CN116904077A - PO film coating liquid and preparation method thereof - Google Patents
PO film coating liquid and preparation method thereof Download PDFInfo
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- CN116904077A CN116904077A CN202311177320.XA CN202311177320A CN116904077A CN 116904077 A CN116904077 A CN 116904077A CN 202311177320 A CN202311177320 A CN 202311177320A CN 116904077 A CN116904077 A CN 116904077A
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- 239000007788 liquid Substances 0.000 title claims abstract description 66
- 239000007888 film coating Substances 0.000 title claims abstract description 54
- 238000009501 film coating Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920002678 cellulose Polymers 0.000 claims abstract description 38
- 239000001913 cellulose Substances 0.000 claims abstract description 38
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 35
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 34
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 27
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 27
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 27
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 22
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 22
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 230000002745 absorbent Effects 0.000 claims abstract description 12
- 239000002250 absorbent Substances 0.000 claims abstract description 12
- 238000010008 shearing Methods 0.000 claims description 30
- 229920002050 silicone resin Polymers 0.000 claims description 24
- -1 octadecyl dimethyl hydroxypropyl sulfobetaine Chemical compound 0.000 claims description 18
- 229940117986 sulfobetaine Drugs 0.000 claims description 18
- 239000002159 nanocrystal Substances 0.000 claims description 16
- 239000004111 Potassium silicate Substances 0.000 claims description 14
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 14
- 235000019353 potassium silicate Nutrition 0.000 claims description 14
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical group [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 18
- 230000003068 static effect Effects 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 230000000694 effects Effects 0.000 description 7
- 230000002045 lasting effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/054—Forming anti-misting or drip-proofing coatings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
A PO film coating liquid and a preparation method thereof belong to the technical field of high polymer materials, wherein the PO film coating liquid consists of polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, high-modulus silicate, hydrophilic nano silicon dioxide, cellulose nanocrystalline, nano cellulose whisker, water-soluble silicone, dispersing agent, water-based ultraviolet absorbent UV-106, antioxidant XH-245 and deionized water; the static contact angle of the cured film obtained by the PO coating liquid prepared by the invention is 5.5-35.3 degrees within 24-240 days, the initial drop property is 13-16 seconds, the drop durability is 84-91 days, and the scratch resistance is 1.7-2.6%.
Description
Technical Field
The invention relates to a PO film coating liquid and a preparation method thereof, and belongs to the technical field of high polymer materials.
Background
Agriculture is the basis of national economy, and along with the development of efficient agriculture, the demand for polyolefin agricultural films (PO films) is huge. When the PO film is used as a greenhouse film, when the temperature near the surface of the plastic film in the greenhouse reaches below the dew point, water vapor in the air can be saturated or supersaturated, and the water vapor can be condensed into water drops on the surface of the water drops to be atomized. The existence of fog drops can lead to the light transmittance to be reduced, so that the lighting of plants is affected, in addition, water vapor is condensed into water drops in the inner layer of the greenhouse and drops on fruits and vegetables, so that crops are eroded or bacteria are bred. Therefore, the PO film with the drip and defogging functions becomes a hot spot for research, manufacture and application in the field of agricultural films, and particularly the PO film with long-acting drip defogging function is of great concern.
The problem of PO film fogging and dripping is solved, an internal addition method and an external coating method are generally adopted, the internal addition method is to mix and blow-mold a substance with surface activity with polyolefin resin to prepare a drip film, one hydrophilic end migrates to the surface of the film to change water drops into a water film to achieve the effect of preventing water drops, but the method has short lasting period of drip defogging and is generally about 3-4 months. The external coating method is to coat the coating liquid with the drip defogging function on the surface of the PO film to form the PO film with the drip defogging function. The external coating method has longer lasting period, which is generally more than 8 months, but the lasting period is difficult to meet the requirements of practical application, and moreover, the adhesive force of the drip defogging film and the polyolefin film formed by the coating method is small because the polarity of the polyolefin surface is very weak, so that the lasting period is difficult to be greatly improved all the time.
Chinese patent CN113956722a discloses a PO film drip agent coating liquid and its production process, which comprises the following components in percentage by weight: 15-45% of nano aluminum sol, 12-15% of nano silicon dioxide, 11-13% of sodium alginate, 8-12% of polyvinylpyrrolidone, 2-8% of film forming agent, 0.5-2% of antioxidant, 1.5-3.5% of ultraviolet absorbent, 3-5% of dispersing agent and the balance of pure water. The film formed by drying the coating liquid prepared by the patent has a smaller contact angle, but the contact angle increases faster along with the time, which proves that the durability of the coating liquid in terms of drip anti-fog function is not good.
Chinese patent CN112280335a discloses a PO film coating liquid and a preparation method thereof, the PO film coating liquid comprises the following components in percentage by weight: 10-50% of nano aluminum sol; 5-15% of a surfactant; 1-10% of film forming agent; the balance of pure water; the grain diameter of the nanometer aluminum sol is 30-100nm; the surfactant is at least two of polyvinylpyrrolidone, hydroxypropyl methylcellulose, ninal 6501, polyoxyethylene ether, emulsifier OP series, and allyl alcohol polyoxyethylene polyoxypropylene ether. The PO film coating liquid contact angle obtained by the patent is prolonged along with time, the increasing speed is relatively high, and the lasting drip anti-fog performance is difficult to achieve.
The defects that the adhesive force is poor and the drip antifogging performance is difficult to last exist in the existing PO film coating liquid are seen, so that the development of the PO film coating liquid with the lasting drip antifogging performance is significant to the agricultural film industry.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a PO film coating liquid and a preparation method thereof, which realize the following aims: the PO film coating liquid with high adhesive force and durable drip anti-fog performance is prepared.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a PO film coating liquid and a preparation method thereof are provided, wherein the PO film coating liquid comprises the following specific formula in parts by weight:
45-70 parts of polyvinylpyrrolidone,
10-20 parts of polyvinyl alcohol,
3-9 parts of polyethyleneimine,
8-15 parts of high modulus silicate,
1-4 parts of hydrophilic nano silicon dioxide,
0.5-0.8 part of cellulose nanocrystalline,
0.4-1 part of nano cellulose whisker,
2-5 parts of water-soluble silicone resin,
1-2 parts of dispersing agent,
0.1 to 0.2 part of aqueous ultraviolet absorber UV-106,
0.1-0.3 part of antioxidant XH-245,
140-170 parts of deionized water;
the high modulus silicate is potassium silicate or sodium metasilicate;
the modulus of the potassium silicate is 2.5-3.5;
the modulus of the sodium metasilicate is 3-4.5;
the particle size of the hydrophilic nano silicon dioxide is 1-30 nm;
the diameter of the cellulose nanocrystalline is 3-10 nm, and the length is 50-150 nm;
the diameter of the nanocellulose whisker is 10-40 nm, and the length of the nanocellulose whisker is 100-200 nm;
the viscosity of the water-soluble silicone resin is 500-3000 mPas;
the dispersing agent is one of octadecyl dimethyl hydroxypropyl sulfobetaine, cocoyl hydroxypropyl sulfobetaine, stearyl hydroxypropyl sulfobetaine and dodecyl hydroxypropyl sulfobetaine;
the following is a further improvement of the above technical scheme:
preparation of PO film coating liquid
According to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 4-7 hours at the dispersing rate of 15000-30000 r/min, the dispersing rate is reduced to 10000-14000 r/min, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 2-5 hours, the PO film coating liquid is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the organic-inorganic hybrid PO film coating liquid is prepared by adding the high-modulus silicate, wherein the high-modulus silicate can obviously improve the scratch resistance of the PO film cured film, and simultaneously improve the cohesive energy of the cured film, so that the bonding force between the cured film and the PO film is stronger, and further the anti-fog performance of the PO film cured film flowing drop is greatly improved;
2. according to the invention, the added cellulose nanocrystalline and nanocellulose whisker are two strong hydrophilic substances, so that the hydrophilicity of a PO coating liquid curing film can be greatly improved, the two substances and hydrophilic nanosilicon dioxide have a certain size complementation effect, so that the surface of the whole curing film is filled with hydrophilic functional groups, further, the contact angle can be greatly reduced, and meanwhile, a large number of hydroxyl groups contained in the cellulose nanocrystalline and nanocellulose whisker can provide strong hydrogen bonding effect, so that the cohesion of the curing film is further enhanced, and the drip anti-fog function of the curing film has durability;
3. according to the invention, the adhesive force between the PO coating liquid curing film and the PO film is improved by adding the water-soluble silicon resin, so that the drip durability and scratch resistance of the PO coating liquid curing film are greatly improved;
4. the added sulfobetaine substances can promote the dispersion uniformity of three substances, namely hydrophilic nano silicon dioxide, cellulose nanocrystalline and nano cellulose whisker, so that the uniformity of the PO coating liquid curing film structure is ensured, and a product with lasting drip anti-fog performance can be finally obtained;
5. the static contact angle of the cured film obtained by the PO coating liquid prepared by the invention is 5.5-35.3 degrees within 24-240 days, the initial drop property is 13-16 seconds, the drop durability is 84-91 days, and the scratch resistance is 1.7-2.6%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Example 1: preparation method of PO film coating liquid
The PO film coating liquid comprises the following specific formula in parts by weight:
60 parts of polyvinylpyrrolidone,
18 parts of polyvinyl alcohol,
7 parts of polyethyleneimine,
13 parts of high modulus silicate,
3 parts of hydrophilic nano silicon dioxide,
0.7 part of cellulose nanocrystalline,
0.8 part of nano cellulose whisker,
3 parts of water-soluble silicone resin,
1.6 parts of dispersing agent,
0.14 part of aqueous ultraviolet absorber UV-106,
0.2 part of antioxidant XH-245,
160 parts of deionized water;
the high modulus silicate is potassium silicate;
the modulus of the potassium silicate is 2.5;
the particle size of the hydrophilic nano silicon dioxide is 15nm;
the diameter of the cellulose nanocrystalline is 6nm, and the length is 90nm;
the diameter of the nanocellulose whisker is 25nm, and the length is 140nm;
the viscosity of the water-soluble silicone resin is 1600 mPa.s;
the dispersing agent is octadecyl dimethyl hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 6 hours at the dispersing rate of 25000 revolutions per minute, the dispersing rate is reduced to 13000 revolutions per minute, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 4 hours, the PO film coating liquid is obtained.
Example 2: preparation method of PO film coating liquid
The PO film coating liquid comprises the following specific formula in parts by weight:
45 parts of polyvinylpyrrolidone,
10 parts of polyvinyl alcohol,
3 parts of polyethyleneimine,
8 parts of high modulus silicate,
1 part of hydrophilic nano silicon dioxide,
0.5 part of cellulose nanocrystalline,
0.4 part of nano cellulose whisker,
2 parts of water-soluble silicone resin,
1 part of dispersing agent,
0.1 part of aqueous ultraviolet absorber UV-106,
0.1 part of antioxidant XH-245,
140 parts of deionized water;
the high modulus silicate is potassium silicate;
the modulus of the potassium silicate is 3.5;
the particle size of the hydrophilic nano silicon dioxide is 1nm;
the diameter of the cellulose nanocrystalline is 3nm, and the length is 50nm;
the diameter of the nanocellulose whisker is 10nm, and the length is 100nm;
the viscosity of the water-soluble silicone resin is 500 mPas;
the dispersing agent is coco hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 4 hours at a dispersing rate of 15000 revolutions per minute, the dispersing rate is reduced to 10000 revolutions per minute, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 2 hours, the PO film coating liquid is obtained.
Example 3: preparation method of PO film coating liquid
The PO film coating liquid comprises the following specific formula in parts by weight:
70 parts of polyvinylpyrrolidone,
20 parts of polyvinyl alcohol,
9 parts of polyethyleneimine,
15 parts of high modulus silicate,
4 parts of hydrophilic nano silicon dioxide,
0.8 part of cellulose nanocrystalline,
1 part of nano cellulose whisker,
5 parts of water-soluble silicone resin,
2 parts of dispersing agent,
0.2 part of aqueous ultraviolet absorber UV-106,
0.3 part of antioxidant XH-245,
170 parts of deionized water;
the high modulus silicate is sodium metasilicate;
the modulus of the sodium metasilicate is 3;
the particle size of the hydrophilic nano silicon dioxide is 30nm;
the diameter of the cellulose nanocrystalline is 10nm, and the length is 150nm;
the diameter of the nanocellulose whisker is 40nm, and the length is 200nm;
the viscosity of the water-soluble silicone resin is 3000 mPa.s;
the dispersing agent is stearyl hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 7 hours at the dispersing rate of 30000 revolutions per minute, the dispersing rate is reduced to 14000 revolutions per minute, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 5 hours, the PO film coating liquid is obtained.
Example 4: preparation method of PO film coating liquid
The PO film coating liquid comprises the following specific formula in parts by weight:
70 parts of polyvinylpyrrolidone,
20 parts of polyvinyl alcohol,
9 parts of polyethyleneimine,
15 parts of high modulus silicate,
4 parts of hydrophilic nano silicon dioxide,
0.8 part of cellulose nanocrystalline,
1 part of nano cellulose whisker,
5 parts of water-soluble silicone resin,
2 parts of dispersing agent,
0.2 part of aqueous ultraviolet absorber UV-106,
0.3 part of antioxidant XH-245,
170 parts of deionized water;
the high modulus silicate is sodium metasilicate;
the modulus of the sodium metasilicate is 4.5;
the particle size of the hydrophilic nano silicon dioxide is 30nm;
the diameter of the cellulose nanocrystalline is 10nm, and the length is 150nm;
the diameter of the nanocellulose whisker is 40nm, and the length is 200nm;
the viscosity of the water-soluble silicone resin is 3000 mPa.s;
the dispersing agent is dodecyl hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 7 hours at the dispersing rate of 30000 revolutions per minute, the dispersing rate is reduced to 14000 revolutions per minute, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 5 hours, the PO film coating liquid is obtained.
Comparative example 1: example 1 based on the addition of no high modulus silicate, 13 parts of high modulus silicate were replaced with 13 parts of polyvinylpyrrolidone in equal amounts, as follows:
the PO film coating liquid comprises the following specific formula in parts by weight:
73 parts of polyvinylpyrrolidone,
18 parts of polyvinyl alcohol,
7 parts of polyethyleneimine,
3 parts of hydrophilic nano silicon dioxide,
0.7 part of cellulose nanocrystalline,
0.8 part of nano cellulose whisker,
3 parts of water-soluble silicone resin,
1.6 parts of dispersing agent,
0.14 part of aqueous ultraviolet absorber UV-106,
0.2 part of antioxidant XH-245,
160 parts of deionized water;
the particle size of the hydrophilic nano silicon dioxide is 15nm;
the diameter of the cellulose nanocrystalline is 6nm, and the length is 90nm;
the diameter of the nanocellulose whisker is 25nm, and the length is 140nm;
the viscosity of the water-soluble silicone resin is 1600 mPa.s;
the dispersing agent is octadecyl dimethyl hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 6 hours at the dispersing rate of 25000 revolutions per minute, the dispersing rate is reduced to 13000 revolutions per minute, then water-soluble silicon resin, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 4 hours, the PO film coating liquid is obtained.
Comparative example 2: example 1 based on the same amount of 0.7 part of cellulose nanocrystals and 0.8 part of nanocellulose whiskers were replaced with 1.5 part of polyvinylpyrrolidone without adding cellulose nanocrystals and nanocellulose whiskers, the specific operation is as follows:
the PO film coating liquid comprises the following specific formula in parts by weight:
61.5 parts of polyvinylpyrrolidone,
18 parts of polyvinyl alcohol,
7 parts of polyethyleneimine,
13 parts of high modulus silicate,
3 parts of hydrophilic nano silicon dioxide,
3 parts of water-soluble silicone resin,
1.6 parts of dispersing agent,
0.14 part of aqueous ultraviolet absorber UV-106,
0.2 part of antioxidant XH-245,
160 parts of deionized water;
the high modulus silicate is potassium silicate;
the modulus of the potassium silicate is 2.5;
the particle size of the hydrophilic nano silicon dioxide is 15nm;
the viscosity of the water-soluble silicone resin is 1600 mPa.s;
the dispersing agent is octadecyl dimethyl hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 6 hours at the dispersing rate of 25000 r/min, the dispersing rate is reduced to 13000 r/min, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 4 hours, the PO film coating liquid is obtained.
Comparative example 3: example 1 based on the fact that no water-soluble silicone resin was added, 3 parts of water-soluble silicone resin was replaced with 3 parts of polyvinylpyrrolidone in equal amounts, and the specific procedure was as follows:
the PO film coating liquid comprises the following specific formula in parts by weight:
63 parts of polyvinylpyrrolidone,
18 parts of polyvinyl alcohol,
7 parts of polyethyleneimine,
13 parts of high modulus silicate,
3 parts of hydrophilic nano silicon dioxide,
0.7 part of cellulose nanocrystalline,
0.8 part of nano cellulose whisker,
1.6 parts of dispersing agent,
0.14 part of aqueous ultraviolet absorber UV-106,
0.2 part of antioxidant XH-245,
160 parts of deionized water;
the high modulus silicate is potassium silicate;
the modulus of the potassium silicate is 2.5;
the particle size of the hydrophilic nano silicon dioxide is 15nm;
the diameter of the cellulose nanocrystalline is 6nm, and the length is 90nm;
the diameter of the nanocellulose whisker is 25nm, and the length is 140nm;
the dispersing agent is octadecyl dimethyl hydroxypropyl sulfobetaine;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 6 hours at the dispersing rate of 25000 revolutions per minute, the dispersing rate is reduced to 13000 revolutions per minute, then high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 4 hours, the PO film coating liquid is obtained.
Comparative example 4: example 1 based on the addition of no dispersant, 1.6 parts of dispersant were replaced with 1.6 parts of polyvinylpyrrolidone in equal amounts, and the specific procedure is as follows:
the PO film coating liquid comprises the following specific formula in parts by weight:
61.6 parts of polyvinylpyrrolidone,
18 parts of polyvinyl alcohol,
7 parts of polyethyleneimine,
13 parts of high modulus silicate,
3 parts of hydrophilic nano silicon dioxide,
0.7 part of cellulose nanocrystalline,
0.8 part of nano cellulose whisker,
3 parts of water-soluble silicone resin,
0.14 part of aqueous ultraviolet absorber UV-106,
0.2 part of antioxidant XH-245,
160 parts of deionized water;
the high modulus silicate is potassium silicate;
the modulus of the potassium silicate is 2.5;
the particle size of the hydrophilic nano silicon dioxide is 15nm;
the diameter of the cellulose nanocrystalline is 6nm, and the length is 90nm;
the diameter of the nanocellulose whisker is 25nm, and the length is 140nm;
the viscosity of the water-soluble silicone resin is 1600 mPa.s;
according to the specific formula of the PO film coating liquid in parts by weight, deionized water, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly put into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 6 hours at the dispersing rate of 25000 revolutions per minute, the dispersing rate is reduced to 13000 revolutions per minute, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 4 hours, the PO film coating liquid is obtained.
Performance test:
the PO film coating solutions obtained in examples 1, 2, 3 and 4 and comparative examples 1, 2, 3 and 4 are poured into a coating solution soaking tank, the shaped PO film is led into the tank through a traction roller, the outer surface of the PO film is coated, and then a PO film sample coated with a corresponding solidified film layer is obtained after hot air drying through a drying oven;
1. contact angle test: immersing a PO film sample in water at 60 ℃, changing the water every 1 hour, measuring and recording contact angle values of experimental samples at 24h, 10d, 30d, 90d, 150d and 240d by using a dynamic and static surface contact angle meter, and the test results are shown in table 1;
2. initial dribbling (time) evaluation: according to GB/T4455-2019 polyethylene blow molding greenhouse film for agriculture, placing a sample on a rapid dripping tester, and aggregating from the beginning of the test to the inner surface of the film to form a first dripping time, wherein the test result is shown in Table 2;
3. durability (time) evaluation, droplet performance failure time: according to GB/T4455-2019 polyethylene blow molding greenhouse film for agriculture, continuously observing a sample on a rapid dripping tester and a specified test condition, wherein the time for the dripping failure area of the film surface to reach a certain value is shown in a table 2;
4. scratch resistance evaluation: the PVC insulating tape is adhered to the film surface, and 100cm of the PVC insulating tape is adhered to the film surface under the condition of applying 300g of load weight 2 After 10 times of up-and-down friction, the coating film is buckled on a water bath kettle with the temperature of 60 ℃ and the scratch degree of the coating film is evaluated through the water drop adhesion degree: drop area/overall membrane surface<5% is excellent, the water drop area/the whole film surface is 5-10% is good, the water drop area/the whole film surface>20% is poor, and the test results are shown in Table 2;
TABLE 1
As can be seen from the data in table 1, comparative example 1 without the high modulus silicate has a slightly larger static contact angle than the 4 examples, indicating that the high modulus silicate has some effect on reducing the static contact angle; in comparative example 2, the static contact angle is greatly increased without adding cellulose nanocrystals and nanocellulose whiskers, and the amplitude of the static contact angle increase is larger and larger with the extension of time, which indicates that the cellulose nanocrystals and nanocellulose whiskers greatly contribute to increasing the hydrophilicity of the cured film; the static contact angle of comparative example 3 was hardly different from that of the four examples, which suggests that the water-soluble silicone resin had little effect on the hydrophilicity of the coating liquid cured film; the static contact angle of comparative example 4 was the largest and the hydrophilicity of comparative example 4 was the worst, indicating that the sulfobetaine species was able to greatly promote the hydrophilicity of the cured film of the coating liquid.
TABLE 2
| Initial drop (seconds) | Drop persistence (Tian) | Scratch resistance (%) | |
| Example 1 | 16 | 90 | 2.3 |
| Example 2 | 13 | 84 | 1.9 |
| Example 3 | 14 | 91 | 1.7 |
| Example 4 | 13 | 87 | 2.6 |
| Comparative example 1 | 28 | 56 | 10.8 |
| Comparative example 2 | 39 | 41 | 5.2 |
| Comparative example 3 | 15 | 53 | 12.1 |
| Comparative example 4 | 86 | 22 | 19.4 |
As can be seen from the data in table 2, comparative example 1 without high modulus silicate, comparative example 2 without cellulose nanocrystals and nanocellulose whiskers, and comparative example 4 without sulfobetaines, which were far worse than the four examples in both their initial drop and drop durability, indicated that these substances contributed to improving the hydrophilicity of the coating solution cured film, with the sulfobetaines having the greatest effect on the hydrophilicity of the coating solution cured film, consistent with the rules shown in table 1; comparative example 3 without the addition of water-soluble silicone resin has no difference in initial drop properties from 4 examples, but has much lower drop durability and scratch resistance than 4 examples, which indicates that the water-soluble silicone resin can increase the adhesion of the coating liquid cured film and the PO film, improve the scratch resistance, and further improve the drop durability; the scratch resistance of comparative examples 1, 3 and 4 is very poor, especially comparative example 4, which shows that the sulfobetaine substances can remarkably improve the dispersion uniformity of hydrophilic nano silicon dioxide and cellulose nano crystals and nano cellulose crystals, thereby improving the adhesive force of a cured film, improving the scratch resistance, the scratch resistance of comparative examples 1 and 3 is very poor, which shows that the high modulus silicate and the water-soluble silicone resin can remarkably improve the adhesive force of the cured film, and the scratch resistance of comparative example 2 is reduced relatively minimally, which shows that the influence of the cellulose nano crystals and nano cellulose whiskers on the scratch resistance of the cured film is limited.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (3)
1. A PO film coating liquid characterized in that:
the PO film coating liquid comprises the following specific formula in parts by weight:
45-70 parts of polyvinylpyrrolidone,
10-20 parts of polyvinyl alcohol,
3-9 parts of polyethyleneimine,
8-15 parts of high modulus silicate,
1-4 parts of hydrophilic nano silicon dioxide,
0.5-0.8 part of cellulose nanocrystalline,
0.4-1 part of nano cellulose whisker,
2-5 parts of water-soluble silicone resin,
1-2 parts of dispersing agent,
0.1 to 0.2 part of aqueous ultraviolet absorber UV-106,
0.1-0.3 part of antioxidant XH-245,
140-170 parts of deionized water;
the high modulus silicate is potassium silicate or sodium metasilicate;
the dispersing agent is one of octadecyl dimethyl hydroxypropyl sulfobetaine, cocoyl hydroxypropyl sulfobetaine, stearyl hydroxypropyl sulfobetaine and dodecyl hydroxypropyl sulfobetaine.
2. The PO film coating liquid according to claim 1, wherein:
the modulus of the potassium silicate is 2.5-3.5;
the modulus of the sodium metasilicate is 3-4.5;
the particle size of the hydrophilic nano silicon dioxide is 1-30 nm;
the diameter of the cellulose nanocrystalline is 3-10 nm, and the length is 50-150 nm;
the diameter of the nanocellulose whisker is 10-40 nm, and the length of the nanocellulose whisker is 100-200 nm;
the viscosity of the water-soluble silicone resin is 500-3000 mPas.
3. The method for preparing a PO film coating liquid according to claim 1, wherein:
the preparation method of the PO film coating liquid comprises the following steps: according to the specific formula of the PO film coating liquid in parts by weight, deionized water, a dispersing agent, hydrophilic nano silicon dioxide, cellulose nano crystal, nano cellulose whisker, an aqueous ultraviolet absorbent UV-106 and an antioxidant XH-245 are firstly placed into a mixing kettle with a high-speed shearing dispersing paddle, after the high-speed shearing dispersing is carried out for 4-7 hours at the dispersing rate of 15000-30000 r/min, the dispersing rate is reduced to 10000-14000 r/min, then water-soluble silicon resin, high-modulus silicate, polyvinylpyrrolidone, polyvinyl alcohol and polyethyleneimine are sequentially added, and after the high-speed shearing dispersing is continued for 2-5 hours, the PO film coating liquid is obtained.
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