CN1073396A - Laminated plastics-metal band and manufacture method thereof - Google Patents

Laminated plastics-metal band and manufacture method thereof Download PDF

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CN1073396A
CN1073396A CN 91107970 CN91107970A CN1073396A CN 1073396 A CN1073396 A CN 1073396A CN 91107970 CN91107970 CN 91107970 CN 91107970 A CN91107970 A CN 91107970A CN 1073396 A CN1073396 A CN 1073396A
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laminated
metal
plastic
basis material
sided
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CN1032796C (en
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张国基
王金亮
马成
王开智
相春照
宫思琴
刘先亭
杨维强
孙学刚
周卫
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QINGDAO PLASTICS FACTORY NO 8
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QINGDAO PLASTICS FACTORY NO 8
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The invention relates to laminated plastics-metal band and processing method thereof that fiber optic cable bonding sheath is used.This laminated band be at least one side of metal tape with composite dry process laminated at least one deck thermoplastic film form.This film is with blowing or single crowded or multi-layer co-extruded the making of The tape casting; Resinous principle is single or blend.The invention solves the laminated bonding problem of plastics and metal, process stabilizing, production cost is low; Product is to the adhesive strength height of sheath, and stablizes constantly under the service condition more than 60 ℃, is good shielding, damp proof insulation and the armoring material of fiber optic cable.

Description

Laminated plastics-metal band and manufacture method thereof
The invention relates to the laminated band of metal and plastic sheeting and the invention of manufacture method thereof, specifically, is the invention about the compound process of adhesion type sheath laminated plastics-metal band, the dry type of fiber optic cable.
Since Post Office in 1963 had been invented the local cable of overall plastic comprehensive sheath structure, comprehensive bonding sheath had replaced the sheath sheath and occupied main status in various communication cable.For cable sheath, adopt laminated plastics-metal band that three big benefits are arranged: first, since the thermoplastic film in the laminated plastics-metal band outside can be when extruding sheath and the resin bed of molten state bond together, the so-called adhesion type sheath of becoming one just behind the cooling and shaping, thereby can improve the stressed situation of fiber optic cable, improve the mechanical performance of fiber optic cable widely.The second, when laminated plastics-metal band is vertical when wrapping on the cable core, vertical overseam is heat sealable, makes laminated plastics-metal band be one cylindric, thereby provides one deck reliable damp-proof layer to fiber optic cable.The 3rd, the plastic sheeting that the metal tape outside layer closes can protect the metal tape that plays shielding action in fiber optic cable to exempt from corrosion.
Make with extrusion composite technology or heat posted combination process as the laminated plastics-metal band of cable shield material abroad.With regard to the final application purpose of this product, most important quality control factor is various polymer and the bonding fastness of metal interlevel and the bonding fastness of laminated plastics-metal band and fiber optic cable sheath in this class laminated plastics-metal band.For example, in No. the 225 946, United States Patent (USP), No. the 2 091 168, BP and the 0 057 No. 994 specification of European patent, just proposed to improve the technical scheme of the bonding fastness under the high or low cementability probe temperature of polyethylene sheathing material and metal-back interlayer.These patents are the improvement to the 413 No. 285 patent of the U.S..Various polymer in the adhesion type sheath of the laminated plastics-metal band production of the method manufacturing that proposes in No. the 0 057 994, this improved performance is to use United States Patent (USP) the 225 No. 946, No. the 2 091 168, BP and the European patent not only at room temperature are (23 ℃) of getting well with the bonding fastness of metal interlevel, and still show higher numerical value under the experimental condition of low temperature (12 ℃) and high temperature (71 ℃).Otherwise, use the bonding fastness of this class of the laminated band of plastic-metal of the 413 No. 285 patent manufacturing of the U.S. then to reduce significantly.Its purpose of technical scheme proposed by the invention is consistent with the purpose that No. the 225 946, United States Patent (USP), No. the 2 091 168, BP and the 0 057 No. 994 specification of European patent will reach, and also is the improvement for the 413 No. 285 patent of the U.S.; But, the method for used manufacturing laminated plastics-metal band and production equipment special and to be laminated in the resinous principle of plastic sheeting layering of close metal tape one side on the metal tape all different with aforementioned patent.
In order to improve the bonding of above-mentioned polyethylene sheathing material and metal-back interlayer, be to substitute in the past ethylene/acrylic acid that custom relatively uses or the adhesive linkage of methacrylic acid copolymer is realized in No. the 0 057 994, No. the 225 946, United States Patent (USP), No. the 2 091 168, BP and European patent by the dual composite membrane that uses a kind of coextrusion.And second layered membrane that the blend polymer of first layered membrane that the coextrusion double-layered compound film of this class is formed by (1) a kind of ethylene/acrylic acid or methacrylic acid copolymer and (2) a kind of polyvinyl resin and ethylene/acrylic acid or methacrylic acid copolymer resin forms is formed.Its first layered membrane is close to metal tape in laminated plastics-metal band, so be called by strap layer; Its second layered membrane is positioned at the outer surface of laminated plastics-metal band, is close to the plastic sheath of fiber optic cable behind stranding, so be called by restrictive coating.For each polymeric layer that makes comprehensive bonding sheath and metal tape bonding firmly, require three bonding interfaces all to have good bonding fastness.These three interfaces are: dual composite membrane by first bonding interface between strap layer and surfaces of metallic strip; Second bonding interface between two layerings of dual composite membrane; And dual composite membrane by the 3rd bonding interface between restrictive coating and sheath inner face.
Will reach good bonding fastness on these three bonding interfaces, its degree of difficulty has very big difference.It is the simplest reaching gratifying fastness on second bonding interface.This is because the used plastic raw materials of two layerings of dual co-extrusion film has great similitude and affinity on chemical composition, their melt is laminated in die cavity to flow out from T pattern mouth as monofilm then, has guaranteed that two layerings almost are inseparable.The 3rd bonding interface is finished when cable factory's stranding.Bonding fastness on this interface is relevant by the resinous principle of sheath tunic with laminated plastics-metal band not only, also with the type and the cabling process relating to parameters of sheathing resin.No. the 2 091 168, No. the 225 946, aforesaid United States Patent (USP), BP and European patent are exactly for the 0 057 No. 994 the material composition of the dual co-extrusion film that contacts with sheath by change, reach adhesive property on what is called the 3rd interface of improving between laminated plastics-metal band and sheath.
When making this laminated plastics-metal band with the dual composite membrane of coextrusion, existing processing method has the heat posted composite algorithm and extrudes composite algorithm.When adopting the heat posted composite algorithm, dual composite membrane is prefabricated.First bonding interface bonding be by the preheating temperature of metal tape to film by on the fusing point of strap layer plastics, after film and the metal tape hot pressing fully cooling realize.When composite algorithm was extruded in employing, two layerings of dual composite membrane were flowed out by same T pattern head, and the different plastic melt of two composition of layer is coated on the metal tape, and first bonding interface is realized behind cooling and shaping on the metal tape by plastic melt.Lean on strap layer identical by the film in the chemical composition of the plastic melt of metal tape one side and the heat posted composite algorithm.Clearly, these two kinds of methods all must be used first layered membrane that is formed by ethylene/acrylic acid or methacrylic acid copolymer resin; And first bonding interface bonding all be by just finishing the cementability of metal after this ethylene/acrylic acid or the methacrylic acid copolymer melted by heating.This point can and all obtain proof among totally 26 embodiment by the text of No. the 0 057 994, No. the 225 946, aforesaid United States Patent (USP), No. the 2 091 168, BP and European patent.
But, because ethylene/acrylic acid or methacrylic acid copolymer resin price are more expensive, by existing international market price, be three times of common polythene resin price, and China can't produce at present, must import, thus limited the development that China's laminated plastics-metal band is produced.Secondly, just as previously mentioned, adopt first bonding interface bonding of the laminated plastics-metal band of extruding composite algorithm and the manufacturing of heat posted composite algorithm by just finishing after this ethylene/acrylic acid or the methacrylic acid copolymer melted by heating.In fact this ethylene/acrylic acid or methacrylic acid copolymer have played similar PUR.In other words, when the fusing point of the approaching this copolymer resin of temperature, for example, in the time of 60~71 ℃, it will descend to the bonding fastness test value of metal tape.This phenomenon can be found out among the embodiment by aforementioned three patents.And this is unfavorable to the cable under the high temperature venting condition, aforementioned just three shortcomings that patent will overcome.
The object of the present invention is to provide and a kind ofly can eliminate above-mentioned shortcoming, and lower laminated plastics-metal band and the manufacture method thereof of production cost.The fiber optic cable adhesion type sheath (60~71 ℃) under higher probe temperature that uses this laminated band to make, bonding fastness test value between its polyethylene sheathing material and metal tape does not only reduce than the above-mentioned bonding fastness test value under normal temperature condition, slightly raises on the contrary.And, when adopting dual co-extrusion membrane structure, because it has substituted more expensive ethylene/acrylic acid or methacrylic acid copolymer resin that at present must import by the composition of first layered membrane of metal tape side by more cheap common polythene resin, has reduced production cost.
The processing method of making laminated plastics-metal band in the present invention is a kind of dry type combination process that has improved.With known heat posted composite algorithm with extrude composite algorithm and compare, this method has process stabilizing, yield rate height, production cost is low, the raw material range of choice is big and utilization rate is high, when producing big length product midway involuntary stoppage do not influence advantages such as product quality.The dry method compounding machine have equipment manufacturing cost low, handle and advantage such as maintenance easily.Compare with composite dry process and equipment that the industry of package compound goods is adopted, improvement of the present invention is to have increased by two cover corona treatment equipments, handles and oil removal treatment is carried out on the surface that unreels the metal tape of back before laminated unreeling polarizing by the metal tape side of the film of back before the gluing respectively; And this processing procedure is to finish when producing laminated plastics-metal band, so claim online processing again.These processing means have improved widely as the polyethylene of the non-polar material bonding fastness to metal.
The laminated band of plastic-metal of the present invention is made up of metal base, plastic sheeting and bonding agent.It is that prior prefabricated plastic sheeting and metal base carried out online preliminary treatment respectively, again adhesive is coated on the plastic basis material, process through composite dry process, its thickness is the thickness sum of bond layer after plastic sheeting, metal base and the curing.
Described plastic sheeting is prefabricated, and its thickness is generally 0.40~0.80mm; Can be that individual layer is extruded or multi-layer co-extruded; The material composition of each layering can be single ethene and the random copolymer resin of vinyl unsaturated carboxylic acid or single vistanex; Also can be by the random copolymer resin of ethene and vinyl unsaturated carboxylic acid and the blend of vistanex blending according to a certain weight ratio.
This film is if the double-layer coextrusion film, and its thickness branch stratum proportion is 3 to 7 to 7 to 3; Preferably 1 to 1.
The resin of this film is if blend, and then the percentage by weight of several resins generally can be divided into:
The first kind: substance A is the vistanex that accounts for gross weight 30%~70%,
Substance B is to account for the ethene of gross weight 70%~30% and the random copolymer resin of vinyl unsaturated carboxylic acid,
This class performed thin film is singly to extrude after with substance A and substance B blend with blow moulding or The tape casting, perhaps substance A or substance B is carried out the made film of layering coextrusion.
Second class: substance A is the vistanex that accounts for the second layering gross weight 30%~70%,
Substance B be the random copolymer resin that accounts for the ethene of the second layering gross weight 70%~30% and vinyl unsaturated carboxylic acid,
Substance C is the first layering vistanex,
This class performed thin film is to carry out co-extrusion made film with substance C with blowing or casting technique method after with substance A and substance B blend.
The random copolymer resin of ethene in the described plastic sheeting and vinyl unsaturated carboxylic acid is ethylene/acrylic acid copolymer resin (EAA) or ethylene/methacrylic acid resin (EMAA) or ethylene/vinyl acetate copolymer resin (EVA) preferably; Vistanex is low density polyethylene (LDPE) (LDPE) or LLDPE (LLDPE) resin preferably.
Preferably density is that 0.919~0.923 gram/cubic centimetre, melt index (MI) are that 2~7 low density polyethylene (LDPE) and acrylic or methacrylic acid monomers content are 9% to the composition of the blending resin of film or second layering of double-layer coextrusion film, melt index (MI) is 1.5~5.5 EAA resin or EMAA resin.The blend weight ratio of two kinds of resins preferably 4 to 6~6 to 4.
The resinous principle of coextruded film first layering preferably density is that 0.919~0.923 gram/cubic centimetre, melt index (MI) are 2~7 low density polyethylene (LDPE) or LLDPE.
Described metal base is that its thickness is generally 9~400 microns by aluminium, copper, steel, aluminium Baogang, copper covered steel, steel alloy, coated steel, the plumbous metal tape of making.Described metal base is preferably zinc-plated steel band, chromium plating steel band, copper strips and aluminium strip.Its thickness is preferably 0.1~0.2 millimeter.
The processing method of laminated plastics-metal band of the present invention is the dry type composite algorithm of having improved.
The technological process of production of this laminated plastics-metal band is seen Fig. 1 and Fig. 2.
The technological process of production is as follows: the film unwinding, it is carried out sided corona treatment by metal side, and make the processing degree be higher than 38 dynes per centimeter, preferably reach 41 dynes per centimeter; Enter the glue spreader gluing again.A kind of bonding agent commonly used is and the identical product of solvent-type double-component polyurethane binder that uses in flexible package composite material is produced.As AD502/CAT10 or the AD503/CAT10 system that produces by Japanese TOYO MORTON company.Enter dry drying tunnel behind the film gluing, drying tunnel length is generally 4~8 meters, is divided into 3 sections, adopts hot air circulation and reduction vaporization formula to carry out drying usually, makes the residual solvent amount in the dried bonding agent be no more than 300PPM, preferably is reduced to below the 100PPM.The online pretreated face of the process of dried film and metal tape carries out hot pressing, and hot pressing is finished by compound steel rider and rubber roll.The temperature of steel rider is 40~80 ℃, is preferably 50~60 ℃.Laminated plastics-metal band after compound is through the cooling steel rider rolling after cooling of band cooling jacket.If the product of one-sided laminated plastic film, directly send into temperature and be 40~60 ℃ constant temperature curing chamber, after taking out after 1~7 day, can cut packing.If the product of bilateral laminated plastic film carries out compound the getting final product of hot pressing one time again with the processing back, another side of metal tape and the film behind the gluing.
The technical condition of production technology of described laminated plastics-metal band sees Table 1.
The best technical condition of production technology of described laminated plastics-metal band sees Table 2.
The technical condition of production technology of table 1 laminated plastics-metal band
The operation title The technical indicator title Plastic basis material (one deck or two-layer) Metal base Laminated band
Unwinding Speed tension force 15-50m/mln 10-100N/m 15-50m/mln 50-500N/m
Sided corona treatment The power meter surface tension 1-2KVA 38-43dyn/cm 1-2KVA 41-56dyn/cm
Gluing Coating weight (doing) 3-5g/m 2
Dry Temperature I section II section III section blast 50±10℃ 60±10℃ 70±10℃ 50-150mmHg
Compound Steel roller faces temperature roll gap pressure recombination velocity 30-80℃ 5-30N/cm 215-50m/mln
Cooling Cooling water temperature Normal temperature
Batch Speed tension force 15-50m/mln 50-150N/m
Slaking Temperature-time 40-60 ℃ 1-7 days
The best technical condition of production technology of table 2 laminated plastics-metal band
The operation title The technical indicator title Plastic basis material (one deck or two-layer) Metal base Laminated band
Unwinding Speed tension force 25-35m/mln 10-50N/m 25-35m/mln 150-300N/m
Sided corona treatment The power meter surface tension 1-2KVA 38-41dyn/cm 1-2KVA 43-50dyn/cm
Gluing Coating weight (doing) 4-5g/m 2
Dry Temperature I section II section III section blast 50±5℃ 60±5℃ 70±5℃ 100-150mmHg
Compound Steel roller faces temperature roll gap pressure recombination velocity 40-60℃ 15-20N/cm 225-35m/mln
Cooling Cooling water temperature Normal temperature
Batch Speed tension force 25-35m/mln 80-120N/m
Slaking Temperature-time 40-60 ℃ 2-3 days
Technological process and technology condition in conjunction with the dry type complex method provide its embodiment:
Embodiment 1
Figure 91107970X_IMG1
Embodiment 2
Figure 91107970X_IMG2
By the product that the foregoing description makes, have the better physical performance, as shown in table 3 after tested:
Table 3
From test result: peel strength is subjected to Temperature Influence, does not only reduce, and slightly raises on the contrary.
A face, B face are meant both sides and two laminated faces of plastic sheeting of steel band or aluminium strip in the table 3.
Description of drawings:
Fig. 1: the laminated processing process block diagram of the one-sided and plastic basis material of metal base.
Fig. 2: the laminated processing process block diagram of the metal covering of the laminated metal tape of single-sided plastic and plastic basis material.

Claims (7)

1, a kind of laminated plastics-metal band, it is characterized in that it is made up of metal base, plastic basis material, adhesive, it is that prior prefabricated plastic basis material and metal base given processing respectively, again adhesive is coated on the plastic basis material, be processed into the belt course condensation material through composite dry process, its thickness is the stack of the thickness of plastic basis material, metal base, adhesive coating.
2, laminated plastics-metal band as claimed in claim 1, it is characterized in that described plastic basis material be by ethene and vinyl unsaturated carboxylic acid monomer random copolymer resin and with vistanex by a certain amount of proportioning with blowing or casting technique carry out singly squeezing, co-extrusion, blend prefabricated film, its thickness is 0.040~0.080mm
This film is if the double-layer coextrusion film, and its thickness branch stratum proportion is 3 to 7 to 7 to 3,
The resin of this film is if blend, and then the part by weight of several resins generally can be divided into:
The first kind: substance A be the vistanex that accounts for gross weight 30%~70%,
Substance B is to account for the ethene of gross weight 70%~30% and the random copolymer resin of vinyl unsaturated carboxylic acid,
This class performed thin film is singly to extrude after with substance A and substance B blend with blow moulding or The tape casting, perhaps substance A or substance B is carried out the made film of layering coextrusion,
Second class: substance A be the vistanex that accounts for the second layering gross weight 30%~70%,
Substance B be the random copolymer resin that accounts for the ethene of the second layering gross weight 70%~30% and vinyl unsaturated carboxylic acid,
Substance C is the first layering vistanex,
This class performed thin film is to carry out co-extrusion made film with substance C with blowing or casting technique method after with substance A and substance B blend.
3, the laminated band of metallo-plastic as claimed in claim 1 is characterized in that described metal base is that its thickness is generally 9~400 microns by aluminium, copper, steel, aluminium Baogang, copper covered steel, steel alloy, coated steel, the plumbous metal tape of making.
4, plastic basis material as claimed in claim 2, the random copolymer resin that it is characterized in that ethene in the described plastic sheeting and vinyl unsaturated carboxylic acid is ethylene/acrylic acid copolymer resin (EAA) or ethylene/methacrylic acid resin (EMAA) or ethylene/vinyl acetate copolymer resin (EVA) preferably, and described vistanex is low density polyethylene (LDPE) (LDPE) or LLDPE (LLDPE) resin preferably.
5, as claim 2,3,4 described laminated plastics-metal bands, it is characterized in that described plastic basis material preferably is the film or the double-layer coextrusion film of composition with the blending resin, preferably density is that 0.919~0.923 gram/cubic centimetre, melt index (MI) are that 2~7 low density polyethylene (LDPE) and acrylic or methacrylic acid monomers content are 9% to the composition of the blending resin of film or second layering of double-layer coextrusion film, melt index (MI) is 1.5~5.5 EAA resin or EMAA resin.The blend weight ratio of two kinds of resins preferably 4 to 6~6 to 4,
The resinous principle of coextruded film first layering preferably density is that 0.919~0.923 gram/cubic centimetre, melt index (MI) are 2~7 low density polyethylene (LDPE) or LLDPE, and this film is if the double-layer coextrusion film, and its thickness divides stratum proportion preferably 1 to 1,
The thickness of described plastic basis material is preferably 0.050~0.070mm,
Described metal base is preferably zinc-plated steel band, chromium plating steel band, copper strips and aluminium strip, and its thickness is preferably 0.1~0.2 millimeter.
6, the processing method of the laminated band of metallo-plastic as claimed in claim 1, it is characterized in that adopting the dry type complex method, be after in advance prefabricated plastic basis material of general and metal base give processing, it is compound that applying adhesive drying processing back and metal base carry out lamination on plastic basis material, batch after the cooling, unload roller and leave standstill slaking, promptly become the laminated band of metallo-plastic
The technological process of production of this laminated plastics-metal band
A. the laminated metal tape of single-sided plastic is one-sided and plastic basis material laminated of metal base, it is that plastic basis material is brought down a fever earlier, again it is carried out sided corona treatment, applying adhesive on the plastic basis material after the processing, after plastic basis material behind the gluing carries out the drying processing earlier, carry out compound with the metal base of handling well again, when plastic basis material carries out above-mentioned operation, metal base is also carried out unwinding, again it is carried out sided corona treatment, just in time to carry out lamination compound with the dry good plastic basis material of gluing for metal base after the processing, should cool off through chill roll earlier by laminated band (one-sided) after compound, batch, the laminated band after batching is placed on curing chamber to carry out the constant temperature slaking and is the laminated metal tape of single-sided plastic again
B. the bilateral laminated plastics-metal band is the laminated of the metal covering of the laminated metal tape of single-sided plastic and plastic basis material, and it is that plastic basis material is carried out unwinding earlier, again it is carried out sided corona treatment, applying adhesive on the plastic basis material after the processing.After plastic basis material behind the gluing carries out the drying processing earlier, metal covering with the laminated metal tape of handling well of single-sided plastic carries out compound again, when plastic basis material carries out above-mentioned operation, the laminated metal tape of single-sided plastic is carried out unwinding earlier, again its metal covering is carried out sided corona treatment, just in time to carry out lamination compound with the dry good plastic basis material of gluing for the laminated metal tape of single-sided plastic after the processing, should cool off through chill roll earlier by laminated band (bilateral) after compound, batch again, laminated band after batching is placed on curing chamber and carries out the constant temperature slaking, is the bilateral laminated plastics-metal band.
Technical condition of production technology according to this laminated plastics-metal band of above-mentioned technological process (one-sided or bilateral):
The unwinding operation: plastic basis material, metal base (or the laminated metal tape of single-sided plastic), its withdrawal speed is 15-50m/min, and unwinding tension respectively is 10-100N/m, 50-500N/m,
The sided corona treatment operation: plastic basis material, metal base (or the laminated metal tape of single-sided plastic), its power is 1-2KVA, surface tension respectively is 38-43dyn/cm, 41-56dyn/cm,
Coating process: coating weight (dry substance) 3-5g/m 2,
Drying process: temperature: 1 section 50+10 ℃, 2 sections 60+10 ℃, 3 sections 70+10 ℃, blast: 50-150mmHg,
Compound working procedure: 30-80 ℃ of clad steel roll surface temperature, roll gap pressure 5-30N/cm 2, recombination velocity 15-50m/min,
Refrigerating work procedure: cooling water temperature is a normal temperature,
Coiling process: (one-sided or bilateral) laminated plastics-metal band, its speed 15-50m/min, tension force 50-150N/m,
Curing step: one-sided or bilateral laminated plastics-metal band, 40-60 ℃ of its environment temperature, constant temperature time 1-7 days.
7, the processing method of laminated plastics-metal band as claimed in claim 6 is characterized in that described dry type composite technology condition is preferably:
The unwinding operation: plastic basis material, metal base (or the laminated metal tape of single-sided plastic), its withdrawal speed is 25-35m/min, surface tension respectively is 20-50N/m, 150-300N/m,
The sided corona treatment operation: plastic basis material, metal base (or the laminated metal tape of single-sided plastic), its power 1-2KVA, surface tension respectively are 38-41dyn/cm, 43-50dyn/cm,
Coating process: coating weight (dry substance) 4-5g/m 2,
Drying process: temperature: 1 section 50+5 ℃, 2 sections 60+5 ℃, 3 sections 70+5 ℃, blast: 100-150mmHg,
Compound working procedure: 40-60 ℃ of steel roller faces temperature, roll gap pressure 15-20N/cm 2, recombination velocity 25-35m/min,
Refrigerating work procedure: coolant water temperature is a normal temperature,
Coiling process: one-sided or bilateral laminated plastics-metal band, its speed 25-35m/min, tension force 80-120N/m,
Curing step: one-sided or bilateral laminated plastics-metal band, 40-60 ℃ of its environment temperature, time 2-3 days.
CN 91107970 1991-12-18 1991-12-18 Laminated plastics-metal band and manufacture thereof Expired - Fee Related CN1032796C (en)

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