CN115975491A - High-barrier coating for lithium battery soft package aluminum plastic film and preparation method thereof - Google Patents
High-barrier coating for lithium battery soft package aluminum plastic film and preparation method thereof Download PDFInfo
- Publication number
- CN115975491A CN115975491A CN202310057038.1A CN202310057038A CN115975491A CN 115975491 A CN115975491 A CN 115975491A CN 202310057038 A CN202310057038 A CN 202310057038A CN 115975491 A CN115975491 A CN 115975491A
- Authority
- CN
- China
- Prior art keywords
- barrier coating
- plastic film
- lithium battery
- soft package
- coating
- 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.)
- Granted
Links
Images
Classifications
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Sealing Battery Cases Or Jackets (AREA)
Abstract
The invention relates to the technical field of battery manufacturing, in particular to a high-barrier coating for a soft package aluminum-plastic film of a lithium battery and a preparation method thereof, the high-barrier coating provided by the application takes modified polyurethane resin as a main framework of a medicament formula, is compounded with a single-layer graphene dispersion liquid, combines the hydrophobic effect of a layered structure of graphene, and is added with small-particle-size alumina sol to play a role in hole sealing and filling, so that the compactness of the coating is improved, the integral water and oxygen resistance effect of the coating is improved, the coating with high barrier property and water and oxygen resistance is prepared, the accelerated aging of water and oxygen on glue used for coating a Nylon layer on the outer side of the soft package aluminum-plastic film is slowed down, and the service life of the battery is prolonged while the battery is used in different harsh environments; the preparation method of the high-barrier coating is simple in process flow and easy to prepare, and meets the requirements of mass production and manufacturing.
Description
Technical Field
The invention relates to the technical field of battery manufacturing, in particular to a high-barrier coating for a lithium battery soft package aluminum-plastic film and a preparation method thereof.
Background
The soft package aluminum-plastic film for the lithium battery is of a multi-layer film structure, and takes an aluminum foil as a film covering basis, wherein two sides of the film covering basis are respectively a PP side with the inner side contacting with electrolyte and a Nylon side with the outer side. The film covering method of the inner PP film of the aluminum-plastic can be divided into a thermal method and a dry method according to different construction processes, but the outer side is unified into the dry method, namely, glue is used for bonding between the Nylon layer and the aluminum foil, the glue system is generally a system of isocyanate and polyalcohol or glue of an epoxy system and the like, and air and water can penetrate through the Nylon layer to accelerate the aging of the glue and reduce the bonding force between the aluminum foil and the glue due to the fact that the outer side is exposed in the atmosphere for a long time, particularly in an environment with higher humidity, so that the surface of the aluminum foil is oxidized and embrittled, the quality of a battery is reduced, and the service life is shortened.
The surface of the traditional Nylon layer is not subjected to surface treatment, and PET can be attached to the surface with the drawing depth requirement or the electrolyte pollution resistance requirement for individual surface protection, but the surface of the Nylon layer of most aluminum plastic film products is not subjected to surface treatment. In recent years, the new energy industry is vigorously popularized by the country, the safety of the battery is increasingly emphasized by manufacturers, and products for improving the barrier effect of the surface of the aluminum-plastic film are particularly urgent in the field of surface treatment of the aluminum-plastic film for the battery.
Disclosure of Invention
In order to solve the problems, the invention provides a high-barrier coating for a soft package aluminum plastic film of a lithium battery and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a high-barrier coating for a soft package aluminum plastic film of a lithium battery comprises the following components in percentage by mass:
3% -5% of a single-layer graphene dispersion liquid;
20-30% of water-soluble modified polyurethane resin;
5% -7% of nano alumina sol;
30-40% of water-soluble auxiliary agent;
the balance being deionized water.
The coating takes the modified polyurethane resin as a main structure of a medicament formula, is compounded with a single-layer modified graphene dispersion liquid, combines the hydrophobic effect of a layered structure of graphene, and is added with small-particle-size alumina sol to play a role in hole sealing and filling, so that the compactness of the coating is further improved, and the overall water resistance and oxygen isolation effects of the coating are improved. The addition of the modified polyurethane resin provides a main framework of the medicament coating, the polyurethane resin is halogen modified resin, has excellent water resistance, has good binding force with the Nylon layer, plays a role in wrapping the surface of the modified graphene, and can improve the overall binding force and uniformity of the high-barrier coating.
Further, the single-layer graphene dispersion liquid is an aqueous single-layer graphene dispersion liquid modified by hydroxyl, carboxyl or amino.
The graphene self-monolayer layer structure has the functions of dispersibility in a water-based system and self hydrophobicity and obstruction maintenance through modification, meanwhile, the surface of the monolayer modified graphene is modified through hydroxyl, carboxyl or amino, the graphene has better water solubility and dispersibility but still has stronger activity, effective binding force cannot be formed with the surface of a Nylon layer, and the binding force and the uniformity of the whole high-obstruction coating can be improved through the wrapping effect of polyurethane resin.
Furthermore, the fineness range of the single-layer graphene dispersion liquid is 0.15-0.5nm.
Further, the water-soluble modified polyurethane resin is anionic waterborne polyurethane, and the structural formula of the water-soluble modified polyurethane resin is shown as the following formula:
wherein N has a value in the range of 8000 to 15000, and wherein R1 and R2 are each independently any one of-C-, -C-C-, and-C-N-structures.
The molecular weight of the water-soluble modified polyurethane resin is 170000-280000, the water-soluble modified polyurethane resin plays a role in wrapping the surface of modified graphene, and the overall bonding force and uniformity of the high-barrier coating can be improved.
Specifically, the anionic waterborne polyurethane is a polyurethane resin modified by functional groups such as halogen and the like, has good binding force with a Nylon layer, and has excellent waterproof effect.
Furthermore, the particle size of the nano alumina sol is 3-5nm, and the effective content is 20% -25%.
The preparation difficulty of the sol with the excessively small size is large, the particle size with the excessively large size cannot form an effective hole sealing effect, on the basis, the alumina sol with the particle size of 0.05-0.1nm can play a role in filling gaps among modified graphene and gaps among modified polyurethane, the compactness of the coating is improved, and on the other hand, the alumina sol particles can also fill up the microporous structure of the Nylon layer, so that the barrier property is improved. Here, the particle size of the oxidized rice sol needs to be smaller than the fineness of the modified graphene.
Further, the water-soluble auxiliary agent is any one of small molecular weight solvents of ethanol, ethylene glycol and isopropanol. By using a low boiling point solvent, the leveling and quick drying effects on the medicament in the coating process are achieved. The addition of solvents with high boiling point, such as ethylene glycol monobutyl ether and the like, which affect the drying time and degree of the coating is avoided, the addition amount is 30-40%, and if the baking capacity of a production line is weak, the addition amount of the solvents can be properly increased, so that the addition amount of the auxiliary agent can be adjusted according to different drying degrees of the coating.
Based on the same inventive concept, the application also provides a preparation method of the high-barrier coating for the soft package aluminum-plastic film of the lithium battery, which comprises the following steps:
s1, weighing deionized water according to a ratio, adding the modified polyurethane resin into the deionized water, and stirring to prepare a mother solution;
s2, adding the single-layer graphene dispersion liquid into the mother liquid prepared in the step S1 according to the proportion, and then stirring;
s3, adding the nano alumina sol into the solution prepared in the step S2 according to the proportion, and continuously stirring;
and S4, adding the water-soluble auxiliary agent into the solution prepared in the step S3 according to the proportion, and uniformly stirring to obtain the high-barrier coating.
Further, in the step S1, the stirring time is 10-30min, and the stirring speed is controlled to be 250-300r/min.
Further, in the step S2, the stirring time is 60-90min, and the stirring speed is controlled at 300-350r/min, so as to ensure that the single-layer graphene dispersion liquid is uniformly dispersed in the mother liquid.
Further, in the step S3, the nano alumina sol needs to be slowly added, the rotating speed is kept to be controlled at 250-300r/min, and the stirring time is 10-30min;
in the step S4, the water-soluble auxiliary agent needs to be slowly added and continuously stirred, the stirring speed is controlled to be 300-350r/min, and the stirring time is 10-30min.
The invention has the following beneficial effects:
1. the high-barrier coating provided by the application has the advantages that the modified polyurethane resin is used as a main body framework of a medicament formula, a single-layer graphene dispersion liquid is compounded, the hydrophobic effect of a layered structure of graphene is combined, meanwhile, the alumina sol with a small particle size is added to play a role in hole sealing and filling, and the compactness of the coating is improved, so that the overall water-resistant and oxygen-insulating effect of the coating is improved, the coating with high barrier property and capable of resisting water and oxygen is prepared, the effect of slowing down the accelerated aging of glue water and oxygen for the Nylon layer used by being coated on the outer side of a soft package aluminum plastic film is realized, the service life of a battery is prolonged while the battery is used in different environments, and meanwhile, the modified polyurethane, the modified graphene and the alumina sol coating have certain strength and can play a certain protection role on the Nylon layer, so that the rigor service life of the soft package battery is improved;
2. the preparation method of the high-barrier coating is simple in process flow and easy to prepare, and meets the requirements of mass production and manufacturing.
Drawings
FIG. 1 is a block diagram of a process for preparing a coating according to some embodiments of the present disclosure.
Detailed Description
In order to facilitate an understanding of the invention, the invention will now be described more fully by way of examples, a preferred embodiment of which is given below. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Other embodiments, which are modifications or equivalents of the inventive concepts herein disclosed, but which do not create inventive results, are within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The numerical values set forth in the examples of the invention are approximations, and may not be obvious. All values within the error range may be included without limiting the specific values disclosed in the embodiments of the present invention, where the error or experimental conditions allow.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Table 1 below is a specific example and comparative example of the present application:
TABLE 1 Components in examples 1-4 and comparative examples 1-2
The modified graphene adopted above is purchased from a product of single-layer graphene aqueous dispersion liquid of Guangzhou Ammi graphene science and technology Co.
The structural formula of the aqueous polyurethane resin used in table 1 is shown as follows:
halogen-modified polyurethane resins available from Asahi New Material science and technology Limited, dongguan, under the type XH-PU4407, with n values of 12000, wherein R1 and R2 refer to the abbreviations for the radicals during the synthesis of the polyurethanes.
The alumina sol used in Table 1 above is an alumina sol product from Ningbo Mininaxin materials science and technology, inc.
Table 1 aqueous adjuvant used was an analytically pure ethanol reagent for alatin.
Referring to FIG. 1, the coatings of examples 1-3 and comparative examples 1-2 were prepared as follows:
s1, firstly weighing deionized water with a specified amount in a formula, then adding the modified polyurethane resin into the deionized water for stirring, wherein the stirring time is 20min, the rotating speed is controlled at 270r/min,
s2, adding the modified graphene dispersion liquid into the mother liquid prepared in the previous step, stirring for 80min, and controlling the rotating speed at 330r/min to ensure that the modified graphene dispersion liquid is uniformly dispersed in the resin solution of the modified polyurethane;
and S3, slowly adding the alumina sol into the mother solution prepared in the previous step, and keeping the rotating speed at 330r/min and stirring for 25min.
And S4, finally, slowly pouring the solvent into the mother liquor prepared in the previous step, continuously stirring, controlling the stirring speed at 330r/min, stirring for 25min, and uniformly stirring to prepare the high-barrier coating.
The high-barrier coating prepared in the examples 1-3 and the comparative examples 1-2 is coated on the surface of the Nylon layer by a roller in the following construction mode to form a high-barrier coating;
step 1), cutting a Nylon film into a size of A4, wherein the Nylon film with the thickness of 25 microns is selected from Nylon films in the Xiamen Long Plastic industry, and the surface of a sample is kept clean in the sample preparation process, so that the local shrinkage of a high-barrier coating can be caused by surface contamination during coating, thereby causing poor appearance or incomplete coating to influence the barrier effect;
step 2) adopting a roller coating method to uniformly coat the medicaments of examples 1-3 and comparative examples 1-2 on the surface of the Nylon layer respectively;
step 3) the plate temperature selected in the above example was 90 ℃ and the wet film amount was selected to be 4g/m 2 In practice, the actual temperature of the Nylon film surface is measured by a plate temperature paper.
Step 4) monitoring the wet film quantity on the surface of the Nylon layer by a production line, and if the wet film quantity is not in the range, adopting a method of replacing a coating roller or diluting a medicament to achieve the recommended range value; if the Nylon layer surface temperature is not within the recommended range, this can be achieved by changing both the line speed and the oven temperature.
And 5) cutting the untreated Nylon film and the Nylon film subjected to the medicament coating treatment into required sizes to be tested.
Specifically, the implementation process has the following requirements:
(1) The coating is uniformly coated on the surface of the Nylon layer by a roller coating mode, and the wet film quantity is required to be more than 2g/m 2 Wherein, in the range of 2-6g/m 2 The amount of the wet film of (1) is proportional to the barrier effect of the coating, but when the amount of the wet film is more than 6g/m 2 In the process, due to the existence of the modified graphene and the aluminum sol in the formula, the coating is too thick, so that the coating of the medicament coating is fogged and white, and the quality grade of the aluminum-plastic film is influenced.
(2) The temperature requirement of the surface of the baked Nylon layer is less than 115 ℃, if the temperature of the surface of the Nylon layer is higher than the temperature, the phenomena of curling and shrinking can occur, the temperature range of the Nylon surface recommended by the coating is 80-110 ℃, and the baking time is 10-30S.
(3) The whole coating section needs to keep the construction environment clean, and raised dust or foreign particles are prevented from being mixed into the agent, so that the surface of the dried Nylon film is flawed, and the quality grade of the aluminum plastic film is reduced.
Specifically, the adopted treatment condition is that the plate temperature is 90 ℃; wet film amount 4g/m 2 (ii) a The coating mode is production line roller coating.
Here, the wet film amount is defined as the weight of the coating material per square meter, and the wet film amount of the resin coating film is generally proportional to the thickness, and may be set to the thickness.
Placing the cut Nylon membrane to be tested into an instrument for testing, wherein the model of the oxygen permeability testing instrument is a testing equipment model of a performance version produced by Mocon and OX-TRAN 2/12 Serles; the water vapor tester is also an H series product produced by Mocon and having the model number of PERMATRAN-W3/34.
The test results are shown in table 2 below:
table 2: results of Performance test in examples 1 to 3 and comparative examples 1 to 2
As can be seen from table 2, the high barrier coatings in examples 1 to 3, compared with the Nylon film as a reference, can greatly reduce the permeability of water vapor and oxygen under specific mixture ratio conditions.
It can be seen from comparative examples 1-2 that increasing or decreasing the content of the waterborne polyurethane affects the appearance of the Nylon film or the bonding force of the coating, and decreasing the content of the waterborne polyurethane causes a decrease in the bonding force, the coating is easy to peel off, and the change in the values of the water vapor transmission rate and the oxygen transmission rate is small. The values of water vapor transmission rate and oxygen transmission rate were increased to the levels of examples 1 to 3 by increasing the content of the aqueous polyurethane, but the resin content was too high, resulting in whitening of the coating layer on the Nylon layer surface and defective appearance.
In a water-resistant test at 65 ℃ 7D on the Nylon side of the aluminum plastic film finished product, the bonding force of the high-barrier coating in comparative examples 1 to 3 on the Nylon side of the aluminum plastic film for the lithium battery soft package can be improved more intuitively.
The high-barrier coating provided by the application is synthesized by taking modified polyurethane resin as a main body framework of a medicament formula, compounding a single-layer graphene dispersion liquid, combining a hydrophobic effect of a layered structure of graphene, adding small-particle-size alumina sol to play a role in hole sealing and filling, and improving the compactness of the coating, so that the overall water-resistant and oxygen-insulating effects of the coating are improved, a water-resistant and oxygen-insulating coating with high barrier property is prepared, the effect of slowing down the accelerated aging of water and oxygen caused by glue used for compounding the outer Nylon layer of the soft package aluminum-plastic film is realized, the service life of a battery is prolonged while the battery is used in different harsh environments, and meanwhile, the coatings of the modified polyurethane, the modified graphene and the alumina sol have certain strength and can play a certain protection role on the Nylon layer, so that the safety and the service life of the soft package battery are improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The high-barrier coating for the soft package aluminum-plastic film of the lithium battery is characterized by comprising the following components in percentage by mass:
3% -5% of a single-layer graphene dispersion liquid;
20-30% of water-soluble modified polyurethane resin;
5% -7% of nano alumina sol;
30-40% of water-soluble auxiliary agent;
the balance being deionized water.
2. The high-barrier coating for the soft package aluminum-plastic film for the lithium battery of claim 1, wherein the single-layer graphene dispersion liquid is an aqueous single-layer graphene dispersion liquid modified by hydroxyl, carboxyl or amino.
3. The high-barrier coating for the lithium battery soft package aluminum-plastic film as claimed in claim 1, wherein the fineness of the single-layer graphene dispersion liquid is in a range of 0.15-0.5nm.
4. The high-barrier coating for the soft package aluminum-plastic film of the lithium battery as claimed in claim 1, wherein the water-soluble modified polyurethane resin is anionic waterborne polyurethane, and the structural formula of the anionic waterborne polyurethane is shown as the following formula:
wherein N has a numerical value in the range of 8000 to 15000, and wherein R1 and R2 are each independently any one of the structures-C-, -C-C-, and-C-N-.
5. The high-barrier coating for the lithium battery soft package aluminum-plastic film as claimed in claim 1, wherein the nano alumina sol has a particle size of 3-5nm and an effective content of 20% -25%.
6. The high-barrier coating for the soft package aluminum-plastic film of the lithium battery as claimed in claim 1, wherein the water-soluble auxiliary agent is any one of small molecular weight solvents of ethanol, ethylene glycol and isopropanol.
7. A method for preparing the high-barrier coating material for the lithium battery soft package aluminum plastic film according to any one of claims 1 to 6, which is characterized by comprising the following steps:
s1, weighing deionized water according to a ratio, adding the modified polyurethane resin into the deionized water, and stirring to prepare a mother solution;
s2, adding the single-layer graphene dispersion liquid into the mother liquid prepared in the step S1 according to the proportion, and then stirring;
s3, adding the nano alumina sol into the solution prepared in the step S2 according to the proportion, and continuously stirring;
and S4, adding the water-soluble auxiliary agent into the solution prepared in the step S3 according to the proportion, and uniformly stirring to obtain the high-barrier coating.
8. The method for preparing the high-barrier coating for the soft package aluminum plastic film of the lithium battery as claimed in claim 7, wherein in the step S1, the stirring time is 10-30min, and the stirring rotation speed is controlled at 250-300r/min.
9. The method for preparing the high-barrier coating for the soft package aluminum-plastic film of the lithium battery as claimed in claim 7, wherein in the step S2, the stirring time is 60-90min, and the stirring speed is controlled to be 300-350r/min, so as to ensure that the single-layer graphene dispersion liquid is uniformly dispersed in the mother liquid.
10. The method for preparing the high barrier coating material for the lithium battery soft pack aluminum plastic film according to claim 7,
in the step S3, the nano alumina sol needs to be slowly added, the rotating speed is kept to be controlled at 250-300r/min, and the stirring time is 10-30min;
in the step S4, the water-soluble auxiliary agent needs to be slowly added and continuously stirred, the stirring speed is controlled to be 300-350r/min, and the stirring time is 10-30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310057038.1A CN115975491B (en) | 2023-01-18 | 2023-01-18 | High-barrier coating for soft-coated aluminum-plastic film of lithium battery and preparation method of high-barrier coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310057038.1A CN115975491B (en) | 2023-01-18 | 2023-01-18 | High-barrier coating for soft-coated aluminum-plastic film of lithium battery and preparation method of high-barrier coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115975491A true CN115975491A (en) | 2023-04-18 |
| CN115975491B CN115975491B (en) | 2023-09-26 |
Family
ID=85974161
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310057038.1A Active CN115975491B (en) | 2023-01-18 | 2023-01-18 | High-barrier coating for soft-coated aluminum-plastic film of lithium battery and preparation method of high-barrier coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975491B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140099537A1 (en) * | 2011-05-23 | 2014-04-10 | Nissan Motor Co., Ltd. | Conductive film, current collector using same, battery and bipolar battery |
| CN110305540A (en) * | 2019-07-04 | 2019-10-08 | 中国乐凯集团有限公司 | A kind of aqueous high-obstructing coating liquid and preparation method thereof |
| CN112521844A (en) * | 2020-12-14 | 2021-03-19 | 宁波富纳新材料科技有限公司 | Quaternary composite thermosetting antifogging coating, protective film comprising quaternary composite thermosetting antifogging coating and preparation method of quaternary composite thermosetting antifogging coating |
| CN113782880A (en) * | 2020-06-05 | 2021-12-10 | 上海紫江新材料科技股份有限公司 | Corrosion-resistant lithium battery aluminum plastic film and preparation method thereof |
| US20220112346A1 (en) * | 2019-01-25 | 2022-04-14 | Michelman, Inc. | Ethylene vinyl alcohol copolymer/ethylene acrylic acid copolymer blend barrier coatings |
-
2023
- 2023-01-18 CN CN202310057038.1A patent/CN115975491B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140099537A1 (en) * | 2011-05-23 | 2014-04-10 | Nissan Motor Co., Ltd. | Conductive film, current collector using same, battery and bipolar battery |
| US20220112346A1 (en) * | 2019-01-25 | 2022-04-14 | Michelman, Inc. | Ethylene vinyl alcohol copolymer/ethylene acrylic acid copolymer blend barrier coatings |
| CN110305540A (en) * | 2019-07-04 | 2019-10-08 | 中国乐凯集团有限公司 | A kind of aqueous high-obstructing coating liquid and preparation method thereof |
| CN113782880A (en) * | 2020-06-05 | 2021-12-10 | 上海紫江新材料科技股份有限公司 | Corrosion-resistant lithium battery aluminum plastic film and preparation method thereof |
| CN112521844A (en) * | 2020-12-14 | 2021-03-19 | 宁波富纳新材料科技有限公司 | Quaternary composite thermosetting antifogging coating, protective film comprising quaternary composite thermosetting antifogging coating and preparation method of quaternary composite thermosetting antifogging coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115975491B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11879069B2 (en) | Graphene orthosilicate/silane composite gel material, and preparation method and use thereof | |
| EP2583834A1 (en) | Modified polyvinyl alcohol coated film used for printing and preparation method thereof | |
| CN105130205A (en) | Preparation method of film-plating liquid for antireflection film of high anti-weathering type photovoltaic glass | |
| CN105385406A (en) | Room temperature vulcanized dual-component polythioether sealant, preparation method and application method thereof | |
| CN110041817A (en) | Smooth coating fluid, aluminum plastic film and lithium ion battery | |
| CN107031163A (en) | A kind of wet sensitive colour changing corrugated case | |
| GB2595009A (en) | Graphene oxide-TEOS/silane composite gel material, preparation method therefor and use thereof | |
| CN115975491A (en) | High-barrier coating for lithium battery soft package aluminum plastic film and preparation method thereof | |
| CN106189921A (en) | A kind of POE packaging adhesive film composite tackifier with high bond strength and application thereof | |
| CN113650386A (en) | Oxygen-resistant film, preparation method thereof and asphalt waterproof coiled material comprising oxygen-resistant film | |
| CN111876063A (en) | Water-based adhesive and application thereof | |
| CN111944378A (en) | Polymer-based waterproof film, preparation method and application thereof | |
| KR20170126516A (en) | A process for optimising a gas barrier coating | |
| CN101302314A (en) | Isolating film and preparation thereof | |
| CN101302315A (en) | Isolating film and preparation thereof colloidal compound film and preparation thereof | |
| CN109233687A (en) | A kind of glued board adhesive | |
| CN107474780A (en) | A kind of plastic-aluminum combined bonding agent and plastic-aluminum combined method | |
| CN114350220A (en) | Super-waterproof colorful coating and preparation method thereof | |
| CN112521890A (en) | Aging-resistant environment-friendly adhesive for plywood and preparation method thereof | |
| CN104263058A (en) | Composition with heat insulation synergistic effect, heat insulation coating and preparation method of coating | |
| CN106634506B (en) | A kind of coating and its preparation method and application for protecting aerostatics envelop materials | |
| CN106590157B (en) | Handkerchief paper stretching environment-friendly printing ink and preparation method thereof | |
| CN109867845A (en) | A kind of plastics and preparation method thereof of anti-aging antistatic | |
| CN112538188A (en) | Intelligent humidity control barrier composite film and preparation method and application thereof | |
| CN108727963A (en) | A kind of wooden door water-repellent paint and preparation method 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 |