CN105062164B - A kind of aqueous wear-resistant coating, aqueous wear-resistant thin film and its preparation method and application - Google Patents
A kind of aqueous wear-resistant coating, aqueous wear-resistant thin film and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of aqueous wear-resistant coating, aqueous wear-resistant thin film and its preparation method and application.This aqueous wear-resistant coating is made up of following component by weight: vinylidene chloride 68 88 parts；Comonomer 15 35 parts；Emulsifying agent 1.5 3.5 parts；Seed emulsifying agent 0.15 0.35 parts；PH regulator 0.03 0.0 parts；Initiator 0.08 0.4 parts；Deionized water 100 parts.Aqueous wear-resistant coating of the present invention can improve coating film property, coating can be prevented because crystallizing the crack performance of uneven appearance, improve crystal property and the filming performance of coating, there is after this aqueous wear-resistant coating film forming good ethanol-tolerant impregnability and antifriction erasing ability.
Description
Technical field
The invention belongs to coating, film and manufacturing technology field thereof, be specifically related to a kind of aqueous wear-resistant coating, aqueous wear-resistant
Thin film and its preparation method and application.
Background technology
Along with industrial expansion, PET (Polyethylene terephthalate), BOPP (Biaxially
Oriented Polypropylene), the nonabsorbable thin-film material such as PP (Polypropylene), PE (polyethylene)
Owing to having chemical property and the mechanical performance of excellence, it is widely used in drawing and photograph film, airless spraying metal film, print
The fields such as the printing of brush, carbon ribbon and packaging material.
But, the nonabsorbable thin-film material such as PET, BOPP, PP, PE, the stock printed as printing and carbon ribbon, but by
Relatively low in the surface tension ratio of these printable fabrics, smooth surface, without pore, superficial attractive forces is little so that it is printability and
Carbon ribbon prints printability and is deteriorated.
In order to improve ink printing and the adhesiveness of carbon ribbon printing by the surface of activation printable fabric, film surface is usual
Carry out sided corona treatment, ultraviolet radiation treatment, plasma treatment or flame treatment.Although adhesion can be improved by these process
Property, but activity is deteriorated in time.
Along with industrialized further development, to the printability of the nonabsorbable thin-film materials such as PET, BOPP, PP, PE and
Carbon ribbon prints adaptive problem and conducts in-depth research.Along with the aqueous of solvated compounds coating, water dispersible polyurethane resin is coated with
Layer, the light solidifying coating of thermoplastic resin and emphasize the research of carboxylic acid and the polyester resin coating of primary amine concentration and study into
Emerging of fruit, the printability of the nonabsorbable thin-film materials such as PET, BOPP, PP, PE and carbon ribbon print adaptive problem and are changed
Kind.But the research and development of science and technology is forever without peak, and PET, BOPP, PP, PE thin film application constantly proposes new demand.
So, printable fabric ink printing and carbon ribbon print to be needed to stand organic solvent erosion dipping and the requirement of scratch-resistant.
Number of patent application be CN200480011148.X patent application in disclose a kind of water-base coating material, aqueous is coated with
Layer reagent comprises the aqueous dispersion polyurethane resin with aromatic cyclic structure, by containing polyester polyhydric alcohol or polyether polyols
Resin the material of alcohol be dispersed in water preparation aqueous dispersion and can be with the cross-linking agent of hydroxyl reaction.By using at molecule
In there is the PEPA of aromatic cyclic structure or polyether polyol as at normal temperatures for the PEPA or poly-of liquid
Ethoxylated polyhydric alcohol, it is possible to improve the adhesiveness to polymer PET.But, the resin such as polyurethane resin, polyester polyhydric alcohol, polyether polyol
Granule, it is possible to dissolved by multiple alcohol (such as ethanol), therefore, be weak to soaking in alcohol.Application No. 200810000781.9
The Abrasion Resistance test method of paint composite disclosed in Chinese patent application and result, 300 g of weight weights, follow for 10 times
Ring/minute speed carry out 10 times circulation scratch resistances result, scratch resistance performance is unable to reach higher level requirement.Chinese patent Shen
Please numbers 96107328.4 to disclose the mixture of polyester resin that a kind of basement membrane coating contains main component and melamine compounds thin
Film.The thin film with such coating shows under high humidity conditions, particularly in water with the excellent adhesiveness of sedimentary
Can, and with the excellent adhesion property of printing-ink.But the coated film of the mixture of alkyd resin and melamine compounds
Cannot solve at organic solvent, particularly the adhesion property after spirit solvent dipping.
Summary of the invention
For overcoming the defect of prior art, it is an object of the invention to provide a kind of aqueous wear-resistant coating, improve coating and become
Film, can prevent coating from crack performance occur because crystallization is uneven, improve crystal property and the filming performance of coating, and this aqueous is resistance to
There is after mill coating film forming good ethanol-tolerant impregnability and antifriction erasing ability.
The technical solution adopted in the present invention is as follows for achieving the above object:
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
Further, in such scheme, described comonomer is acrylic acid, acrylic acid methyl ester., 1-Octyl acrylate, propylene
Acid isobutyl ester, hydroxyethyl methylacrylate, isobornyl methacrylate, lauryl methacrylate maleic acid, propylene
Two or more in acetoacetic ester is with arbitrarily than mixture.
Further, in such scheme, described emulsifying agent be paraoctyl phenol polyoxyethylene ether, glyceryl monostearate,
One or more in sorbitol three stearic acid ester, Sodium styrene sulfonate, sodium laurylsulfate, Teepol are to appoint
Meaning compares mixture.
Further, in such scheme, described seed emulsifying agent be sodium citrate, sodium alkyl benzene sulfonate, stearic acid sodium salt,
One or more in sodium lauryl sulphate, N-domiphen are with arbitrarily than mixture.
Further, in such scheme, described PH regulator is in glacial acetic acid, hydrophosphate, ethanedioic acid, bicarbonate
One.
Further, in such scheme, described initiator is tert-butyl hydroperoxide and the mixture of rongalite or mistake
The mixture of the mixture of potassium sulfate and sodium sulfite or Ammonium persulfate. and sodium thiosulfate.
Another object of the present invention is to provide a kind of aqueous wear-resistant thin film, there is good anti-wear performance and ethanol-tolerant leaching
Stain ability；This aqueous wear-resistant thin film is with on basement membrane by aqueous wear-resistant coatings of the present invention, is formed after drying
Film.
Third object of the present invention is to provide the preparation method of a kind of aqueous wear-resistant thin film；This preparation method step bag
Include
1) coating fluid is prepared: add in aqueous wear-resistant coating of the present invention and account for aqueous wear-resistant coating total amount 0-30%
Silica slurry make coating fluid；
2) coating: precoat primer on base material, is uniformly coated on precoating primer after primer solidifies by above-mentioned coating fluid
Coating is formed on base material；
3) dry solidification: step 2) coating after coating through drying successively, solidification after formed aqueous wear-resistant thin film.
Further, step 3 in said method) drying mode be far-infrared ray drying and hot air drying；Solidification process exists
Carrying out under heating condition, solidification temperature is 50-60 DEG C, and hardening time is 40-72 hour.
Fourth object of the present invention be aqueous wear-resistant thin film of the present invention with film, airless spraying metal film,
Application in printing, carbon ribbon printing and packaging material.
Specifically, described aqueous wear-resistant thin film preparation photograph film or airless spraying metal film or printing material,
Or the application in carbon ribbon printed material or packaging material.
The beneficial effects of the present invention is: aqueous wear-resistant coating of the present invention can improve coating film property, can prevent
Uniformly there is crack performance because of crystallization cloth in coating, improves crystal property and the filming performance of coating, this aqueous wear-resistant coating film forming
After have good ethanol-tolerant impregnability and antifriction erasing ability.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail.
Aqueous wear-resistant coating of the present invention, this aqueous wear-resistant coating is made up of following component by weight:
As further scheme, aqueous wear-resistant coating of the present invention, this aqueous wear-resistant coating by weight by with
Lower component forms:
As further scheme, aqueous wear-resistant coating of the present invention, this aqueous wear-resistant coating by weight by with
Lower component forms:
As further scheme, aqueous wear-resistant coating of the present invention, this aqueous wear-resistant coating by weight by with
Lower component forms:
Further, in such scheme, described comonomer is acrylic acid, acrylic acid methyl ester., 1-Octyl acrylate, propylene
Acid isobutyl ester, hydroxyethyl methylacrylate, isobornyl methacrylate, lauryl methacrylate maleic acid, propylene
Two or more in acetoacetic ester is with arbitrarily than mixture.The consumption of comonomer has shadow to the film forming degree of crystallinity of coating
Ringing, comonomer consumption makes the most greatly film deliquescing, the least makes film become fragile.In the present invention, by controlling comonomer parts by weight
Can effectively control the fragility after aqueous wear-resistant coating film forming for 15-35 part, meet the needs of application.
After aqueous wear-resistant coating forms coating, owing to molecular structure and the emulsifying agent of polymer cooperate so that being coated with strata
Polymer particle can play combination efficacy effect on molecular structure, it is ensured that the crystallization rate of compositions, percent crystallization in massecuite and one-tenth
Film temperature.Emulsifying agent can be effectively increased crystal property and the filming performance of polymer；The selection of emulsifying agent simultaneously also can be straight
Connecing affects whether the coated film of aqueous coating emulsion has ability and the characteristic of rub resistance of ethanol-tolerant dipping.In the present invention,
All can stick to film surface owing to polymer is coated with dried polymer at film surface with emulsifier molecules, form ethanol-tolerant
Dipping, the coating of rub resistance；Further, in such scheme, described emulsifying agent is paraoctyl phenol polyoxyethylene ether, glycerol
One in single-hard ester acid ester, sorbitol three stearic acid ester, Sodium styrene sulfonate, sodium laurylsulfate, Teepol or
Two or more with arbitrarily than mixture.
Further, in such scheme, described seed emulsifying agent be sodium citrate, sodium alkyl benzene sulfonate, stearic acid sodium salt,
One or more in sodium lauryl sulphate, N-domiphen are with arbitrarily than mixture.
In the present invention, the consumption of emulsifying agent and seed emulsifying agent is to the granular size of aqueous wear-resistant coating emulsion and particle diameter
Having an impact, the too big then emulsion particle of its consumption is little, otherwise then granule is big, and viscosity is high.The most in the present invention can also be by control
The consumption of the consumption of emulsifying agent processed and seed emulsifying agent controls the granular size of aqueous wear-resistant coating emulsion and the size of particle diameter.
In the present invention, the parts by weight of emulsifying agent are 1.5-3.5 part, preferably 2.0-3.0 part.The parts by weight of seed emulsifying agent are
0.15-0.35 part, preferably 0.2-0.33 part.
The consumption of PH regulator directly affects the free radical activity of above-mentioned initiator and the stability of vinylidene chloride monomer；Cause
This, in the present invention the parts by weight of PH regulator be 0.03-0.06 part can effectively ensure that initiator freedom and activity and
The stability of vinylidene chloride monomer；Wherein, the consumption of preferred PH regulator is 0.04-0.05 part.It addition, the research of the present invention
Find that the type of PH regulator also can affect the free radical activity of initiator and the stability of vinylidene chloride monomer, in order to further
Improving free radical activity and the stability of vinylidene chloride monomer of initiator, in such scheme, described PH regulator is ice second
One in acid, hydrophosphate, ethanedioic acid, bicarbonate.
In the research process of the present invention, inventor finds that initiator amount can affect aqueous wear-resistant coating film forming post polymerization
The molecular weight of thing；The molecular weight of the biggest polymer of initiator amount diminishes, become fragile after coating film forming, and rub resistance is deteriorated, consumption
The least, then polymer molecular weight is big, and course of reaction is easily slagged tap；Therefore, in the present invention, the parts by weight of initiator are 0.08-0.4
Part, preferably 0.1-0.2 part.It addition, the type of initiator also can affect the molecular weight of aqueous wear-resistant coating film forming post-consumer polymer；
Further, in such scheme, described initiator be tert-butyl hydroperoxide, potassium peroxydisulfate, Ammonium persulfate. and sodium sulfite,
One in azodiisobutyronitrile, sodium thiosulfate, rongalite.Preferably tert-butyl hydroperoxide and the mixture of rongalite, mistake
Potassium sulfate and the one in sodium sulfite mixture or Ammonium persulfate. and sodium thiosulfate.
Another object of the present invention is to provide a kind of aqueous wear-resistant thin film, there is good anti-wear performance and ethanol-tolerant leaching
Stain ability；This aqueous wear-resistant thin film is with on basement membrane by aqueous wear-resistant coatings of the present invention, is formed after drying
Film.
Third object of the present invention is to provide the preparation method of a kind of aqueous wear-resistant thin film；This preparation method step bag
Include
1) coating fluid is prepared: add in aqueous wear-resistant coating of the present invention and account for aqueous wear-resistant coating total amount 0-30%
Silicon dioxide Asia make coating fluid；
2) coating: precoat primer on base material, is uniformly coated on precoating primer after primer solidifies by above-mentioned coating fluid
Coating is formed on base material；
3) dry solidification: step 2) coating after coating through drying successively, solidification after formed aqueous wear-resistant thin film.
Further, step 3 in said method) drying mode be far-infrared ray drying or hot air drying；Wherein, hot air drying
Dry temperature is 95-120 DEG C；Solidification process is carried out in a heated condition, and solidification temperature is 50-60 DEG C, and hardening time is 40-72
Hour.Preferably use far-infrared ray drying, because infrared drying can prevent coating surface skinning, contribute to being dried of coating.
Fourth object of the present invention be aqueous wear-resistant thin film of the present invention with film, airless spraying metal film,
Application in printing, carbon ribbon printing and packaging material.
Specifically, described aqueous wear-resistant thin film preparation photograph film or airless spraying metal film or printing material,
Or the application in carbon ribbon printed material or packaging material.
The following is specific embodiment of the present invention, in the following embodiments, if no special instructions, reagent used and raw material
All can be obtained by buying pattern.
Embodiment 1
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
2 one kinds of aqueous wear-resistant coating of embodiment, this aqueous wear-resistant coating is made up of following component by weight:
Embodiment 3
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
Embodiment 4
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
Embodiment 5
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
Embodiment 6
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
Embodiment 7
A kind of aqueous wear-resistant coating, this aqueous wear-resistant coating is made up of following component by weight:
Application Example 1:
(1) configuration coating fluid: take the aqueous wear-resistant coating described in 10KG embodiment 1, stand for standby use after filtration；
(2) coating: the 50 transparent BOPP of μm, as base material, process → be coated with primer → infrared drying → hot blast through surface corona
It is dried → applied coating solution → infrared drying → hot air drying → rolling；Wherein, the coating weight of primer is 0.5g/, coating fluid
Coating weight be 2.5g/, far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contribute to coating be dried, heat
Air-drying dry temperature is 100 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 55 DEG C, 72 hours.
Application Example 2:
(1) configuration coating fluid: take the aqueous wear-resistant coating described in 10KG embodiment 2, stand for standby use after filtration；
(2) coating: the 50 transparent BOPP of μm, as base material, process → be coated with primer → infrared drying → hot blast through surface corona
It is dried → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, coating fluid
Coating weight be 3.5g/, far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contribute to coating be dried, heat
Air-drying dry temperature is 120 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 55 DEG C, 72 hours.
Application Example 3:
(1) configuration of coating fluid: take the aqueous wear-resistant coating described in 10KG embodiment 3, adds 1kg silicon dioxide Asia slurry and stirs
Mix 15 minutes, stand for standby use after filtration；
(2) coating process: the 50 transparent BOPP of μm, as base material, process → be coated with primer → infrared drying → heat through surface corona
Air-dry dry → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, coating
The coating weight of liquid is 2.5g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to being dried of coating,
The temperature of hot air drying is 95 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 60 DEG C, 72 hours.
Application Example 4:
(1) configuration of coating fluid: take the aqueous wear-resistant coating of 10KG embodiment 4, adds the slurry stirring 15 of 2kg silicon dioxide Asia
Minute, filter, stand for standby use；
(2) coating process: the 50 transparent BOPP of μm, as base material, process → be coated with primer → infrared drying → heat through surface corona
Air-dry dry → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, coating
The coating weight of liquid is 2.5g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to being dried of coating,
The temperature of hot air drying is 100 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 50 DEG C, 72 hours.
Application Example 5:
(1) configuration of coating fluid: take the aqueous wear-resistant coating of 10KG embodiment 5, adds the slurry stirring 15 of 2kg silicon dioxide Asia
Minute, filter, stand for standby use；
(2) once coating: the 50 transparent BOPP of μm, as base material, process → be coated with primer → infrared drying → heat through surface corona
Air-dry dry → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, coating
The coating weight of liquid is 2.5g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to being dried of coating,
The temperature of hot air drying is 120 DEG C, and coating machine speed is 150m/min；
(3) secondary coating: the back side of the 50 transparent BOPP of μm processes → be coated with primer → infrared drying → hot blast through surface corona
It is dried → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, coating fluid
Coating weight be 2.5g/, far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contribute to coating be dried, heat
Air-drying dry temperature is 100 DEG C, and coating machine speed is 150m/min；
(4) ripening: cooking conditions is 60 DEG C, 72 hours, prepares coated on both sides thin film.
Application Example 6:
(1) configuration of applied coating solution: take 10KG embodiment 6 aqueous wear-resistant coating and filter, stand for standby use；
(2) coating: 50 μm aluminum plated PETs, as base material, process (face) → painting primer → infrared drying through surface corona
→ hot air drying → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/,
The coating weight of aqueous wear-resistant coating is 2.5g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to
Being dried of coating, the temperature of hot air drying is 120 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 55 DEG C, 72 hours.
Application Example 7:
(1) configuration of coating fluid: take 10KG aqueous wear-resistant coating and filter, stand for standby use；
(2) coating: 50 μ aluminum plated PETs, as base material, process (face) → painting primer → infrared drying → heat through surface corona
Air-dry dry → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, coating
The coating weight of liquid is 3.5g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to being dried of coating,
The temperature of hot air drying is 120 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 50 DEG C, 72 hours.
Application Example 8:
(1) configuration of coating fluid: the aqueous wear-resistant coating taking 10KG embodiment 1 filters, stand for standby use；
(2) coating process: 50 μm aluminum plated PETs → surface corona processes (face) → painting primer → infrared drying → hot air drying
Dry → applied coating solution → infrared drying → hot air drying → rolling.Wherein, the coating weight of primer is 0.5g/, aqueous wear-resistant
The coating weight of coating is 1.0g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to the dry of coating
Dry, the temperature of hot air drying is 100 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 60 DEG C, 72 hours.
Performance test
1. (89, method of testing is to use ethanol wear-resistant tester to standard GB/T1768 79 of rub resistance test, adds 500g weight
Counterweight, infiltrate the ethanol of 99.7% concentration with white cotton, rub back and forth, recording ink starts number of times when destroying.And root
Need load to take the above-mentioned prepared ethanol-tolerant dipping of certain size, rub resistance coated film according to detection, survey its properties result
As shown in table 1.
Table 1: the performance test results
Can be seen that ethanol-tolerant of the present invention dipping, rub resistance coating have excellent rub resistance from the test result of upper table 1
Performance and ethanol-tolerant are immersion.
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to limit the scope of protection of the invention with this,
The change of any unsubstantiality that those skilled in the art is done on the basis of the present invention and replacement belong to institute of the present invention
Claimed scope.
Claims (2)
1. the preparation method of an aqueous wear-resistant thin film, it is characterised in that aqueous wear-resistant coating is by the component group of following weight portion
Become:
Vinylidene chloride 88 parts
Acrylic acid methyl ester. 15 parts
Paraoctyl phenol polyoxyethylene ether 3.5 parts
Sodium citrate 0.35 part
Glacial acetic acid 0.03 part
Tert-butyl hydroperoxide and 0.08 part of the mixture of rongalite
Deionized water 100 parts；
Wherein tert-butyl hydroperoxide mixes with the ratio of rongalite 1:1 in mass ratio；
Preparation method comprises the steps:
(1) configuration coating fluid: take 10KG above-mentioned aqueous wear-resistant coating, stand for standby use after filtration；
(2) coating: the 50 transparent BOPP of μm, as base material, process → be coated with primer → infrared drying → hot air drying through surface corona
→ applied coating solution → infrared drying → hot air drying → rolling；Wherein, the coating weight of primer is 0.5g/, the painting of coating fluid
Cloth amount is 3.5g/, and far infrared is rapidly heated dry, is possible to prevent coating surface skinning, contributes to being dried of coating, hot air drying
Dry temperature is 120 DEG C, and coating machine speed is 150m/min；
(3) ripening: cooking conditions is 55 DEG C, 72 hours.
The aqueous wear-resistant thin film that the preparation method of aqueous wear-resistant thin film the most according to claim 1 obtains.
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