CN111234135A - Back coating material for bar code carbon ribbon and preparation method and application thereof - Google Patents
Back coating material for bar code carbon ribbon and preparation method and application thereof Download PDFInfo
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- CN111234135A CN111234135A CN202010181315.6A CN202010181315A CN111234135A CN 111234135 A CN111234135 A CN 111234135A CN 202010181315 A CN202010181315 A CN 202010181315A CN 111234135 A CN111234135 A CN 111234135A
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- back coating
- coating material
- carbon ribbon
- barcode
- methacrylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J31/00—Ink ribbons; Renovating or testing ink ribbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09D151/085—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention relates to the technical field of back coating materials, in particular to a back coating material for a barcode carbon ribbon and a preparation method and application thereof. The invention provides a back coating material for a barcode carbon ribbon, which comprises a compound with a structure shown in a formula I. The back coating material for the bar code carbon ribbon has excellent heat resistance and smoothness, and the connecting structures of ethylene glycol, propylene glycol and the like in the material and the hydroxyl on the surface of the PET substrate form intermolecular force and chemical bonds, so that the adhesive force of the back coating material is good. The compound with the structure shown in the formula I can exist in an aqueous emulsion system, and can avoid pollution of organic solvents to the atmosphere.
Description
Technical Field
The invention relates to the technical field of back coating materials, in particular to a back coating material for a barcode carbon ribbon and a preparation method and application thereof.
Background
The bar code carbon ribbon is called 'carbon ribbon' for short, is an important material in bar code printer printing, and is mainly matched with a bar code printer by adopting a thermal transfer printing technology. Under the action of heat and pressure of the printing head of the bar code printer, characters and bar code information on the bar code carbon ribbon are transferred to the label.
The barcode carbon ribbon structurally comprises a top coating, an ink layer, an inner coating, a ribbon base and a back coating which are sequentially stacked. The back coating is a coating on the back of the slaughtering carbon belt and plays a role in reducing printing head abrasion, reducing static electricity generation and improving heat conduction.
The heat resistance and smoothness of the back coating not only affect the service life of the printing head, but also relate to the printing effect, and the poor heat resistance can cause the printed files to be fuzzy and the printed contents to be adhered; poor slip can result in bar code carbon ribbons that are easily broken when printing bar codes and also result in high print noise.
The back coating is formed on the protective film on the back surface of the carbon ribbon by adopting a mode that back coating liquid is solidified on the back surface of the carbon ribbon, so that the heat resistance and the smoothness of the carbon ribbon are improved. However, in the prior art, the back coating liquid contains organic solvent, which is easy to cause air pollution. Therefore, the development of aqueous emulsion type back coating materials is urgently needed.
Disclosure of Invention
The invention aims to provide a back coating material for a barcode carbon ribbon, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a back coating material for a barcode carbon ribbon, which comprises a compound with a structure shown in a formula I and an organic solvent, wherein the compound with the structure shown in the formula I is as follows:
wherein m is 1-20, n is 1-200, l is 1-20, A is 1-700, B is 0.1-50, and C is 1-300; r1Is polyether; the structural formula of the polyether is as follows: CH (CH)2CH2CH2O(CH2CH2O)a(CH2CH2CH3O)bCH3Wherein a is 0-20, b is 0-20;
r is-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2OCH2CH2OH、-CH2CH2OCH3、-CH2CH2OCH2CH2OCH3One or more of the above;
the number average molecular weight Mn of the compound with the structure shown in the formula I is 50000-70000, and the weight average molecular weight Mw is 70000-90000;
the solid content of the back coating material for the barcode carbon ribbon is 25-30%.
The invention also provides a preparation method of the back coating material for the barcode carbon ribbon, which comprises the following steps:
mixing polyether modified silicone oil containing methacrylic acid groups, methacrylate, methacrylic acid, a catalyst and water, and carrying out emulsion polymerization reaction to obtain the back coating material for the barcode carbon ribbon;
the polyether modified silicone oil containing methacrylic acid groups has a structure shown in a formula II:
wherein m is 1-20, n is 1-200, and l is 1-20; r1Is polyether; the structural formula of the polyether is as follows: CH (CH)2CH2CH2O(CH2CH2O)a(CH2CH2CH3O)bCH3Wherein a is 0-20, b is 0-20; r2Is methacryloxypropyl.
Preferably, the methacrylate is one or more of ethylene glycol methacrylate, propylene glycol methacrylate, diethylene glycol methacrylate, ethylene glycol methyl ether methacrylate and diethylene glycol methyl ether methacrylate.
Preferably, the catalyst is one or more of hydrogen peroxide, ammonium peroxide, urea peroxide and sodium peroxide sulfate.
Preferably, the mass ratio of the polyether modified silicone oil containing methacrylic acid groups to the methacrylic acid ester to the methacrylic acid is (1-3): (1-4.5): (1-4.5).
Preferably, the mass ratio of the total mass of the methacrylic group-containing polyether-modified silicone oil, the methacrylic acid ester, and the methacrylic acid to water is 1: (2-4).
Preferably, the mass ratio of the mass of the catalyst to the mass of the mixture obtained by mixing is (0.01-0.1): 100.
preferably, the temperature of the emulsion polymerization reaction is 70-90 ℃, and the time of the emulsion polymerization reaction is 2-6 h.
The invention also provides the application of the back coating material for the barcode carbon ribbon in the technical scheme or the back coating material for the barcode carbon ribbon prepared by the preparation method in the technical scheme in the printing field.
The invention provides a back coating material for a barcode carbon ribbon, which comprises a compound with a structure shown in a formula I. The back coating material for the bar code carbon ribbon has excellent heat resistance and smoothness, and the connecting structures of ethylene glycol, propylene glycol and the like in the material and the hydroxyl on the surface of the PET substrate form intermolecular force and chemical bonds, so that the adhesive force of the back coating material is good. The compound with the structure shown in the formula I can exist in an aqueous emulsion system, and can avoid pollution of organic solvents to the atmosphere.
Detailed Description
The invention provides a back coating material for a barcode carbon ribbon, which comprises a compound with a structure shown in a formula I and an organic solvent, wherein the compound with the structure shown in the formula I is as follows:
wherein m is 1-20, n is 1-200, l is 1-20, A is 1-700, B is 0.1-50, and C is 1-300; r1Is polyether; the structural formula of the polyether is as follows: CH (CH)2CH2CH2O(CH2CH2O)a(CH2CH2CH3O)bCH3Wherein a is 0-20, b is 0-20;
r is-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2OCH2CH2OH、-CH2CH2OCH3、-CH2CH2OCH2CH2OCH3One or more of the above;
the number average molecular weight Mn of the compound with the structure shown in the formula I is 50000-70000, and the weight average molecular weight Mw is 70000-90000;
the solid content of the back coating material for the barcode carbon ribbon is 25-30%.
In the present invention, when said R is-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2OCH2CH2OH、-CH2CH2OCH3、-CH2CH2OCH2CH2OCH3In the case of two or more of (a), it is to be understood that R in each structural unit of the compound having the structure of formula I may be the same or different.
In the invention, the back coating material for the barcode carbon ribbon also preferably comprises impurity substances generated in the preparation process of the back coating material for the barcode carbon ribbon; the present invention is not limited to any particular impurity substance.
The invention also provides a preparation method of the back coating material for the barcode carbon ribbon, which comprises the following steps:
mixing polyether modified silicone oil containing methacrylic acid groups, methacrylate, methacrylic acid, a catalyst and water, and carrying out emulsion polymerization reaction to obtain the back coating material for the barcode carbon ribbon;
the polyether modified silicone oil containing methacrylic acid groups has a structure shown in a formula II:
wherein m is 1-20, n is 1-200, and l is 1-20; the structural formula of the polyether is as follows: CH (CH)2CH2CH2O(CH2CH2O)a(CH2CH2CH3O)bCH3Wherein a is 0-20, b is 0-20; r2Is methacryloxypropyl.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
In the invention, the methacrylate is preferably one or more of ethylene glycol methacrylate, propylene glycol methacrylate, diethylene glycol methacrylate, ethylene glycol methyl ether methacrylate and diethylene glycol methyl ether methacrylate; when the methacrylate is two or more of the above specific choices, the present invention does not have any particular limitation on the ratio of the specific materials, and the specific materials may be mixed in any ratio.
In the invention, the catalyst is preferably one or more of hydrogen peroxide, ammonium peroxide sulfate, urea peroxide and sodium peroxide; when the catalyst is more than two of the above specific choices, the invention has no special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion.
In the invention, the mass ratio of the polyether modified silicone oil containing methacrylic acid groups, the methacrylate and the methacrylic acid is preferably (1-3): (1-4.5): (1-4.5), more preferably (1.5-2.5): (1.5-4.0): (1.5-4.0), most preferably (1.8-2.2): (2.0-3.0): (2.0-3.0).
In the present invention, the mass ratio of the total mass of the methacrylic group-containing polyether-modified silicone oil, the methacrylic acid ester, and the methacrylic acid to water is preferably 1: (2-4), more preferably 1: (2.5 to 3.5), most preferably 1: (2.8-3.2); the mass ratio of the mass of the catalyst to the mass of the mixture obtained by mixing is preferably (0.01-0.1): 100, more preferably (0.03 to 0.08): 100, most preferably (0.04 to 0.06): 100.
the present invention does not limit the mixing in any particular way, and the mixing may be carried out by a process known to those skilled in the art.
In the invention, the temperature of the emulsion polymerization reaction is preferably 70-90 ℃, more preferably 75-85 ℃, and most preferably 78-82 ℃; the time of the emulsion polymerization reaction is preferably 2-6 h, more preferably 3-5 h, and most preferably 4 h.
In the invention, a product system obtained after the emulsion polymerization reaction is finished does not need to be subjected to post-treatment, namely the back coating material for the bar code carbon ribbon; the solid content of the compound with the structure shown in the formula I in the back coating material for the bar code carbon ribbon is preferably 25-30%, and more preferably 26-28%.
The invention also provides the application of the back coating material for the barcode carbon ribbon in the technical scheme or the back coating material for the barcode carbon ribbon prepared by the preparation method in the technical scheme in the printing field. The method of the present invention is not particularly limited, and may be carried out by a method known to those skilled in the art.
The back coating material for barcode carbon ribbon and the preparation method and application thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
60g of methacrylic group-containing polyether-modified silicone oil (l 15, m 6, n 100, a 10, b 0), 60g of ethylene glycol methacrylate, 60g of propylene glycol methacrylate, 120g of methacrylic acid, 700g of water and 1g of sodium peroxide were mixed and emulsion polymerization was carried out (80 ℃ C., 4 hours) to obtain a barcode carbon tape back coating material having a solid content of 28%.
The number average molecular weight Mn of the compound with the structure shown in the formula I in the back coating material for the barcode carbon ribbon is 57382, and the weight average molecular weight Mw is 71883. Wherein A is 166-170, B is 0.6-0.7, C is 263-267, and R is-CH2CH2OH and-CH2CH2CH2OH。
Example 2
60g of a methacrylic group-containing polyether-modified silicone oil (l 8, m 15, n 150, a 5, b 12), 72g of ethylene glycol methacrylate, 72g of diethylene glycol methyl ether methacrylate, 115g of methacrylic acid, 760g of water, 0.5g of urea peroxide and 0.4g of hydrogen peroxide were mixed and emulsion polymerization was carried out (80 ℃ C., 4h) to obtain a barcode carbon tape back coating material having a solid content of 27%.
The number average molecular weight Mn of the compound with the structure shown in the formula I in the bar code carbon tape back coating material is 63837, and the weight average molecular weight Mw is 89805. Wherein A is 184-188, B is 0.5-0.7, C is 266-270, R is-CH2CH2OH and-CH2CH2OCH2CH2OCH3。
Example 3
75g of a methacrylic group-containing polyether-modified silicone oil (l ═ 10, m ═ 10, n ═ 50, a ═ 0, b ═ 12), 80g of ethylene glycol methyl ether methacrylate, 55g of ethylene glycol methacrylate, 95g of methacrylic acid, 820g of water, and 0.6g of ammonium peroxide were mixed, and emulsion polymerization was carried out (80 ℃ C., 4h) to obtain a barcode carbon tape back coating material having a solid content of 26%.
The number average molecular weight Mn of the compound with the structure shown in the formula I in the bar code carbon tape back coating material is 53738, and the weight average molecular weight Mw is 81852. Wherein A is 171 to 175, B is 0.9 to 1.1, C is 192 to 196, and R is-CH2CH2OH，-CH2CH2OCH3。
Example 4
65g of a methacrylic group-containing polyether-modified silicone oil (l 5, m 5, n 20, a 10, b 10), 35g of ethylene glycol methacrylate, 50g of propylene glycol methacrylate, 60g of methacrylic acid, 420g of water, 0.2g of urea peroxide and 0.2g of sodium peroxide were mixed and emulsion polymerization was carried out (80 ℃ C., 4h) to obtain a barcode carbon tape backing material having a solid content of 30%.
The number average molecular weight Mn of the compound with the structure shown in the formula I is 66307, and the weight average molecular weight Mw is 75826. Wherein, A is 192-196, B is 2.4-2.5, C is 220-224, R is-CH2CH2OH and-CH2CH2CH2OH。
Test example
The back coating material for the barcode ribbon described in examples 1 to 4 was subjected to performance tests of heat resistance, adhesion, friction coefficient and printing noise, and test results and test standards were shown in table 1:
table 1 test standards and test results for the back coating materials for barcode carbon ribbons described in examples 1 to 4
As can be seen from table 1, the thermal transfer barcode ribbons prepared by using the back coating material for the barcode ribbons described in examples 1 to 4 as the back coating material for producing the thermal transfer barcode ribbons were continuously printed by using a barcode ribbon printer until the printing head had jelly to affect printing, and the number of continuously printed sheets was used as the evaluation standard of the adhesive force, the larger the number of continuously printed sheets was, the better the adhesive force was, and the worse the adhesive force was. Meanwhile, the bar code carbon ribbon printer is used for printing at different energy levels and different printing speeds, the phenomena of printing blurring, carbon ribbon breakage and the like are avoided as the standard, the higher the energy level is, the faster the speed is, the excellent heat resistance is indicated, and otherwise, the poor heat resistance is indicated. Meanwhile, the back coating material for the barcode carbon ribbon has a low friction coefficient and printing noise.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The back coating material for the barcode carbon ribbon is characterized by comprising a compound with a structure shown in a formula I and water, wherein the compound with the structure shown in the formula I is as follows:
wherein m is 1-20, n is 1-200, l is 1-20, A is 1-700, B is 0.1-50, and C is 1-300; r1Is polyether; the structural formula of the polyether is as follows: CH (CH)2CH2CH2O(CH2CH2O)a(CH2CH2CH3O)bCH3Wherein a is 0-20, b is 0-20;
r is-CH2CH2OH、-CH2CH2CH2OH、-CH2CH2OCH2CH2OH、-CH2CH2OCH3、-CH2CH2OCH2CH2OCH3One or more of the above;
the number average molecular weight Mn of the compound with the structure shown in the formula I is 50000-70000, and the weight average molecular weight Mw is 70000-90000;
the solid content of the back coating material for the barcode carbon ribbon is 25-30%.
2. The method for preparing the back coating material for the barcode carbon ribbon as claimed in claim 1, which comprises the steps of:
mixing polyether modified silicone oil containing methacrylic acid groups, methacrylate, methacrylic acid, a catalyst and water, and carrying out emulsion polymerization reaction to obtain the back coating material for the barcode carbon ribbon;
the polyether modified silicone oil containing methacrylic acid groups has a structure shown in a formula II:
wherein m is 1-20, n is 1-200, and l is 1-20; r1Is polyether; the structural formula of the polyether is as follows: CH (CH)2CH2CH2O(CH2CH2O)a(CH2CH2CH3O)bCH3Wherein a is 0-20, b is 0-20; r2Is methacryloxypropyl.
3. The method according to claim 2, wherein the methacrylate is one or more of ethylene glycol methacrylate, propylene glycol methacrylate, diethylene glycol methacrylate, ethylene glycol methyl ether methacrylate, and diethylene glycol methyl ether methacrylate.
4. The preparation method of claim 2, wherein the catalyst is one or more of hydrogen peroxide, ammonium peroxide, urea peroxide and sodium peroxide sulfate.
5. The preparation method according to claim 2, wherein the mass ratio of the polyether modified silicone oil containing methacrylic acid groups to the methacrylic acid ester to the methacrylic acid is (1-3): (1-4.5): (1-4.5).
6. The production method according to claim 5, wherein the mass ratio of the total mass of the methacrylic group-containing polyether-modified silicone oil, the methacrylate ester, and the methacrylic acid to water is 1: (2-4).
7. The method according to claim 2, wherein the mass ratio of the mass of the catalyst to the mass of the mixture obtained by mixing is (0.01 to 0.1): 100.
8. the method according to claim 2, wherein the temperature of the emulsion polymerization is 70 to 90 ℃ and the time of the emulsion polymerization is 2 to 6 hours.
9. The application of the back coating material for the barcode carbon ribbon as defined in claim 1 or the back coating material for the barcode carbon ribbon prepared by the preparation method as defined in any one of claims 2 to 8 in the printing field.
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| CN202010181315.6A CN111234135B (en) | 2020-03-16 | 2020-03-16 | Back coating material for bar code carbon ribbon and preparation method and application thereof |
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| JP2013155274A (en) * | 2012-01-30 | 2013-08-15 | Seiko Epson Corp | Ink composition for inkjet |
| US20150353751A1 (en) * | 2013-03-07 | 2015-12-10 | Fujifilm Corporation | Inkjet ink composition, inkjet recording method, printed material, and process for producing molded printed material |
| CN107903364A (en) * | 2017-11-23 | 2018-04-13 | 河南省科学院化学研究所有限公司 | Barcode ribbon back coating resin and preparation method thereof and barcode ribbon back coating liquid and its application |
| US20180155482A1 (en) * | 2015-08-31 | 2018-06-07 | Byk-Chemie, Gmbh | Copolymers containing polyether-polysiloxane macromonomer units, process of their preparation and their use in coating compositions and polymeric moulding compounds |
| CN109181429A (en) * | 2018-09-04 | 2019-01-11 | 天津市赢事达办公用品厂 | A kind of water-soluble back coating liquid and preparation method thereof for heat transfer printing carbon tape |
-
2020
- 2020-03-16 CN CN202010181315.6A patent/CN111234135B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013155274A (en) * | 2012-01-30 | 2013-08-15 | Seiko Epson Corp | Ink composition for inkjet |
| US20150353751A1 (en) * | 2013-03-07 | 2015-12-10 | Fujifilm Corporation | Inkjet ink composition, inkjet recording method, printed material, and process for producing molded printed material |
| US20180155482A1 (en) * | 2015-08-31 | 2018-06-07 | Byk-Chemie, Gmbh | Copolymers containing polyether-polysiloxane macromonomer units, process of their preparation and their use in coating compositions and polymeric moulding compounds |
| CN107903364A (en) * | 2017-11-23 | 2018-04-13 | 河南省科学院化学研究所有限公司 | Barcode ribbon back coating resin and preparation method thereof and barcode ribbon back coating liquid and its application |
| CN109181429A (en) * | 2018-09-04 | 2019-01-11 | 天津市赢事达办公用品厂 | A kind of water-soluble back coating liquid and preparation method thereof for heat transfer printing carbon tape |
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Inventor after: Yue Xiufeng Inventor after: Deng Lixia Inventor after: Liu Haijun Inventor after: Liu Pengju Inventor after: Caiqianjie Inventor after: Lu Guodong Inventor after: Liu Tiantian Inventor before: Yue Xiufeng Inventor before: Deng Lixia Inventor before: Liu Haijun Inventor before: Liu Pengju Inventor before: Caiqianjie Inventor before: Lu Guodong Inventor before: Liu Tiantian |
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