CN101070403B - Blow-moulded film interface molecular film and production process - Google Patents
Blow-moulded film interface molecular film and production process Download PDFInfo
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- CN101070403B CN101070403B CN200710015874A CN200710015874A CN101070403B CN 101070403 B CN101070403 B CN 101070403B CN 200710015874 A CN200710015874 A CN 200710015874A CN 200710015874 A CN200710015874 A CN 200710015874A CN 101070403 B CN101070403 B CN 101070403B
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- 239000002120 nanofilm Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920000098 polyolefin Polymers 0.000 claims abstract description 22
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 230000003068 static effect Effects 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010096 film blowing Methods 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 230000000630 rising effect Effects 0.000 claims description 3
- 206010019133 Hangover Diseases 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims description 2
- 230000000975 bioactive effect Effects 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 3
- 230000002708 enhancing effect Effects 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 238000000071 blow moulding Methods 0.000 abstract 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- -1 Polyethylene Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Laminated Bodies (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Greenhouses (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention discloses the formula and production process of a kind of blow-molding film-interface molecular film, which belongs to chemical field. the formula of blow-molding film-interfacemolecular film is composed of high-activity surfactant, nanometer micro-powder of silicon, titanium, zinc, aluminum, and distilled water. There are two kinds of processes for preparing the molecular film: a) one prepares organized molecular film on the interface during the blow-molding process of polyolefine film, and uses the central rotating gas-liquid distributor to atomize the prepared liquidonto the bubble surface of the film for interface processing; b) the another prepares organized molecular film on the surface of prepared polyolefine film, which includes,by using 1 to 3 slots, the prepared liquid is placed in the slots respectively for processing the immersed interface of polyolefine film. The present invention which selects the green and non-pollution materials, can thoroughlysolve the problems of drops flowing and fog dispersing, effectively shield UV for reducing its damage to polyolefine film, and transform UV into the red light which is beneficial for plants, and increase the transparency of polyolefine film.
Description
Technical field
The present invention relates to a kind of method at polyolefin film interfacial preparation one deck molecular film as thin as a wafer, especially a kind of blow-moulded film interface molecular film and production technique thereof belong to chemical field.
Background technology
Existing polyolefin film interfacial surface tension is higher, and is hydrophobic, will form intensive little droplet if use agricultural booth, influences printing opacity and the underproduction; The drip agent that adds in using has been eliminated the face droplet, but owing to drip agent is separated out the fog that produces in the canopy; The interior non-drop fog-eliminating agent method of adding is temporarily dealt with problems, and but will lose efficacy within 5 months; Add in addition ultraviolet screening agent then only shielding do not change the waste light source; Add fluorescent material and make the light conversion so not lasting, the cost that timeliness is long is too high again; How added auxiliary agent in addition transparency is descended, again contaminate environment.
Summary of the invention
The objective of the invention is to overcome the problem that exists in the above-mentioned ordinary method, and provide a kind of method that on the polyolefin film interface, prepares Organized Molecular Films, this method can design drip, fog dispersal, light shield, the light conversion of film, the timeliness of high transparent and high insulation as required arbitrarily, reduces cost significantly.Use this kind method and can produce drip, fog dispersal, light shield, light conversion, the splendid film of high transparent and high heat insulation effect.
Technical scheme of the present invention is: this kind blow-moulded film interface molecular film, it is characterized in that, and comprise a kind of high active surfactant: silane series of surfactants, quaternary ammonium salt surface active agent, fluorine or fluorocarbon surfactant; A kind of through chemically treated nano silicone micro mist or titanium, zinc powder: as, nanometer grade silica, Nano titanium dioxide, nano level zinc oxide, nano level aluminium sesquioxide etc.; With a kind of high purity distilled water.Wherein high surfactant and nano silicone micro mist or titanium, zinc powder content are 1%-6%, and distilled water content is 99%-94%.Per ten thousand m
2The polyolefin film material needs this kind blow-moulded film interface molecular film formula 20-100kg.
The present invention prepares Organized Molecular Films on the interface in polyolefin film blowing process production craft step is as follows:
(1), earlier tensio-active agent and the nanoparticle handled are dissolved into distilled water respectively, arrive together according to the prescription of variant production demand is composite again, stir, then composite good solution is injected in the stainless steel vessel, pass through filter and enter water pump;
(2), the throttling set with water pump and accurate measurement injects rotation or fixed part flow arrangement with solution;
(3), according to the variant production needs, with high-pressure airless shower nozzle or adjustable gas-liquid shower nozzle liquid is generated vaporific droplet, immerse 90-100 ℃ the film bubble top layer that online production is risen with tractive force with direct projection and drift dual mode;
(4), by film bubble temperature, make the spontaneous film bubble that is adsorbed on of the chemical bond of bioactive molecule go up to form and arrange Organized Molecular Films closely, evaporate excessive moisture simultaneously;
(5), film bubble internal spraying, the air input and the free air delivery of regulating the film bubble with automatic voltage regulator are with an amount of eliminating water vapour;
(6), by increasing traction pressure and take off roll quantity, with static and pressure strengthen molecular film and base material adsorptive power, set up electrostatic power unit in case of necessity;
(7) if the molecular film component is complicated and thicker, easily produce not film forming hangover, can wash at the later process water, and then oven dry.
The present invention prepares Organized Molecular Films on the polyolefin film interface of having made production craft step is as follows:
(1) earlier tensio-active agent and the nanoparticle of handling are dissolved into distilled water respectively, stir to together according to the prescription of variant production demand is composite again, inject 1-3 liquid tank;
(2) polyolefin film with rolling is placed on the passive let off roll, by supporting and launch the device of film, film is soaked interface processing with its surface in tank, make it to generate the orderly interface of self-assembly molecular film (film can single face also can two-sided immersion);
(3) by the first cover traction and flattening device film is introduced drying unit, with the film oven dry of soaking;
(4) by second cover traction wrap-up or the folding device, film take-up is become finished product;
(5) the many products of functional requirement need to soak → dry → soak → technology of drying again again.
Blown film of the present invention is meant the film of making of blow moiding method of materials such as LDPE, LLDPE, EVA, mLLDPE, PP, and the thickness of the blow-moulded film interface molecular film of producing according to technology of the present invention is 10-100nm.
The present invention carries out having used in the interface processing process Organized Molecular Films with polyolefin film film bubble surface and becomes film theory: LB (physical film deposition method) film for three kinds; SA (chemical bond film) film; MD (static film) film.Specifically comprise: (a) make film forming stoste be adsorbed onto on the polyolefin film bubble surface (physical film deposition method) with spray pattern and immersion way; (b) film forming makes film forming stoste be adsorbed onto on the polyolefin film bubble surface (physical film deposition method) with spray pattern and immersion way; (b) after film forming stoste is attached on the polyolefin film bubble surface, silane series of surfactants, quaternary ammonium salt surface active agent, fluorine or fluorocarbon surfactant head base are adsorbed on the film bubble interface (chemical bond film); (c) film produces static by a plurality of tractions on the film forcing machine, increases interfacial adsorption intensity or set up electrostatic power unit in spray process, and film process carries out more intactly (static film) under static helps; (d) steep surperficial high temperature by film and make surface water become water vapour, get rid of outside the film bubble.
Beneficial effect of the present invention is: covered the polyolefin film interface owing to form the orderly arrangement of the lipophilic head base of the tensio-active agent of molecular film, its tail base has adsorbed inorganic micro powder and has formed the hydrophilic interface of new molecular film, drip fog dispersal problem thoroughly solves, can be synchronous with the life-span of polyolefin film; Add nano level titanium dioxide and silicon-dioxide in the molecular film, can effectively shield UV-light polyolefin film is injured, and UV-light is converted into the crop red light beneficial; Because the nanoparticle nucleogenesis not only can be not transparent because of adding the inorganic powder influence, also can increase the polyolefin film transmittance; Employed silane series of surfactants, fluorine or fluorocarbon surfactant, nano silicone micro mist or titanium, zinc powder all are green non-poisonous materials.
Embodiment
Embodiment 1: it is thick to produce 7 meters wide 0.08mm with three layers of blowing plastic sheeting for farm use unit, and internal layer prepares the plastic sheeting for farm use of interface molecular film:
Common film-blowing process is known.Prescription according to long-acting anti-dropping fog dispersal and light conversion:
Polyethylene film 100m
2
Silane surface active agent 0.2-0.7g
20% nano silicone or aluminum solutions 7-12g
Distilled water 200-1000g
Earlier tensio-active agent and nano-particle solution are added the less water stirring respectively, it is composite to together to add enough distilled water again, stirs.Then mixed solution is injected stainless steel cask, inject rotary flow divider through delicate metering with the high-pressure pump of pressure 〉=8MP; Steep internal spraying by the high-pressure airless shower nozzle at film; The direct projection droplet directly is attached to the film bubble surface of rising, flies away droplet and has upwards filled up the blank that direct projection is dripped in the distraction procedure at the film bubble; Under 〉=90 ℃ temperature action, water vapor steeps surface isolation from film, extrudes the unit inner cold system by improved film and discharges the film bubble; Produce 20kv static, (should not set up electrostatic power unit simultaneously in spraying) during a plurality of take off roll by setting up if voltage reaches.Extrude the unit second traction through film and promptly become finished product.This film clarity is very high, and the drip elimination fog effect all reaches more than 8 months, and tangible light conversion effect is arranged, and temperature of shed is higher about 2 ℃ than normal stream drip defogging film.
Embodiment 2: it is thick to produce 7 meters wide 0.08mm with three layers of blowing plastic sheeting for farm use unit, the plastic sheeting for farm use of outer layer preparation interface molecular film:
Common film-blowing process is known.Prescription according to light shield and light conversion:
Polyethylene film 100m
2
Silane surface active agent 0.2-0.7g
20% nano grade titanium or zinc solution 7-12g
Distilled water 200-1000g
Earlier tensio-active agent and nano-particle solution are added the less water stirring respectively, it is composite to together to add enough distilled water again, stirs.Then mixed solution is injected stainless steel cask, with the liquor pump of pressure 〉=0.2MP and 〉=air pump of 0.6MP injects fixed shunt through delicate metering; Steep external spraying by the gas-liquid shower nozzle at film; Mainly directly be attached to the film bubble surface of rising by the direct projection droplet; Under 〉=90 ℃ temperature action, water vapor steeps surface isolation from film, discharges outdoor by changing exhaust system; Produce 20kv static, (should not set up electrostatic power unit simultaneously in spraying) during a plurality of take off roll by setting up if voltage reaches.Extrude the unit second traction through film and promptly become finished product.This film clarity is very high, and is fine to the ultravioletlight screening effect, and collaborative hindered amine as light stabilizer has the ageing-resistant effect of anti-agricultural chemicals, and regulatable smooth conversion effect is arranged, and temperature of shed is higher about 2 ℃ than normal film.
Embodiment 3: with the monovolume blown film of having produced, and the interface molecular film of double-deck preparation to print:
According to reducing surface tension and the close prescription that moistens the angle:
Polyethylene film 100m
2
Quaternary ammonium salt surface active agent 0.15-0.55g
20% nano silicone solution 6-10g
Distilled water 200-1000g
Earlier tensio-active agent and nano-particle solution are added the less water stirring respectively, it is composite to together to add enough distilled water again, stirs.Then the liquid for preparing is injected 1 liquid tank; The film of the monovolume made is placed on the driven roll film is decontroled, put polyolefin film into liquid tank by expanding unit and carry out two-sided immersion and handle, make it to generate the orderly interface of self-assembly molecular film; By 1 guide reel film is introduced dryer again, make finished product by rolling or folding device.This film printing performance is fine, and firm coloration also is difficult for fading.
Claims (1)
1. in polyolefin film blowing process, on the interface, prepare the production method of blown film interface Organized Molecular Films, it is characterized in that,
(1), by per ten thousand m
2Polyolefin film material need raw material total amount is that the ratio of 20-100kg takes by weighing raw material, and described raw material comprises any tensio-active agent in silane series of surfactants, quaternary ammonium salt surface active agent, fluorine or the fluorocarbon surfactant; A kind of through chemically treated nanometer grade silica or Nano titanium dioxide or Nano-class zinc oxide; With a kind of high purity distilled water; Wherein, the content weight percent of tensio-active agent and above-mentioned nanometer grade silica or Nano titanium dioxide or Nano-class zinc oxide is 1%-6%, and distilled water content weight percent is 99%-94%; Tensio-active agent and the above-mentioned nanometer grade silica handled or Nano titanium dioxide or Nano-class zinc oxide are dissolved into distilled water respectively, composite arriving together, stir, then composite good solution is injected in the stainless steel vessel, enter water pump through filter;
(2), the throttling set with water pump and accurate measurement injects rotation or fixed part flow arrangement with solution;
(3), with high-pressure airless shower nozzle or adjustable gas-liquid shower nozzle liquid is generated vaporific droplet, with the direct projection and 90-100 ℃ the film bubble top layer of dual mode immersion online production that drift about with the tractive force rising;
(4), by film bubble temperature, make the spontaneous film bubble that is adsorbed on of the chemical bond of bioactive molecule go up to form and arrange Organized Molecular Films closely, evaporate excessive moisture simultaneously, the thickness of the blow-moulded film interface molecular film of production is 10-100nm;
(5), film bubble internal spraying, the air input and the free air delivery of regulating the film bubble with automatic voltage regulator are with an amount of eliminating water vapour;
(6), by increasing traction pressure and take off roll quantity, with the adsorptive power of static and pressure enhancing molecular film and base material;
(7) if the molecular film component is complicated and thicker, easily produce not film forming hangover, in the flushing of later process water, and then oven dry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710015874A CN101070403B (en) | 2007-06-07 | 2007-06-07 | Blow-moulded film interface molecular film and production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710015874A CN101070403B (en) | 2007-06-07 | 2007-06-07 | Blow-moulded film interface molecular film and production process |
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| Publication Number | Publication Date |
|---|---|
| CN101070403A CN101070403A (en) | 2007-11-14 |
| CN101070403B true CN101070403B (en) | 2010-05-19 |
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| CN200710015874A Active CN101070403B (en) | 2007-06-07 | 2007-06-07 | Blow-moulded film interface molecular film and production process |
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| Country | Link |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6171945B1 (en) * | 1998-10-22 | 2001-01-09 | Applied Materials, Inc. | CVD nanoporous silica low dielectric constant films |
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| CN1506433A (en) * | 2002-12-06 | 2004-06-23 | 北京化工大学 | Spray-type agricultural plastic shed film anti-fog and water-repellent agent and preparation method thereof |
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2007
- 2007-06-07 CN CN200710015874A patent/CN101070403B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075104C (en) * | 1995-03-17 | 2001-11-21 | 住友化学工业株式会社 | Antifogging agent composition and agricultural film coated therewith |
| US6171945B1 (en) * | 1998-10-22 | 2001-01-09 | Applied Materials, Inc. | CVD nanoporous silica low dielectric constant films |
| CN1394918A (en) * | 2001-07-06 | 2003-02-05 | 韩巍 | Nano Water dispersion medium composition, its preparation method and application |
| CN1410394A (en) * | 2001-09-24 | 2003-04-16 | 中国科学院理化技术研究所 | Method for forming metal composite titanium dioxide nano particle film on ceramic surface |
| CN1506433A (en) * | 2002-12-06 | 2004-06-23 | 北京化工大学 | Spray-type agricultural plastic shed film anti-fog and water-repellent agent and preparation method thereof |
| CN1718625A (en) * | 2005-08-04 | 2006-01-11 | 沈阳华龙农地膜制造有限公司 | Nano-silicon oxide modified polyolefin composite canopy film and its production technology |
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| Title |
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| 王洪梅，赵中一，陈莉莉.二氧化钛亲水性技术现状.环境科学动态 2.2003,(2),36-39. |
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| CN101070403A (en) | 2007-11-14 |
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Denomination of invention: Blow-moulded film interface molecular film and production process Effective date of registration: 20180723 Granted publication date: 20100519 Pledgee: Bank of Dezhou Limited by Share Ltd. Liaocheng branch Pledgor: Liaocheng Prosperous Plastic Industry Co.,Ltd. Registration number: 2018370000133 |
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