CN112062923B - Waterborne polyurethane-urea dispersion for nail polish and preparation method thereof - Google Patents
Waterborne polyurethane-urea dispersion for nail polish and preparation method thereof Download PDFInfo
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
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- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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Abstract
The invention discloses an aqueous polyurethane-urea dispersion for nail polish and a preparation method thereof. The aqueous polyurethane-urea dispersion mainly comprises: 28-35 parts of polycaprolactone sulfonic acid sodium isophthalate diol, 7-13 parts of polycaprolactone diol, 4-8 parts of micromolecule chain extender, 32-37 parts of polyisocyanate, 0.05-0.2 part of catalyst and 41-46 parts of solvent. Wherein the polycaprolactone sulfonic sodium isophthalate diol is mainly prepared by the reaction of isophthalic acid-5-sodium sulfonate, 6-caprolactone and micromolecule diol monomers; and mixing polycaprolactone sulfonic acid group sodium isophthalate diol with polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a solvent, heating for reaction, dropwise adding a methyl ethyl ketone solution of 3-aminopropyltriethoxysilane, emulsifying, and distilling under reduced pressure to obtain the waterborne polyurethane-urea dispersoid. The aqueous polyurethane-urea dispersoid synthesized by the invention has excellent gloss, adhesive force, wear resistance and waterproof performance and no odor, and can be used for nail polish and other cosmetics.
Description
Technical Field
The invention relates to the technical field of resin synthesis, in particular to an aqueous polyurethane-urea dispersion for nail polish and a preparation method thereof.
Background
The traditional water-based nail polish is prepared by stirring and mixing additives such as water, a water-based film-forming agent, a pigment, essence and the like, wherein the water-based film-forming agent is mainly prepared from alkyd resin or acrylic acid, organic solvents such as benzene, toluene, xylene and the like can be added in the process of preparing the water-based film-forming agent from the alkyd resin or the acrylic acid, and the organic solvents cannot be removed although the content of the organic solvents is reduced by some measures in the preparation process; a small amount of organic solvent still can emit pungent smell which can cause psychological rejection of nail polish users, seriously endanger human health and pollute the environment. To address such problems, fragrances are often added to the formulations to mask the pungent odor. In addition, the traditional water-based nail polish has some defects, such as poor gloss, weak adhesion and easy change when meeting water.
According to the invention, through improvement of raw materials and a preparation process, the aqueous polyurethane-urea dispersion which is odorless and has excellent gloss, adhesion, toughness, wear resistance and water resistance when formed into a film can be prepared, and the aqueous polyurethane-urea dispersion can be used for preparing nail polish and other cosmetic fields.
Disclosure of Invention
The invention aims to provide an aqueous polyurethane-urea dispersion for nail polish and a preparation method thereof, which aim to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the aqueous polyurethane-urea dispersoid for the nail polish comprises the following raw materials, by weight, 28-35 parts of polycaprolactone sulfonic acid group isophthalic acid sodium diol, 7-13 parts of polycaprolactone diol, 4-8 parts of micromolecular chain extender, 32-37 parts of polyisocyanate, 0.05-0.2 part of catalyst and 41-46 parts of solvent.
Preferably, the molecular weight of the polycaprolactone diol in the technical scheme is 2000, and the hydroxyl value equivalent of the polycaprolactone sulfonic acid group sodium isophthalate diol is 340.
Furthermore, the polycaprolactone sulfonic acid group sodium isophthalate diol is mainly prepared by reacting isophthalic acid-5-sodium sulfonate, 6-caprolactone and micromolecule diol monomers.
Further, the small molecular diol monomer is any one of 1, 2-ethanediol, 1, 3-propanediol and 1, 4-butanediol.
Further, the polyisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate; preferably, the polyisocyanate is isophorone diisocyanate.
Further, the small molecular chain extender is any one of ethylene glycol, diethylene glycol, 1, 4-cyclohexyl glycol and 1, 2-decanediol.
Further, the catalyst is any one of stannous octoate, dibutyltin dilaurate and dibutyltin diacetate, and preferably, the catalyst is dibutyltin dilaurate.
Further, the solvent is methyl ethyl ketone.
A preparation method of an aqueous polyurethane-urea dispersion for nail polish comprises the following steps;
(1) preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, and heating for reaction; vacuum dehydrating to obtain isophthalic acid-5-sodium sulfonate ester diol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing, stirring, adding a catalyst stannous octoate, heating, maintaining the pressure with nitrogen, and reacting; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, and heating for reaction; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and carrying out heat preservation reaction; adding deionized water, stirring at high speed, emulsifying, cooling, and distilling under reduced pressure to obtain the aqueous polyurethane-urea dispersoid for nail polish.
The method comprises the following steps of (1) carrying out esterification reaction on isophthalic acid-5-sodium sulfonate and micromolecular diol monomers to generate isophthalic acid-5-sodium sulfonate ester diol containing terminal hydroxyl groups and sodium sulfonate salt groups, and carrying out addition reaction on the isophthalic acid-5-sodium sulfonate ester diol and caprolactone to generate polycaprolactone sulfonic acid group isophthalic acid sodium diol containing the terminal hydroxyl groups, the sodium sulfonate salt groups and an caprolactone structure; the diol contains terminal hydroxyl and can be used as a polyol monomer for polyurethane resin synthesis; the water-based dispersion is obtained by high-speed stirring and emulsification in water and contains sodium sulfonate groups, and the water solubility is higher; the caprolactone structure endows the caprolactone structure with flexibility and adhesion, and the benzene ring structure endows the caprolactone structure with molecular rigidity and crystallinity.
The polyurethane-polyurea resin is synthesized by reacting polycaprolactone sulfonic acid group sodium isophthalate diol with polycaprolactone diol, a micromolecule chain extender and polyisocyanate, on one hand, the polycaprolactone sulfonic acid group sodium isophthalate diol structurally contains two terminal hydroxyl groups and can be used as a polyol monomer to participate in the synthesis reaction of a prepolymer of polyurethane resin, and on the other hand, the polycaprolactone sulfonic acid group sodium isophthalate diol structurally contains two sulfonate side chain groups and functionally replaces carboxylate hydrophilic chain extenders such as dimethylolpropionic acid, dimethylolbutyric acid and the like or sulfonate hydrophilic chain extenders such as ethylene diamine ethyl sulfonic acid sodium salt and the like in the prior art. Therefore, polycaprolactone sulfonic sodium isophthalate diol is used as a raw material to synthesize polyurethane-polyurea resin, and chain extension reaction of hydrophilic chain extenders such as dimethylolpropionic acid, dimethylolbutyric acid and ethylenediamine ethanesulfonic acid sodium salt or neutralization reaction of carboxylate is not required; the obtained resin prepolymer can be stirred and emulsified after being added with water to prepare the waterborne polyurethane-urea dispersoid.
Further, a method for preparing the waterborne polyurethane-urea dispersion for nail polish comprises the following steps;
(1) preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 215-245 ℃, and reacting for 2-4 h; vacuum dehydrating for 30-40min to obtain 5-sodium sulfoisophthalate glycol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.095 to-0.098 Mpa, stirring, adding a catalyst stannous octoate, heating to 145 ℃ for 137 and maintaining the pressure of nitrogen, and reacting for 40-60 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 40-50min, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 80-85 ℃, and reacting for 4-5 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 10-20min under heat preservation; adding deionized water, stirring at high speed of 700 and 900r/min, and emulsifying for 20-40 min; and cooling to 47-53 ℃, decompressing to vacuum, distilling, and collecting methyl ethyl ketone fraction to obtain the waterborne polyurethane-urea dispersion for the nail polish. The prepared waterborne polyurethane-urea dispersion for nail polish has the solid content of 48-52 percent, and preferably has the solid content of 50 percent.
In the step, the methyl ethyl ketone solvent is used in two parts, wherein 1/2 parts of the methyl ethyl ketone solvent are used for preparing a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; and the residual 1/2 methyl ethyl ketone is used for mixing with polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate and a catalyst.
In the step, the adding amount of water and glacial acetic acid is respectively 1% and 0.2% of the adding amount of 3-aminopropyl triethoxysilane; for accelerating the hydrolysis of 3-aminopropyltriethoxysilane; the mass ratio of the methyl ethyl ketone solvent to the 3-aminopropyltriethoxysilane is 10: 1.
Further, in the preparation process of the waterborne polyurethane-urea dispersion for nail polish, the weight ratio of the polycaprolactone sulfonic acid group isophthalic acid sodium diol, the polycaprolactone diol, the micromolecular chain extender and the polyisocyanate substance is 2: 1: 4: 8.
compared with the prior art, the invention has the following beneficial effects:
1. the preparation process is improved, and methyl ethyl ketone is used as a solvent in two steps; the first step is to prepare a solution with 3-aminopropyltriethoxysilane, which can improve the dispersibility of 3-aminopropyltriethoxysilane on the surface of nail and other substances; and the second step is mixed with polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a micromolecule chain extender, polyisocyanate and a catalyst, so that the intermiscibility of the components is improved. After the emulsification reaction is finished, the reduced pressure distillation method is adopted to efficiently remove the methyl ethyl ketone fraction in the system, so that the aqueous polyurethane-urea dispersoid is ensured to contain no organic solvent and heavy metal and has extremely low smell.
2. The method comprises the steps of carrying out esterification reaction on m-phthalic acid-5-sodium sulfonate and a micromolecular diol monomer to obtain m-phthalic acid-5-sodium sulfonate ester diol containing terminal hydroxyl and sodium sulfonate groups; then, under the catalysis of stannous octoate, 6-caprolactone is subjected to ring-opening addition by using isophthalic acid-5-sodium sulfonate ester diol and 6-caprolactone to finally form polycaprolactone sulfonic acid group sodium isophthalate diol which contains terminal hydroxyl and sodium sulfonate groups and has a caprolactone structure; polycaprolactone sulfonic sodium isophthalate diol is used as a polyol monomer and reacts with macromolecular polyester polyol and polyisocyanate to synthesize polyurethane-polyurea resin; the chain extension reaction of hydrophilic chain extenders such as dimethylolpropionic acid, dimethylolbutyric acid, ethylene diamine ethanesulfonic acid sodium salt and the like or the neutralization reaction of carboxylate are not required to be carried out; adding deionized water into the polyurethane-polyurea resin, and emulsifying to obtain a waterborne polyurethane-urea dispersoid; the preparation process is relatively simplified, and the prepared waterborne polyurethane-urea dispersoid has excellent gloss, adhesive force, toughness, wear resistance and waterproof performance and is suitable for the field of cosmetics such as nail polish.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of an aqueous polyurethane-urea dispersion for nail polish comprises the following steps;
the material composition comprises, by weight, 28 parts of polycaprolactone sulfonic acid group sodium isophthalate diol, 7 parts of polycaprolactone diol, 4 parts of micromolecule chain extender, 32 parts of polyisocyanate, 0.05 part of catalyst and 41 parts of solvent.
(1) Preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 215 ℃, and reacting for 2 hours; vacuum dehydrating for 30min to obtain isophthalic acid-5-sodium sulfonate ester diol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.095 Mpa, stirring, adding a catalyst stannous octoate, heating to 137 ℃, maintaining the pressure in nitrogen, and reacting for 40 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 40min, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 80 ℃, and reacting for 4 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 10min under the condition of heat preservation; adding deionized water, stirring at high speed of 700r/min, and emulsifying for 20 min; cooling to 47 ℃, decompressing to vacuum, distilling to obtain the waterborne polyurethane-urea dispersoid for the nail polish. In the step, the mass ratio of the polycaprolactone sulfonic acid group sodium isophthalate diol, the polycaprolactone diol, the micromolecule chain extender and the polyisocyanate substance is 2: 1: 4: 8.
example 2
A preparation method of an aqueous polyurethane-urea dispersion for nail polish comprises the following steps;
the material composition comprises, by weight, 31 parts of polycaprolactone sulfonic acid group sodium isophthalate diol, 11 parts of polycaprolactone diol, 6 parts of micromolecule chain extender, 35 parts of polyisocyanate, 0.1 part of catalyst and 44 parts of solvent.
(1) Preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 232 ℃, and reacting for 3 hours; vacuum dehydrating for 35min to obtain isophthalic acid-5-sodium sulfonate ester diol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.096 Mpa, stirring, adding a catalyst stannous octoate, heating to 140 ℃, maintaining the pressure in nitrogen, and reacting for 50 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 45min, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 82 ℃, and reacting for 4.5 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 15min under the condition of heat preservation; adding deionized water, stirring at high speed of 750r/min, and emulsifying for 36 min; cooling to 51 ℃, decompressing to vacuum, distilling to obtain the waterborne polyurethane-urea dispersoid for the nail polish. In the step, the mass ratio of the polycaprolactone sulfonic acid group sodium isophthalate diol, the polycaprolactone diol, the micromolecule chain extender and the polyisocyanate substance is 2: 1: 4: 8.
example 3
A preparation method of an aqueous polyurethane-urea dispersion for nail polish comprises the following steps;
the material composition comprises, by weight, 35 parts of polycaprolactone sulfonic acid group sodium isophthalate diol, 13 parts of polycaprolactone diol, 8 parts of micromolecule chain extender, 37 parts of polyisocyanate, 0.2 part of catalyst and 46 parts of solvent.
(1) Preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 245 ℃, and reacting for 4 hours; vacuum dehydrating for 40min to obtain isophthalic acid-5-sodium sulfonate ester diol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.098 Mpa, stirring, adding a catalyst stannous octoate, heating to 145 ℃, maintaining the pressure of nitrogen, and reacting for 60 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 50min, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 85 ℃, and reacting for 5 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 20min under the condition of heat preservation; adding deionized water, stirring at high speed of 900r/min, and emulsifying for 40 min; cooling to 53 ℃, decompressing to vacuum, distilling to obtain the waterborne polyurethane-urea dispersoid for the nail polish. In the step, the mass ratio of the polycaprolactone sulfonic acid group sodium isophthalate diol, the polycaprolactone diol, the micromolecule chain extender and the polyisocyanate substance is 2: 1: 4: 8.
comparative example 1
A preparation method of an aqueous polyurethane-urea dispersion for nail polish comprises the following steps;
the material composition comprises, by weight, 31 parts of polycaprolactone sulfonic acid group sodium isophthalate diol, 11 parts of polycaprolactone diol, 6 parts of micromolecule chain extender, 35 parts of polyisocyanate, 0.1 part of catalyst and 44 parts of solvent.
(1) Preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 232 ℃, and reacting for 3 hours; vacuum dehydrating for 35min to obtain isophthalic acid-5-sodium sulfonate ester diol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.096 Mpa, stirring, adding a catalyst stannous octoate, heating to 140 ℃, maintaining the pressure in nitrogen, and reacting for 50 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 45min, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 82 ℃, and reacting for 4.5 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 15min under the condition of heat preservation; adding deionized water, stirring at high speed of 750r/min, and emulsifying for 36 min; the waterborne polyurethane-urea dispersion for nail polish is prepared. In the step, the mass ratio of the polycaprolactone sulfonic acid group sodium isophthalate diol, the polycaprolactone diol, the micromolecule chain extender and the polyisocyanate substance is 2: 1: 4: 8.
comparative example 2
A preparation method of an aqueous polyurethane-urea dispersion for nail polish comprises the following steps;
the material composition comprises, by weight, 31 parts of polycaprolactone sulfonic acid group sodium isophthalate diol, 11 parts of polycaprolactone diol, 6 parts of micromolecule chain extender, 35 parts of polyisocyanate, 0.1 part of catalyst and 44 parts of solvent.
(1) Preparing polycaprolactone sodium sulfoisophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 232 ℃, and reacting for 3 hours; vacuum dehydrating for 35min to obtain isophthalic acid-5-sodium sulfonate ester diol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.096 Mpa, stirring, adding a catalyst stannous octoate, heating to 140 ℃, maintaining the pressure in nitrogen, and reacting for 50 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sodium sulfoisophthalate diol;
(2) preparation of aqueous polyurethane-urea dispersions: mixing deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 45min, and naturally cooling to obtain 3-aminopropyl triethoxysilane solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 82 ℃, and reacting for 4.5 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 15min under the condition of heat preservation; adding deionized water, stirring at high speed of 750r/min, and emulsifying for 36 min; cooling to 51 ℃, decompressing to vacuum, distilling to obtain the waterborne polyurethane-urea dispersoid for the nail polish. In the step, the mass ratio of the polycaprolactone sulfonic acid group sodium isophthalate diol, the polycaprolactone diol, the micromolecule chain extender and the polyisocyanate substance is 2: 1: 4: 8.
experimental comparison and analysis
Examples 1-3 are the present technical solution,
in comparative example 1, after the emulsification reaction in the preparation step, the reduced pressure distillation operation was not performed; the rest is the same as the embodiment 2;
in comparative example 2, methyl ethyl ketone was selected to be mixed with each component at one time, and it was not used for the preparation of 3-aminopropyltriethoxysilane, and the rest was the same as in example 2.
The nail varnishes prepared in examples 1-3 and comparative examples 1-2 were subjected to an odor test using aqueous polyurethane-urea dispersions; the odor of the Volatile Organic Compounds (VOCs) is evaluated by detecting the content of the volatile organic compounds through artificial olfaction and gas chromatography, and the detection result is shown in the following table 1;
| example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Content of VOCs, mk/kg | Not detected out | Not detected out | Not detected out | 3.06 | 0.08 |
| Smell(s) | Has no odor | Has no odor | Has no odor | Obvious smell | Has slight odor |
TABLE 1
10g of each of the aqueous polyurethane-urea dispersions prepared in examples 1 to 3 and comparative examples 1 to 2 was prepared into 5 parts of a nail polish equivalent in amount; coating nail polish on a tetrafluoroethylene sheet to form a film; the physical properties of the film were measured: visual inspection of the film appearance; the gloss of the films was determined according to the "determination of 20 °, 60 ° and 85 ° specular gloss of paint films of GB/T9754-2007 color paints and varnishes without metallic pigments"; measuring the pencil hardness of the film according to GB/T6739-2006 determination of paint film hardness by pencil method; the water resistance of the film was determined according to GB/T1733-1993 determination of Water resistance of paint films; the firmness of the film was determined according to nail polish industry standard QB/T2287-2011; the detection results are shown in the following table 2;
| appearance of the product | Gloss 60 ° | Hardness of pencil | Water resistance | Firmness | |
| Example 1 | Is flat and smooth | 92.4 | 2B | Does not start to change | No square lattice falls off |
| Example 2 | Is flat and smooth | 93.5 | 2B | Does not start to change | No square lattice falls off |
| Example 3 | Is flat and smooth | 92.8 | 2B | Does not start to change | No square lattice falls off |
| Comparative example 1 | Is flat and smooth | 87.5 | 3B | Does not start to change | No square lattice falls off |
| Comparative example 2 | With bubble | 63.0 | 3B | Get up and change | No square lattice falls off |
TABLE 2
As can be seen from the data in tables 1-2, the aqueous polyurethane-urea dispersion for nail polish prepared in the technical scheme of examples 1-3 is odorless by manual detection, and the content of VOCs in the gas chromatography is extremely low and does not reach the detection limit of 0.2 mk/kg; the dispersion shows good appearance, gloss, hardness, water resistance, and adhesion (fastness) after forming into a film. Comparative example 1 since the vacuum distillation operation was not performed during the preparation, a small amount of organic solvent remained in the dispersion, resulting in a marked odor, and a content of VOCs of 3.06mk/kg, and slightly weak gloss and hardness. Comparative example 2 compared with the examples, the absence of methyl ethyl ketone in the formulation of 3-aminopropyltriethoxysilane resulted in slightly poor interface dispersion of the coupling agent, unsatisfactory adhesion, uneven appearance, blistering of the film, and lower gloss, hardness, and water resistance. In conclusion, the aqueous polyurethane-urea dispersion prepared by the technical scheme is basically odorless, and has the advantages of smooth and flat film formation, and excellent glossiness, hardness, water resistance and adhesion.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. An aqueous polyurethane-urea dispersion for nail polish, characterized by; a method for preparing an aqueous polyurethane-urea dispersion comprising the steps of;
(1) preparing polycaprolactone sulfonic sodium isophthalate diol; mixing 5-sodium sulfoisophthalate and a micromolecular diol monomer, adding a titanium catalyst, heating to 215-245 ℃, and reacting for 2-4 h; vacuum dehydrating for 30-40min to obtain 5-sodium sulfoisophthalate glycol; mixing 6-caprolactone and 5-sodium sulfoisophthalate diol, vacuumizing to a vacuum degree of-0.095 to-0.098 Mpa, stirring, adding a catalyst stannous octoate, heating to 145 ℃ for 137 and maintaining the pressure of nitrogen, and reacting for 40-60 min; adding dichloromethane to dissolve the reaction solution, filtering to remove the precipitate, and obtaining polycaprolactone sulfonic acid group sodium isophthalate diol;
(2) preparing an aqueous polyurethane-urea dispersion; taking a methyl ethyl ketone solvent, adding deionized water and glacial acetic acid, stirring, dropwise adding 3-aminopropyl triethoxysilane, stirring for 40-50min, and naturally cooling to obtain a 3-aminopropyl triethoxysilane-methyl ethyl ketone solution; mixing polycaprolactone sulfonic acid group sodium isophthalate diol, polycaprolactone diol, a small molecular chain extender, polyisocyanate, a catalyst and a methyl ethyl ketone solvent, heating to 80-85 ℃, and reacting for 4-5 hours; dripping a prepared 3-aminopropyltriethoxysilane-methyl ethyl ketone solution in advance, and reacting for 10-20min under heat preservation; adding deionized water, stirring at high speed of 700 and 900r/min, and emulsifying for 20-40 min; cooling to 47-53 deg.C, vacuum-drying, and distilling to obtain aqueous polyurethane-urea dispersion for nail polish.
2. The aqueous polyurethane-urea dispersion for nail polish of claim 1, wherein: the small molecular diol monomer is any one of 1, 2-ethanediol, 1, 3-propanediol and 1, 4-butanediol.
3. The aqueous polyurethane-urea dispersion for nail polish of claim 1, wherein: the polyisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and lysine diisocyanate.
4. The aqueous polyurethane-urea dispersion for nail polish of claim 1, wherein: the micromolecular chain extender is any one of ethylene glycol, diethylene glycol, 1, 4-cyclohexyl glycol and 1, 2-decanediol.
5. The aqueous polyurethane-urea dispersion for nail polish of claim 1, wherein: the catalyst is any one of stannous octoate, dibutyltin dilaurate and dibutyltin diacetate.
6. The aqueous polyurethane-urea dispersion for nail polish of claim 1, wherein: the weight ratio of the polycaprolactone sulfonic acid group sodium isophthalate diol to the polycaprolactone diol to the micromolecule chain extender to the polyisocyanate is 2: 1: 4: 8.
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