CN109734872B - Aqueous polyurethane dispersion and single-component aqueous adhesive comprising same and used for PVC (polyvinyl chloride) calendering coating - Google Patents
Aqueous polyurethane dispersion and single-component aqueous adhesive comprising same and used for PVC (polyvinyl chloride) calendering coating Download PDFInfo
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Abstract
The invention relates to an aqueous polyurethane dispersion and a single-component aqueous adhesive for a PVC (polyvinyl chloride) calendering coating, which comprises the aqueous polyurethane dispersion. The adhesive has both soft hand feeling and bonding strength. The aqueous adhesive consists of the following components: the water-based polyurethane coating comprises a water-based polyurethane dispersion, a water-based leveling agent, a water-based wetting agent, a water-based defoaming agent, a pH regulator and a thickening agent. The invention also relates to a roll coating process method used by the single-component water-based adhesive for the calendering coating. The single-component water-based adhesive for the PVC calendering coating can be used for compounding PVC paste and a textile substrate, comprises a blade coating process and a roller coating process, has high initial adhesion strength, stable peeling strength, plasticizer resistance and high jungle resistance, and can be widely used for packaging bags, raincoats, tablecloths, curtains and the like.
Description
Technical Field
The invention relates to an aqueous polyurethane dispersion and a single-component aqueous adhesive for a PVC (polyvinyl chloride) calendering coating, which comprises the aqueous polyurethane dispersion, in particular to a calendering coating aqueous adhesive for a PVC coating applied to a roller coating process, and a preparation method of the single-component aqueous adhesive for the PVC coating.
Background
The polyvinyl chloride resin has high chemical stability, so that the polyvinyl chloride resin can be used for manufacturing various fields such as anticorrosive pipelines, pipe fittings, oil pipelines, centrifugal pumps, blowers and the like. In daily life, polyvinyl chloride is used to manufacture PVC artificial leather and PVC coatings. After PVC and plasticizer are mixed and plasticized, a three-roll or four-roll calender is utilized, and after high temperature, the mixture is directly coated on a textile substrate to prepare a transparent or coloring textile coating with a specified thickness. However, a large amount of plasticizer and other materials are added during the production of the PVC calendering coating, and in the long-time use process, the PVC layer is separated from the fabric substrate due to the migration of the plasticizer, so that the service life is shortened, a bonding layer needs to be coated.
The patent No. CN101463242A describes a two-component environment-friendly polyurethane adhesive for PVC film dry-type compounding and a manufacturing method thereof, and relates to a PVC film for dry-type compounding.
Patent No. CN105401458A describes a deodorizing PVC synthetic leather and a production method thereof, mainly describing a manufacturing method of the deodorizing PVC synthetic leather, wherein the formula of PVC accounts for an important part, only aqueous polyurethane is proposed as a binder, and the detailed description is omitted.
Patent No. CN 102433765B describes a method for manufacturing environment-friendly semi-polyurethane leather, which only changes the foaming middle layer of water-based synthetic leather into PVC foaming, adopts a transfer method, coats a water-based polyurethane adhesive on the PVC foaming layer by blade coating, and then attaches a textile substrate; this patent characteristics roller coat or blade coating to textile substrate after, directly calendering PVC paste, compound PVC coating.
Patent No. CN102618204B describes a hot melt adhesive for artificial leather bonding layers and a preparation method thereof, which are mainly applied to the field of artificial leather, wherein the described epoxy resin modified waterborne polyurethane contains nitrile-butadiene rubber emulsion, chloroprene rubber achieves the hot melt effect, and a curing agent is added to achieve the performance of high resistance.
Disclosure of Invention
According to a first aspect of the present invention, there is provided an aqueous polyurethane dispersion prepared by the steps of: reacting an aliphatic isocyanate, an aromatic isocyanate, a polyol in a solvent (preferably a ketone solvent such as acetone, methyl ethyl ketone, etc.) in the presence of a catalyst until the NCO reaches 5.0-8.0%, preferably about 6.8%; adding a small molecular alcohol chain extender, a hydrophilic chain extender and a second part of solvent to continue the reaction until NCO reaches 1..5-2.5, preferably 1.70-2.0%; then adding a third part of solvent for dilution and cooling, adding a neutralizing agent for neutralization, adding water for dispersion under stirring, adding a small molecular amine chain extender, and continuing stirring for reaction; then separating the solvent from the obtained emulsion containing the solvent by distillation to obtain a solvent-free aqueous polyurethane dispersion;
wherein the molar ratio of the aromatic isocyanate to the aliphatic isocyanate is 0.2-4: 1, preferably 0.5-2: 1, preferably a mixture of toluene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate in a molar ratio of 0.2-4: 1;
the amount of hydrophilic chain extender is 2 to 10% by weight, preferably 3 to 7% by weight, of the total amount of isocyanate and polyol;
preferably, the molar ratio of the aromatic isocyanate to the polyol is 2.0-8: 1, preferably 2-6.5: 1.
Wherein the kind and proportion of isocyanate determine the hand feeling, and the adipic acid series crystalline polyol provides excellent bonding strength.
Further, the selected polyol has a molecular weight of 500-6000 daltons, preferably 1000-5000 daltons, such as one or more of poly (adipic acid-ethylene glycol) polyol, poly (adipic acid-1, 4-butanediol) polyol, poly (adipic acid-1, 6-hexanediol polyol), more preferably one or two of poly (adipic acid-1, 4-butanediol) polyol, poly (adipic acid-1, 6-hexanediol polyol).
Further, the small molecule chain extender (without carboxylate) comprises a small molecule alcohol chain extender and a small molecule amine chain extender, the small molecule alcohol chain extender can be one or more selected from 1, 4-butanediol, ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1, 4-cyclohexanediol and neopentyl glycol, and the small molecule amine chain extender can be one or more selected from ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 2, 3-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine and 1, 4-cyclohexanediamine. The mass ratio of the small molecular alcohol chain extender to the small molecular amine chain extender can be 1: 0.3 to 5, preferably 1: 0.5-2. The small molecule chain extender may be used in an amount of 1 to 6wt%, preferably 2 to 4wt%, of the total amount of the isocyanate (including aliphatic isocyanate, aromatic isocyanate) and the polyol.
Further, the hydrophilic chain extender is selected from small molecule diol compounds with carboxylate groups, preferably comprising one or more of dimethylolpropionic acid, dimethylolbutyric acid, tartaric acid, N-dimethylolmaleamic acid.
The reaction temperature may be 50 to 90 deg.C, preferably 60 to 80 deg.C, and the reaction time may be 2 to 24 hours.
The solvent is preferably a ketone solvent, such as acetone, methyl ethyl ketone and the like, and the mass ratio of the first part of solvent, the second part of solvent and the third part of solvent can be 1: 1.5-5: 3-15. The total amount of the solvent may be 50 to 200wt% of the total mass of the polyol, the aromatic isocyanate and the aliphatic isocyanate.
The catalyst may be selected from one or more of commonly used organic bismuth catalysts such as bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, and the like, and the catalyst may be present in the reaction system in an amount of 50 to 200 mass ppm.
The neutralizing agent is preferably an amine neutralizing agent, such as triethylamine, and is used in an amount sufficient to neutralize to pH 6.5-7.5.
The invention further provides a method for preparing the aqueous polyurethane dispersion, which comprises the steps of adding the polyalcohol, the aliphatic isocyanate, the aromatic isocyanate, a first part of solvent (such as ketone) and a proper amount (such as 50-200 mass ppm) of catalyst into a reactor, and reacting at 50-90 ℃, preferably 60-80 ℃ until the NCO reaches 5.0-8.0%, preferably about 6.8%; adding a small molecular alcohol chain extender, a hydrophilic chain extender and a second part of solvent to continue the reaction until NCO reaches 1..5-2.5, preferably 1.70-2.0%; then adding a third part of solvent to dilute and reduce the temperature (for example, to 30-50 ℃), adding a neutralizing agent to neutralize, adding water for dispersion under high-speed stirring, adding a small molecular amine chain extender and continuing stirring for reaction; the solvent-free aqueous polyurethane dispersion is then obtained after the solvent, such as acetone, has been separated off from the resulting emulsion containing the solvent, such as acetone, by distillation.
The invention also provides a single-component water-based adhesive for PVC (polyvinyl chloride) calendering coating, which is suitable for roller coating and comprises the following components: 80-95 parts of the aqueous polyurethane dispersion, 0.1-0.5 part of an aqueous flatting agent, 0.1-0.5 part of an aqueous wetting agent, 0.1-0.5 part of an aqueous defoaming agent, a proper amount of a pH regulator, 0.5-3 parts of an alkali swelling thickener and 0.5-3 parts of an associative thickener.
Further, the pH regulator comprises one or more of organic amine, ammonia water and sodium hydroxide.
Furthermore, the alkali swelling thickener is a polyacrylic acid saline-alkali swelling emulsion, has the characteristic of efficiently thickening a water phase, and can effectively maintain viscosity and improve the construction performance in the use and dilution process. The associative thickener is a hydrophobic associative water-soluble polymer, and is especially a high-viscosity associative thickener, so that the high viscosity of the high-shear knife coating and roller coating process is ensured, and the sizing amount and the bonding performance of the aqueous adhesive are ensured.
The invention further provides a preparation method of the single-component water-based adhesive for the PVC calendering coating, which comprises the following steps:
step 1: mixing and stirring the aqueous polyurethane dispersoid, water, an aqueous defoaming agent, an aqueous flatting agent and an aqueous wetting agent;
step 2: adding pH regulator, stirring, and controlling pH to 9-10;
and step 3: and (3) adding an alkali swelling thickener and an association type thickener into the mixture obtained in the step (2), uniformly stirring at a high speed, discharging the mixture and packaging.
The use method of the PVC calendering coating water-based adhesive comprises the following two steps:
(1) blade coating: coating the PVC calendering coating aqueous adhesive on a textile base material by a scraper directly, drying the coating in a drying oven, and calendering and compounding the PVC paste to obtain a calendering coating;
(2) and (3) roller coating: adding the PVC calendering coating aqueous adhesive into half of boiled water with the same weight, adopting a method of net roll coating, drying in a drying oven, and calendering and compounding the PVC paste to obtain a calendering coating;
by adopting the technical scheme, compared with the prior art, the invention has the following advantages:
1. the PVC calendering coating water-based adhesive is single-component polyurethane, the solvent is water, the solvent is not involved, and the PVC calendering coating water-based adhesive has the unique properties of safety, environmental protection, no taste and low cost.
2. The amount and neutralization degree of the chain extender are controlled by an acetone method process and raw material aromatic isocyanate. The obtained polyurethane-urea aqueous dispersion has the characteristics of small particle size, high viscosity, easy thickening, anti-thinning property, high bonding strength and the like.
3. The thickening agent used in the prior art is an associative thickening agent, and only thickens hydrophobic structures such as polyurethane molecular weight and the like, but does not thicken substances such as water and the like; the adhesive is prepared by compounding alkali swelling and association type thickening agents, and through synergistic effect, the aqueous phase and the resin phase are thickened to achieve low solid content and high viscosity, and when the aqueous phase and the resin phase are diluted to 15% of solid content, the aqueous phase and the resin phase still have certain viscosity, so that the adhesive is particularly suitable for a roller coating process, is simple and easy to implement, and accurately controls the gluing amount.
4. The PVC calendering coating prepared by the invention has very high initial adhesion strength, stable post-peeling strength, plasticizer resistance and higher jungle resistance, and can be widely used for packaging bags, raincoats, tablecloths, curtains and the like.
Detailed Description
The technical solution of the present invention is described in detail below by examples, but the scope of the present invention is not limited to the examples.
The products used in the examples:
TEGO-245 (waterborne leveling agent, polysiloxane polyether copolymer, winning chemistry);
BYK-024 (defoamer, mixture of foam-destroying silicone and hydrophobic solid polyethylene glycol, Pico chemical);
AMP 95(PH modifier (2-amino-2-methyl-1-propanol, dow, usa);
toluene diisocyanate (TDI-80) (Vanhua chemical group, Inc.);
dicyclohexylmethane diisocyanate (HMDI) available from Wanhua chemical group, Inc.
Example 1
240g of dehydrated 1, 4-butanediol adipate (molecular weight 3000), 50g of TDI-80, 20g of HMDI, 36.5g of acetone and a suitable amount of catalyst (bismuth isooctanoate, 100ppm) were added to a 1L four-neck round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 60-80 ℃ until the NCO reached 6.8%. 8g of 1, 4-butanediol, 14g of dimethylolpropionic acid and 80g of acetone were added and the reaction was continued at 60 ℃ until the NCO had reached 1.70. Then 200g of acetone is added for dilution and temperature reduction to 40 ℃, 9.51g of triethylamine is added for neutralization for 10min, 503g of water is added under high-speed stirring for stirring and dispersion, 3.0g of ethylenediamine is added for continuous stirring reaction for 15 min. After separating off the acetone from the acetone-containing emulsion obtained by distillation, a solvent-free aqueous polyurethane dispersion is obtained with a particle size of 45 nm.
100 parts of the obtained waterborne polyurethane are taken and added into a dispersion tank, and the rotating speed is 400 r/min. Slowly dropwise adding a leveling wetting agent TEGO 2450.2, a defoaming agent BYK 0240.2 and a pH regulator AMP 950.05, increasing the rotating speed to 600r/min, stirring for 10min, and adding a thickening agent
1.5 parts of (A) a reaction product,
and 2 parts. Rotating speed 1000r/min, stirring for 10mins, and packaging to obtain the PVC calendering coating adhesive. The slurry was prepared with a viscosity of about 2000-4000 cp.
Example 2
240g of dehydrated 1, 4-butanediol adipate (molecular weight 2000), 50g of TDI-80, 35g of HMDI, 36.6g of acetone and a suitable amount of catalyst (bismuth isooctanoate, 100ppm) were added to a 1L four-neck round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 60-80 ℃ until the NCO reached 6.99%. 8g of 1, 4-butanediol, 15g of dimethylolpropionic acid and 80g of acetone were added and the reaction was continued at 60 ℃ until the NCO had reached 1.81. Then 210g of acetone is added for dilution and cooling to 40 ℃, 10.2g of triethylamine is added for neutralization for 10min, 503g of water is added under high-speed stirring for stirring and dispersion, 4.2g of ethylenediamine is added for continuous stirring reaction for 15 min. After separating off the acetone from the acetone-containing emulsion obtained by distillation, a solvent-free aqueous polyurethane dispersion is obtained with a particle size of 50 nm.
Will be described100 parts of waterborne polyurethane is taken and added into a dispersion tank, and the rotating speed is 400 r/min. Slowly dropwise adding a leveling wetting agent TEGO 2450.2, a defoaming agent BYK 0240.2 and a pH regulator AMP 950.05, increasing the rotating speed to 600r/min, stirring for 10min, and adding a thickening agent
1.6 parts of (A) a reaction product,
2.3 parts. Rotating speed 1000r/min, stirring for 10mins, and packaging to obtain the PVC calendering coating adhesive. The slurry was prepared with a viscosity of about 2000-4000 cp.
Comparative example 1
240g of dehydrated 1, 4-butanediol adipate (molecular weight 2000), 78g of TDI-80, 40.3g of acetone and a suitable amount of catalyst (bismuth isooctanoate, 100ppm) were added to a 1L four-neck round-bottomed flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 60-80 ℃ until the NCO reached 7.69%. 8.5g of 1, 4-butanediol, 18g of dimethylolpropionic acid and 50g of acetone were added and the reaction was continued at 60 ℃ until the NCO had reached 1.78. Then adding 220g of acetone for dilution, cooling to 40 ℃, adding 12.2g of triethylamine for neutralization for 10min, adding 643g of water for stirring and dispersing under high-speed stirring, adding 4.2g of ethylenediamine, and continuing stirring and reacting for 15 min. After separating off the acetone from the resulting acetone-containing emulsion by distillation, a solvent-free aqueous polyurethane dispersion is obtained with a particle size of 48 nm.
100 parts of the obtained waterborne polyurethane are taken and added into a dispersion tank, and the rotating speed is 400 r/min. Slowly dropwise adding a leveling wetting agent TEGO 2450.2, a defoaming agent BYK 0240.2 and a pH regulator AMP 950.05, increasing the rotating speed to 600r/min, stirring for 10min, and adding a thickening agent
1.5 parts of (A) a reaction product,
2.2 parts. Rotating speed 1000r/min, stirring for 10mins, and packaging to obtain the PVC calendering coating adhesive. The slurry was prepared with a viscosity of about 2000-4000 cp.
Comparative example 2
240g of dehydrated poly (1, 4-butylene adipate) (molecular weight 2000), 117.4g of HMDI40.3g of acetone, and an appropriate amount of catalyst (bismuth isooctanoate, 100ppm) were charged into a 1L four-necked round bottom flask equipped with a nitrogen inlet/outlet, and the mixture was stirred at 60-80 ℃ until NCO reached 7.69%. 8.5g of 1, 4-butanediol, 18g of dimethylolpropionic acid and 50g of acetone were added and the reaction was continued at 60 ℃ until the NCO had reached 1.78. Then adding 220g of acetone for dilution, cooling to 40 ℃, adding 12.2g of triethylamine for neutralization for 10min, adding 643g of water for stirring and dispersing under high-speed stirring, adding 4.2g of ethylenediamine, and continuing stirring and reacting for 15 min. After separating off the acetone from the acetone-containing emulsion obtained by distillation, a solvent-free aqueous polyurethane dispersion is obtained with a particle size of 44 nm.
100 parts of the obtained waterborne polyurethane are taken and added into a dispersion tank, and the rotating speed is 400 r/min. Slowly dropwise adding a leveling wetting agent TEGO 2450.2, a defoaming agent BYK 0240.2 and a pH regulator AMP 950.05, increasing the rotating speed to 600r/min, stirring for 10min, and adding a thickening agent
1.5 parts of (A) a reaction product,
2.2, stirring at the rotating speed of 1000r/min for 10mins, and packaging to obtain the PVC calendering coating adhesive. The slurry was prepared with a viscosity of about 2000-4000 cp.
Comparative example 3
240g of dehydrated 1, 4-butanediol adipate (molecular weight 2000), 55g of TDI-80, 35g of HMDI, 36.1g of acetone and a suitable amount of catalyst (bismuth isooctanoate, 100ppm) were added to a 1L four-neck round-bottom flask equipped with a nitrogen inlet and outlet, and the mixture was stirred at 60-80 ℃ until the NCO reached 7.56%. 16g of 1, 4-butanediol, 6g of dimethylolpropionic acid and 90g of acetone were added and the reaction was continued at 60 ℃ until the NCO had reached 1.88. Then adding 220g of acetone for dilution, cooling to 40 ℃, adding 4.1g of triethylamine for neutralization for 10min, adding 643g of water for stirring and dispersing under high-speed stirring, adding 4.5g of ethylenediamine, and continuing stirring and reacting for 15 min. After separating off the acetone from the acetone-containing emulsion obtained by distillation, a solvent-free aqueous polyurethane dispersion is obtained with a particle size of 188 nm.
Application formula and process
Taking 100 parts of slurry; and adding 100 parts of water, uniformly dispersing, coating the mixture on a textile substrate by a roller, controlling the gluing amount to be 7-10g/m, and performing dry calendering and compounding to obtain the PVC coating.
Remarking:
the particle size test method comprises the following steps: a malvern particle size instrument was used.
The jungle resistance test method comprises the following steps: and rolling the PVC calendering coating, putting the rolled PVC calendering coating into a constant temperature and humidity box with the temperature of 70 ℃ and the humidity of 95%, taking out the rolled PVC calendering coating for 36 hours, and carrying out adhesive force and other performance comparison on a control group.
The peel strength test method comprises the following steps:
pH test method: a pH meter was used.
The stability test method comprises the following steps: taking 1 kg of slurry into a 1 kg plastic bottle, sealing, standing in a 50 ℃ oven for 2 weeks, taking 0.5 kg of slurry, adding 0.5 kg of water, placing in the 1 kg plastic bottle, sealing, standing in the 50 ℃ oven for 2 weeks, and observing whether the bottom has sedimentation and whether the performance is stable.
And (3) viscosity testing: BrookFIELD viscometer.
And (4) analyzing results:
1. from example 2 and comparative example 1, comparative example 2, it is shown that the aqueous adhesive for PVC calendering prepared from toluene diisocyanate TDI has higher resistance than hexamethylene diisocyanate HMDI, and is more resistant to hydrolysis especially under high temperature and high humidity conditions; because TDI contains benzene rings, the synthesized prepolymer has higher strength and tolerance; however, the polyurethane dispersion synthesized by TDI and PBA alone has no crystallization property and can not be subjected to hot melt adhesion, so that the selection of the combination of HMDI and TDI is an important discovery of the patent.
2. According to the embodiment 2 and the comparative example 3, by controlling the synthetic formula of the hydrophilic chain extender and the like, the particle size is controlled to be 0-100nm, the thickening efficiency is better, the anti-thinning capability is better, the construction performance is wider, and particularly, the roller coating process is adopted, so that the method has higher applicability in the production process of the PVC calendering coating;
3. the matching of different thickeners, including thickeners such as alkali swelling, association type and the like, has great influence on the construction performance of the aqueous adhesive for PVC calendering.
Claims (15)
1. A one-component aqueous adhesive for PVC calendering coating suitable for roller coating, which comprises: 80-95 parts of aqueous polyurethane dispersoid, 0.1-0.5 part of aqueous flatting agent, 0.1-0.5 part of aqueous wetting agent, 0.1-0.5 part of aqueous defoaming agent, a proper amount of pH regulator, 0.5-3 parts of alkali swelling thickener and 0.5-3 parts of associative thickener,
wherein the aqueous polyurethane dispersion is prepared by the steps of: aliphatic isocyanate, aromatic isocyanate and polyol are reacted in a first part of solvent in the presence of a catalyst until NCO reaches 5.0-8.0%; adding a micromolecular alcohol chain extender, a hydrophilic chain extender and a second part of solvent to continue reacting until NCO reaches 1.5-2.5%; then adding a third part of solvent for dilution and cooling, adding a neutralizing agent for neutralization, adding water for dispersion under stirring, adding a small molecular amine chain extender, and continuing stirring for reaction; then separating the solvent from the obtained emulsion containing the solvent by distillation to obtain a solvent-free aqueous polyurethane dispersion;
wherein, the dosage of the hydrophilic chain extender is 2 to 10 weight percent of the total amount of the isocyanate and the polyalcohol;
the molar ratio of the aromatic isocyanate to the polyol is 2.0-8: 1, and the selected polyol is adipic acid series crystalline polyester polyol with the molecular weight of 500-; the aromatic isocyanate and the aliphatic isocyanate are a mixture of toluene diisocyanate and 4, 4' -dicyclohexylmethane diisocyanate in a molar ratio of 0.2-4: 1.
2. The single-component aqueous adhesive according to claim 1, wherein the pH regulator comprises one or more of organic amine, ammonia water and sodium hydroxide;
the alkali swelling thickener is polyacrylic acid salt-alkali swelling emulsion, and the association thickener is hydrophobic association type water-soluble polymer.
3. The one-pack aqueous adhesive according to claim 1, wherein the associative thickener is a high viscosity associative thickener.
4. The single-component aqueous adhesive according to claim 1, wherein the catalyst is an organic bismuth catalyst, and a small molecular alcohol chain extender, a hydrophilic chain extender and a second part of solvent are added to continue the reaction until NCO reaches 1.70-2.0%;
the molar ratio of aromatic isocyanate to aliphatic isocyanate is 0.5-2: 1;
the dosage of the hydrophilic chain extender is 3 to 7 weight percent of the total amount of the isocyanate and the polyalcohol;
the molar ratio of the aromatic isocyanate to the polyol is 2-6.5: 1.
5. The one-component aqueous adhesive of claim 1, wherein the selected polyol is an adipic acid-series crystalline polyester polyol having a molecular weight of 1000-.
6. The single-component aqueous adhesive according to claim 1, wherein the adipic acid series crystalline polyester polyol is one or more selected from the group consisting of a polyadipic acid-ethylene glycol polyol, a polyadipic acid-1, 4-butanediol polyol, and a polyadipic acid-1, 6-hexanediol polyol.
7. The single-component aqueous adhesive according to claim 6, wherein the adipic acid series crystalline polyester polyol is one or two selected from the group consisting of a 1, 4-butanediol polyadipate polyol, and a 1, 6-hexanediol polyadipate polyol.
8. The single-component aqueous adhesive according to any one of claims 1 to 7, wherein the small-molecular alcohol chain extender is one or more selected from 1, 4-butanediol, ethylene glycol, propylene glycol, methyl propylene glycol, diethylene glycol, 1, 4-cyclohexanediol and neopentyl glycol, and the small-molecular amine chain extender is one or more selected from ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, 2, 3-butylenediamine, 1, 5-pentylenediamine, 1, 6-hexylenediamine and 1, 4-cyclohexanediamine; and/or
The hydrophilic chain extender is selected from small molecule diol compounds with carboxylate groups.
9. The one-component aqueous adhesive according to claim 8, wherein the mass ratio of the small-molecular alcohol chain extender to the small-molecular amine chain extender is 1: 0.3 to 5, wherein the dosage of the small molecular alcohol chain extender and the small molecular amine chain extender is 1 to 6 weight percent of the total amount of the isocyanate and the polyalcohol; and/or
The hydrophilic chain extender is selected from one or more of dimethylol propionic acid, dimethylol butyric acid, tartaric acid and N, N-dimethylol maleamic acid.
10. The one-component aqueous adhesive according to claim 9, wherein the mass ratio of the small-molecular alcohol chain extender to the small-molecular amine chain extender is 1: 0.5-2, wherein the dosage of the small molecular alcohol chain extender and the small molecular amine chain extender is 2-4wt% of the total amount of the isocyanate and the polyalcohol.
11. The single-component aqueous adhesive according to any one of claims 1 to 7, wherein the solvent is a ketone solvent, and the mass ratio of the first part of solvent to the second part of solvent to the third part of solvent is 1: 1.5-5: 3-15, wherein the total amount of the solvent is 50-200 wt% of the total mass of the polyalcohol, the aromatic isocyanate and the aliphatic isocyanate.
12. The one-part aqueous adhesive according to claim 11, wherein the ketone solvent is selected from acetone and methyl ethyl ketone.
13. The one-component aqueous adhesive according to claim 1, wherein the preparation step of the aqueous polyurethane dispersion comprises adding the polyol, the aliphatic isocyanate, the aromatic isocyanate, the first part of the solvent and a proper amount of the catalyst into a reactor, and reacting at 50-90 ℃ until NCO reaches 5.0-8.0%; adding a micromolecular alcohol chain extender, a hydrophilic chain extender and a second part of solvent to continue reacting until NCO reaches 1.5-2.5%; then adding a third part of solvent for dilution and cooling, adding a neutralizing agent for neutralization, adding water for dispersion under high-speed stirring, adding a small molecular amine chain extender, and continuing stirring for reaction; the solvent-free aqueous polyurethane dispersion is then obtained after the solvent has been separated off from the solvent-containing emulsion by distillation.
14. The one-component aqueous adhesive according to claim 13, wherein the aqueous polyurethane dispersion is prepared by adding a polyol, an aliphatic isocyanate, an aromatic isocyanate, a first part of a solvent, and a proper amount of an organic bismuth catalyst into a reactor, and reacting at 60-80 ℃ until NCO reaches 6.8%; adding a micromolecular alcohol chain extender, a hydrophilic chain extender and a second part of solvent to continue reacting until NCO reaches 1.70-2.0%; then adding a third part of solvent for dilution and cooling to 30-50 ℃, adding a neutralizing agent for neutralization, adding water for dispersion under high-speed stirring, adding a small molecular amine chain extender, and continuing stirring for reaction; the solvent-free aqueous polyurethane dispersion is then obtained after the solvent has been separated off from the solvent-containing emulsion by distillation.
15. The process for preparing the one-component aqueous adhesive for PVC calender coating according to any one of claims 1 to 14, comprising the steps of:
step 1: mixing and stirring the aqueous polyurethane dispersoid, water, an aqueous defoaming agent, an aqueous flatting agent and an aqueous wetting agent;
step 2: adding pH regulator, stirring, and controlling pH to 9-10;
and step 3: and (3) adding an alkali swelling thickener and an association type thickener into the mixture obtained in the step (2), uniformly stirring at a high speed, discharging the mixture and packaging.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190803A (en) * | 2011-03-22 | 2011-09-21 | 北京市射线应用研究中心 | Internal-crosslinking aqueous polyurethane emulsion and preparation method thereof |
| CN103087286A (en) * | 2013-01-07 | 2013-05-08 | 中国科学院过程工程研究所 | Waterborne polyurethane elastic dispersion and preparation method thereof |
| CN103275334A (en) * | 2013-06-07 | 2013-09-04 | 安徽大学 | Preparation method of waterborne polyurethane containing fluorescent dye |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
| CN107760247A (en) * | 2017-11-02 | 2018-03-06 | 温州国仕邦高分子材料有限公司 | Waterborne polyurethane shoe adhesive and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TW200932771A (en) * | 2008-01-25 | 2009-08-01 | Great Eastern Resins Ind Co Ltd | Improved process of preparing high performance waterborne aliphatic-aromatic mixed polyurethanes |
| US8841369B2 (en) * | 2011-03-30 | 2014-09-23 | Basf Se | Latently reactive polyurethane dispersion with activatable crosslinking |
-
2018
- 2018-12-25 CN CN201811591438.6A patent/CN109734872B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190803A (en) * | 2011-03-22 | 2011-09-21 | 北京市射线应用研究中心 | Internal-crosslinking aqueous polyurethane emulsion and preparation method thereof |
| CN103087286A (en) * | 2013-01-07 | 2013-05-08 | 中国科学院过程工程研究所 | Waterborne polyurethane elastic dispersion and preparation method thereof |
| CN103275334A (en) * | 2013-06-07 | 2013-09-04 | 安徽大学 | Preparation method of waterborne polyurethane containing fluorescent dye |
| CN106243319A (en) * | 2016-07-28 | 2016-12-21 | 上海维凯光电新材料有限公司 | Aqueous polyurethane emulsion of resistance to bending and preparation method thereof |
| CN107760247A (en) * | 2017-11-02 | 2018-03-06 | 温州国仕邦高分子材料有限公司 | Waterborne polyurethane shoe adhesive and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| "合成革用水性聚氨酯胶黏剂的制备及性能研究";卢敏等;《聚氨酯》;20110331;第78-81页 * |
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