CN110746812B - Thixotropic mixtures containing nonionic polyurethane compounds and aqueous leather surface treatment coatings comprising the same - Google Patents
Thixotropic mixtures containing nonionic polyurethane compounds and aqueous leather surface treatment coatings comprising the same Download PDFInfo
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- CN110746812B CN110746812B CN201911066227.5A CN201911066227A CN110746812B CN 110746812 B CN110746812 B CN 110746812B CN 201911066227 A CN201911066227 A CN 201911066227A CN 110746812 B CN110746812 B CN 110746812B
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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
- C09D7/45—Anti-settling agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C09D7/60—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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention discloses a thixotropic mixture containing a nonionic polyurethane compound and a water-based leather surface treatment coating containing the thixotropic mixture. The thixotropic mixtures containing nonionic polyurethane compounds comprise polymers prepared from diisocyanates, polyethylene glycols and polyhydroxy compounds/C12-C22 fatty alcohols, and auxiliaries. The water-based leather surface treatment coating has excellent anti-settling performance and excellent application performance, a base material treated by the coating has good gloss representation and blackness, and the preparation method and the application method are simple and easy to operate.
Description
Technical Field
The invention relates to the field of leather surface treatment coatings, in particular to a thixotropic mixture containing a low-solid high-efficiency nonionic polyurethane compound and a water-based leather surface treatment coating containing the thixotropic mixture, and application of the thixotropic mixture in improving the thixotropy of the water-based leather surface treatment coating.
Background
With the increasing living standard and the strengthening of environmental awareness in recent years, people have increasingly pursued high quality of life and have increasingly deep expectations on the comfort and texture of products. At present, the water-based leather is widely applied to the production of products such as bags, clothes, shoes and the like, and has good physical characteristics, flexing resistance, good softness, high tensile strength and air permeability. The matte product with soft color is worried by consumers pursuing leisure, fashion and individuality because of the strong texture and the elegant and comfortable feeling. The surface of the water-based leather often needs to be treated by some surface treatment coatings to have a matte effect, and compared with the plastic feeling generated by an excessively bright surface, the surface of the matte surface has a little hair like the surface of frosted glass, so that the surface after being coated has the natural and soft nature of genuine leather, meanwhile, the light pollution can be avoided, and the maintenance is more convenient. With the gradual development of the coating process, the water-based leather is widely subjected to surface treatment in a roller coating mode. The roller coating uses a roller as a carrier of the coating, the coating forms a wet film with a certain thickness on the surface of the roller, and then the roller contacts with the object to be coated in the rotating process to coat the coating on the surface of the object to be coated. Therefore, the water-based leather surface treatment coating is very important.
The formula of the water-based leather surface treatment coating contains the matt powder, so that the coating needs higher low shear viscosity in the storage process to prevent the matt powder from settling; in the process of roller coating, the coating sizing amount is too large due to too high shear viscosity, the thickness and the cost of a paint film are increased, the coating sizing amount is too low due to too low shear viscosity, so that the paint film cannot cover fine grains of leather, and meanwhile, the paint film is quickly dried before being leveled, so that the surface effect of the leather is poor; the addition of the auxiliary agent can cause the performance loss of the coating, so that the efficiency of the auxiliary agent is improved as much as possible, and the addition amount of the auxiliary agent is reduced.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problem to be solved by the invention is to provide an aqueous leather surface treatment coating containing a thixotropic mixture of a low-solid high-efficiency nonionic polyurethane compound, wherein the aqueous leather surface treatment coating can comprise an aqueous polyurethane resin, a wetting agent, a leveling agent, a solvent, a defoaming agent, a matting powder, a thixotropic mixture containing a nonionic polyurethane compound and water.
Accordingly, in a first aspect the present invention provides a thixotropic mixture comprising a non-ionic polyurethane;
the thixotropic mixture containing the nonionic polyurethane compound is prepared by adopting the following raw materials to react:
A) a non-ionic polyurethane compound;
B) auxiliary agent: the auxiliary agent is selected from one or more of polyol ether and/or surfactant;
C) water;
the dosage of each component is as follows:
100 parts by weight of component A);
75 to 120 parts by weight of component B);
component C)155 and 280 parts by weight.
Further, the adjuvant is selected from one or more of polyol ethers and/or surfactants, especially non-ionic surfactants.
The nonionic polyurethane chemical is prepared by adopting the following raw material reaction:
d1, a diisocyanate dissolved with a catalyst (D2), wherein the diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), 4-diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) or dicyclohexylmethane diisocyanate (HMDI), and the catalyst is one or more of an organic bismuth catalyst and an organic tin catalyst;
d3, polyethylene glycol, wherein the polyethylene glycol is selected from polyethylene glycols having a weight average molecular weight between (inclusive) 500 and 20,000 daltons;
d4, a mixture of polyols, wherein the mixture of polyols is a mixture of polyol (D5) which may be C3-C60 compounds (including hydrocarbons, esters, etc.) having 2 or more, especially 3-5 (e.g. 3) hydroxyl groups, and C12-C22 fatty alcohol (D6), the polyol preferably being one or more of castor oil, trimethylolpropane and 1,2, 3-trihydroxybutane.
The thixotropic mixture containing the nonionic polyurethane compound is prepared by mixing the components A) and the non-ionic polyurethane compound, wherein the components A) are 100 parts by weight,
the using amount of D1 is 2-12 parts, preferably 3.5-8.5 parts, wherein, the using amount of D2 is 0.01-0.1 part;
the dosage of D3 is 68-97 parts, preferably 72-94.5 parts;
d4 (mixture of D5 and D6) is used in an amount of 1 to 20 parts, preferably 2 to 18.5 parts, wherein,
d5 is used in 0.7-7 parts, preferably 1.3-6.5 parts;
d6 is used in an amount of 0.3 to 13 parts, preferably 0.7 to 12 parts.
The auxiliary agent is selected from one or more of mono-triethylene glycol mono C1-C4 alkyl ether in polyol ether, mono-tripropylene glycol C1-C4 alkyl ether such as ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol methyl ether, tripropylene glycol butyl ether and tripropylene glycol methyl ether, and/or a surfactant, preferably a nonionic surfactant such as one or more of fatty alcohol polyoxyethylene ether, span and tween.
The nonionic polyurethane compound and the auxiliary agent are uniformly mixed in a stirring manner, the rotating speed is 200-6000 rpm, the time is 10-150 minutes, and the temperature can be 10-80 ℃; the preferred rotating speed can be selected from 600 to 2000rpm, the mixing time can be selected from 30 to 60 minutes, and the temperature can be selected from 30 to 60 ℃;
then adding deionized water according to the same way, and uniformly mixing by stirring at the rotating speed of 200-5000 rpm for 10-150 minutes at the temperature of 10-80 ℃; the preferred speed of rotation may be selected to be 500 to 2000rpm, the mixing time may be selected to be 30 to 60 minutes, and the temperature may be preferably 30 to 60 degrees celsius.
The method for preparing the nonionic polyurethane compound may be a method for preparing polyurethane, and may be a bulk synthesis method or a solution synthesis method, and in a preferred embodiment, the bulk synthesis method is selected. The preparation method of the nonionic polyurethane compound is well known and understood by those of ordinary skill in the relevant art, and is not particularly limited. For example, it can be prepared by the following steps: adding polyethylene glycol into a reactor, removing water under negative pressure (preferably pressure less than 100Pa), introducing nitrogen into the reactor to relieve pressure, adding polyhydroxy compound/C12-C22 fatty alcohol, and stirring; adding a proper amount of catalyst (such as an organic bismuth catalyst) and isocyanate under the protection of nitrogen, and reacting for 1.5-4 hours at 75-95 ℃ to obtain the nonionic polyurethane compound.
The preparation method of the thixotropic mixture containing the nonionic polyurethane compound comprises the following step of uniformly mixing the nonionic polyurethane compound and the auxiliary agent in a stirring manner, wherein the rotation speed is 200-6000 rpm, the time is 10-150 minutes, and the temperature can be 10-80 ℃. The preferred speed may be selected from 600 to 2000rpm, the mixing time may be selected from 30 to 60 minutes, and the temperature may be selected from 30 to 60 degrees celsius. Then adding deionized water according to the same way, and uniformly mixing by stirring at the rotating speed of 200-5000 rpm for 10-150 minutes at the temperature of 10-80 ℃. The preferred speed of rotation may be selected to be 500 to 2000rpm, the mixing time may be selected to be 30 to 60 minutes, and the temperature may be preferably 30 to 60 degrees celsius.
The invention also provides the application of the thixotropic mixture containing the nonionic polyurethane compound in the water-based leather surface treatment coating, and the thixotropic mixture containing the nonionic polyurethane compound is added into a water-based leather surface treatment coating formula to improve the storage stability, the application property and the application property of the water-based leather surface treatment coating.
The invention also provides a water-based leather surface treatment coating which comprises the thixotropic mixture. More specifically, the aqueous coating comprises 0.5 to 4 weight percent of the thixotropic non-ionic polyurethane chemistry-containing mixture, based on the total weight of the aqueous coating.
The aqueous leather surface treatment coating may be any aqueous leather surface treatment coating known in the art, which generally comprises from 15 to 50 wt%, especially from 20 to 30 wt%, of an aqueous polyurethane resin, based on the weight of the aqueous leather surface treatment coating; except that the thixotropic admixture comprising the nonionic polyurethane compound of the present invention is added, it may include other components that are typical for aqueous coatings, including but not limited to aqueous polyurethane-type emulsions, wetting agents, defoamers, coalescents, leveling agents, and the like, and such ingredients and amounts thereof are known to those skilled in the art. The aqueous leather surface treatment coating of the present invention comprises 0.5 to 4 wt% of the thixotropic mixture, based on the total weight of the aqueous coating. More specifically, the nonionic polyurethane compound may be included in an amount of 0.1 to 1.2 wt% and the auxiliary in an amount of 0.1 to 1.2 wt%, based on the total weight of the aqueous coating material.
In a more specific embodiment, the present invention provides an aqueous leather surface treatment coating comprising:
the amount of the thixotropic mixture containing the nonionic polyurethane chemistry is 0.5-4 wt% of the total weight of the raw materials (including the aqueous polyurethane resin, water, the wetting agent, the defoaming agent, the flatting agent and the film-forming assistant).
The aqueous polyurethane resin is any known product generally used in the art for aqueous leather surface treatment coatings, and commercially available products, such as Wanhua chemical, can be used
3458。
THE ADVANTAGES OF THE PRESENT INVENTION
The water-based leather surface treatment coating has excellent anti-settling performance and excellent application performance, a base material treated by the coating has good gloss representation and blackness, and the preparation method and the application method are simple and easy to operate.
Detailed Description
It is first noted that in the following description, the endpoints of the ranges are considered to be limiting and include other values within the tolerance, including, but not limited to, values not significantly different from the corresponding endpoint associated with the invention. Where ranges and ratios recited herein are combinable, for example, where 1-30 is recited for a particular parameter, it is understood that ranges of 1-10, 1-20, 10-25, etc., are also hereby contemplated and included.
Unless otherwise indicated, all percentage amounts in the following description are percentages by weight.
Preparation examples
Methods of preparing synergistic mixture solutions for improving sag resistance of aqueous coatings, including the raw materials and weights provided in the table, and specific preparation method descriptions.
Preparation of example 1
| Type of raw material | Name of raw materials | Weight (D) |
| Polyethylene glycol | PEG8000 | 36.5g |
| Polyhydroxy compounds | Castor oil | 3.10g |
| Fatty alcohols | Behenyl alcohol | 6.00g |
| Catalyst and process for preparing same | BICAT8108 | 0.05g |
| Diisocyanate | IPDI | 4.06g |
| Auxiliary agent | Diethylene glycol butyl ether | 54.68g |
| Water (W) | Deionized water | 124.28g |
The specific operation is as follows:
PEG 8000(36.5g) was added to a 500mL three-necked flask and the water removed at 110 ℃ under negative pressure (less than 100Pa) for 2 hours. Cooling to 85 ℃, introducing nitrogen into the three-neck flask to release pressure, adding castor oil (3.10g) and behenyl alcohol (6.00g) into the three-neck flask, and stirring by using a machine until the mixture is uniformly stirred; IPDI (4.06g) dissolved with BICAT8108(0.05g) was added under nitrogen protection and reacted at 85 ℃ for 2.5 hours to obtain a nonionic polyurethane compound.
When the temperature was lowered to 50 ℃, diethylene glycol monobutyl ether (54.68g) was added to the above nonionic polyurethane compound and mixed and stirred for 30 minutes at 1000rpm in a mechanical stirring manner, and then deionized water (124.28g) was added and mixed and stirred for 30 minutes at 1000rpm in a mechanical stirring manner to obtain a thixotropic mixture with a solid content of 21.7%.
Preparation of example 2
| Type of raw material | Name of raw materials | Weight (D) |
| Polyethylene glycol | PEG8000 | 50.0g |
| Polyhydroxy compounds | Castor oil | 2.34g |
| Fatty alcohols | Octadecanol | 1.56g |
| Catalyst and process for preparing same | BICAT8108 | 0.05g |
| Diisocyanate | HMDI | 3.28g |
| Auxiliary agent | Diethylene glycol butyl ether | 57.23g |
| Water (W) | Deionized water | 114.46g |
The specific operation is as follows:
PEG 8000(50.0g) was added to a 500mL three-necked flask and the water removed at 110 ℃ under negative pressure (less than 100Pa) for 2 hours. Cooling to 85 ℃, introducing nitrogen into the three-neck flask to release pressure, adding castor oil (2.34g) and octadecanol (1.56g) into the three-neck flask, and mechanically stirring until the mixture is uniformly stirred; HMDI (3.28g) dissolved with BICAT8108(0.05g) was added under nitrogen protection and reacted at 85 ℃ for 2.5 hours to obtain a nonionic polyurethane compound.
When the temperature was lowered to 50 ℃, diethylene glycol monobutyl ether (57.23g) was added to the above nonionic polyurethane compound and mixed and stirred for 30 minutes at 1000rpm in a mechanical stirring manner, and then deionized water (114.46g) was added and mixed and stirred for 30 minutes at 1000rpm in a mechanical stirring manner to obtain a thixotropic mixture having a solid content of 25%.
Preparation of example 3
| Type of raw material | Name of raw materials | Weight (D) |
| Polyethylene glycol | PEG8000 | 50.0g |
| Polyhydroxy compounds | Castor oil | 2.23g |
| Fatty alcohols | Cetyl alcohol | 1.49g |
| Catalyst and process for preparing same | BICAT8108 | 0.05g |
| Diisocyanate | HMDI | 3.28g |
| Auxiliary agent | Diethylene glycol butyl ether | 57.05g |
| Water (W) | Deionized water | 114.1g |
PEG 8000(50.0g) was added to a 500mL three-necked flask and the water removed at 110 ℃ under negative pressure (less than 100Pa) for 2 hours. Cooling to 85 ℃, introducing nitrogen into the three-neck flask to relieve pressure, adding castor oil (2.23g) and hexadecanol (1.49g) into the three-neck flask, and mechanically stirring until the mixture is uniformly stirred; HMDI (3.28g) dissolved with BICAT8108(0.05g) was added under nitrogen protection and reacted at 85 ℃ for 2.5 hours to obtain a nonionic polyurethane compound.
When the temperature was lowered to 50 ℃, diethylene glycol monobutyl ether (57.05g) was added to the above nonionic polyurethane compound, and the mixture was stirred for 30 minutes at 1000rpm with mechanical stirring, and then deionized water (114.1g) was added, and the mixture was stirred for 30 minutes at 1000rpm with mechanical stirring, to obtain a thixotropic mixture with a solid content of 25%.
Preparation of example 4
| Type of raw material | Name of raw materials | Weight (D) |
| Polyethylene glycol | PEG8000 | 85.0g |
| Polyhydroxy compounds | Castor oil | 1.50g |
| Fatty alcohols | Octadecanol | 0.80g |
| Catalyst and process for preparing same | BICAT8108 | 0.05g |
| Diisocyanate | IPDI | 3.18g |
| Auxiliary agent | Diethylene glycol butyl ether | 90.53g |
| Water (W) | Deionized water | 181.06g |
The specific operation is as follows:
PEG 8000(85.0g) was added to a 500mL three-necked flask and the water removed at 110 ℃ under negative pressure (less than 100Pa) for 2 hours. Cooling to 85 ℃, introducing nitrogen into the three-neck flask to release pressure, adding castor oil (1.50g) and octadecanol (0.80g) into the three-neck flask, and mechanically stirring until the mixture is uniformly stirred; IPDI (3.18g) dissolved with BICAT8108(0.05g) was added under nitrogen protection and reacted at 85 ℃ for 2.5 hours to obtain a nonionic polyurethane compound.
When the temperature was lowered to 50 ℃, diethylene glycol monobutyl ether (90.53g) was added to the above nonionic polyurethane compound and mixed and stirred for 30 minutes at 1000rpm in a mechanical stirring manner, and then deionized water (181.06g) was added and mixed and stirred for 30 minutes at 1000rpm in a mechanical stirring manner to obtain a thixotropic mixture with a solid content of 25%.
Preparation of example 5
| Type of raw material | Name of raw materials | Weight (D) |
| Polyethylene glycol | PEG6000 | 40.5g |
| Polyhydroxy compounds | Castor oil | 2.70g |
| Fatty alcohols | Octadecanol | 3.75g |
| Catalyst and process for preparing same | BICAT8108 | 0.05g |
| Diisocyanate | IPDI | 3.91g |
| Auxiliary agent | Diethylene glycol butyl ether | 40.72g |
| Water (W) | Deionized water | 81.46g |
The specific operation is as follows:
PEG 6000(40.5g) was added to a 500mL three-necked flask and water was removed at 110 ℃ under negative pressure (pressure less than 100Pa) for 2 hours. Cooling to 85 ℃, introducing nitrogen into the three-neck flask to release pressure, adding castor oil (2.70g) and octadecanol (3.75g) into the three-neck flask, and mechanically stirring until the mixture is uniformly stirred; IPDI (3.91g) dissolved with BICAT8108(0.05g) was added under nitrogen protection and reacted at 85 ℃ for 2.5 hours to obtain a nonionic polyurethane compound.
When the temperature was lowered to 50 ℃, diethylene glycol monobutyl ether (40.72g) was added to the above nonionic polyurethane compound and mixed and stirred for 30 minutes at 1000rpm with mechanical stirring, and then deionized water (81.46g) was added and mixed and stirred for 30 minutes at 1000rpm with mechanical stirring to obtain a thixotropic mixture with a solid content of 29.4%.
Test examples
A coating for water-based leather surface treatment, comprising the following raw materials and their weights:
| formulation for aqueous leather surface treatment coating (in order of addition) | Weight (D) |
| Aqueous polyurethane resin | 25.0g |
| Isopropanol (IPA, Chinese medicine reagent) | 6.0g |
| Deionized water | 15.0g |
| Matting powder (S401, from the Guangzhou Renwei science and technology Co., Ltd.) | 4.0g |
| Wetting agent (Silok-8108R, from Siloke) | 0.8g |
| Deionized water | 47.9g |
| Antifoaming agent (NXZ, St. Nuo. Proco., Japan) | 0.3g |
| Flatting agent (Silok-8030F, from siloke) | 1.0g |
| Total up to | 100.0g |
A preparation method of a water-based leather surface treatment coating comprises the following steps:
(1) weighing the raw materials according to the weight of the raw materials of the water-based leather surface treatment coating listed in the table 2;
(2) in the mixer, aqueous polyurethane resin is orderly arranged
3458. Stirring and mixing isopropanol and deionized water at the rotating speed of 300rpm/min, increasing the rotating speed to 700rpm/min after mixing, adding matting powder, and dispersing for 10-15min at the rotating speed;
(3) adding a wetting agent, deionized water, a defoaming agent and a flatting agent into the stirrer in sequence, and stirring at the rotating speed of 700rpm/min for 10-15 min;
(4) reducing the stirring speed to 150rpm/min, and defoaming for 0.5-1h until the bubbles in the stirrer completely disappear;
(5) adding a certain amount of the thixotropic mixture containing the nonionic polyurethane compound or other thickening agents into the stirrer, and stirring at the rotating speed of 700rpm/min for 25-35min to obtain the water-based paint with excellent thixotropy.
The coating for the water-based leather surface treatment comprises one of the following components:
a: 2 weight percent of deionized water is used instead of the anti-sagging performance technology;
b: 2 wt% thickener (commercially available product Z606 from mixoan department fine chemicals ltd., solid content 50%);
c: 2% by weight of thickener (commercial product)
605 from the Wanhua chemical group, Inc., solids content 40%);
d: 2% by weight of the thixotropic mixture according to the invention containing the nonionic polyurethane compound of preparation example 1 (solids content 21.7%);
e: 2% by weight of a thixotropic mixture containing a nonionic polyurethane compound according to preparation example 2 of the present invention (solid content: 25%);
f: 2% by weight of a thixotropic mixture containing a nonionic polyurethane compound according to preparation example 3 of the present invention (solid content: 25%);
g: 2% by weight of a thixotropic mixture containing a nonionic polyurethane compound according to preparation example 4 of the present invention (solid content: 25%);
h: 2% by weight of a thixotropic mixture containing a nonionic polyurethane compound according to preparation example 5 of the present invention (solid content: 29.4%);
the viscosity of the aqueous coating was measured using a brookfield viscometer at different rotational speeds and the test data is shown in table 3. It can be seen that in the low shear viscosity range (<10.0rpm) and high shear viscosity range (>30rpm) which play an important role in thixotropy, the low shear viscosity of paints D, E, F, G and H containing the mixture solution of the present invention is very significantly higher than that of paint a without additional thickener and paint B with other thickener and also higher than that of paint C with other thickener, while the high shear viscosity is higher than that of paint a without additional thickener and paint C with other thickener and lower than that of paint B with other thickener, which is effective in improving thixotropy, has higher low shear viscosity and lower high shear viscosity, and can significantly enhance workability and storage stability of the paints. While the coating containing both thixotropic blend D, E, F, G and H had excellent jetness, the coating of the comparative example resulted in poor jetness of the leather surface.
The viscosity test results are shown in the following table.
The results of the application performance tests are shown in the following table.
Note: the degree of blackness was scored with a best score of 5 and a worst score of 1.
As can be seen from the viscosity test results and the application performance test results, the thixotropic mixture containing the nonionic polyurethane compound added in the invention has excellent blackness while improving the storage stability and the workability, and does not influence the application performance of a paint film.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the light of the present specification, or directly/indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (12)
1. A thixotropic mixture containing a nonionic polyurethane compound is prepared by reacting the following raw materials:
A) a non-ionic polyurethane compound;
B) auxiliary agent: the auxiliary agent is selected from one or more of polyol ether and/or surfactant;
C) water;
the dosage of each component is as follows:
100 parts by weight of component A);
75 to 120 parts by weight of component B);
component C)155 and 280 parts by weight;
the nonionic polyurethane compound is prepared by adopting the following raw materials through reaction:
d1 and diisocyanate dissolved with a catalyst D2, wherein the diisocyanate is selected from one or more of Toluene Diisocyanate (TDI), 4-diphenylmethane diisocyanate (MDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI) or dicyclohexylmethane diisocyanate (HMDI), and the catalyst is one or more of an organobismuth catalyst and an organotin catalyst;
d3, polyethylene glycol, wherein the polyethylene glycol is selected from polyethylene glycols having a weight average molecular weight between 500 and 20,000 daltons;
d4, a mixture of polyhydroxy compounds, wherein the mixture of polyhydroxy compounds is a mixture of polyhydroxy compounds D5 and C12-C22 fatty alcohol D6, and the polyhydroxy compounds are selected from one or more of castor oil, trimethylolpropane and 1,2, 3-trihydroxybutane;
the nonionic polyurethane compound is prepared by the following steps: adding polyethylene glycol into a reactor, removing water under negative pressure, introducing nitrogen into the reactor to relieve pressure, adding a mixture of polyhydroxy compound D5 and C12-C22 fatty alcohol D6, and stirring uniformly; adding a proper amount of catalyst and isocyanate under the protection of nitrogen, and reacting for 1.5-4 hours at 75-95 ℃ to obtain a nonionic polyurethane compound;
wherein, the weight of the component A) is 100 parts,
the dosage of D1 is 2-12 parts, wherein, the dosage of D2 is 0.01-0.1 part;
the dosage of D3 is 68-97 parts;
d4 is a mixture of D5 and D6 in an amount of 1-20 parts, wherein,
the dosage of D5 is 0.7-7 parts;
d6 is used in 0.3-13 parts.
2. The thixotropic mixture containing nonionic polyurethane compounds according to claim 1, wherein the amount of the thixotropic admixture is 100 parts by weight based on the component A),
the dosage of D1 is 3.5-8.5 parts, wherein, the dosage of D2 is 0.01-0.1 part;
the dosage of D3 is 72-94.5 parts;
the dosage of D4 is 2-18.5 parts, wherein,
the dosage of D5 is 1.3-6.5 parts;
d6 is used in 0.7-12 parts.
3. The thixotropic mixture containing non-ionic polyurethane compounds according to claim 1 or 2, wherein the auxiliaries are selected from one or more of mono-triethylene glycol mono C1-C4 alkyl ethers, mono-tripropylene glycol C1-C4 alkyl ethers in polyol ethers, and/or surfactants.
4. The thixotropic mixture containing a nonionic polyurethane compound according to claim 3 wherein the adjuvant is selected from one or more of ethylene glycol butyl ether, ethylene glycol methyl ether, diethylene glycol butyl ether, diethylene glycol methyl ether, tripropylene glycol butyl ether, tripropylene glycol methyl ether, and/or a nonionic surfactant.
5. The thixotropic mixture of non-ionic polyurethane compound containing according to claim 4 wherein the non-ionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether, span, tween.
6. The thixotropic mixture comprising non-ionic polyurethane compounds according to claim 1 or 2, wherein the negative pressure is a pressure of less than 100 Pa; the catalyst is an organic bismuth catalyst.
7. The method of preparing the thixotropic mixture of claims 1-6 including the nonionic polyurethane compound includes mixing the nonionic polyurethane compound and the auxiliary agent by stirring at 200 to 6000rpm for 10 to 150 minutes at a temperature of 10 to 80 ℃;
then adding deionized water according to the same way, and uniformly mixing by stirring at the rotating speed of 200-5000 rpm for 10-150 minutes at the temperature of 10-80 ℃.
8. The preparation method according to claim 7, wherein the nonionic polyurethane compound and the auxiliary agent are uniformly mixed by stirring at a rotation speed of 600 to 2000rpm for 30 to 60 minutes at a temperature of 30 to 60 ℃;
then adding deionized water according to the same way, and uniformly mixing by stirring at the rotating speed of 500-2000 rpm for 30-60 minutes at the temperature of 30-60 ℃.
9. Use of the thixotropic admixture comprising a non-ionic polyurethane compound according to any one of claims 1 to 6 for aqueous leather surface treatment coatings.
10. An aqueous leather surface treatment coating comprising from 0.5 to 4 wt%, based on the total weight of the aqueous coating, of the thixotropic mixture comprising non-ionic polyurethane chemistry of any one of claims 1-6.
11. An aqueous leather surface treatment coating comprising:
the thixotropic admixture of nonionic polyurethane chemistry of any one of claims 1 to 6, which is used in an amount of 0.5 to 4 weight percent based on the total weight of the foregoing raw materials.
12. The aqueous leather surface treatment coating of claim 11, wherein it comprises:
the thixotropic mixture containing the nonionic polyurethane chemistry is used in an amount of 0.5 to 4 weight percent based on the total weight of the raw materials.
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