CN107604671B - Large-tow carbon fiber oiling agent for wet process and preparation method thereof - Google Patents
Large-tow carbon fiber oiling agent for wet process and preparation method thereof Download PDFInfo
- Publication number
- CN107604671B CN107604671B CN201710850974.2A CN201710850974A CN107604671B CN 107604671 B CN107604671 B CN 107604671B CN 201710850974 A CN201710850974 A CN 201710850974A CN 107604671 B CN107604671 B CN 107604671B
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- silicone oil
- compound
- wet process
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a large-tow carbon fiber oiling agent for a wet process and a preparation method thereof, wherein the oiling agent comprises 80-90 parts by mass of a compound A shown as a formula (I), 1-3 parts by mass of an antioxidant, 1-3 parts by mass of polyether modified silicone oil and 5-15 parts by mass of a nonionic surfactant. The invention meets the requirements of long-time use of the oil agent on no roller adhesion, lasting antistatic property and good high-temperature heat resistance, effectively protects the carbon fiber, meets the preparation requirement of the wet process large-tow carbon fiber, and improves the quality of the carbon fiber.
Description
Technical Field
The invention relates to an oiling agent, in particular to a large-tow carbon fiber oiling agent for a wet process and a preparation method thereof, and belongs to the technical field of oiling agents.
Background
In 2016, the global carbon fiber consumption exceeds 7.6 ten thousand tons, the main application fields are industry, aerospace, sports goods, automobiles, pressure vessels and the like, and the wind power blade (mainly used for an I-shaped support framework inside the blade) is worthy of being noticed to surpass the application field of aerospace which becomes the carbon fiber. With the increasing tension of environmental protection situation and the increasing increase of clean energy demand, the rapid development of wind power as a clean energy source applied in scale must be realized in a long time in the future, and the use amount of carbon fiber as a main supporting material is greatly increased.
In the production of carbon fibers, the quality and the performance of an oiling agent have important influence on the quality of the carbon fibers, belong to a class of control raw materials, and can ensure the smooth production of the carbon fibers and improve the quality of the carbon fibers. It can be said that high-quality carbon fibers cannot be produced without a stable, reliable and excellent-performance oil agent. At present, the oil agent for the domestic carbon fiber production still depends on import seriously.
The rapid development of the application technology and the increase of the using amount in the civil field of carbon fibers require carbon fibers with better quality and lower price, and the large tows produced by the carbon fibers are effective methods for solving the cost problem. Because the number of filaments in the filament bundle is multiplied, the amount of the oil agent passing through the drying roller in unit time is also multiplied, the static charge on the precursor is easier to accumulate, and the problems of oil agent cross-linking roller sticking, poor antistatic property and the like are easier to occur compared with the production of small-tow carbon fibers.
In the published data, a large tow oil agent has been reported in many ways, for example, in chinese patent document CN201110300362.9, amino silicone oil with low viscosity, low ammonia value and high viscosity and high ammonia value is proposed to be compounded as a main agent of the oil agent, thereby effectively solving the problems that the carbon fiber oil agent is easy to layer and can not be stirred and recovered. Chinese patent document CN201110369956.5 proposes a method of compounding amino silicone oil with low viscosity, low ammonia value and high viscosity and high ammonia value, and adding a certain amount of amide compound and epoxy group addition product as main agents of oil agents, wherein the method can effectively improve the antistatic problem of the oil agents. However, all of the above oil agents have a problem of insufficient heat resistance as a whole, and the oil film surface tends to be poor in elasticity and brittle at high temperatures.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the large-tow carbon fiber oiling agent for the wet process and the preparation method thereof, which can meet the requirements of no roller sticking, lasting antistatic property and good high-temperature heat resistance when the oiling agent is used for a long time, effectively protect the carbon fiber, meet the preparation requirement of the large-tow carbon fiber for the wet process and improve the quality of the carbon fiber.
The technical scheme of the invention is as follows:
a large-tow carbon fiber oiling agent for a wet process comprises the following components:
the structural formula of the compound A is shown as the formula (I):
in the formula (I), a is 0-1, b is 70-130, c is 0-1, and a, b and c are integers;
more preferably, a is 0 to 1, b is 80 to 100, c is 0 to 1, and a, b, and c are integers.
According to the invention, the compound A is part of quaternary ammonium salt modified aminopropyl silicone oil, is cationic, and simultaneously endows the amino silicone oil with good adsorbability and antistatic property on carbon fiber precursors.
According to the present invention, the antioxidant is not particularly required, and may be dissolved in a nonionic surfactant, and preferably is one or a mixture of two or more of isooctyl 3, 5-di-tert-butyl-4-hydroxyphenyl propionate, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N-1, 6-hexamethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionamide, didodecanediol thiodipropionate, and dioctadecyl thiodipropionate.
According to the invention, the polyether modified silicone oil has no special requirements, and preferably, the polyether modified silicone oil is side chain polyoxyethylene modified silicone oil;
the polyether modified silicone oil has better spreadability due to low surface tension, and can greatly reduce the dosage of the nonionic surfactant.
According to the invention, preferably, the nonionic surfactant is a compound mixture consisting of polyoxyethylene polyoxypropylene block copolymer and alkyl alcohol polyoxyethylene ether; further preferably, the mass ratio of the polyoxyethylene polyoxypropylene block copolymer to the alkyl alcohol polyoxyethylene ether is 1: (1 to 4), more preferably 1: 2.
according to the present invention, preferably, the compound a is prepared by the following method:
adding amino silicone oil, isopropanol accounting for 50% of the total material mass, potassium carbonate accounting for 1-2% of the total material mass and 3-halogen-2-hydroxypropyl trimethyl ammonium halide into a reactor, wherein the molar ratio of amino to the 3-halogen-2-hydroxypropyl trimethyl ammonium halide in the amino silicone oil is 1: (0.3-0.6), stirring, heating to 85-90 ℃, refluxing for 4h, cooling to room temperature, filtering, evaporating the solvent under reduced pressure, finally reducing the pressure to 133Pa, heating to 120 ℃, and removing micromolecules to obtain the compound A.
The prepared compound A can keep a liquid state at a high temperature of 260 ℃, overcomes the roller sticking problem, has a smooth surface and good elasticity when subjected to heat treatment for 1h at 350 ℃ in an air environment, overcomes the problem that amino silicone oil becomes brittle at a high temperature, and plays a better protection role on carbon fibers.
According to the preparation method of the compound A, the amino silicone oil is preferably side chain aminopropyl silicone oil, the preferred kinematic viscosity is 90-200 cp, and the ammonia value is 0.15-0.20 mmol/g. When the viscosity of aminopropyl silicone oil is too low, the heat resistance is insufficient, when the viscosity is too high, crosslinking is easy, when the ammonia value is too low, the reaction effect with 3-halogen-2-hydroxypropyl trimethyl ammonium halide is poor, and when the amino value is too high, crosslinking is easy.
Preferably, the 3-halogen-2-hydroxypropyl trimethyl ammonium halide and the halogen are preferably chlorine or bromine, and the molar ratio of the 3-halogen-2-hydroxypropyl trimethyl ammonium halide to the amino group in the amino silicone oil is preferably 0.3-0.6: 1. The heat-resistant effect and the antistatic effect are poor when the molar ratio is lower than 0.3:1, the surface of an oil solution film is brittle after heat treatment for 1h at 350 ℃ in an air atmosphere, and the product is colloidal and difficult to emulsify when the molar ratio is higher than 0.6: 1.
According to the invention, the preparation method of the large-tow carbon fiber oiling agent for the wet process comprises the following steps:
adding the compound A, the antioxidant, the polyether modified silicone oil and the nonionic surfactant into a disperser, stirring at low speed, dripping deionized water, neutralizing with acetic acid to be neutral after phase inversion, and finally obtaining stable emulsion with the particle size of 0.01-0.5 mu m through high-speed dispersion or high-pressure homogenization, namely the large-tow carbon fiber oil agent for the wet process.
The invention has not been described in detail, but is processed according to the conventional technology in the field.
The invention has the beneficial effects that:
the compound A is used as a main component in the formula of the wet process large-tow carbon fiber oiling agent, the roller is not bonded in a cross-linking manner at high temperature, the compound A is more easily adsorbed to a protofilament due to the cationic property of the compound A, has antistatic property and better effect than an external antistatic agent, the viscosity of the compound A is increased due to the ionization effect of the quaternary ammonium salt, the falling of the oiling agent during steam drafting is reduced, the protofilament is well protected, the compound A can keep the elasticity of a film in an air environment at 350 ℃, and the pre-oxidation process and the low-temperature carbonization process of the carbon fiber are effectively protected. The formula of the invention can meet the preparation requirement of wet process large tow carbon fiber.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of Compound A-1 in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are conventional raw materials, and the equipment used is conventional equipment, commercially available products.
Example 1 preparation of Compound A
10Kg of aminopropyl silicone oil (viscosity 150cp, ammonia value 0.16mmol/g), 5Kg of isopropanol, 220gK2CO3And 230g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (content: 65%), stirring, heating to 85-90 deg.C, refluxing for 4 hr, cooling to room temperature, filtering, vacuum evaporating to remove solvent, and mixingReducing the pressure to 133Pa, heating to 120 ℃ to remove small molecules, and obtaining the colorless and transparent compound A-1.
The nuclear magnetic hydrogen spectrum of compound A-1 is shown in FIG. 1, and the solvent is CDCl3. Wherein chemical shift δ -0.099 is a silicon methyl proton peak, δ -0.536 is a proton peak of a methylene group linked to silicon, δ -1.651 is a proton peak of a methylene group linked to a silicon methylene group, δ -2.719-2.737 is a proton peak of a methylene group linked to a nitrogen atom of a non-quaternary ammonium salt and a proton peak of an amino group, δ -3.475 is a proton peak of a methyl group on a nitrogen atom of a quaternary ammonium salt, and δ -7.285 is a solvent proton peak.
Example 2 preparation of Compound A
10Kg of aminopropyl silicone oil (viscosity 100cp, ammonia value 0.18mmol/g), 5Kg of isopropanol, 220gK2CO3And 175g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (the content is 65 percent), stirring, heating to 85-90 ℃, refluxing for 4 hours, cooling to room temperature, filtering, evaporating under reduced pressure to remove the solvent, finally reducing the pressure to 133Pa, heating to 120 ℃ to remove micromolecules, and obtaining the colorless and transparent compound A-2.
Examples 3 to 5
The specific mixture ratio and the composition are shown in table 1, and the preparation steps are as follows:
mixing the materials, stirring and dripping water, neutralizing the mixture to be neutral by using acetic acid after phase inversion, and finally obtaining stable emulsion with the particle size of 0.01-0.5 mu m through high-speed dispersion or high-pressure homogenization treatment, namely the large-tow carbon fiber oiling agent for the wet process.
Comparative example 1 preparation of Compound A
10Kg of aminopropyl silicone oil (viscosity 100cp, ammonia value 0.18mmol/g), 5Kg of isopropanol, 220gK2CO3And 520g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (the content of 65 percent) are stirred, the temperature is increased to 85 to 90 ℃, the reflux is carried out for 4 hours, the mixture is cooled to the room temperature, the filtration is carried out, the solvent is removed by reduced pressure evaporation, the pressure is finally reduced to 133Pa, the temperature is increased to 120 ℃, and the micromolecules are removed, so that colorless transparent jelly is obtained, and the emulsification is difficult.
Comparative example 2 preparation of Compound A
10Kg aminopropyl silicone oil (viscosity 10) was added to the reactor0cp, ammonia value 0.18mmol/g), 5Kg isopropanol, 220gK2CO3And 80g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (the content is 65 percent), stirring, heating to 85-90 ℃, refluxing for 4 hours, cooling to room temperature, filtering, evaporating under reduced pressure to remove the solvent, finally reducing the pressure to 133Pa, heating to 120 ℃ to remove micromolecules, and obtaining colorless transparent liquid A-3.
Comparative examples 1 to 5
The specific mixture ratio and the composition are shown in table 1, and the preparation steps are as follows:
mixing the materials, stirring and dripping water, neutralizing with acetic acid after phase inversion, and finally obtaining the stable emulsion with the grain diameter of 0.01-0.5 mu m through high-speed dispersion or high-pressure homogenization treatment.
TABLE 1
Note: the experimental line is a T300-grade wet process large-tow carbon fiber production line.
A-4 in Table 1 is side chain aminopropyl modified silicone oil, with a kinematic viscosity of 100cp and an ammonia value of 0.18 mmol/g;
a-5 in Table 1 is side chain aminopropyl modified silicone oil, with a kinematic viscosity of 3000cp and an ammonia value of 0.15 mmol/g;
in Table 1, B-1 is an antistatic agent SN-octadecyl dimethyl hydroxyethyl ammonium nitrate.
B-2 in Table 1 is cetyltrimethylammonium chloride.
The antioxidant in Table 1 is isooctyl 3, 5-di-tert-butyl-4-hydroxyphenylpropionate.
In table 1, the polyether-modified silicone oil is a side chain polyoxyethylene-modified silicone oil.
In Table 1, the surfactant is prepared by compounding polyoxyethylene polyoxypropylene block copolymer and AEO according to the mass ratio of 1: 2.
The raw material components in table 1 are all in parts by mass.
As can be seen from Table 1, the application effects of the compounds in the embodiments 3 to 5 are good, the number of sticking rollers is effectively reduced by using the compound A, the compound A has good heat resistance and antistatic effect, and the carbon fiber quality is good;
compared with the examples, comparative example 1, which uses compound A-3 in an amount lower than the quaternary ammonium salt modification amount of the present invention, has problems of poor antistatic effect and more broken filaments, indicating that the heat resistance of A-3 is poor; comparative examples 2 and 3, use the amino silicone oil of low, high viscosity that does not modify with quaternary ammonium salt separately, the broken filament appears in the carbon fiber in comparative example 1, show that the finish heat resistance is very poor, the roller-sticking phenomenon appears very fast in comparative example 2, and the carbon fiber broken filament is many, the intensity is low, because the amino silicone oil of high viscosity exceeds 2 because of the amino quantity on the monomolecular chain, the cross-linking reaction takes place easily, in addition, although the amino silicone oil of high viscosity is low in heat resistance and good in viscosity, the broken filament does not appear, still can not play a good protective action, the broken filament is many, the phenomenon of carbon fiber.
Compared with example 4, comparative example 4 adopts amino silicone oil which is not modified by quaternary ammonium salt, has large static electricity, and shows that the antistatic effect of the amino silicone oil modified by quaternary ammonium salt is obviously improved.
Compared with example 1, in comparative example 5, polyether modified silicone oil is not added, so that the phenomena of more broken filaments and slight reduction of carbon fiber strength occur, because the oil agent without polyether modified silicone oil is not spread uniformly on the surface of the precursor locally, and the protection effects are different.
Claims (10)
1. The large-tow carbon fiber oiling agent for the wet process is characterized by comprising the following components:
80-90 parts by mass of compound A
1-3 parts by mass of antioxidant
1-3 parts by mass of polyether modified silicone oil
5-15 parts by mass of a nonionic surfactant;
the structural formula of the compound A is shown as the formula (I):
（I），
in the formula (I), a =1, b = 70-130, c =1, and a, b and c are integers.
2. The large-tow carbon fiber oiling agent for the wet process according to claim 1, wherein the antioxidant is one or a compound mixture of more than two of 3, 5-di-tert-butyl-4-hydroxy-phenyl-propionic acid isooctyl ester, β - (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionic acid N-octadecyl ester, N-1, 6-hexamethylene-bis [3- (3, 5-di-tert-butyl-4-hydroxy-phenyl) propionamide, didodecanediol thiodipropionate and dioctadecyl thiodipropionate.
3. The large-tow carbon fiber oiling agent for the wet process according to claim 1, wherein the polyether modified silicone oil is side chain polyoxyethylene modified silicone oil.
4. The large-tow carbon fiber oiling agent for the wet process according to claim 1, wherein the nonionic surfactant is a compound mixture consisting of a polyoxyethylene polyoxypropylene block copolymer and an alkyl alcohol polyoxyethylene ether;
the mass ratio of the polyoxyethylene polyoxypropylene block copolymer to the alkyl alcohol polyoxyethylene ether is 1: (1-4).
5. A compound A for a large-tow carbon fiber oiling agent is shown in a formula (I):
（I），
in the formula (I), a =1, b = 70-130, c =1, and a, b and c are integers.
6. A process for the preparation of compound a according to claim 5, comprising the steps of:
adding amino silicone oil, isopropanol accounting for 50% of the total material mass, potassium carbonate accounting for 1-2% of the total material mass and 3-halogen-2-hydroxypropyl trimethyl ammonium halide into a reactor, wherein the molar ratio of amino to the 3-halogen-2-hydroxypropyl trimethyl ammonium halide in the amino silicone oil is 1: (0.3-0.6), stirring, heating to 85-90 ℃, refluxing for 4h, cooling to room temperature, filtering, evaporating the solvent under reduced pressure, finally reducing the pressure to 133Pa, heating to 120 ℃, and removing micromolecules to obtain the compound A.
7. The method for preparing the compound A according to claim 6, wherein the amino silicone oil is side chain aminopropyl silicone oil.
8. The method of claim 7, wherein the side chain aminopropyl silicone oil has a kinematic viscosity of 90cp to 200cp and an ammonia value of 0.15mmol/g to 0.20 mmol/g.
9. The method for preparing compound a according to claim 6, wherein the 3-halo-2-hydroxypropyltrimethylammonium halide and the halogen are chlorine or bromine;
the molar ratio of the 3-halogen-2-hydroxypropyl trimethyl ammonium halide to the amino in the amino silicone oil is 0.3-0.6: 1.
10. The preparation method of the large-tow carbon fiber oiling agent for the wet process according to claim 1, which comprises the following steps:
adding the compound A, the antioxidant, the polyether modified silicone oil and the nonionic surfactant into a disperser, stirring at a low speed, dropwise adding deionized water, neutralizing with acetic acid to be neutral after phase inversion, and finally obtaining a stable emulsion with the particle size of 0.01-0.5 mu m through high-speed dispersion or high-pressure homogenization, namely the large-tow carbon fiber oil agent for the wet process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710850974.2A CN107604671B (en) | 2017-09-20 | 2017-09-20 | Large-tow carbon fiber oiling agent for wet process and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710850974.2A CN107604671B (en) | 2017-09-20 | 2017-09-20 | Large-tow carbon fiber oiling agent for wet process and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107604671A CN107604671A (en) | 2018-01-19 |
| CN107604671B true CN107604671B (en) | 2020-04-21 |
Family
ID=61060086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710850974.2A Active CN107604671B (en) | 2017-09-20 | 2017-09-20 | Large-tow carbon fiber oiling agent for wet process and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107604671B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6693633B1 (en) * | 2019-10-07 | 2020-05-13 | 竹本油脂株式会社 | Aqueous liquid of treatment agent for carbon fiber precursor and carbon fiber precursor |
| CN113897708B (en) * | 2021-11-18 | 2022-07-12 | 中复神鹰碳纤维股份有限公司 | Oiling agent for polyacrylonitrile carbon fiber precursor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101876096A (en) * | 2009-11-26 | 2010-11-03 | 中复神鹰碳纤维有限责任公司 | Production method of proto-filament oiling agent in carbon fiber production process |
| CN102312300A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院化学研究所 | Low-surface-tension organosilicon spinning oil for preparing polyacrylonitrile-based carbon fibers |
-
2017
- 2017-09-20 CN CN201710850974.2A patent/CN107604671B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101876096A (en) * | 2009-11-26 | 2010-11-03 | 中复神鹰碳纤维有限责任公司 | Production method of proto-filament oiling agent in carbon fiber production process |
| CN102312300A (en) * | 2010-07-08 | 2012-01-11 | 中国科学院化学研究所 | Low-surface-tension organosilicon spinning oil for preparing polyacrylonitrile-based carbon fibers |
Non-Patent Citations (2)
| Title |
|---|
| 周建华 等.聚硅氧烷季铵盐抗菌柔软整理剂的合成.《有机硅材料》.2006,第20卷(第5期),第238-242页. * |
| 聚硅氧烷季铵盐抗菌柔软整理剂的合成;周建华 等;《有机硅材料》;20061031;第20卷(第5期);第1.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107604671A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2020182111A1 (en) | Molybdenum disulfide hybrid flame retardant coated with phosphorus-nitrogen-zinc two-dimensional supramolecule and application thereof | |
| CN107604671B (en) | Large-tow carbon fiber oiling agent for wet process and preparation method thereof | |
| CN101613952B (en) | Finishing oil for manufacturing of continuous silicone carbide fiber and application process thereof | |
| CN107503157B (en) | Carbon fiber oil agent for dry-jet wet spinning process and preparation method thereof | |
| WO2017169632A1 (en) | Acrylic fiber treatment agent and use thereof | |
| WO2019245671A1 (en) | Finish composition | |
| CN115806685B (en) | Polyimide film and preparation method thereof | |
| CN115109260B (en) | Heat-resistant carbon fiber precursor oiling agent and preparation method thereof | |
| CN113354756B (en) | Bio-based halogen-free flame retardant, preparation thereof and halogen-free flame-retardant water-based acrylic coating | |
| CN106866961A (en) | A kind of preparation method of polyaniline composite ganoine conductive graphene material | |
| CN107190514B (en) | A kind of large-tow carbon fiber finish | |
| TWI718953B (en) | Treatment agent for carbon fiber precursor and carbon fiber precursor | |
| CN107141674B (en) | Polyvinyl alcohol and phosphoric acid compound blended film and preparation method thereof | |
| CN108547149B (en) | Preparation method of antistatic agent for spinning oil | |
| CN101113570A (en) | Organosilicon flexible smooth agent and process for preparing the same | |
| CN117004127A (en) | Chitosan-based high-flame-retardance MPP pipe and preparation method thereof | |
| CN111204998A (en) | Organic-inorganic hybrid high-temperature-resistant basalt fiber impregnating compound and preparation method thereof | |
| CN105713429A (en) | Printing plate protective adhesive and preparation method thereof | |
| CN106544760B (en) | A kind of carbon fibre precursor is oil solution dedicated and preparation method thereof | |
| CN113429782B (en) | Transparent polyamide resin and preparation method thereof | |
| CN111188098B (en) | Flame-retardant polymer fiber material and preparation method thereof | |
| Liu et al. | Enhanced the thermal stability of polyvinyl chloride via synergistic effects of basic lanthanum tartrate with zinc stearate and pentaerythritol | |
| CN114182392A (en) | Heat-resistant non-silicon carbon fiber oil agent and preparation and application thereof | |
| TW202140645A (en) | Polarizing film and method for producing same | |
| CN111593572A (en) | Antistatic high-performance fiber treating agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No. 985, Fenghuangshan Road, Yangting Industrial New Area, Weihai City, Shandong Province, 264204 Patentee after: Xinyuan chemical (Shandong) Co.,Ltd. Address before: No. 985, Fenghuangshan Road, Yangting Industrial New Area, Weihai City, Shandong Province, 264204 Patentee before: WEIHAI NEWERA CHEMICAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |