CN101250274B - Multifunctional environment protection gas-phase rust-proofing film and preparation method thereof - Google Patents
Multifunctional environment protection gas-phase rust-proofing film and preparation method thereof Download PDFInfo
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- CN101250274B CN101250274B CN2008100471466A CN200810047146A CN101250274B CN 101250274 B CN101250274 B CN 101250274B CN 2008100471466 A CN2008100471466 A CN 2008100471466A CN 200810047146 A CN200810047146 A CN 200810047146A CN 101250274 B CN101250274 B CN 101250274B
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Abstract
A multifunctional environmental-friendly gas phase rust-preventing film and a preparing method thereof are disclosed. The gas phase rust-preventing film is prepared through the mixing coextrusion blow molding by 90-95% basal plastic and 5-10% addition agent according to the weight proportion, wherein the addition agent is formed by raw materials with proportion by weight 65-80% gas phase inhibitor, 2-5% dispersing lubricating agent and 15-30% carrier plastic according to the weight proportion, wherein the gas phase inhibitor employs the combination of sodium tetraborate, ammonium molybdate and laurate cyclohexylamine. The preparation process comprises mixing gas phase inhibitor, dispersing lubricating agent and carrier plastic of the addition agent raw materials to pelletize, then evenly mixing addition agent particles with basal plastic, setting the temperature in 130-180 DEG C, conducting coextrusion blow molding in a plastic blowing machine, thereby preparing the multifunctional environmental-friendly gas phase rust-preventing film. And the gas phase inhibitor has no toxic components in the combination and excellent rust-preventing effect, which is not only suitable to black metals, but also is suitable to the requirements ofnon-ferrous metal rust-preventing packages, has low cost, which is only one third or even one second of imported like products, and can completely replace the imported products.
Description
Technical field
The present invention relates to adapt to the thin-film material of the nontoxic rustproof packing needs of multiple metal products, refer to a kind of multifunctional environment protection gas-phase rust-proofing film and preparation method thereof particularly.
Background technology
For metal products particularly for the packing of cold-rolled steel goods, traditional wrapping material roughly have following two classes: the one, be covered with the volatile rust preventive paper of plastics film as thin as a wafer, the toughness of this wrapping paper is relatively poor, than cracky, its packing is usually intake in the process of transporting or depositing, inhibiter lost efficacy after water inlet for some time, the slushing oil rete is destroyed, causes metal products to get rusty; The 2nd, plastics film adds that braid is overlying on the paper, this type of anti-tarnish paper toughness better, cracky not, but it is thicker, hard and be difficult for sealing, the moisture or the water capacity easily enter in its packing and cause that metal products gets rusty.In addition, paper and plastics are difficult to effective recycling because of material is different fully, not only can waste resource, and can serious environment pollution.
In order to solve the existing defective of above-mentioned wrapping material, improve the physical strength and the rustless property of film based packaging material, adapt to the needs of metallurgical plate, coiled material and large-scale electronic product heavy duty packing, the gas-phase antirusting plastic film that those skilled in the art have successively developed various components replaces traditional product.Existing gas-phase antirusting plastic film generally is to be base-material with the polyolefin resin, adds vapour-phase inhibitor (VCI), the rustproof packaging material of making through extrusion blow.Its manufacturing process is to add certain binding agent in the vapor phase corrosion inhibitor agent solution at first, is coated on the carrier thin film again, progressively changes the antirusting plastic film of the resin of multiple different performance being made single or multiple lift by coextrusion blow into for simplifying technology afterwards.Material as carrier has polyethylene, polypropylene, glassine paper etc., as the material of binding agent polyvinyl acetate, polyacrylic acid ethene fat and the polyvinyl alcohol butyl ester or the like that contracts is arranged.Yet, no matter be the plastics antirust film of application type or still there is weak point in the plastics antirust film of blowing type: the former is in the process that packing is used, its vapour-phase inhibitor (VCI) coating can be transferred to packaged material surface, thereby pollutes packaged metal or metal products.Though the latter has certain sealing and high waterproof and dampproof and long-acting antirust performance, but mostly contain nitrite such as dicyclohexyl amine nitrite etc. in its vapour-phase inhibitor (VCI) on the one hand, this type of nitrite is very harmful to human body, can not satisfy the requirement of current environmental protection standard or standard, the preparation of its vapour-phase inhibitor (VCI) is mainly at ferrous metal on the other hand, and the subassembly of non-ferrous metal or non-ferrous metal and ferrous metal is not then had due rust-proof effect.In addition, some gas phase plastics antirust film adopts some fusing points to be lower than 100 ℃ vapour-phase inhibitor (VCI) as one of component, also to arrive 120～130 ℃ and the temperature of plastic membrane blowing moulding is minimum, these low-melting inhibiter not only cause lubricating substance in the production process, immiscible, and the rustless property of film also will be reduced.
Summary of the invention
The object of the present invention is to provide a kind of nontoxicity composition, favorable rust preventing effect, with low cost, can be suitable for ferrous metal, can be suitable for multifunctional environment protection gas-phase rust-proofing film that non-ferrous metal or ferrous metal and non-ferrous metal subassembly rustproof packing need and preparation method thereof again.
For achieving the above object, the multifunctional environment protection gas-phase rust-proofing film that the present invention developed, form with 5～10% additive mixing coextrusion blow by 90～95% matrix plastic by weight ratio, described additive is made up of 65～80% vapour-phase inhibitor, 2～5% dispersed lubricant and 15～30% carrier plastics by weight ratio, and described vapour-phase inhibitor adopts the combination of sodium tetraborate, ammonium molybdate and three kinds of materials of lauric acid hexahydroaniline.
Above-mentioned matrix plastic can adopt PE, modified PE or its combination, and above-mentioned dispersed lubricant can adopt polyethylene wax, and above-mentioned carrier plastics can adopt PE or modified PE.
Further, above-mentioned matrix plastic adopts the combination of LDPE and LLDPE, and above-mentioned dispersed lubricant adopts polyethylene wax, and above-mentioned carrier plastics adopt LDPE or ethylene-vinyl acetate copolymer EVA.
Further, the weight proportion of three kinds of materials is a sodium tetraborate in the above-mentioned vapour-phase inhibitor: ammonium molybdate: lauric acid hexahydroaniline=1～2: 1～2: 1.5～3; The optimum weight proportioning is a sodium tetraborate: ammonium molybdate: lauric acid hexahydroaniline=1: 2: 3.
The preparation method of above-mentioned multifunctional environment protection gas-phase rust-proofing film may further comprise the steps:
1) choosing of matrix plastic raw material: select the plastic grain of blow temperatures in 130～200 ℃ of scopes standby by described weight proportion;
2) choosing of additive raw material: select vapour-phase inhibitor, dispersed lubricant and carrier plastics standby by described weight proportion; Wherein, vapour-phase inhibitor is selected the combination of sodium tetraborate, ammonium molybdate and three kinds of materials of lauric acid hexahydroaniline, and the carrier plastics are also selected the plastic grain of blow temperatures in 130～200 ℃ of scopes;
3) preparation of additive: with step 2) selected carrier plastics, vapour-phase inhibitor and dispersed lubricant are put into and are mixed 15～30 minutes in the homogenizer, the frictional heat that produces by homogenizer makes the carrier plastic grain be clamminess, make dispersed lubricant to melt under the effect of shear heat, discharging when vapour-phase inhibitor sticks on the carrier plastics equably, naturally cooling drops into and carries out granulation in the tablets press;
4) preparation of gas-phase antirusting film: the plastic grain that additive granules that step 3) obtained and step 1) are chosen mixes; put into extruding in the charging basket of blow moulding machine; in 130～180 ℃ temperature range, carry out coextrusion film blowing, promptly can be made into multifunctional environment protection gas-phase rust-proofing film.
The vapour-phase inhibitor that the present invention develops in the gas-phase antirusting film adopts the effective sodium tetraborate of multiple metallic substance, ammonium molybdate and three kinds of material optimum combinations of lauric acid hexahydroaniline, has abandoned poisonous and hazardous nitrite, and its advantage is:
The one, it can not discharge toxic and harmful, not produce peculiar smell, free from environmental pollution in the packing use, satisfy the requirement of national environmental standard fully, guarantees staff's health.
The 2nd, the fusing point of itself and plastic basis material is approaching, be penetrated in the plastic basis material easily and combine together with it, have that intensity height, sealing property are stable, the characteristics of good antirust property, waterproof, protection against the tide and antirust for a long time, and ability is saline and alkaline, chemical mediator and hot and humid, isolation or shielding to packaged product are good, make corrosive mediums such as extraneous obnoxious flavour, moisture content be difficult to be penetrated in the packing.
The 3rd, its assembly has synergy, can give full play to inherent physics and chemical rustless property separately, the rustproof packing that is suitable for multiple metallic substance such as steel, copper material, aluminium, galvanized sheet, tin plate, silicon steel sheet and manufacturing part thereof, the cold-rolled products that help under the transportation of domestic open, the outdoor storage condition are antirust, especially the siliconized plate of high added value, as thin as a wafer plate seal up for safekeeping antirust.
The 4th, its material is single; cost is lower than traditional paper laminated film wrapping material, belongs to nuisanceless saving type wrapping material, can not only bring good economic benefit to enterprise; and can reclaim once more and to utilize, the saving of environment protection and national resources is had the important social benefit.
Embodiment
Below in conjunction with specific embodiment multifunctional environment protection gas-phase rust-proofing film of the present invention and preparation method thereof is described in further detail:
Embodiment 1:
At first; take by weighing vapour-phase inhibitor (VCI) raw material sodium tetraborate 1kg, ammonium molybdate 2kg, lauric acid hexahydroaniline 3kg; dispersed lubricant material polyethylene wax 0.3kg; carrier plastic raw materials LDPE2.5kg; after each component mixed; put in the homogenizer and mixed 20 minutes; the frictional heat that produces by homogenizer makes the LDPE particle be clamminess, make polyethylene wax to melt under the effect of shear heat; discharging when VCI sticks on the LDPE equably; behind the naturally cooling; put into again and carry out granulation in the tablets press, obtain the additive granules for preparing.Then; in two-to-one ratio; take by weighing matrix plastic raw material LDPE60kg, LLDPE30kg; itself and the additive granules for preparing are mixed; put into extruding in the charging basket of blow moulding machine, in 130～180 ℃ temperature range, carry out coextrusion film blowing, be blow molded into the tubular membrane that thickness is 0.10mm; cut and batch, can obtain multifunctional environment protection gas-phase rust-proofing film of the present invention.
Embodiment 2:
At first; take by weighing vapour-phase inhibitor (VCI) raw material sodium tetraborate 2kg, ammonium molybdate 1kg, lauric acid hexahydroaniline 1.5kg; dispersed lubricant material polyethylene wax 0.2kg; carrier plastic raw materials EVA2.0kg; after each component mixed; put in the homogenizer and mixed 20 minutes; the frictional heat that produces by homogenizer makes the LDPE particle be clamminess, make polyethylene wax to melt under the effect of shear heat; discharging when VCI sticks on the EVA equably; behind the naturally cooling; put into again and carry out granulation in the tablets press, obtain the additive granules for preparing.Then; ratio in one to one; take by weighing matrix plastic raw material LDPE40kg, LLDPE40kg; itself and the additive granules for preparing are mixed; put into extruding in the charging basket of blow moulding machine, in 130～180 ℃ temperature range, carry out coextrusion film blowing, be blow molded into the tubular membrane that thickness is 0.10mm; cut and batch, can obtain multifunctional environment protection gas-phase rust-proofing film of the present invention.
Embodiment 3:
At first; take by weighing vapour-phase inhibitor (VCI) raw material sodium tetraborate 1.5kg, ammonium molybdate 1.5kg, lauric acid hexahydroaniline 1.5kg; dispersed lubricant material polyethylene wax 0.3kg; carrier plastic raw materials LDPE1.5kg; after each component mixed; put in the homogenizer and mixed 20 minutes; the frictional heat that produces by homogenizer makes the LDPE particle be clamminess, make polyethylene wax to melt under the effect of shear heat; discharging when VCI sticks on the LDPE equably; behind the naturally cooling; put into again and carry out granulation in the tablets press, obtain the additive granules for preparing.Then; ratio in three to one; take by weighing matrix plastic raw material LDPE45kg, LLDPE15kg; itself and the additive granules for preparing are mixed; put into extruding in the charging basket of blow moulding machine, in 130～180 ℃ temperature range, carry out coextrusion film blowing, be blow molded into the tubular membrane that thickness is 0.10mm; cut and batch, can obtain multifunctional environment protection gas-phase rust-proofing film of the present invention.
Embodiment 4:
At first; take by weighing vapour-phase inhibitor (VCI) raw material sodium tetraborate 2kg, ammonium molybdate 2kg, lauric acid hexahydroaniline 3kg; dispersed lubricant material polyethylene wax 0.5kg; carrier plastic raw materials LDPE2.5kg; after each component mixed; put in the homogenizer and mixed 20 minutes; the frictional heat that produces by homogenizer makes the LDPE particle be clamminess, make polyethylene wax to melt under the effect of shear heat; discharging when VCI sticks on the LDPE equably; behind the naturally cooling; put into again and carry out granulation in the tablets press, obtain the additive granules for preparing.Then; in two-to-one ratio; take by weighing matrix plastic raw material LDPE60kg, LLDPE30kg; itself and the additive granules for preparing are mixed; put into extruding in the charging basket of blow moulding machine, in 150～180 ℃ temperature range, carry out coextrusion film blowing, be blow molded into the tubular membrane that thickness is 0.10mm; cut and batch, can obtain multifunctional environment protection gas-phase rust-proofing film of the present invention.
Embodiment 5:
At first; take by weighing vapour-phase inhibitor (VCI) raw material sodium tetraborate 2kg, ammonium molybdate 2kg, lauric acid hexahydroaniline 1.5kg; dispersed lubricant material polyethylene wax 0.2kg; carrier plastic raw materials EVA1.5kg; after each component mixed; put in the homogenizer and mixed 20 minutes; the frictional heat that produces by homogenizer makes the EVA particle be clamminess, make polyethylene wax to melt under the effect of shear heat; discharging when VCI sticks on the EVA equably; behind the naturally cooling; put into again and carry out granulation in the tablets press, obtain the additive granules for preparing.Then; take by weighing matrix plastic raw material LDPE82.8kg; itself and the additive granules for preparing are mixed; put into extruding in the charging basket of blow moulding machine; in 150～180 ℃ temperature range, carry out coextrusion film blowing; be blow molded into the tubular membrane that thickness is 0.10mm, cut and batch, can obtain multifunctional environment protection gas-phase rust-proofing film of the present invention.
In the various embodiments described above, the colour batch or the fire retardant that can also when coextrusion film blowing, add an amount of different colours, make the plastics anti-rust film present required color or have certain flame retardant resistance, these additional characteristics can not produce any detrimentally affect to the rustless property of plastics film.
Table 1 has been listed multifunctional environment protection gas-phase rust-proofing film of the present invention and the external comparing result of like product in test for rust preventing ability.External like product is selected the market sale product of clean happy spy of the U.S. and Thyssen for use, its market price is higher than two to three times of antirust films of the present invention, from comparative test result as can be known: antirust film of the present invention all is better than volatile rust prevention discrimination test, humid heat test and the test of gas phase corrosion inhibiting ability or equals external like product, but its price has only 1/2nd or 1/3rd of external like product, and have no side effect, free from environmental pollution, meet the requirement of national environmental standard, fully can the substituting import one product.
Table 1: the simultaneous test of clean happy spy of the film of the present invention and the U.S. and Thyssen product
Claims (5)
1. multifunctional environment protection gas-phase rust-proofing film, it is characterized in that: this gas-phase antirusting film is formed with 5～10% additive mixing coextrusion blow by 90～95% matrix plastic by weight ratio, described additive is made up of 65～80% vapour-phase inhibitor, 2～5% dispersed lubricant and 15～30% carrier plastics by weight ratio, described vapour-phase inhibitor adopts the combination of sodium tetraborate, ammonium molybdate and three kinds of materials of lauric acid hexahydroaniline, and the weight proportion of three kinds of materials is a sodium tetraborate: ammonium molybdate: lauric acid hexahydroaniline=1～2: 1～2: 1.5～3.
2. multifunctional environment protection gas-phase rust-proofing film according to claim 1 is characterized in that: described matrix plastic adopts PE, modified PE or its combination, and described dispersed lubricant adopts polyethylene wax, and described carrier plastics adopt PE or modified PE.
3. multifunctional environment protection gas-phase rust-proofing film according to claim 1 is characterized in that: described matrix plastic adopts the combination of LDPE and LLDPE, and described dispersed lubricant adopts polyethylene wax, and described carrier plastics adopt LDPE or EVA.
4. according to claim 1 or 2 or 3 described multifunctional environment protection gas-phase rust-proofing films, it is characterized in that: the weight proportion of three kinds of materials is a sodium tetraborate in the described vapour-phase inhibitor: ammonium molybdate: lauric acid hexahydroaniline=1: 2: 3.
5. the preparation method of the described multifunctional environment protection gas-phase rust-proofing film of claim 1 may further comprise the steps:
1) choosing of matrix plastic raw material: select the plastic grain of blow temperatures in 130～200 ℃ of scopes standby by described weight proportion;
2) choosing of additive raw material: select vapour-phase inhibitor, dispersed lubricant and carrier plastics standby by described weight proportion; Wherein, vapour-phase inhibitor is selected the combination of sodium tetraborate, ammonium molybdate and three kinds of materials of lauric acid hexahydroaniline, and the carrier plastics are also selected the plastic grain of blow temperatures in 130～200 ℃ of scopes;
3) preparation of additive: with step 2) selected carrier plastics, vapour-phase inhibitor and dispersed lubricant are put into and are mixed 15～30 minutes in the homogenizer, stirring the frictional heat that produces by high speed machine makes the carrier plastic grain be clamminess, make dispersed lubricant to melt under the effect of shear heat, discharging when vapour-phase inhibitor sticks on the carrier plastics equably, naturally cooling drops into and carries out granulation in the tablets press;
4) preparation of gas-phase antirusting film: the plastic grain that additive granules that step 3) obtained and step 1) are chosen mixes; put into extruding in the charging basket of blow moulding machine; in 130～180 ℃ temperature range, carry out coextrusion film blowing, promptly can be made into multifunctional environment protection gas-phase rust-proofing film.
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| CN102775665B (en) * | 2012-06-25 | 2014-01-22 | 李玲 | Antirust master batch applicable to various metallic surfaces and coating and plating layers of metallic surfaces and preparation and application |
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| CN104311970B (en) * | 2014-11-10 | 2016-06-22 | 青岛鑫盈鑫包装材料有限公司 | 2-phenylethyl-1-boric acid diethanolamine ester gas-phase anti-rust master batch and its preparation method and application |
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| CN105780009B (en) * | 2016-01-26 | 2018-06-19 | 上海三汰包装材料有限公司 | A kind of preparation method of volatile rust prevention card |
| CN105818507A (en) * | 2016-03-18 | 2016-08-03 | 安徽三联泵业股份有限公司 | Anti-rusting and shrinking packaging plastic film for pump |
| CN105646988A (en) * | 2016-03-22 | 2016-06-08 | 苏州特聚新材料科技有限公司 | Heat resistant rustproof barrier film and preparation method |
| CN106243467A (en) * | 2016-09-23 | 2016-12-21 | 吴来星 | Novel antirust cover layer of curtain coating type and preparation method thereof |
| CN110240743A (en) * | 2019-06-11 | 2019-09-17 | 苏州特聚新材料科技有限公司 | A kind of intercept type antirust film and preparation method |
| CN110861288A (en) * | 2019-11-30 | 2020-03-06 | 南通永余防锈材料有限公司 | Preparation method of novel high-strength gas-phase anti-rust film |
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