CN102120903A - Water-resistant modified polyvinyl alcohol coating liquid and preparation method thereof, and coating formed by coating liquid - Google Patents
Water-resistant modified polyvinyl alcohol coating liquid and preparation method thereof, and coating formed by coating liquid Download PDFInfo
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- CN102120903A CN102120903A CN 201110004629 CN201110004629A CN102120903A CN 102120903 A CN102120903 A CN 102120903A CN 201110004629 CN201110004629 CN 201110004629 CN 201110004629 A CN201110004629 A CN 201110004629A CN 102120903 A CN102120903 A CN 102120903A
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Abstract
The invention discloses water-resistant modified polyvinyl alcohol coating liquid and a preparation method thereof, and a coating formed by the coating liquid. The water-resistant modified polyvinyl alcohol coating liquid comprises the following components in part by mass: 5 to 20 parts of polyvinyl alcohol, 45 to 95 parts of water, 0.1 to 3 parts of nano inorganic substance, 0.8 to 6 parts of modifier, 0.2 to 3 parts of catalyst, 0.05 to 1 part of coupling agent, 1 to 10 parts of regulating agent, 0.05 to 5 parts of adhesion accelerator, 0 to 0.5 part of leveling agent and 0 to 2 parts of wetting agent. The preparation method comprises the following steps of: adding the polyvinyl alcohol into water; heating and stirring; preserving the heat when the temperature is between 90 and 95 DEG C to ensure that the polyvinyl alcohol is dissolved completely; cooling to normal temperature; adding the nano inorganic substance, the catalyst and the modifier and completely stirring; and adding the coupling agent, the regulating agent, the adhesion accelerator, the leveling agent and the wetting agent during use and stirring uniformly. The coating formed by the water-resistant modified polyvinyl alcohol coating liquid prepared by the method has excellent properties.
Description
Technical field
The present invention relates to the coating of a kind of water-fast modified PVA paint, its preparation method and formation thereof.
Background technology
In recent years, along with the continuous development of foodstuffs industry, to the also lifting gradually of performance requriements of wrapping material, as barrier to oxygen, carbonic acid gas, moisture etc.
Kai Fa high-barrier flexible packing material is polyvinylidene dichloride (PVDC) the earliest, is mainly used in the packing of products such as high-end food, medicine, cigarette.But the PVDC molecule contains a large amount of chlorine atoms, produces a large amount of dioxin gas contaminate environment during burning, and PVDC is difficult to natural degradation simultaneously.
Ethylene-vinyl alcohol copolymer (EVOH) is one of substitute of PVDC, EVOH is the modification kind of PVA, but the EVOH price is higher, belong to polar polymer, can't be directly compound with the versatility material, necessary usefulness adhesive resin and expensive multi-layer co-extruded equipment in the production process, cost is very high, and this material barrier property is subjected to the influence of humidity very big, must adopt the five-layer co-squeezing device fabrication, improves its barrier.
Polyvinyl alcohol (PVA) is a kind of polyhydroxylated polymer, and its molecular formula is (C
2H
4O)
n, water-absorbent is strong, can be water-soluble, because the effect of its intermolecular hydrogen bonding, and the density height, the gas barrier property excellence, but its fusing point is up to 220～240 ℃, and decomposition temperature is low, and 160 ℃ of beginning etherificates, 200 ℃ begin to decompose, and make it be difficult to thermoplasticity processing.At present, commercially available PVA film adopts casting method production mostly, but the applying of a series of drawbacks limit PVA films that casting method is produced.
When adopting traditional watersoluble modified PVA paint, though coating performance can reach general packing instructions, but because the polyvinyl alcohol intramolecularly contains the hydroxyl of a large amount of strongly hydrophilics, can form hydrogen bond with water under the hygrometric state, and associate with water with the form of hydrogen bond, the variation of the PVA product performance generation matter after associating with water, it is fine and close crosslinked that it can't be realized in water-based system, and not high with the adhesive power of base material.
In the prior art, because in the material of the modified PVA that is adopted, the addition of functional agent is excessive, the stability of coating fluid is reduced, phenomenons such as coating can produce contraction in membrane surface, the coating uniformity coefficient is not enough and coating comes off easily, and the shelf lives of coating fluid is shorter.
Chinese patent application 200410034455.1 discloses a kind of modified PVA paint and manufacture craft thereof, by adding auxiliary agents such as nano silicon oxide, coupling agent, tackifier, softening agent, make the steam penetrating capacity and the oxygen transit dose of polyvinyl alcohol coating layer that tangible improvement arranged, but the water tolerance of coating, levelling property, sticking power and coating homogeneity are relatively poor.
Therefore, this area still needs to provide a kind of steady quality, keeps the high-obstructing coating liquid of superior in gas barrier property simultaneously.
Summary of the invention:
The purpose of this invention is to provide that a kind of water-resistant coating is good, strong adhesion, good leveling property, coating good uniformity, adaptability is strong and can keep the coating of high-obstructing coating liquid, its preparation method and the formation thereof of superior in gas barrier property.
For solving the problems of the technologies described above, technical scheme of the present invention is:
Described water-fast modified PVA paint, comprise following component: 5～20 parts of polyvinyl alcohol, 45～95 parts in water, 0.1～3 part of nano-inorganic substance, 0.8～6 part of properties-correcting agent, 0.2～3 part of catalyzer, 0.05～1 part of coupling agent, 1～10 part of conditioning agent, 0.05～5 part of adhesion promoter, 0～2 part of 0～0.5 part of flow agent and wetting agent, described umber is mass fraction.
The alcoholysis degree of described polyvinyl alcohol is 80～99.9%, and the polymerization degree is 1700～1900.
Described nano-inorganic substance is one or more the mixture of any proportioning in nano silicon oxide, nano-titanium oxide, nano aluminium oxide and the nanoclay.
Described properties-correcting agent is one or more the mixture of any proportioning in modified melamine-formaldehyde resin, urea-formaldehyde resin and the sodium tetraborate; Be preferably modified melamine-formaldehyde resin, urea-formaldehyde resin or sodium tetraborate.
It is 310～520 methylated melamine formaldehyde resins that described modified melamine-formaldehyde resin is preferably molecular weight; It is 132～200 urea-formaldehyde resin that described urea-formaldehyde resin is preferably molecular weight.
Described catalyzer is that concentration is that 35～37% hydrochloric acid or concentration are 84～86% phosphoric acid.
Described coupling agent is one or more the mixture of any proportioning in methoxy silane, titanate and the vinyl silanes; Be preferably methoxy silane, titanate or vinyl silanes; More preferably γ-glycidyl ether oxygen propyl trimethoxy silicane, alkanolamine titanic acid ester or vinyltriethoxysilane.
Described conditioning agent is methyl alcohol, ethanol or both any proportioning mixtures.
Described adhesion promoter is the alkoxyl group non-ionic compound; Be preferably Silok628 or Silok629.
Described flow agent is the mixture of polyacrylacid ester compounds, organosilicon compound or both any proportionings; Be preferably polyacrylacid ester compounds or organosilicon compound; More preferably RM-2020 or Silok 8333.The mass fraction of described flow agent is preferably 0.01～0.5 part.
Described wetting agent is the mixture of organic silicon modified by polyether class, nonionic class or both any proportionings; Be preferably organic silicon modified by polyether class or nonionic class; More preferably Silok8000 or PE-100.The mass fraction of described wetting agent is preferably 0.01～2 part.
The preparation method of described water-fast modified PVA paint is: polyvinyl alcohol is added in the entry heat up, stir, treat to be incubated when temperature reaches 90～95 ℃, allow polyvinyl alcohol fully dissolve; After treating that temperature is reduced to normal temperature, add nano-inorganic substance, catalyzer and properties-correcting agent, fully stir; Add coupling agent, conditioning agent, adhesion promoter, flow agent and wetting agent during use, stir, added early the performance that can influence coating fluid.
The coating fluid of gained of the present invention can be a basement membrane with polyethylene (PE), polypropylene (PP), polyamide (PA) or polyethylene terephthalate (PET).
Compared with prior art, the adding of the adhesion promoter water tolerance, sticking power, levelling property, coating homogeneity, gas barrier property and the adaptability that make water-fast modified PVA paint be applied to the coating that forms on the basement membrane all has the improvement of certain degree; The adding of flow agent makes above-mentioned each performance that further improvement arranged; Being added in of wetting agent guaranteed that good water tolerance has been arranged, under the sticking power, levelling property, the inhomogeneity condition of coating, gas barrier property and adaptability have had further to be improved.
Embodiment:
The present invention will be described in more detail below in conjunction with example, and the evaluation method of using in the implementation example is as follows:
(1) oxygen transit dose: measure according to standard GB/T1038-2000.
(2) steam penetrating capacity: measure according to standard GB/T1037-1988.
(3) water tolerance:
Three of different sites interceptings are of a size of 125mm * 25mm film as sample on the high-isolation film after the coating, then the sample coating layer are affixed on the sheet glass inwardly, and use the scotch tape edge sealing.2/3 of three sample board length are soaked in 48h in the water.After soak finishing, if coating layer does not have foamings, wrinkling, phenomenon such as come off illustrates that water tolerance is fine, otherwise illustrates that then water tolerance is relatively poor.
(4) levelling property:
Recover or reach even smooth-flat-surface required time to represent to film, within the 10min levelling film for levelling property better, otherwise relatively poor.
(5) coating uniformity:
Adopt the following tincture of iodine to test the coating homogeneity of estimating coating: after getting the cotton rod dipping tincture of iodine, it evenly to be applied in the surface that scribbles coating.If coating presents uniform yellow or Vandyke brown, the coating coating then is described evenly; Otherwise if occur not color change interval in the coating, then coating is inhomogeneous.
(6) adhesivity:
Be affixed on painting layer surface with scotch tape, peel off with 180 ° then, very poor if coating layer is adhered to explanation sticking power; If adhering to, coating layer do not get off to illustrate that sticking power is fine.
Comparative example 1
According to the 4 preparation modified PVA paints of the embodiment in the Chinese patent application 200410034455.1.
Comparative example 2
This comparative example is that (polymerization degree is 1700 by 10 parts polyvinyl alcohol, down together), 78 parts water, 1 part nano silicon, 5 parts of molecular weight are 350～500 methylated melamine formaldehyde resin, 0.2 the concentration of part is 36～38% hydrochloric acid, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.8 part (available from energy Dehua, Nanjing worker company limited), 5 parts of methyl alcohol are formed.90～95 ℃ of fully dissolvings, it is even to treat that temperature is reduced to the nano silicon, methylated melamine formaldehyde resin, the mixed in hydrochloric acid that add said ratio behind the normal temperature with above-mentioned polyvinyl alcohol water; Adding coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane, methyl alcohol fully mix before using, and promptly get water-fast modified PVA paint.
Embodiment 1
Present embodiment is the polyvinyl alcohol by 10 parts, 78 parts water, 1 part nano silicon, 5 parts of molecular weight are 350～500 methylated melamine formaldehyde resin, 0.2 the concentration of part is 36～38% hydrochloric acid, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.8 part, 1.5 parts of adhesion promoter Silok628 and 5 parts of methyl alcohol are formed.90～95 ℃ of fully dissolvings, it is even to treat that temperature is reduced to the nano silicon, methylated melamine formaldehyde resin, the mixed in hydrochloric acid that add said ratio behind the normal temperature with above-mentioned polyvinyl alcohol water; Adding coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane, adhesion promoter Silok628, methyl alcohol fully mix before using, and promptly get water-fast modified PVA paint.
Embodiment 2
Present embodiment is the polyvinyl alcohol by 10 parts, 78 parts water, 1 part nano silicon, 5 parts of molecular weight are 350～500 methylated melamine formaldehyde resin, 0.2 the concentration of part is 36～38% hydrochloric acid, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.8 part, 1.5 parts of adhesion promoter Silok628,0.5 part of flow agent RM-2020 and 5 parts of methyl alcohol are formed.90～95 ℃ of fully dissolvings, it is even to treat that temperature is reduced to the nano silicon, methylated melamine formaldehyde resin, the mixed in hydrochloric acid that add said ratio behind the normal temperature with above-mentioned polyvinyl alcohol water; Adding coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane, adhesion promoter Silok628, flow agent RM-2020, methyl alcohol fully mix before using, and promptly get water-fast modified PVA paint.
Embodiment 3
Present embodiment is the polyvinyl alcohol by 6 parts, 49 parts water, 0.5 the nano aluminium oxide of part, 1 part molecular weight is 350～500 methylated melamine formaldehyde resin, 0.2 the concentration of part is 85% phosphoric acid, the mixture of coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.1 part, 0.1 part of adhesion promoter Silok628,0.03 part of flow agent Silok8333 and 2 parts of methanol is formed.Above-mentioned polyvinyl alcohol water 90～95 ℃ of fully dissolvings, is treated that temperature reduces to the nano silicon, methylated melamine formaldehyde resin, the phosphoric acid that add said ratio behind the normal temperature and mix; Adding coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane, adhesion promoter Silok628, flow agent RM-2020, methyl alcohol fully mix before using, and promptly get water-fast modified PVA paint.
Embodiment 4
Present embodiment is the polyvinyl alcohol by 11 parts, 71 parts water, 1.5 the nanoclay of part and the mixture of nano silicon oxide, 2.3 the molecular weight of part is 140～200 urea-formaldehyde resin, 0.9 the concentration of part is 85% phosphoric acid acid, coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane of 0.26 part, 1.9 parts of adhesion promoter Silok629,0.15 part of flow agent RM-2020 and 4 parts of ethanol are formed.Above-mentioned polyvinyl alcohol water 90～95 ℃ of fully dissolvings, is treated that temperature reduces to the nano silicon, urea-formaldehyde resin, the phosphoric acid that add said ratio behind the normal temperature and mix; Adding coupling agent γ-glycidyl ether oxygen propyl trimethoxy silicane, adhesion promoter Silok629, flow agent RM-2020, ethanol fully mix before using, and promptly get water-fast modified PVA paint.
Embodiment 5
Present embodiment is the polyvinyl alcohol by 15 parts, 88 parts water, 2 parts the nano silicon and the mixture of nano-titanium oxide, 3.5 the sodium tetraborate of part, 1.5 the concentration of part is 36～38% hydrochloric acid, the mixture of 0.54 part coupling agent vinyltriethoxysilane (available from morning twilight chemical industry company limited), 2.5 parts of adhesion promoter Silok628,0.3 part of flow agent RM-2020,0.03 part of wetting agent Silok8000 and 7 parts of methanol is formed.90～95 ℃ of fully dissolvings, it is even to treat that temperature is reduced to the nano silicon, sodium tetraborate, the mixed in hydrochloric acid that add said ratio behind the normal temperature with above-mentioned polyvinyl alcohol water; Add coupling agent vinyltriethoxysilane, adhesion promoter Silok628, flow agent RM-2020, wetting agent Silok8000, methyl alcohol and alcoholic acid mixture before using and fully mix, promptly get water-fast modified PVA paint.
Embodiment 6
Present embodiment is the polyvinyl alcohol by 19 parts, 95 parts water, 2.8 the nano titanium oxide of part, 5 parts molecular weight is 350～500 methylated melamine formaldehyde resin, 2.5 the concentration of part is 36～38% hydrochloric acid, 0.85 part coupling agent alkanolamine titanic acid ester (blocking chemical industry company limited available from the Hangzhou Jesse), 4.8 parts of adhesion promoter Silok629,0.48 part of flow agent Silok8333,1.8 parts of wetting agent PE-100 and 9 parts of methyl alcohol are formed.90～95 ℃ of fully dissolvings, it is even to treat that temperature is reduced to the nano titanium oxide, methylated melamine formaldehyde resin, the mixed in hydrochloric acid that add said ratio behind the normal temperature with above-mentioned polyvinyl alcohol water; Adding coupling agent alkanolamine titanic acid ester, adhesion promoter Silok629, flow agent RM-2020, wetting agent PE-100, methyl alcohol fully mix before using, and promptly get water-fast modified PVA paint
Be that coating 2 μ m are thick on the polyethylene terephtalate basement membrane of 20 μ m at thickness with the PVA paint of the foregoing description preparation, every performance test results sees Table 1 behind the drying and forming-film.
As shown in Table 1, compare the prepared PVA paint of the present invention with comparative example lower gas permeation amount, excellent water tolerance, levelling property, stronger sticking power and be coated with homogeneity are preferably preferably arranged.
The performance evaluation result of table 1 coating
Annotate: ★ ★ ★ representative is fine; ★ ★ representative better; The ★ representative is very poor;
The prepared water-fast modified PVA paint of the present invention is coated with 4 μ m on CPP, PA, PE basement membrane thick, and the ventilation property detected result sees Table 2 behind the drying and forming-film.
As shown in Table 2, the prepared coating fluid of the present invention all has lower oxygen transit dose and steam penetrating capacity on dissimilar basement membranes, and therefore gained PVA paint of the present invention as can be known has stronger adaptability.
Oxygen transit dose (the cm of table 2 coating
3/ m
224h01Mpa) and steam penetrating capacity (g/m
224h)
Claims (18)
1. water-fast modified PVA paint, it is characterized in that, comprise following component: 5～20 parts of polyvinyl alcohol, 45～95 parts in water, 0.1～3 part of nano-inorganic substance, 0.8～6 part of properties-correcting agent, 0.2～3 part of catalyzer, 0.05～1 part of coupling agent, 1～10 part of conditioning agent, 0.05～5 part of adhesion promoter, 0～2 part of 0～0.5 part of flow agent and wetting agent, described umber is mass fraction.
2. water-fast modified PVA paint according to claim 1 is characterized in that, the alcoholysis degree of described polyvinyl alcohol is 80～99.9%, and the polymerization degree is 1700～1900.
3. water-fast modified PVA paint according to claim 1 is characterized in that, described nano-inorganic substance is one or more the mixture of any proportioning in nano silicon oxide, nano-titanium oxide, nano aluminium oxide and the nanoclay.
4. water-fast modified PVA paint according to claim 1 is characterized in that, described properties-correcting agent is one or more the mixture of any proportioning in modified melamine-formaldehyde resin, urea-formaldehyde resin and the sodium tetraborate.
5. water-fast modified PVA paint according to claim 4 is characterized in that, described terpolycyantoamino-formaldehyde resin is that molecular weight is 310～520 methylated melamine formaldehyde resins; Described urea-formaldehyde resin is that molecular weight is 132～200 urea-formaldehyde resin.
6. water-fast modified PVA paint according to claim 1 is characterized in that, described catalyzer is that concentration is that 35～37% hydrochloric acid or concentration are 84～86% phosphoric acid.
7. water-fast modified PVA paint according to claim 1 is characterized in that, described coupling agent is the mixture of one or more any proportioning in methoxy silane coupling agent, titanate coupling agent and the vinyl silicane coupling agent.
8. water-fast modified PVA paint according to claim 7 is characterized in that, described coupling agent is γ-glycidyl ether oxygen propyl trimethoxy silicane, alkanolamine titanic acid ester or vinyltriethoxysilane.
9. water-fast modified PVA paint according to claim 1 is characterized in that, described conditioning agent is methyl alcohol, ethanol or both any proportioning mixtures.
10. water-fast modified PVA paint according to claim 1 is characterized in that, described adhesion promoter is the alkoxyl group non-ionic compound.
11. water-fast modified PVA paint according to claim 10 is characterized in that, described adhesion promoter is Silok 628 or Silok629.
12. water-fast modified PVA paint according to claim 1 is characterized in that, described flow agent is the mixture of polyurethanes compound, organosilicon compound or both any proportionings; The mass fraction of described flow agent is 0.01～0.5 part.
13. water-fast modified PVA paint according to claim 12 is characterized in that, described flow agent is ROHM AND HAAS RM-2020 or Silok 8333.
14. water-fast modified PVA paint according to claim 1 is characterized in that, described wetting agent is the mixture of organic silicon modified by polyether class, nonionic class or both any proportionings; The mass fraction of described wetting agent is 0.01～2 part.
15. water-fast modified PVA paint according to claim 14 is characterized in that, described wetting agent is Silok8000 or PE-100.
16. the preparation method of any described water-fast modified PVA paint of claim 1 to 15 is characterized in that, polyvinyl alcohol is added in the entry heat up, and stirs, and treats to be incubated when temperature reaches 90～95 ℃, allows polyvinyl alcohol fully dissolve; Be cooled to normal temperature, add nano-inorganic substance, catalyzer and properties-correcting agent, fully stir; Add coupling agent, conditioning agent, adhesion promoter, flow agent and wetting agent during use, stir.
17. any coating that described water-fast modified PVA paint forms on basement membrane among the claim 1-15.
18. coating according to claim 17 is characterized in that described basement membrane is polyethylene, polypropylene, polymeric amide or polyethylene terephthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110004629 CN102120903A (en) | 2011-01-11 | 2011-01-11 | Water-resistant modified polyvinyl alcohol coating liquid and preparation method thereof, and coating formed by coating liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110004629 CN102120903A (en) | 2011-01-11 | 2011-01-11 | Water-resistant modified polyvinyl alcohol coating liquid and preparation method thereof, and coating formed by coating liquid |
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| CN 201110004629 Pending CN102120903A (en) | 2011-01-11 | 2011-01-11 | Water-resistant modified polyvinyl alcohol coating liquid and preparation method thereof, and coating formed by coating liquid |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122171A (en) * | 2013-02-05 | 2013-05-29 | 保定宝轶塑料有限公司 | Method for preparing nano polyvinyl alcohol coating liquid by adopting sol-gel method and coating formed by nano polyvinyl alcohol coating liquid |
| CN104946037A (en) * | 2015-07-16 | 2015-09-30 | 天津科技大学 | Coating liquid for preparing uvioresistant polyester film and preparation method thereof |
| CN105924867A (en) * | 2016-05-20 | 2016-09-07 | 苏州倍力特物流设备有限公司 | High-barrier packaging composite film and preparing method thereof |
| CN105986489A (en) * | 2016-01-26 | 2016-10-05 | 芜湖环瑞汽车内饰件有限公司 | Soft wear-resistant superfine polyurethane imitation-leather automobile seat fabric and production method thereof |
| CN107556832A (en) * | 2016-07-01 | 2018-01-09 | 穗晔实业股份有限公司 | The forming method of coating with the easy clean characteristic of drying and the coating using the coating |
| CN108867164A (en) * | 2018-06-20 | 2018-11-23 | 广州市宝绅纸塑有限公司 | A kind of improvement macromolecule coating fluid and the preparation method and application thereof |
| CN111171720A (en) * | 2020-03-24 | 2020-05-19 | 常州天瑞新材料科技有限公司 | Inorganic nano-coating and preparation method thereof |
| CN112500748A (en) * | 2020-12-08 | 2021-03-16 | 宜宾五粮液股份有限公司 | Material used as inner wall coating of wine brewing fermentation container and preparation method of coating |
| CN113817282A (en) * | 2021-09-30 | 2021-12-21 | 青岛科技大学 | Oxygen-barrier coating for packaging material and preparation method thereof |
| CN114806051A (en) * | 2022-05-26 | 2022-07-29 | 佛山清粤新材料科技有限公司 | Preparation method of modified polyvinyl alcohol/thermoplastic resin composite material |
| CN115304968A (en) * | 2022-08-15 | 2022-11-08 | 广东新纪源复合材料股份有限公司 | Formula and preparation method of nano modified PVA (polyvinyl alcohol) |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103122171A (en) * | 2013-02-05 | 2013-05-29 | 保定宝轶塑料有限公司 | Method for preparing nano polyvinyl alcohol coating liquid by adopting sol-gel method and coating formed by nano polyvinyl alcohol coating liquid |
| CN104946037A (en) * | 2015-07-16 | 2015-09-30 | 天津科技大学 | Coating liquid for preparing uvioresistant polyester film and preparation method thereof |
| CN105986489A (en) * | 2016-01-26 | 2016-10-05 | 芜湖环瑞汽车内饰件有限公司 | Soft wear-resistant superfine polyurethane imitation-leather automobile seat fabric and production method thereof |
| CN105924867A (en) * | 2016-05-20 | 2016-09-07 | 苏州倍力特物流设备有限公司 | High-barrier packaging composite film and preparing method thereof |
| CN107556832B (en) * | 2016-07-01 | 2019-11-29 | 穗晔实业股份有限公司 | The forming method of coating with the easy clean characteristic of water repellent and the coating using the coating |
| CN107556832A (en) * | 2016-07-01 | 2018-01-09 | 穗晔实业股份有限公司 | The forming method of coating with the easy clean characteristic of drying and the coating using the coating |
| CN108867164A (en) * | 2018-06-20 | 2018-11-23 | 广州市宝绅纸塑有限公司 | A kind of improvement macromolecule coating fluid and the preparation method and application thereof |
| CN111171720A (en) * | 2020-03-24 | 2020-05-19 | 常州天瑞新材料科技有限公司 | Inorganic nano-coating and preparation method thereof |
| CN112500748A (en) * | 2020-12-08 | 2021-03-16 | 宜宾五粮液股份有限公司 | Material used as inner wall coating of wine brewing fermentation container and preparation method of coating |
| CN112500748B (en) * | 2020-12-08 | 2022-03-18 | 宜宾五粮液股份有限公司 | Material used as inner wall coating of wine brewing fermentation container and preparation method of coating |
| CN113817282A (en) * | 2021-09-30 | 2021-12-21 | 青岛科技大学 | Oxygen-barrier coating for packaging material and preparation method thereof |
| CN114806051A (en) * | 2022-05-26 | 2022-07-29 | 佛山清粤新材料科技有限公司 | Preparation method of modified polyvinyl alcohol/thermoplastic resin composite material |
| CN114806051B (en) * | 2022-05-26 | 2023-06-06 | 佛山清粤新材料科技有限公司 | Preparation method of modified polyvinyl alcohol/thermoplastic resin composite material |
| CN115304968A (en) * | 2022-08-15 | 2022-11-08 | 广东新纪源复合材料股份有限公司 | Formula and preparation method of nano modified PVA (polyvinyl alcohol) |
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Application publication date: 20110713 |