CN107556832A - The forming method of coating with the easy clean characteristic of drying and the coating using the coating - Google Patents
The forming method of coating with the easy clean characteristic of drying and the coating using the coating Download PDFInfo
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- CN107556832A CN107556832A CN201610514048.3A CN201610514048A CN107556832A CN 107556832 A CN107556832 A CN 107556832A CN 201610514048 A CN201610514048 A CN 201610514048A CN 107556832 A CN107556832 A CN 107556832A
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Abstract
The present invention provides the forming method of a kind of coating with the easy clean characteristic of drying and the coating using the coating.The coating with the easy clean characteristic of drying includes：The polyvinyl alcohol of all-hydrolytic type and hydrogeneous silicones, wherein hydrogeneous silicones is bonded with polyvinyl alcohol reaction so that the polyvinyl alcohol is transformed into the easy clean characteristic of drying by water-wet behavior.Using the coating of the coating with the easy clean characteristic of drying forming method the step of it is as follows.Base material is provided.In coating gap filler and drying on base material.In the coating that the present invention is coated with gap filler.Finally, high temperature drying with formed using the present invention drying easy-cleaning paint coating.The present invention is with the easy clean characteristic of preferable durability and drying.
Description
Technical field
A kind of forming method of coating the present invention relates to coating and using the coating, more particularly to it is a kind of have dial
The forming method of the coating of the easy clean characteristic of water and the coating of the use coating.
Background technology
In the technology of existing water-repellent oil-repellent, it is surface-treated mostly using fluororesin or silicones, but this kind of fluororesin
Or silicones is because molecular weight is small, film forming characteristics is bad, therefore when above-mentioned fluororesin or silicones are coated on into porous substrate table
During face, itself is easily infiltrated into hole, therefore substrate surface can not be completely covered to form continuous coated face.In addition, by
It is poor in the chemical reactivity of small molecule fluororesin or silicones, it is not easy to produce good key with the substrate surface being applied
Knot, therefore durability is poor, after wiping for several times, the easy clean characteristic of its drying can be broken because of fluororesin or silicone coatings
Badly fade away.Therefore, in the vestige caused by removing oil pen, the ink of oil pen can be penetrated into by destroyed coating
In base material, and cause non-removable vestige.In addition, it is coated on porous substrate surface using above-mentioned fluororesin or silicones
When, it can change the sense of touch on surface, and be unfavorable for merchandise sales.Thus, there is provided a kind of with the easy clean characteristic of drying and resistance to
The good coating of long property, and this coating is machined in porous substrate surface to form the side of the easy clean coating of drying of tool durability
Method will inscribe as a following important subject.
The content of the invention
The present invention provides the forming method of a kind of coating with the easy clean characteristic of drying and the coating using the coating,
It has preferable durability and the easy clean characteristic of drying.
The present invention provides a kind of coating with the easy clean characteristic of drying, including：All-hydrolytic type (full-hydrolysis)
Polyvinyl alcohol (polyvinyl alcohol, PVA) and hydrogeneous silicones (Hydrogen silicone).The all-hydrolytic type
Polyvinyl alcohol the degree of polymerization between 300~2600.The weight ratio of the all-hydrolytic type polyvinyl alcohol and hydrogeneous silicones
Example is 0.5~4 times.The hydrogeneous silicones is bonded with all-hydrolytic type polyvinyl alcohol reaction so that the all-hydrolytic type gathers
Vinyl alcohol is transformed into the easy clean characteristic of drying by water-wet behavior.
In one embodiment of this invention, the coating with the easy clean characteristic of drying, in addition to：Crosslinking agent and levelling
Auxiliary agent.The content of crosslinking agent is 0.1~30 percentage by weight of the coating.The content of leveling auxiliary agent is the 0.1 of the coating
~30 percentage by weights.
In one embodiment of this invention, it is water-soluble to include glyoxal water solution, glutaraldehyde water solution, boric acid for the crosslinking agent
Liquid, borax solution, water-based isocyanate or its combination.
In one embodiment of this invention, the degree of polymerization of the all-hydrolytic type polyvinyl alcohol is between 1400~2600.
The present invention provides a kind of forming method of the coating with the easy clean characteristic of drying, and its step includes：
(1) base material is provided.
(2) optionally the first drying process is then carried out in being coated with gap filler on the base material.
(3) in coating of the coating with the easy clean characteristic of drying on the gap filler, the second drying process is then carried out, with
Form the coating with the easy clean characteristic of drying.The coating with the easy clean characteristic of drying includes：The poly- second of all-hydrolytic type
Enol and hydrogeneous silicones.The degree of polymerization of the polyvinyl alcohol of the all-hydrolytic type is between 300~2600.The all-hydrolytic
The part by weight of type polyvinyl alcohol and hydrogeneous silicones is 0.5~4 times.The hydrogeneous silicones and the all-hydrolytic type polyethylene
Alcohol reaction bond so that the all-hydrolytic type polyvinyl alcohol is transformed into the easy clean characteristic of drying by water-wet behavior.
In one embodiment of this invention, the base material includes wallpaper, fabric, glass, wall or its combination.
In one embodiment of this invention, the gap filler includes water soluble polymer, water-based emulsion, described has drying
The coating of easy clean characteristic or its combination.
In one embodiment of this invention, the water soluble polymer includes polyvinyl alcohol (PVA), polyvinylpyrrolidone
(PVP) or it is combined.The water-based emulsion includes polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), propylene
Acid resin (Acrylic resin) emulsion, polyurethane (PU) emulsion or its combination.
In one embodiment of this invention, the step of being coated with the gap filler on the substrate includes one layer or more of coating
The layer gap filler.
In one embodiment of this invention, the temperature of second drying process is between 130 DEG C to 170 DEG C, and institute
The time of the second drying process is stated between 3 points to 10/.
Based on a kind of above-mentioned, coating of present invention offer, it utilizes the polyvinyl alcohol and Silicon Containing Hydrogen resin reaction of all-hydrolytic type
Bond so that the all-hydrolytic type polyvinyl alcohol is transformed into the easy clean characteristic of drying by water-wet behavior.Because the all-hydrolytic type gathers
There is chemical bonded refractory, therefore, the durability of the coating belonging to it is preferable, and also has drying between vinyl alcohol and hydrogeneous silicones
Easy clean characteristic.In addition, polyvinyl alcohol has the characteristic of grease resistance solvent in itself, and have preferably with most of substrate surfaces
Adhesive force, therefore extra durability and easy clean characteristic can be provided.In addition, the present invention also provides a kind of painting using the coating
The forming method of layer.The forming method is prior to being coated with gap filler on base material, and then in being coated with the coating on gap filler.
The hole in base material can be filled due to gap filler, its coating for subsequently to be coated with forms a continuous surface.Consequently, it is possible to this
Invention can avoid the hole that the ink of oil pen in the prior art is penetrated into base material, and the drying that can thereby lift the coating is easy
Clean ability.
For features described above of the invention and advantage can be become apparent, special embodiment below, and it is detailed to coordinate accompanying drawing to make
Carefully it is described as follows.
Brief description of the drawings
Fig. 1 is the diagrammatic cross-section of the coating of one embodiment of the invention.
Reference：
100：Base material；
102：Gap filler；
104：Coating.
Embodiment
One embodiment of the invention provides a kind of coating with the easy clean characteristic of drying, and it includes the polyethylene of all-hydrolytic type
Alcohol and hydrogeneous silicones.Because polyvinyl alcohol is rich in hydroxyl (i.e. OH functional groups), therefore it can be dehydrated with hydrogeneous silicones
Reaction, and be bonded to the main chain of hydrogeneous silicones.The polyvinyl alcohol of so-called all-hydrolytic type refers to dredge in polyvinyl alcohol acetate
Water-based acetoxy group is hydrolyzed into hydrophilic hydroxyl, so as to form polyvinyl alcohol, and the degree of polyvinyl alcohol acetate hydrolysis
More than or equal to 95% mol ratio.Because the hydroxyl in the polyvinyl alcohol of all-hydrolytic type is hydrophily, itself has grease resistance
The characteristic of solvent, and there is preferable adhesive force with most of substrate surfaces, therefore, oily ink (can be for example oil pen or
Other oil-dirts) do not penetrate into the coating being made up of the polyvinyl alcohol of all-hydrolytic type.Consequently, it is possible to its can be lifted it is described
The durability of coating and easy clean characteristic.Further, since the all-hydrolytic type polyvinyl alcohol is bonded with Silicon Containing Hydrogen resin reaction, it makes
Obtain the all-hydrolytic type polyvinyl alcohol and the easy clean characteristic of drying is transformed into by water-wet behavior.Therefore, it is small compared to of the prior art
Molecule fluororesin or silicones, the durability of the coating of the present embodiment is preferable, and also has the easy clean characteristic of drying.It is so-called durable
Property refers to that the coating will not reduce the easy clean characteristic of its drying because of wiping.About each included by the coating of the present embodiment
Being described as follows for item composition, wherein example and content cited by every composition etc. is only used as illustrative purposes, and is not used to limit
The fixed present invention.
The all-hydrolytic type polyvinyl alcohol of the present embodiment is 0.5~4 times with the part by weight of hydrogeneous silicones.The all-hydrolytic
Type polyvinyl alcohol refers to the polyvinyl alcohol that degree of hydrolysis is more than or equal to 95%, and its degree of polymerization can be for example 300~2600.Implement one
In example, the degree of polymerization of the all-hydrolytic type polyvinyl alcohol can be for example 1400~2600.
The overall solid content of the coating with the easy clean characteristic of drying of the present embodiment can be for example 1%~30%.It is real one
Apply in example, the overall solid content of drying easy-cleaning paint can be for example 10%~20%.The hydrogeneous silicones refers in silicones knot
There is the silicones of Si-H chemical bonds in structure.Position of the Si-H chemical bonds in hydrogeneous silicones can be end group, side base or two
Person is had concurrently, but the present invention is not limited.The end group refers to the least significant end that Si-H chemical bonds are located at hydrogeneous silicones macromolecular chain；
And the side base then refers to the side that Si-H chemical bonds are located at hydrogeneous silicones macromolecular chain.In one embodiment, the Silicon Containing Hydrogen
Resin can be for example methyl hydrogen silicones (methyl hydrogen silicone), ethyl hydrogen silicones (ethyl
Hydrogen silicone) or its combination.
In addition, in the drying easy-cleaning paint of the present embodiment, crosslinking agent and leveling auxiliary agent are optionally included with.The friendship
The content for joining agent is 0.1~30 percentage by weight of the coating.It is water-soluble that crosslinking agent can mix the all-hydrolytic type polyvinyl alcohol
Liquid, it after the drying can be polyvinyl alcohol crosslinked with the all-hydrolytic type, to improve the water resistance of the coating and intensity.Separately
Outside, when uncrosslinked, partial cross-linked dose also serves as antiseptic to use.In one embodiment, crosslinking agent can be for example second two
The aldehyde aqueous solution, glutaraldehyde water solution, boric acid aqueous solution, borax solution, water-based isocyanate or its combination, as long as cross-linking poly-
The crosslinking agent of vinyl alcohol all can be used.The crosslinking agent be can be used alone or be used in mixed way, and the present invention is not limited.The stream
The content of flat auxiliary agent is 0.1~30 percentage by weight of the coating.Leveling auxiliary agent it is available so that coatings on base material after
Can voluntarily equably levelling and cover substrate surface.In one embodiment, leveling auxiliary agent can be for example isopropanol, ethylene glycol, fourth
Glycol, dipropylene glycol monomethyl ether, modified silicone resin (be, for example, BYK-333), acrylic copolymer (being, for example, BYK-3440) or
The suitable material of others, as long as the leveling auxiliary agent of coating levelling can be helped all to can be used.The leveling auxiliary agent can be used alone or
It is used in mixed way, the present invention is not limited.
Fig. 1 is the diagrammatic cross-section of the manufacturing process of the coating of one embodiment of the invention.
The present invention provides a kind of forming method of coating 104 using the coating, and its step is as follows.First, there is provided base
Material 100.In one embodiment, base material 100 can be for example wallpaper, fabric, glass, wall or its combination.But the invention is not restricted to
This, as long as the coating can be coated with thereon, the species of base material 100 can select on demand.
Then, optionally in coating gap filler 102 on base material 100, and the first drying process is carried out.Gap filler 102
Effect in the hole in base material 100 is filled, to avoid post-coatings in coating because hole seepage can not be in base material 100
Surface forms successional coating 104.In one embodiment, it can be for example painting in the step of coating gap filler 102 on base material 100
One layer of cloth or multilayer gap filler 102.Gap filler 102 can be for example water soluble polymer, water-based emulsion, it is described have drying it is easy
The coating of clean characteristic or its combination.In one embodiment, water soluble polymer can be for example polyvinyl alcohol (PVA), polyethylene pyrrole
Pyrrolidone (PVP) or its combination.Water-based emulsion can for example polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA),
Acrylic resin (Acrylic resin) emulsion, polyurethane (PU) emulsion or its combination.The gap filler 102 is visual different
Substrate property decides whether to use, and it, which can be used alone, one kind or is applied in combination a variety of gap fillers 102, as long as in gap filler 102
Each composition compatibility license, the present invention is not limited.In other embodiments, gap filler 102 also can be for example
Water-insoluble molecule, non-aqueous emulsion or its combination.In one embodiment, the temperature of the first drying process is between 130 DEG C to 170
Between DEG C.The time of first drying process is between 3 points to 10/.
In addition, being also optionally added additive in gap filler 102 to adjust the surface tension of gap filler 102, enter
And cause gap filler 102 that there is smooth surface.In one embodiment, additive may include the material of silicones class.Silicones class
Material can be for example polyether-modified dimethyl-silicon resin, polyether-modified phenyl methyl silicones, Siloxane-Oxyalkylene Copolymers or
It is combined.But the invention is not restricted to this, as long as the surface tension of gap filler 102 can be adjusted, the species of additive can be on demand
To select.
Afterwards, in being coated with the coating on gap filler 102.In one embodiment, the coating is coated with gap filler 102
The step of can be for example coating one layer or layered coating.The coating includes polyvinyl alcohol and the Silicon Containing Hydrogen tree of all-hydrolytic type
Fat.The degree of polymerization of the polyvinyl alcohol of the all-hydrolytic type of the present embodiment is between 300~2600.In one embodiment, it is described complete
The degree of polymerization of hydrolysis-type polyvinyl alcohol is between 1400~2600.The weight of the all-hydrolytic type polyvinyl alcohol and hydrogeneous silicones
Amount ratio is 0.5~4 times.In one embodiment, the hydrogeneous silicones can be for example methyl hydrogen silicones, ethyl hydrogen silicones
Or its combination.
In addition, the coating of the present embodiment is optionally included with crosslinking agent and leveling auxiliary agent.The content of the crosslinking agent
For 0.1~30 percentage by weight of the coating.In one embodiment, crosslinking agent can be for example glyoxal water solution, glutaraldehyde
The aqueous solution, boric acid aqueous solution, borax solution, water-based isocyanate or its combination.The content of the leveling auxiliary agent is the painting
0.1~30 percentage by weight of material.In one embodiment, leveling auxiliary agent can be for example isopropanol, ethylene glycol, butanediol, dipropyl
Glycol monomethyl ether, modified silicone resin (being, for example, BYK-333), acrylic copolymer (being, for example, BYK-3440) or other suitable
Material.
Then, the second drying process is carried out so that the polyvinyl alcohol of the all-hydrolytic type and the Silicon Containing Hydrogen resin reaction
Bond, with coating 104 of the formation with the easy clean characteristic of drying on gap filler 102.In one embodiment, second drying process
Temperature is between 130 DEG C to 170 DEG C.The time of second drying process is between 3 points to 10/.In one embodiment,
The temperature of two drying process can be between 150 DEG C to 170 DEG C.
In order to illustrate the present invention coating and using the coating coating 104, be exemplified below experimental example and
Comparative example with illustrate the present invention coating preparation method and using the coating coating 104 forming method and its spy
Property, wherein each component content and making step etc. are by way of example only, without application to limit the present invention.
《Experimental example 1~4》
Material explanation
1、PVA1：The all-hydrolytic resin of 10% percentage by weight, the degree of polymerization 1700.
2、PVA2：The all-hydrolytic resin of 20% percentage by weight, the degree of polymerization 300.
3、PVA3：The partial hydrolysis resin of 10% percentage by weight, the degree of polymerization 500.
4th, acrylic emulsion：Selected in table 1 for Styrene And Chloroalkyl Acrylates copolymer resin emulsion, Gu composition be 47 ±
1%.
5th, water-based PU resins：Gu the water-based PU resins of composition 35 ± 1%.
6th, hydrogeneous silicones：Active ingredient is 50% resin emulsion.
7th, fluororesin：For C6 fluothane co-polymers, Gu composition is 20 ± 1%.
Embodiment
With bar cladding process by the constituent in experimental example 1~4 and comparative example 1~4 with #14 bars be coated on 50mm ×
In 150mm element glass, reuse hot air drier and dried under conditions of 150 DEG C × 5 minutes, as test print.
Evaluation method
A. water droplet angle：The water droplet angle of print film is measured using water droplet contact angle measurement instrument.
B. water resistance：Print film coated surface is wiped with wet cloth, whether observation film coated surface produces defect, if surface is in sticky
Shape, surface loss of gloss, surface lack material etc., certified products should with it is consistent before test.
C. easy wiping：Print surface is streaked with oil pen, is with 70% alcohol wipe surface, certified products again after to be dried
Surface can not remain oiliness board pen ink vestige.
D. durability is easily wiped：Repetition applies easy wiping test three times, and alcohol must be waited before applying and is dried.
From upper table 1, the water resistance of experimental example 1~4, easy wiping and easily wiping durability are all better than comparative example 1
~4.
《Experimental example 5~7》
Embodiment
The constituent of experimental example 1 is coated on 130mm × 160mm wallpaper with #14 bars with bar cladding process, then made
Dried with hot air drier under conditions of 150 DEG C × 5 minutes, that is, complete to apply the number of plies one layer (i.e. experimental example 5).Afterwards, may be used
Repeat to make two layers (i.e. experimental examples 6) and three layers (i.e. experimental examples 7) according to the demand number of plies.
Evaluation method
Scribbled, sprayed again after to be dried with 70% alcohol on wallpaper sample with oil pen, wiped using toilet paper and remove oil
Property pen touch mark, observe oil pen's ink leakage situation (i.e. leakage) and oil pen's inkblot residual degree it is (i.e. easy clean
Property) evaluated.
Table 2
From upper table 2, apply the number of plies compared with multilayer (such as experimental example 7) leakage and easy clean property better than apply the number of plies compared with
Few layer (such as experimental example 5).
In summary, the present invention provides a kind of coating, and it utilizes the polyvinyl alcohol and Silicon Containing Hydrogen resin reaction of all-hydrolytic type
Bond so that the all-hydrolytic type polyvinyl alcohol is transformed into the easy clean characteristic of drying by water-wet behavior.Because the all-hydrolytic type gathers
There is chemical bonded refractory, therefore, the durability of the coating belonging to it is preferable, and also has drying between vinyl alcohol and hydrogeneous silicones
Easy clean characteristic.In addition, the present invention also provides a kind of forming method of the coating using the coating.The forming method prior to
It is coated with gap filler on base material, and then in being coated with the coating on gap filler.The hole in base material can be filled due to gap filler,
Its coating for subsequently to be coated with forms a continuous surface.Consequently, it is possible to the present invention can avoid oil pen in the prior art
The hole that penetrates into base material of ink, can thereby lift the easy clean ability of drying of the coating.
Although the present invention is disclosed as above with embodiment, so it is not limited to the present invention, any art
Middle those of ordinary skill, without departing from the spirit and scope of the present invention, when a little change and retouching can be made, in the present invention
In the range of.
Claims (10)
- A kind of 1. coating with the easy clean characteristic of drying, it is characterised in that including：The polyvinyl alcohol of all-hydrolytic type, its degree of polymerization is between 300~2600；AndHydrogeneous silicones, the part by weight of the all-hydrolytic type polyvinyl alcohol and hydrogeneous silicones is 0.5~4 times, wherein described Hydrogeneous silicones is bonded with all-hydrolytic type polyvinyl alcohol reaction so that the all-hydrolytic type polyvinyl alcohol is turned by water-wet behavior Become the easy clean characteristic of drying.
- 2. coating according to claim 1, it is characterised in that also include：Crosslinking agent, its content are 0.1~30 percentage by weight of the coating；AndLeveling auxiliary agent, its content are 0.1~30 percentage by weight of the coating.
- 3. coating according to claim 2, it is characterised in that the crosslinking agent includes glyoxal water solution, glutaraldehyde water Solution, boric acid aqueous solution, borax solution, water-based isocyanate or its combination.
- 4. coating according to claim 1, it is characterised in that the degree of polymerization of the all-hydrolytic type polyvinyl alcohol is between 1400 Between~2600.
- A kind of 5. forming method of the coating with the easy clean characteristic of drying, it is characterised in that including：Base material is provided；Optionally in being coated with gap filler on the base material, the first drying process is then carried out；In coating of the coating with the easy clean characteristic of drying on the gap filler, the second drying process is then carried out, with described in formation Coating with the easy clean characteristic of drying, wherein the coating with the easy clean characteristic of drying includes：The polyvinyl alcohol of all-hydrolytic type And hydrogeneous silicones, the degree of polymerization of the polyvinyl alcohol of the all-hydrolytic type is between 300~2600, and the all-hydrolytic type The part by weight of polyvinyl alcohol and hydrogeneous silicones is 0.5~4 times, wherein the all-hydrolytic type polyvinyl alcohol and the Silicon Containing Hydrogen Resin reaction is bonded so that the all-hydrolytic type polyvinyl alcohol is transformed into the easy clean characteristic of drying by water-wet behavior.
- 6. the forming method of coating according to claim 5, it is characterised in that the base material includes wallpaper, fabric, glass Glass, wall or its combination.
- 7. the forming method of coating according to claim 5, it is characterised in that the gap filler includes water-soluble high score Son, water-based emulsion, the coating with the easy clean characteristic of drying or its combination.
- 8. the forming method of coating according to claim 7, it is characterised in that the water soluble polymer includes polyethylene Alcohol, polyvinylpyrrolidone or its combination, the water-based emulsion include polyvinyl acetate, polymethyl methacrylate, propylene Acid resin emulsion, polyaminoester emulsion or its combination.
- 9. the forming method of coating according to claim 5, it is characterised in that be coated with the gap filler on the substrate The step of include be coated with one or more layers described gap filler.
- 10. the forming method of coating according to claim 5, it is characterised in that the temperature of second drying process is situated between Between 130 DEG C to 170 DEG C, and the time of second drying process is between 3 points to 10/.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2805748C2 (en) * | 2021-11-08 | 2023-10-23 | Василий Владимирович Ригин | Composition for creating protective layer on surface of paper |
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| CN104610487A (en) * | 2014-12-31 | 2015-05-13 | 北京天维宝辰化学产品有限公司 | Vac-veova emulsion, preparation method of vac-veova emulsion and redispersible latex powder |
| CN105131672A (en) * | 2015-09-06 | 2015-12-09 | 天长市银狐漆业有限公司 | Scrubbing-resistant anti-microbial inner wall emulsion paint |
| CN105199128A (en) * | 2015-11-12 | 2015-12-30 | 上海韬鸿化工科技有限公司 | Waterproof, anti-ultraviolet and antioxidant forwards-sprayed BLF back light film and preparation method thereof |
| CN105603827A (en) * | 2015-12-25 | 2016-05-25 | 中国制浆造纸研究院 | Method for producing environment-friendly and high-resistance food wrapping paper |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2805748C2 (en) * | 2021-11-08 | 2023-10-23 | Василий Владимирович Ригин | Composition for creating protective layer on surface of paper |
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