CN102863688B - Halogen-free fire resistance resin composite and use the insulated line of this resin combination - Google Patents
Halogen-free fire resistance resin composite and use the insulated line of this resin combination Download PDFInfo
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- CN102863688B CN102863688B CN201210078483.8A CN201210078483A CN102863688B CN 102863688 B CN102863688 B CN 102863688B CN 201210078483 A CN201210078483 A CN 201210078483A CN 102863688 B CN102863688 B CN 102863688B
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Abstract
The present invention relates to halogen-free fire resistance resin composite and use the insulated line of this resin combination.Can be suitable for being used as also can effectively prevent from crimping the electric wire adding and produce bad order man-hour when the terminal of junctor is little than ever with the distance of the crimping drift crimping processing machine even if the invention provides, namely can with the kind of various crimp connector, crimp the halogen-free fire resistance resin composite of the insulating coating material of the electric wire that the condition of processing is suitable for accordingly and use the insulated line of this resin combination.Following form this resin combination as solution method of the present invention: containing (A) resinous principle [to comprise (a1) melting peak temperature be polypropylene 35 ~ 70 quality %, (a2) melting peak temperature of more than 160 DEG C is ethene-alpha-olefin copolymer 25 ~ 60 quality % and (a3) of less than 90 DEG C has carried out modification vinyl copolymer 5 ~ 20 quality % with unsaturated carboxylic acid or derivatives thereof] 100 mass parts and (B) metal hydrate 120 ~ 250 mass parts.
Description
Technical field
The present invention relates to halogen-free fire resistance resin composite and use the insulated line of this resin combination.
Background technology
As the coating material of the insulated line of the inside distribution for electric/electronic device (hreinafter referred to as " insulating coating material ".), polyvinyl chloride (PVC) compound or what coordinated the halogen-system fire retardant containing bromine atoms or chlorine atom in molecule is that the resin combination of principal constituent is widely known by the people with vinyl copolymer.But, there are the following problems in recent years: when not implementing suitable process and they discarded, the softening agent coordinated in insulating coating material, heavy metal stabilizer meeting stripping, or when making them burn, produce corrosive gases, two by halogen compounds contained in insulating coating material sometimes
english class.Therefore, have studied use and do not worry that the bittern-free flame-proof material of the generation of the stripping, halogen system gas etc. of the heavy metal be harmful to carries out the technology of insulating wrapped to electric wire.
In bittern-free flame-proof material, show flame retardant resistance by mixing not halogen-containing fire retardant in resin.As so not halogen-containing fire retardant, such as use the metal hydrate such as magnesium hydroxide, aluminium hydroxide, in addition, as the resin being mixed with this fire retardant, such as, use polyethylene, polypropylene, vinyl copolymer (ethene-butene-1 copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene-diene terpolymer etc.).
With regard to distribution in equipment, from the aspect of security, require that very high flame retardant resistance benchmark such as meets the VW-1 of UL standard, good crimping processibility.Here, " crimping processibility " refers to, as shown in Figure 1, Figure 2 and Figure 3, slow down in the junctor 2 that the framework 22 of part 23 and metal terminal 21 form by with the injector being called as crimping drift (punching pin) 3 shown in Fig. 3 insulated line 1 being inserted to be embedded in by having resinous strain, terminal 21 punctures the insulating coating material 12 of insulated line 1 and contacts with conductor 11, thus operability when connecting insulated line 1 and junctor 2.
Can omit the insulating coating material 12 of the end of removing insulated line 1 when connecting due to this crimping processing and make the strip operation that conductor 11 exposes, and can connect many insulated lines 1 in the lump, the method therefore as attended operation excellence is practical.As the crimping processibility required by distribution, add in crimping and do not produce bad order particularly important man-hour.As shown in Figure 4, bad order comprises following situation: slow down part 23 in the strain of the framework 22 of junctor 2, insulating coating material 12 produce distortion and compared with determinating reference 4 projection, insulated line 1 is easily come off from junctor 2; And the extending therearound of part that the breakage of insulating coating material 12 contacts with conductor 11 at terminal 21, conductor 11 exposes and makes conductor 11 easily deterioration.Can be suitable for make flame retardant resistance and crimping excellent in workability equipment in the halogen-free fire resistance resin composite of insulating coating material 12 of distribution be disclosed in such as following patent documentation 1 ~ 3.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2002-114878 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-036226 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2005-048168 publication
Summary of the invention
The problem that invention will solve
But, as shown in figures 1-4, roughly U-shaped terminal 21 (following, also referred to as " roughly U-shaped terminal ".) directly over, insulating coating material 12 is pushed to upward, on the other hand, in its vicinity, by crimping drift (punching pin) 3, insulating coating material 12 is pressed downwards.Therefore, roughly U-shaped terminal 21 produces large sstrain with the insulating coating material 12 crimped between drift (punching pin) 3.Rupture because insulating coating material 12 is not enough to bear this strain, therefore roughly the breakage of the insulating coating material 12 of the surrounding of U-shaped terminal 21 is expanded and causes exposing (with reference to Fig. 5) of conductor 11.
Along with various junctor in recent years and the progress of the exploitation of crimping processing machine, the combination of the junctor used and crimping processing machine is also diversified, according to its combination, crimping drift (punching pin) 3 and the distance roughly between U-shaped terminal 21 also can be different (with reference to Fig. 6.In addition, in figure 6, crimping drift (punching pin) 3 and the distance roughly between U-shaped terminal 21 is represented with a, b, c, d).In such a case, with can guarantee to crimp compared with drift (punching pin) 3 situation larger with the distance roughly between U-shaped terminal 21, when having to reduce this distance, the strain that insulating coating material produces has the tendency of increase, easily causes exposing of the conductor ruptured with coating material.Therefore, require exploitation not by the impact crimping drift (punching pin) and the distance size roughly between U-shaped terminal, and the insulating coating material exposed of the conductor caused by the breakage expansion of coating material not easily occurs.
In addition, above-mentioned crimping adds in the bad order in man-hour, and the distortion that strain slows down the insulating coating material of part adds in crimping apply shear-stress to insulating coating material owing to slowing down the friction of part with strain thus there occurs the distortion of viscous deformation man-hour.Can think the yielding stress of insulating coating material, stress when namely stress does not increase and strains increase, is the stress that viscous deformation starts, if this stress can be made to be greater than the shear-stress rubbing and cause, then can prevents distortion.But there is the feature of recoverable deformation and viscous deformation in resin material, the situation that therefore cannot define yielding stress is also more owing to usually having simultaneously.Therefore, the standard of stress when increasing as viscous deformation and start, using the standard of the stress (50% modulus) during the elongation 50% of tension test as distortion difficulty.
In addition, the expansion of the roughly breakage of the insulating coating material of the surrounding of U-shaped terminal produces when insulating coating material is not enough to bear strain.Therefore, if the elongation at break of insulating coating material is large, then damaged expansion is difficult to occur.Halogen-free resin composition for high flame-retardant, is difficult to increase 50% modulus and elongation at break simultaneously.
Therefore, the object of the invention is to, even if provide a kind of being suitable for be used as also can effectively prevent from crimping the electric wire adding and produce bad order man-hour when the terminal of junctor is little than ever with the distance of the crimping drift crimping processing machine, namely can with the kind of various crimp connector, crimp the halogen-free fire resistance resin composite of the insulating coating material of the electric wire that the condition of processing is suitable for accordingly and use the insulated line of this resin combination.
Solve the method for problem
The present invention is the invention made in view of the above problems, and the present inventor etc. conduct in-depth research, and found that, various matter left pending can consist of insulating coating material and solve the composition coordinated by regulation, thus completes the present invention.That is, by the invention provides following halogen-free fire resistance resin composite and using the insulated line of this resin combination.
[1] halogen-free fire resistance resin composite, it contains (A) resinous principle [to comprise (a1) melting peak temperature be polypropylene 35 ~ 70 quality %, (a2) melting peak temperature of more than 160 DEG C is that ethene-alpha-olefin copolymer 25 ~ 60 quality % of less than 90 DEG C and (a3) have carried out vinyl copolymer 5 ~ 20 quality % of modification with unsaturated carboxylic acid or derivatives thereof] 100 mass parts and (B) metal hydrate 120 ~ 250 mass parts.
[2] halogen-free fire resistance resin composite described in aforementioned [1], aforementioned (a2) melting peak temperature forming aforementioned (A) resinous principle is that the ethene-alpha-olefin copolymer of less than 90 DEG C is made up of one kind or two or more ethene-alpha-olefin copolymer.
[3] aforementioned [1] or the halogen-free fire resistance resin composite described in [2], aforementioned (a3) unsaturated carboxylic acid or derivatives thereof forming aforementioned (A) resinous principle is maleic anhydride.
[4] halogen-free fire resistance resin composite according to any one of aforementioned [1] ~ [3], aforementioned (a3) vinyl copolymer forming aforementioned (A) resinous principle is selected from least a kind of multipolymer in the group that is made up of ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer.
[5] insulated line, it is that the insulating coating material of the halogen-free fire resistance resin composite according to any one of involved aforementioned [1] ~ [4], surface of conductor is coated.
Invention effect
According to the present invention, even if provide a kind of being suitable for be used as also can effectively prevent from crimping the electric wire adding and produce bad order man-hour when the terminal of junctor is little than ever with the distance of the crimping drift crimping processing machine, namely can with the kind of various crimp connector, crimp the halogen-free fire resistance resin composite of the insulating coating material of the electric wire that the condition of processing is suitable for accordingly and use the insulated line of this resin combination.
Accompanying drawing explanation
Fig. 1 represents electric wire to insert the stereographic map being embedded in junctor and carrying out the state crimping processing.
Fig. 2 is the major portion orthographic plan of Fig. 1.
Fig. 3 represents that electric wire is inserted into the sectional view that the strain being embedded in junctor slows down the state of part.
Fig. 4 represents that the strain being coated on junctor of electric wire slows down the sectional view of the state of portion deforms.
Fig. 5 is the orthographic plan representing the state that the conductor of electric wire exposes at the terminal periphery of junctor.
Fig. 6 is the orthographic plan representing the terminal of junctor and the position relationship of injector (crimping the crimping drift (punching pin) of processing machine).
Nomenclature
1: insulated line
11: conductor
12: insulating coating material
2: junctor
21: terminal
22: framework
23: strain slows down part
3: crimping drift
31: the projection of position on orthographic plan of crimping drift
4: become the line slowing down the determinating reference of the coated projection of part in strain
A, b, c, d: terminal and the distance crimping drift
Embodiment
[summary of embodiment]
The halogen-free fire resistance resin composite of present embodiment is the resin combination containing resinous principle and metal hydrate, it contains (A) resinous principle [to comprise (a1) melting peak temperature be polypropylene 35 ~ 70 quality %, (a2) melting peak temperature of more than 160 DEG C is ethene-alpha-olefin copolymer 25 ~ 60 quality % of less than 90 DEG C and (a3) have carried out modification vinyl copolymer 5 ~ 20 quality % with unsaturated carboxylic acid or derivatives thereof] 100 mass parts and (B) metal hydrate 120 ~ 250 mass parts.In addition, the insulated line of present embodiment be the surface of conductor by the coated electric wire of insulating coating material, be that the insulating coating material of the involved above-mentioned halogen-free fire resistance resin composite in surface of conductor is coated.
Here, " melting peak temperature " refers to and measures in (DSC) at means of differential scanning calorimetry, the temperature on the summit of the endotherm(ic)peak of DSC curve when heating up with rate of heating 10 DEG C/min.Peak overlapping and exist more than 2 when, be set to the temperature on the summit at the large peak of heat absorption flow.The endotherm(ic)peak of more than 2 when polypropylene is the multipolymer of propylene and other a small amount of composition or the mixture of polypropylene and other a small amount of component of polymer when occur.In the present invention, the polyacrylic validity in resin combination obtains when main component has high melting peak temperature.
[the 1st embodiment]
The halogen-free fire resistance resin composite of the 1st embodiment of the present invention is described.The halogen-free fire resistance resin composite of present embodiment contains (A) resinous principle [to comprise (a1) melting peak temperature be polypropylene 35 ~ 70 quality %, (a2) melting peak temperature of more than 160 DEG C is ethene-alpha-olefin copolymer 25 ~ 60 quality % of less than 90 DEG C and (a3) have carried out modification vinyl copolymer 5 ~ 20 quality % with unsaturated carboxylic acid or derivatives thereof] 100 mass parts and (B) metal hydrate 120 ~ 250 mass parts.Below, each moiety of the halogen-free fire resistance resin composite of present embodiment is described.
(A) resinous principle
In the resin combination of present embodiment, (A) resinous principle comprises (a1) melting peak temperature to be as mentioned above polypropylene 35 ~ 70 quality %, (a2) melting peak temperature of more than 160 DEG C be ethene-alpha-olefin copolymer 25 ~ 60 quality % of less than 90 DEG C and (a3) have carried out vinyl copolymer 5 ~ 20 quality % of modification with unsaturated carboxylic acid or derivatives thereof.Below, each constituent (a1) ~ (a3) of (A) resinous principle is described.
(a1) melting peak temperature is the polypropylene of more than 160 DEG C
The melting peak temperature effective composition of 50% modulus that to be the polypropylene (following, sometimes referred to as " (a1) composition ") of more than 160 DEG C be for increasing resin combination, uses melting peak temperature to be the polypropylene of more than 160 DEG C.When melting peak temperature is less than 160 DEG C, the effect increasing 50% modulus of resin combination is insufficient.In addition, the upper limit of melting peak temperature not by the special restriction with the relation of this effect, but is preferably less than 180 DEG C.
(a1) use level of composition is 35 ~ 70 quality % in (A) resinous principle 100 quality %.During less than 35 quality %, the effect increasing 50% modulus of resin combination is insufficient, and during more than 70 quality %, the elongation at break of resin combination extremely reduces.Wherein, the use level of (a1) composition is preferably 40 ~ 60 quality %.
As the polypropylene being used as (a1) composition, such as, can enumerate homo-polypropylene, Atactic Polypropelene, block polypropylene etc.Wherein, preferred homo-polypropylene, block polypropylene, further preferred block polypropylene.These polypropylene are the materials be polymerized by propylene and a small amount of copolymer composition, as copolymer composition, can enumerate ethene, alpha-olefin (such as, 1-butylene, 1-hexene, 4-methyl-1-pentene etc.).Polypropylene as (a1) composition can be used alone a kind, also can mix two or more to use.
(a2) melting peak temperature is the ethene-alpha-olefin copolymer of less than 90 DEG C
(a2) melting peak temperature is that the ethene-alpha-olefin copolymer of less than 90 DEG C is (below, also referred to as " (a2) composition ".) be to acceptance (B) metal hydrate, increase the effective composition of elongation at break of resin combination, use melting peak temperature is the ethene-alpha-olefin copolymer of less than 90 DEG C.When melting peak temperature is more than 90 DEG C, the effect increasing the elongation at break of resin combination is insufficient.In addition, the lower limit of melting peak temperature by the special restriction with the relation of this effect, but melting peak temperature less than 30 DEG C time, measure and become very difficult.
(a2) use level of composition is 30 ~ 60 quality % in (A) resinous principle 100 quality %.During less than 30 quality %, the effect increasing the elongation at break of resin combination is insufficient, and during more than 60 quality %, 50% modulus of resin combination is not enough.Wherein, the use level of (a2) composition is preferably 35 ~ 55 quality %.
As the ethene-alpha-olefin copolymer being used as (a2) composition, the multipolymer of the alpha-olefin of such as ethene and carbonatoms 3 ~ 8 can be enumerated as preference.As the alpha-olefin of carbonatoms 3 ~ 8, such as propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene etc. can be enumerated.As ethene-alpha-olefin copolymer, the ethene-alpha-olefin copolymer etc. LDPE (Low Density Polyethylene), LLDPE (straight-chain Low Density Polyethylene), VLDPE (ultra-low density polyethylene) can enumerated and synthesize under single-point catalyst exists.Ethene-alpha-olefin copolymer as (a2) composition can be used alone a kind, also can mix two or more to use.
(a3) vinyl copolymer of modification has been carried out with unsaturated carboxylic acid or derivatives thereof
(a3) vinyl copolymer of modification has been carried out (below, also referred to as " (a3) composition " with unsaturated carboxylic acid or derivatives thereof.) be to improving the adaptation of (B) metal hydrate with (A) resinous principle, increasing the effective composition of 50% modulus of resin combination.
(a3) use level of composition is 5 ~ 20 quality % in (A) resinous principle 100 quality %.During less than 5 quality %, the effect increasing 50% modulus of resin combination is insufficient, and during more than 20 quality %, the elongation at break of resin combination extremely reduces.Wherein, the use level of (a3) composition is preferably 5 ~ 10 quality %.
As be used as (a3) composition carried out the vinyl copolymer of modification with unsaturated carboxylic acid or derivatives thereof, such as can enumerate ethylene-vinyl acetate copolymer; The ethylene-acrylate copolymer such as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; The ethylene-methyl acrylate multipolymers etc. such as ethylene methyl methacrylate multipolymer and ethylene-ethyl methacrylate multipolymer.Wherein, optimal ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer.As unsaturated carboxylic acid, such as, can enumerate vinylformic acid, methacrylic acid, toxilic acid, fumaric acid, methylene-succinic acid etc.As the derivative of unsaturated carboxylic acid, such as, can enumerate maleic anhydride, maleic mono-ester, fumaric monoalkylester, methylene-succinic acid monoesters, acrylate, methacrylic ester, maleic acid diester, dimethyl ester, methylene-succinic acid diester etc.In unsaturated carboxylic acid or derivatives thereof, preferred maleic anhydride.Can be used alone a kind as (a3) composition with the vinyl copolymer that unsaturated carboxylic acid or derivatives thereof has carried out modification, also can mix two or more to use.
(B) metal hydrate
In resin combination of the present invention, (B) metal hydrate is used as fire retardant.About the ratio of components of (B) metal hydrate relative to (A) resinous principle, be 120 ~ 250 mass parts relative to (A) resinous principle 100 mass parts, be preferably 150 ~ 200 mass parts.Less than the flame retardant resistance that can not get resistance to practicality during 120 mass parts, during more than 250 mass parts, original elongation at break reduces.
As (B) metal hydrate in resin combination of the present invention, such as, can enumerate aluminium hydroxide, magnesium hydroxide, calcium hydroxide etc.These (B) metal hydrates can be suitable for using, but the particle diameter preferably with the scope of 0.1 ~ 2.0 μm is as its particle diameter and not agglomerative metal hydrate.In addition, also can be to improve for the purpose of processibility etc., the material that its surface is processed by lipid acid, fatty acid metal salt, silane coupling agent, aluminium system coupling agent, titanic acid ester system coupling agent, phosphoric acid ester etc.
(C) other composition
In the resin combination of present embodiment, except above-mentioned (A) resinous principle and (B) metal hydrate, as required, the additives such as such as lubricant, processing aid, flame retardant, inorganic filler, linking agent, crosslinking coagent, antioxidant, metal passivator, stablizer, compatilizer, carbon black, tinting material can be also suitable for adding as (C) other composition in the scope not damaging object of the present invention.
As antioxidant, can 4 be enumerated, 4 '-dioctyl-diphenylamine, N, N '-diphenyl-para-phenylene diamine, 2, 2, 4-trimethylammonium-1, the amine system antioxidants such as the polymkeric substance of 2-dihydroquinoline, four (3-(3, 5-di-tert-butyl-hydroxy phenyl) propionate, 3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid stearyl, 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) the phenol system antioxidant such as benzene, two (2-methyl-4-(the positive alkylthio propionyloxy of 3-)-5-tert-butyl-phenyl) thioether, 2-mercaptobenzimidazole and zinc salt thereof, the sulphur system antioxidants etc. such as tetramethylolmethane-four (3-lauryl-thiopropionate).
As metal passivator, N can be enumerated, N '-bis-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hydrazine, 3-(N-salicylyl) amino-1,2,4-triazole, 2,2 '-oxamide is two-(ethyl 3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester) etc.
As flame retardant, weighting agent, carbon, clay, zinc oxide, stannic oxide, titanium oxide, magnesium oxide, molybdenum oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, silicoorganic compound, quartz, talcum, calcium carbonate, magnesiumcarbonate, zinc borate, white carbon(ink) etc. can be enumerated.
As lubricant, hydrocarbon system, fatty acid series, fatty acid amide system, ester system, alcohol system, metallic soap system etc. can be enumerated.
[the 2nd embodiment]
The insulated line of the 2nd embodiment of the present invention is described.The insulated line of present embodiment has the coated formation of the insulating coating material of the involved above-mentioned halogen-free fire resistance resin composite in surface of conductor.Below, each constituent is described.
(conductor)
As the conductor of the insulated line for present embodiment, such as, single line or the twisted wire of soft copper can be used.In addition, each heart yearn of single line or twisted wire, except bare wire, can also use zinc-plated, nickel plating, silver-plated, gold-plated etc.From the view point of the metal evil deterioration suppressing the resin combination caused by copper, preferred plating line, further preferred tinned wire.As wire diameter, preferably 0.38 ~ 0.61mm.
(insulating coating material)
Insulating coating material for the insulated line of present embodiment comprises above-mentioned halogen-free fire resistance resin composite.Insulating coating material such as can be extruded coated above-mentioned resin combination to conductor and be formed.As the thickness of insulating coating material, be not particularly limited, such as, be generally about 0.1 ~ 5mm, preferably 0.14 ~ 0.25mm.During less than 0.1mm, electrical insulating property is not enough, and sometimes cannot obtain sufficient voltage rating, during more than 5mm, the external diameter of electric wire is thicker, and the distribution in equipment, save space reduce sometimes.
In the insulated line of present embodiment, can resin-coated composition be extruded to conductor and directly form insulating coating material, also can further to improve for the purpose of thermotolerance, make to extrude coated after insulating coating material be cross-linked.As method when carrying out crosslinked, can use that the electronbeam irradiation of common method is crosslinked, chemically crosslinked.
When electronbeam irradiation is cross-linked, extruding resin-coated composition after forming insulating coating material, can be cross-linked by utilizing common method to irradiate electron rays.The dosage preferably 1 ~ 30Mrad of electron rays, in order to efficiently be cross-linked, also allyl group based compound, the N such as methacrylate ester compound, triallylcyanurate such as Viscoat 295 can be added in resin combination, the multi-functional compounds of the divinyl based compounds such as maleimide amine compound, Vinylstyrene such as N '-1,3-phenylene dimaleimide etc. is as crosslinking coagent.
When chemically crosslinked, organo-peroxide can be added as linking agent in resin combination, extrude coated after be cross-linked by utilizing common method to carry out heat treated.
Embodiment
Below, further describe the present invention based on embodiment, but the present invention is not by any restriction of these embodiments.
(embodiment 1)
Use closed mixing machine, mix each constituent with the cooperation composition shown in table 1 and table 2, and carry out mixing until material temperature 200 DEG C, after using mill to carry out sheet material to resulting materials, carry out granulating.Like this, the halogen-free fire resistance resin composite of embodiment 1 is obtained.Use 40mm φ forcing machine, the resin combination of gained extruded in the tinned wird (heart yearns of stranded 7 external diameter 0.16mm) being coated on external diameter 0.48mm with coated thickness 0.15mm.Then, 1Mrad is irradiated to it and accelerates electron rays, obtain insulated line.In addition, table 2 is the tables of each constituent specifically representing the cooperation composition shown in table 1.
(embodiment 2 ~ 5)
Except by coordinating composition to become except the cooperation composition shown in table 1 and table 2, operating similarly to Example 1, obtaining flame retardant resin composition and insulated line.In addition, in embodiment 5, do not irradiate acceleration electron rays.
(comparative example 1 ~ 9)
Except by coordinating composition to become except the cooperation composition shown in table 1 and table 2, operating similarly to Example 1, obtaining flame retardant resin composition and insulated line.
Table 1
Table 2
(evaluation of characteristic)
For the insulating coating material of flame retardant resin composition and the insulated line that comprise gained, carry out the evaluation of characteristic shown below.That is, the evaluation of the tensile properties of insulating coating material and the crimping processibility of insulated line and flame retardant resistance is carried out.Show the result in table 1.In addition, in Table 1, the situation (qualified) characteristic being met determinating reference is denoted as zero, the situation (defective) not meeting determinating reference is denoted as ×.
(evaluation of the tensile properties of insulating coating material)
Extract conductor out from the insulated line of gained, draw speed 500mm/ minute, distance between bench marks carries out the tension test of insulating coating material under the condition of 25mm.About elongation at break with from 50% modulus that stress extension curve is obtained, obtain the mean value of each sample 3 test film.Resolved by CAE and the target value of 50% modulus and elongation at break is set as more than 21MPa, more than 300% respectively.
(evaluation of the crimping processibility of insulated line)
The insulated line of gained is crimped on wiring closet apart from the junctor of 1.5mm, number of terminals 15.As junctor, be used in that the width that strain slows down the gap that part makes insulated line pass through is 0.32mm in minimum part, the junctor that is 0.18mm with the width in the roughly gap of U-shaped terminal embedded conductor at the thickness (length direction of insulated line) that minimum part is 0.20mm, roughly U-shaped terminal.Carry out under the condition that terminal and the distance crimping drift of junctor are 0.02mm at minimum place.For the insulated line 150 of 10 samples of crimping, observe and slow down the distortion of insulating coating material of part and the breakage of the insulating coating material around terminal, according to following benchmark, using underproof for neither one situation as target in strain.For the distortion of insulating coating material, as shown in Figure 3, situation protruding upward for insulating coating material 12 compared with the front end (representing with the two dot chain line of symbol 4) of slowing down part 23 with strain is set to defective (being denoted as ×), the situation of not projection is set to qualified (being denoted as zero).For the breakage of insulating coating material 12, will from roughly frontal, the situation that conductor 11 exposes is set to defective (being denoted as ×).
(evaluation of the flame retardant resistance of insulated line)
For the insulated line of gained, implement the VW-1 Vertical Flame Test recorded in 1080 of touchstone UL1581.Test is, repeat 5 times to light a fire with vertically fixing insulated line sample 15 seconds, stop 15 seconds after, differentiate that whether within 60 seconds absorbent cotton that is whether flame-out, that lay in bottom prolong burning because of burning dropping, whether the kraft paper installed on the top of sample burns or burn.Here, 5 samples are tested, the situation of prolonging burning of all stopped working within 60 seconds, the do not have absorbent cotton of bottom and the kraft paper on top is set to qualified (being denoted as zero).
(result of evaluation)
As shown in Table 1, in embodiment 1 ~ 5, for the composition of halogen-free fire resistance resin composite (insulating coating material), [polypropylene 35 ~ 70 quality % that (a1) melting peak temperature is more than 160 DEG C is comprised relative to (A) resinous principle, (a2) melting peak temperature is ethene-alpha-olefin copolymer 25 ~ 60 quality % of less than 90 DEG C and (a3) have carried out modification vinyl copolymer 5 ~ 20 quality % with unsaturated carboxylic acid or derivatives thereof] (B) metal hydrate is adjusted to 120 ~ 250 mass parts by 100 mass parts, embodiment 1 ~ 5 all meets the determinating reference of the tensile properties of insulating coating material and the crimping of insulated line and flame retardant resistance.Although preventing from crimping 50% modulus important in the bad order adding man-hour and elongation at break and exist the relation of growth and decline, but by being formed (A) resinous principle with above-mentioned use level blending, as the polypropylene that 50% modulus of (a1) composition is high, as the ethene-alpha-olefin copolymer that the acceptability of (B) metal hydrate of (a2) composition is high, the vinyl copolymer of modification has been carried out with olefinically unsaturated carboxylic acid derivatives as raising (B) metal hydrate of (a3) composition and the adaptation of (A) resinous principle, taking into account of 50% modulus and elongation at break can be realized.
On the other hand, when comparative example 1 ~ 9, all cannot reach taking into account of 50% modulus and elongation at break.That is,
Comparative example 1 due to melting peak temperature be that the polyacrylic use level of more than 160 DEG C is many, melting peak temperature is that the use level of the ethene-1-olefin copolymer of less than 90 DEG C is few, therefore elongation at break is little, and in crimping processing, coated breakage expansion expands, and causes conductor to expose.
Comparative example 2 due to melting peak temperature be that the polyacrylic use level of more than 160 DEG C is few, melting peak temperature is that the use level of the ethene-alpha-olefin copolymer of less than 90 DEG C is many, and therefore 50% modulus is little, in crimping processing, produce coated distortion.
Comparative example 3 due to the use level of the vinyl copolymer having carried out modification with olefinically unsaturated carboxylic acid derivatives many, therefore elongation at break is little, crimping processing in coated breakage expansion expand, cause conductor to expose.
Comparative example 4 due to the use level of the vinyl copolymer having carried out modification with olefinically unsaturated carboxylic acid derivatives few, therefore 50% modulus is little, crimping processing in produce coated distortion.
Comparative example 5 is because cooperation melting peak temperature is higher than the ethene-alpha-olefin copolymer of 90 DEG C, the use level of the ethene-alpha-olefin copolymer that melting peak temperature is less than 90 DEG C is few, therefore elongation at break is little, and in crimping processing, coated breakage expansion expands, and causes conductor to expose.
Comparative example 6 is because polyacrylic melting peak temperature is less than 160 DEG C, and therefore 50% modulus is little, in crimping processing, produce coated distortion.
Comparative example 7 due to the use level of magnesium hydroxide few, therefore flame retardant resistance is low, VW-1 test in can not stop working.
Comparative example 8 due to the use level of magnesium hydroxide many, therefore elongation at break is little, crimping processing in coated breakage expansion expand, cause conductor to expose.
Comparative example 9 due to will the bittern-free flame-proof material of conventional art be employed as insulating coating material, therefore 50% modulus and elongation at break little, crimping processing in coated breakage expansion expand, cause conductor to expose, and produce coated distortion.
Claims (4)
1. a halogen-free fire resistance resin composite, resinous principle 100 mass parts that it contains (A) and (B) metal hydrate 120 ~ 250 mass parts, described (A) resinous principle comprises polypropylene 35 ~ 70 quality % that (a1) melting peak temperature is more than 160 DEG C, (a2) melting peak temperature is ethene-alpha-olefin copolymer 25 ~ 60 quality % of less than 90 DEG C, (a3) vinyl copolymer 5 ~ 20 quality % of modification has been carried out with unsaturated carboxylic acid or derivatives thereof, wherein, described (a3) vinyl copolymer forming described (A) resinous principle is selected from by ethylene-vinyl acetate copolymer, at least a kind of multipolymer in the group of ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer composition.
2. halogen-free fire resistance resin composite as claimed in claim 1, described (a2) melting peak temperature of (A) resinous principle described in forming is that the ethene-alpha-olefin copolymer of less than 90 DEG C is made up of one kind or two or more ethene-alpha-olefin copolymer.
3. halogen-free fire resistance resin composite as claimed in claim 1 or 2, described (a3) unsaturated carboxylic acid or derivatives thereof forming described (A) resinous principle is maleic anhydride.
4. an insulated line, it is that the insulating coating material of the halogen-free fire resistance resin composite according to any one of the involved claims 1 to 3 in surface of conductor is coated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011149927A JP5712823B2 (en) | 2011-07-06 | 2011-07-06 | Insulated wire for connector pressure welding |
| JP2011-149927 | 2011-07-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102863688A CN102863688A (en) | 2013-01-09 |
| CN102863688B true CN102863688B (en) | 2015-12-02 |
Family
ID=47442833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210078483.8A Expired - Fee Related CN102863688B (en) | 2011-07-06 | 2012-03-22 | Halogen-free fire resistance resin composite and use the insulated line of this resin combination |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5712823B2 (en) |
| CN (1) | CN102863688B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015000913A (en) * | 2013-06-14 | 2015-01-05 | 日立金属株式会社 | Non-halogen flame-retardant resin composition, and wires and cables prepared using the same |
| CN103483671B (en) * | 2013-10-12 | 2016-09-14 | 苏州宝兴电线电缆有限公司 | A kind of fireproofing cable material without halide and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3280105B2 (en) * | 1991-12-13 | 2002-04-30 | 日本石油化学株式会社 | Crosslinkable flame retardant composition |
| JPH06306214A (en) * | 1993-04-22 | 1994-11-01 | Nippon Petrochem Co Ltd | Flame retardant interior trim material |
| JP4002061B2 (en) * | 2000-10-03 | 2007-10-31 | 古河電気工業株式会社 | Flame retardant resin composition for covering electric wire or optical fiber and wiring material using the same |
-
2011
- 2011-07-06 JP JP2011149927A patent/JP5712823B2/en not_active Expired - Fee Related
-
2012
- 2012-03-22 CN CN201210078483.8A patent/CN102863688B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013014720A (en) | 2013-01-24 |
| JP5712823B2 (en) | 2015-05-07 |
| CN102863688A (en) | 2013-01-09 |
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