT2Ak25 " of 15 weight part silane treatment Ltd., Asahi Fiber Glass Co., Ltd. product) as the compound of mineral filler and 5 weight part formulas (II-3) as reactive organophosphorous fire retardant.The mixture that produces uses side-flow type twin screw extruder (by Japan Steel Works, Ltd. makes) to mediate the acquisition resin granular material in 220 ℃.Resin granular material in 80 ℃ of dryings 7 hours, is used injection moulding machine (α 50C type is made by FANUC Ltd.) then, is 215 ℃ at resin temperature, and die head temperature is to carry out molding under 50 ℃ the condition.With the cross section of the goods after the SEM observation moulding, determine micro phase separation structure, show spherulitic texture with thin layer configuration and even island structure.
Then, goods are used from the gamma-radiation of cobalt 60 source and are carried out irradiation with the dosage of 25kGy after the moulding.Obtain the arc extinguishing resin molding goods of embodiment 2 like this.Observe the cross section of these arc extinguishing resin molding goods with SEM, determine micro phase separation structure, show to have the thin layer configuration and the even spherulitic texture of island structure.
Embodiment 3
At first, in nitrogen atmosphere, in 220 ℃ of melting mixing, 53 weight part polyolefin resines (" EVAL-L104B ", Kuraray Co., product) and 20 weight part polyoxymethylene-acetaldehyde copolymers (" Tenac-C 4520 " Ltd., Asahi Kasei Corporation product), described polyolefin resin contains the 0.58mol hydroxyl with respect to the 1mol methylene radical, and described polyoxymethylene-acetaldehyde copolymer contains the repeating unit that is derived from formaldehyde of 90mol%.Then, add 15 weight part boehmites (" BMT-10 ", Kawai Lime Co., Ltd. product) as the compound of mineral filler and 12 weight part formulas (I-18) as reactive organophosphorous fire retardant.The mixture that produces uses side-flow type twin screw extruder (by Japan Steel Works, Ltd. makes) to mediate the acquisition resin granular material in 220 ℃.Resin granular material in 80 ℃ of dryings 7 hours, is used injection moulding machine (α 50C type is made by FANUC Ltd.) then, is 215 ℃ at resin temperature, and die head temperature is to carry out molding under 50 ℃ the condition.With the cross section of the goods after the SEM observation moulding, determine micro phase separation structure, show spherulitic texture with thin layer configuration and even island structure.
Then, goods are used from the gamma-radiation of cobalt 60 source and are carried out irradiation with the dosage of 25kGy after the moulding.Obtain the arc extinguishing resin molding goods of embodiment 3 like this.Observe the cross section of these arc extinguishing resin molding goods with SEM, determine micro phase separation structure, show to have the thin layer configuration and the even spherulitic texture of island structure.
Comparative example 1
The resin granular material of comparative example 1 is to mediate to obtain under the condition identical with embodiment 1, and difference is responding property of not blending organophosphorous fire retardant.Institute's pellet that obtains uses injection moulding machine (α 50C type is made by FANUC Ltd.) then in 80 ℃ of dryings 7 hours, is 215 ℃ at resin temperature, and die head temperature is to carry out molding under 50 ℃ the condition.Obtain the arc extinguishing resin molding goods of comparative example 1 like this.
Comparative example 2
The resin granular material of comparative example 2 is to mediate to obtain under the condition identical with embodiment 2, and its difference is responding property of not blending organophosphorous fire retardant.Institute's pellet that obtains uses injection moulding machine (α 50C type is made by FANUC Ltd.) then in 80 ℃ of dryings 7 hours, is 215 ℃ at resin temperature, and die head temperature is to carry out molding under 50 ℃ the condition.Obtain the arc extinguishing resin molding goods of comparative example 2 like this.
Comparative example 3
The arc extinguishing resin molding goods of comparative example 3 obtain to mediate with embodiment 2 same way as, difference is that the reactive organophosphorous fire retardant that uses among the embodiment 2 is not shown the organophosphorous fire retardant (" HCA-HQ " of reactive additive types, Sanko Chemical Industry Co., the Ltd. product) substitute.
Comparative example 4
The arc extinguishing resin molding goods of comparative example 4 are to mediate acquisition in the mode identical with embodiment 2, difference is that the reactive organophosphorous fire retardant that uses among the embodiment 2 is substituted by brominated flame-retardant (" GreatLakes pdbs-80 ", Great Lakes Chemical Corporation product).
Comparative example 5
The arc extinguishing resin molding goods of comparative example 5 are to mediate acquisition in the mode identical with embodiment 2, what difference was that embodiment 2 uses contains the polyolefin resin (" EVAL-L104B " of 0.58mol hydroxyl with respect to the 1mol methylene radical, Kuraray Co., Ltd. product) substituted by polyvinyl resin (" HJ362 ", NipponPolyethylene Corporation product).
Comparative example 6
At first, use kneader, with 25 weight part unsaturated polyester resins (" 7525 ", Japan U-PiCACo., Ltd. product), 35 weight part Al (OH)
3, 5 parts by weight of styrene-vinyl acetate copolymer, 0.3 weight part t-butyl peroxy-Z initiators for polymerization and 4-7 weight part viscosity modifier kneaded together.In kneading process, add the mineral filler (" 03.JAFT2Ak25, Asahi Fiber Glass Co., Ltd. product) of the glass fibre of 35 weight part silane treatment and disperse, obtain the body molding compounds.This body molding compounds is carried out molding and polymerization 140-150 ℃ of temperature range.Like this, obtain the arc extinguishing resin molding goods of comparative example 6.
Comparative example 7
By mediating 99.8 weight part Nylon 6s (" UBE nylon 101 5B ", UBE Industries, Ltd. product) and 0.2 weight part antioxidant (" IRGANOX 1010 " are provided by Nihon Ciba-Geigie KK), obtain resin granular material.This resin granular material in 105 ℃ of dryings 4 hours, then, is used injection moulding machine (α 50C type is made by FANUC Ltd.), is 260 ℃ at resin temperature, and die head temperature is to carry out molding under 85 ℃ the condition.Obtain the arc extinguishing resin molding goods of comparative example 7 like this.
The molded character of the arc extinguishing resin molding goods that evaluation embodiment 1 to 3 and comparative example 1 to 7 make.Resin moulded product is used for the spark chamber 13 of isolating switch shown in Figure 1, the arc extinguishing resin molding goods are carried out short-circuit test, thermotolerance test and flame retardant resistance test.
In short-circuit test, the electric current of 3 phase 440V/50kA is by the contactor segment under the closure state, and then, removable contact part is opened, and produces flame current.To the interruption character (arc extinction performance) of this flame current, disconnect and the infringement (resistance to pressure) and the surface appearance (thermotolerance) of arc extinguishing device detected.
When short-circuit current was successfully interrupted, current interruptions character was appointed as " acceptable ".
When visual inspection can not detect in the moulding process when producing bubble or tear drop phenomenon, molded character is appointed as " acceptable ".
Flame-retardant nature is estimated according to following UL-94 test.Prepare testing plate (5 inches long, and 1/2 inch wide thick with 3.2mm) according to UL-94.Contact 10 seconds with this testing plate vertical fixing and with the Bunsen burner flame, write down combustion time.After extinguishing, this testing plate contacts 10 seconds once more with flame, writes down combustion time.According to burning total time, secondary extinguishes back red heat burning (the red heat combustion) time of (luminous) and the drop of existence is lighted cotton, distinguishes according to UL-94.
The metallic pollution situation is stayed in 120 ℃ of environment the contact resistance after 300 hours and is estimated by measuring sample.When contact resistance was not higher than 50m Ω, the metallic pollution situation was appointed as " acceptable ".
Above-mentioned test the results are shown in table 1.
Table 1
| Short circuit then tries | Molded character | Flame-retardant nature (UL-94) | Metallic pollution | |||
| Character (arc extinction performance) is interrupted in short circuit | Disconnect ﹠ infringement (resistance to pressure) | Surface appearance (thermotolerance) | ||||
| Embodiment 1 | Can accept (good current interruptions character) | Can accept (harmless) | Well | Well | V-0 | Can accept |
| |
Can accept (good current interruptions character) | Can accept (harmless) | Well | Well | V-0 | Can accept |
| Embodiment 3 | Can accept (good current interruptions character) | Can accept (harmless) | Well | Well | V-0 | Can accept |
| Comparative example 1 | Can accept (good current interruptions character) | Infringement | Well | Well | HB | Can accept |
| Comparative example 2 | Can accept (good current interruptions character) | Infringement | Well | Well | HB | Can accept |
| Comparative example 3 | Can accept (good current interruptions character) | Infringement | Well | Well | V-2 | Unacceptable |
| Comparative example 4 | Can accept (good current interruptions character) | Infringement | Well | Well | V-0 | Unacceptable |
| Comparative example 5 | Unacceptable | Infringement | Well | Well | HB | Can accept |
| Comparative example 6 | Can accept (good current interruptions character) | Infringement | Well | Difference (generation mold flashing) | V-1 | Can accept |
| Comparative example 7 | Can accept (good current interruptions character) | Infringement | Well | Difference (observing tear drop) | HB | Can accept |
Can know by the result of table 1 and to know that the arc extinguishing resin molding goods of embodiment 1 to 3 show excellent flame-retardant performance matter, thermotolerance and molded character.Use can effectively be eliminated the electric arc that produces by the isolating switch of the arc extinguishing device that these arc extinguishing resin molding goods are made between contactor segment in the current interruptions process, and because the infringement phenomenon is not observed in the arc extinguishing effect in spark chamber.
Claims (9)
1. arc extinguishing resin molding goods, these goods comprise resin combination, said composition contains polyolefin resin (A), also comprise reactive organophosphorous fire retardant (B) with unsaturated end key, in the described resin (A), the part of the hydrogen atom in methene chain is replaced by hydroxyl, and the content of hydroxyl is in the 0.2-0.7mol scope with respect to the 1mol methylene radical, this molded resin carries out irradiation after moulding, crosslinked to carry out.
2. arc extinguishing molded resin as claimed in claim 1, it is characterized in that, described resin combination also comprises polyacetal resin (C), its content is to be the 5-90 weight part with respect to 100 weight part polyolefin resines (A), polyacetal resin (C) contains the repeating unit that is derived from formaldehyde, and its ratio is in the 75-100mol% scope.
3. arc extinguishing molded resin as claimed in claim 1 or 2, it is characterized in that, described resin combination also contains the mineral filler (D) that is selected from one or more following types: glass fibre, barium titanate palpus crystalline substance, aerosil particles, boehmite, talcum, magnesiumcarbonate and metal hydroxides, the content of mineral filler is in the scope of 1-70 weight %.
4. as each described arc extinguishing molded resin among the claim 1-3, it is characterized in that the decomposition latent heat of described polyolefin resin (A) is at least 30cal/g.
5. as each described arc extinguishing molded resin among the claim 1-4, it is characterized in that described polyolefin resin (A) is an ethylene-vinyl alcohol copolymer.
6. as each described arc extinguishing molded resin among the claim 1-5, it is characterized in that, described reactive organophosphorous fire retardant (B) is that the content of reactive organophosphorous fire retardant (B) is 0.5-20 weight % in the resin combination by the organo phosphorous compounds of following chemical formula (I) and/or chemical formula (II) expression;
In the formula, R
1To R
4Represent CH separately
2=CY
1-Y
2-, or contain heteroatomic simple function aromatic hydrocarbon group, R
5Expression contains heteroatomic difunctionality aromatic hydrocarbon group;
X
1To X
4Separately the expression be selected from following group :-O-,-NH-,-(CH
2=CY
1-Y
2) N-, and X
1To X
4In at least one group contain-NH-or-(CH
2=CY
1-Y
2) N-;
R
1To R
4And X
1To X
4In at least one group contain CH
2=CY
1-Y
2-;
Y
1Expression hydrogen atom or methyl; With
Y
2The expression carbon number be 1-5 alkylidene group or-COO-Y
3-, Y wherein
3The expression carbon number is the alkylidene group of 1-5;
In the formula, in a molecule, comprise at least one P-C key;
Ar
1And Ar
2Represent that separately carbon number mostly is 20 and do not contain the difunctionality aromatic hydrocarbon group of the hydrogen that flows most, n is 0,1 or 2 integer; R
6To R
10Expression is selected from following group :-NHCH separately
2CH=CH
2,-N (CH
2CH=CH
2)
2,-OCH
2CH=CH
2,-CH
2CH=CH
2,-CH
2CH
2OCH=CH
2,-(C
6H
4)-CH=CH
2,-O (C
6H
4)-CH=CH
2,-CH
2(C
6H
4)-CH=CH
2,-NH (C
6H
4)-CH=CH
2,-N (CH
2CH=CH
2)-(C
6H
4)-CH=CH
2,-O-R-OOC-C (R ')=CH
2,-NH-R-NHCO-C (R ')=CH
2Mostly be most 12 aryl with carbon number, wherein R represents that carbon number is the alkylidene group of 2-5, R ' expression hydrogen atom or methyl;
R
6To R
10In at least one group contain-CH=CH
2Group or-C (CH
3)=CH
2Group.
7. as each described arc extinguishing molded resin among the claim 2-6, it is characterized in that described polyacetal resin (C) is formaldehyde-acetaldehyde copolymer or yuban.
8. as each described arc extinguishing molded resin among the claim 2-7, it is characterized in that described polyacetal resin (C) is dispersed in the polyolefin resin (A), form micro phase separation structure.
9. an isolating switch comprises the fixed contact part with fixed contact piece; Removable contact part, it has removable contactor segment and contacts to reach with the fixed contact part, and carries out closure and opening action with the fixed contact part; And the arc extinguishing device, the electric arc that produces when being used for eliminating the open and close action between fixed contact part and removable contact part; Wherein, the arc extinguishing device comprises as each described arc extinguishing resin molding goods among the claim 1-8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006-314499 | 2006-11-21 | ||
| JP2006314499 | 2006-11-21 | ||
| JP2006314499A JP4817316B2 (en) | 2006-11-21 | 2006-11-21 | Arc extinguishing resin processed product and circuit breaker using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101186728A true CN101186728A (en) | 2008-05-28 |
| CN101186728B CN101186728B (en) | 2011-10-19 |
Family
ID=39326636
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101934348A Expired - Fee Related CN101186728B (en) | 2006-11-21 | 2007-11-21 | Arc extinguishing resin molding articles and breaker using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4817316B2 (en) |
| CN (1) | CN101186728B (en) |
| DE (1) | DE102007055667B4 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113517163A (en) * | 2021-07-23 | 2021-10-19 | 西安理工大学 | Strong air-blowing current-limiting high-voltage circuit breaker arc extinguish chamber |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006054030B4 (en) * | 2006-11-16 | 2010-06-17 | Abb Ag | Electrical switching device |
| JP4655094B2 (en) | 2008-02-08 | 2011-03-23 | 富士電機機器制御株式会社 | Arc extinguishing resin processed product and circuit breaker using the same |
| JP4529034B2 (en) | 2008-05-16 | 2010-08-25 | 富士電機機器制御株式会社 | Arc extinguishing resin processed product and circuit breaker using the same |
| DE102018109389A1 (en) * | 2018-04-19 | 2019-10-24 | Tdk Electronics Ag | switching device |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1480661A (en) * | 1965-05-21 | 1967-08-07 | ||
| JPS57202003A (en) * | 1981-06-03 | 1982-12-10 | Hitachi Ltd | Sf6 gas insulating electric device and method of producing same |
| TW293130B (en) * | 1994-03-10 | 1996-12-11 | Mitsubishi Electric Corp | |
| JP2002251932A (en) * | 1994-05-23 | 2002-09-06 | Mitsubishi Electric Corp | Method for converting metals scattered in arcing into insulation material |
| JPH08185785A (en) * | 1994-12-28 | 1996-07-16 | Mitsubishi Electric Corp | Circuit breaker |
| JP2960873B2 (en) * | 1995-09-07 | 1999-10-12 | 日本ユニカー株式会社 | Flame retardant ethylene resin composition |
| AU2003275594A1 (en) * | 2002-10-23 | 2004-05-13 | Fuji Electric Holdings Co., Ltd. | Molded resin for electrical part and process for producing the same |
| EP1659148B1 (en) * | 2003-08-01 | 2013-09-18 | Fuji Electric Co., Ltd. | Reactive flame retardant and flame-retardant processed resin obtained with the same |
-
2006
- 2006-11-21 JP JP2006314499A patent/JP4817316B2/en not_active Expired - Fee Related
-
2007
- 2007-11-21 DE DE102007055667A patent/DE102007055667B4/en not_active Expired - Fee Related
- 2007-11-21 CN CN2007101934348A patent/CN101186728B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113517163A (en) * | 2021-07-23 | 2021-10-19 | 西安理工大学 | Strong air-blowing current-limiting high-voltage circuit breaker arc extinguish chamber |
| CN113517163B (en) * | 2021-07-23 | 2023-02-28 | 西安理工大学 | Strong air-blowing current-limiting type arc extinguish chamber of high-voltage circuit breaker |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102007055667B4 (en) | 2013-06-20 |
| CN101186728B (en) | 2011-10-19 |
| DE102007055667A1 (en) | 2008-05-29 |
| JP4817316B2 (en) | 2011-11-16 |
| JP2008130375A (en) | 2008-06-05 |
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