CN109651582B - Waterborne polyurethane ink binder and preparation method thereof - Google Patents
Waterborne polyurethane ink binder and preparation method thereof Download PDFInfo
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- CN109651582B CN109651582B CN201811422822.3A CN201811422822A CN109651582B CN 109651582 B CN109651582 B CN 109651582B CN 201811422822 A CN201811422822 A CN 201811422822A CN 109651582 B CN109651582 B CN 109651582B
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- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention discloses a water-based polyurethane ink binder and a preparation method thereof, wherein the water-based polyurethane ink binder is prepared from the following components in parts by weight: 20-40 parts of diisocyanate, 20-30 parts of polymer polyol, 20-30 parts of polytetramethylene ether glycol, 20-30 parts of phthalic anhydride polyester polyol, 10-20 parts of sulfonate polyether polyol, 10-20 parts of nonionic chain extender, 0.5-2.0 parts of small molecular chain extender, 0.1-0.5 part of catalyst and 150-250 parts of water; the water resistance of the invention can be fundamentally solved, the blending stability is ensured, the adhesive force with a printing substrate can be improved, the energy consumption is low, the efficiency is high, the water resistance and the environmental protection performance can be fundamentally solved, the service life of the water-based polyurethane ink binder is prolonged, the application range of the binder is expanded, and the invention has very important significance for the polyurethane industry, the ink industry and the packaging industry.
Description
Technical Field
The invention relates to a polyurethane ink binder and a preparation method thereof.
Background
Ink is an important material for printing, and it represents patterns and characters on a printing material by printing. Inks are generally composed of pigments, binders, solvents, and adjuvants, which are uniformly mixed and repeatedly rolled to form a viscous colloidal fluid. The ink is widely used for various printings such as books and periodicals, packaging decoration, building decoration and the like, and along with the increase of social demands, the variety and the yield of the ink are correspondingly expanded and increased.
The traditional solvent type ink, such as the technical scheme related to the invention with the application number of 200710027060.2, needs toluene, has great harm to human bodies due to toluene residues, and has great potential safety hazard when being used for packaging in food or medical industries. The invention creation with the application number of 200910044647.3 discloses an alcohol-soluble ink formula, which uses alcohol as a solvent, does not use benzene and ketone which are extremely harmful to human bodies as the solvent, and has low product stability.
The water-based ink takes water as a solvent, and compared with solvent-based ink, the water-based ink greatly improves the working environment of ink manufacturers and printing operators, thereby reducing the harm of harmful substances to the bodies of the ink manufacturers and the printing operators, and solving the problems of emission and pollution existing in the current packaging and printing industries. As a key component of the ink, the ink vehicle directly affects the performance properties of the ink, such as viscosity, adhesion, gloss, and drying speed. The waterborne polyurethane is formed by dispersing polyurethane in water, is nontoxic, pollution-free and non-combustible, meets the requirement of environmental protection, and is widely applied to the fields of coatings, adhesives and the like. As a binder of the water-based ink, the water-based polyurethane has the advantages of good adhesive force, good flexibility, high tensile strength, friction resistance and the like, and the water-based polyurethane with excellent performance plays an increasingly important role in the field of the water-based ink. The invention with the application number of 200910044561.0 discloses an environment-friendly water-based polyurethane ink and a preparation method thereof, and the product can be applied to the requirements of paper, plastics, card making and the like. The invention with application number 201410684355.7 provides a high-performance water-based polyurethane ink scheme, which has excellent adhesive force, good stability, fast drying speed and strong film-forming performance on flexible packaging films. The invention of application number 201610577065.1 discloses an environment-friendly hydrophobic waterborne polyurethane ink and a preparation method thereof, and the prepared ink has strong adhesive force, good water resistance and environmental protection, can remarkably improve the water resistance of printing ink and expand the application range thereof. However, the aqueous polyurethanes described in the currently published reports have some problems: the hydrophilic group is mainly carboxyl, the hydrophilicity of the carboxylate is relatively poor, the use amount is large, compared with solvent type polyurethane, the water resistance is difficult to solve fundamentally, the reaction time of the hydrophilic chain extender is long, and the production efficiency is not high; the ionic stability of the carboxylate is not good enough, more auxiliaries are required to be added for preparing the ink, and the stability of the ink is not guaranteed; triethylamine used for neutralizing carboxyl has strong toxicity, is applied to the field of food packaging, has safety risk, and can cause instability of pH of the emulsion due to volatilization of triethylamine and influence storage stability of the polyurethane emulsion due to catalytic hydrolysis of the carboxyl; in the synthetic process of the waterborne polyurethane, the used organic solvent acetone is flammable and explosive, and the acetone needs to be removed, so that the preparation process is increased, and the time and the energy are consumed; in the process of removing acetone, the aqueous polyurethane has the possibility of unstable agglomeration. A new preparation method of the waterborne polyurethane is found, so that the water resistance and the environmental protection performance of the waterborne polyurethane are fundamentally improved, the service life of the waterborne polyurethane ink is prolonged, the application range of the waterborne polyurethane ink is expanded, and the waterborne polyurethane ink has very important significance for the polyurethane industry, the ink industry and the packaging industry.
Disclosure of Invention
The invention aims to disclose a polyurethane ink binder and a preparation method thereof, which are used for overcoming the defects of the existing water-based polyurethane ink binder,
the aqueous polyurethane ink binder is prepared from the following components in parts by weight:
the diisocyanate is selected from at least two of Toluene Diisocyanate (TDI), 1, 6-Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), diphenylmethane 4, 4-diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI) and tetramethylxylylene diisocyanate (TMXDI);
preferably:
the diisocyanate is a mixture of isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI), and the weight ratio of isophorone diisocyanate to dicyclohexylmethane diisocyanate is 1: 0.2-5; preferably: isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1: 0.5-2;
the polymer polyol is at least one selected from adipic acid type polyester polyol with the number average molecular weight of 1000-3000, polycaprolactone and polycarbonate; wherein, the micromolecular alcohol in the polyester polyol synthetic raw material is selected from one or more of 2-methyl-1, 3-propylene glycol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, neopentyl glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol and diethylene glycol;
preferably, the adipic acid type polyester polyol is selected from one or more of polyhexamethylene adipate (PHA), neopentyl glycol adipate (PNA), and hexanediol-neopentyl glycol adipate copolyester (PHNA);
the phthalic anhydride polyester polyol is polyester polyol based on phthalic anhydride-1, 6 hexanediol;
the structural general formula of the sulfonate polyether polyol is as follows:
wherein n is1+n2＝3～10。
The sulfonate polyether polyol can be prepared by adopting a method reported in a patent CN 200580023287;
the nonionic chain extender is polyethylene glycol monomethyl ether with single functionality based on ethylene oxide polymerization;
the chain extender is at least one selected from 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, neopentyl glycol or 1, 6-hexanediol;
the catalyst is selected from environment-friendly organic bismuth catalysts;
the weight solid content of the aqueous polyurethane ink binder is 35-50%;
the preparation method of the waterborne polyurethane ink binder comprises the following steps:
in an inert atmosphere, mixing the polymer polyol, polytetramethylene ether glycol, phthalic anhydride polyester polyol, sulfonate polyether polyol, a nonionic chain extender, a micromolecule chain extender and a catalyst, adding the diisocyanate, and reacting at 80-100 ℃ for 3-4h to obtain a prepolymerization reaction system;
and (3) reducing the temperature of the prepolymerization reaction system to below 50 ℃, and adding water for emulsification to obtain the aqueous polyurethane ink binder.
The inert gas may be, for example, nitrogen gas;
the aqueous polyurethane ink binder provided by the invention is widely applied to the field of aqueous ink.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the polyether polyol grafted with sulfonate groups and the nonionic chain extender as the structures for providing the hydrophilicity of polyurethane, and compared with the water-based polyurethane ink connecting material adopting carboxylic acid type hydrophilic groups in the prior art, the water resistance can be fundamentally solved because no carboxyl is available; the ionic stability of the carboxylate is poor, more auxiliaries are required to be added for preparing the ink, the stability of the ink is not guaranteed, and the stability of the prepared auxiliaries can be ensured by using ions and non-ions of the sulfonate as hydrophilic groups; the strong polarity of the sulfonate can improve the adhesive force with a printing substrate, and the adhesive fastness of the product is obvious; does not need to use a triethylamine neutralizing agent with strong toxicity, is applied to the field of food packaging, and is safe and environment-friendly to use; meanwhile, the product does not cause instability due to the change of the pH value of the polyurethane emulsion due to the volatilization of the neutralizing agent, the carboxyl has obvious acid catalysis hydrolysis characteristics, the storage stability of the polyurethane emulsion is influenced, the storage period of the product is seriously reduced, and the comprehensive performance of the polyurethane emulsion is obviously reduced.
(2) The invention adopts a solvent-free one-step method for preparation, in the synthesis process of the waterborne polyurethane, all processes are carried out in one reactor, and a flammable and explosive organic solvent acetone is not used, so that the emulsion does not need to be transferred to desolventizing equipment for desolventizing, the production safety operation risk is reduced, the preparation process flow is simple, the production efficiency is greatly improved, and the energy consumption is reduced; because acetone does not need to be removed, the problem of agglomeration instability possibly generated in the desolventizing process of the waterborne polyurethane does not occur.
The aqueous polyurethane ink binder prepared by the invention has low production energy consumption and high efficiency, can fundamentally solve the problems of water resistance and environmental protection, prolongs the service life of the aqueous polyurethane ink binder and expands the application range of the aqueous polyurethane ink binder, and has very important significance for polyurethane industry, ink and packaging industry.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the technical personnel according to the invention make improvements and modifications, which still belong to the protection scope of the invention.
The following examples of the invention use the following starting materials:
adipic acid type polyester polyol:
PHA, poly (hexanediol adipate), hydroxyl value 56mg KOH/g, number average molecular weight 2000 g/mol;
PNA, poly neopentyl glycol adipate, hydroxyl value 56mg KOH/g, number average molecular weight 2000 g/mol;
PHNA, polyhexamethylene adipate-neopentyl glycol copolyester with a hydroxyl value of 56mg KOH/g and a number average molecular weight of 2000 g/mol;
PTMEG, polytetramethylene ether glycol, hydroxyl value 56mg KOH/g, number average molecular weight 2000 g/mol;
PHPA, phthalic anhydride polyester polyol, hydroxyl value of 56mg KOH/g, number average molecular weight of 2000 g/mol;
PolyES, sulfonate polyether polyol, n1+n2＝5～7。
M-PEG, a non-ionic chain extender, a hydroxyl value of 56mg KOH/g and a number average molecular weight of 1000 g/mol;
catalyst, advanced chemistry
8108；
The starting materials in the following examples which are not mentioned above are all commercially available.
Example 1
50g PHA, 50g PTMEG, 50g PHPA, 25g PolyES, 25g M-PEG, 25g isophorone diisocyanate, 25g dicyclohexylmethane diisocyanate, 1.25g 1, 6-ethanediol, 0.25g dicyclohexylmethane diisocyanate after vacuum dehydration under the protection of dry nitrogen
8108 adding the mixture into a reaction vessel, and reacting for 3.5 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and then adding 375g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 40 percent by weight.
Example 2
25g PHA, 25g PNA, 50g PTMEG, 50g PHPA, 20g PolyES, 25g M-PEG, 35g isophorone diisocyanate, 40g dicyclohexylmethane diisocyanate, 4.5g 1, 6-ethanediol, 0.25g 1, 6-ethanediol
8108 adding the mixture into a reaction vessel, and reacting for 4 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and then adding 375g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 42 percent.
Example 3
Under the protection of dry nitrogen, 35g PHA, 15g PNA, 50g PTMEG and 50g PTMEG after vacuum dehydration were added20g of PolyES, 25g of M-PEG, 30g of isophorone diisocyanate, 40g of dicyclohexylmethane diisocyanate, 2.5g of 1, 6-ethanediol, 0.25g of
8108 adding the mixture into a reaction vessel, and reacting for 4 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and then adding 375g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 41 percent by weight.
Example 4
75g PHA, 75g PTMEG, 75g PHPA, 45g PolyES, 45g M-PEG, 45g isophorone diisocyanate, 45g dicyclohexylmethane diisocyanate, 3g 1, 6-ethanediol and 1g dicyclohexylmethane diisocyanate after vacuum dehydration are added under the protection of dry nitrogen
8108 adding the mixture into a reaction vessel, and reacting for 3.5 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and then adding 580g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 41 percent by weight.
Example 5
75g of PHNA, 75g of PTMEG, 75g of PHPA, 35g of PolyES, 45g of M-PEG, 45g of isophorone diisocyanate, 55g of dicyclohexylmethane diisocyanate, 6g of 1, 6-ethanediol and 1g of ethylene glycol after vacuum dehydration are added under the protection of dry nitrogen
8108 adding the mixture into a reaction vessel, and reacting for 4 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and adding 545g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 43 percent by weight.
Example 6
Under the protection of dry nitrogen, 75g of PHNA, 75g of PTMEG, 75g of PHPA, 40g of PolyES,45g of M-PEG, 45g of isophorone diisocyanate, 50g of dicyclohexylmethane diisocyanate, 4.5g of 1, 6-ethanediol, 1g of
8108 adding the mixture into a reaction vessel, and reacting for 4 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and adding 560g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 42 percent by weight.
Example 7
60g PHA, 60g PTMEG, 60g PHPA, 40g PolyES, 40g M-PEG, 40g isophorone diisocyanate, 40g dicyclohexylmethane diisocyanate, 4g 1, 6-ethanediol and 1g dicyclohexylmethane diisocyanate after vacuum dehydration are added under the protection of dry nitrogen
8108 adding the mixture into a reaction vessel, and reacting for 3.5 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and then adding 500g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 41 percent by weight.
Example 8
30g PHA, 30g PNA, 60g PTMEG, 60g PHPA, 30g PolyES, 40g M-PEG, 40g isophorone diisocyanate, 30g dicyclohexylmethane diisocyanate, 4g 1, 6-ethanediol, 1g 1 after vacuum dehydration under the protection of dry nitrogen
8108 adding the mixture into a reaction vessel, and reacting for 4 hours at the temperature of 98 ℃ under mechanical stirring to obtain a prepolymerization reaction system; and (3) reducing the temperature of the prepolymerization reaction system to be below 50 ℃, and then adding 430g of water for emulsification to obtain the aqueous polyurethane ink binder with the solid content of 43 percent by weight.
Comparative example 1
This comparative example is based on example 1, with all the PolyES replaced by dimethylolpropionic acid:
under the protection of dry nitrogen, adding 50g of PHA, 50g of PTMEG, 50g of PHPA, 25g of M-PEG, 25g of isophorone diisocyanate and 25g of dicyclohexylmethane diisocyanate which are subjected to vacuum dehydration into a reaction vessel, and reacting at 90 ℃ for 3 hours under mechanical stirring to obtain a prepolymerization reaction system; the prepolymerization reaction system is cooled to below 60 ℃, and 7.5g of dimethylolpropionic acid, 1.25g of 1, 6-ethanediol, 200g of acetone and 0.5g of
8108, reacting for 3 hours at 60 ℃ under mechanical stirring to obtain a chain extension reaction system; reducing the temperature of a chain extension reaction system to below 50 ℃, adding 5.6g of triethylamine to react for 30min, adding 445g of water to emulsify to obtain polyurethane emulsion, and removing the solvent acetone by reduced pressure distillation to obtain the water-based polyurethane ink binder with the weight solid content of 35%.
Comparative example 2
This comparative example was based on comparative example 1, replacing all the PolyES and M-PEG with dimethylolpropionic acid:
under the protection of dry nitrogen, adding 50g of PHA, 50g of PTMEG, 50g of PHPA, 25g of isophorone diisocyanate and 25g of dicyclohexylmethane diisocyanate which are subjected to vacuum dehydration into a reaction vessel, and reacting at 90 ℃ for 2.5 hours under mechanical stirring to obtain a prepolymerization reaction system; the prepolymerization reaction system is cooled to below 60 ℃, and 9.2g of dimethylolpropionic acid, 1.25g of 1, 6-ethanediol, 200g of acetone and 1.0g of
8108, reacting for 4 hours at 60 ℃ under mechanical stirring to obtain a chain extension reaction system; reducing the temperature of a chain extension reaction system to below 50 ℃, adding 6.9g of triethylamine to react for 30min, adding 438g of water to emulsify to obtain polyurethane emulsion, and removing solvent acetone through reduced pressure distillation to obtain the aqueous polyurethane ink binder with the weight solid content of 33%.
The aqueous polyurethane ink vehicles obtained in examples 1-8 and comparative example 1/2 were tested for properties and the results are shown in Table 1 below.
Adhesion force: the test is carried out according to GB/T13217.7-1991, the judgment standard is that more than 90% of the printing coating is remained on the plastic film, and the adhesive force is good; the printing coating remains 80-90% on the plastic film, and has good adhesive force; 70-80% of printing coating remains on the plastic film, and the adhesive force is good; 60-70% of printing coating is remained on the plastic film, and the adhesive force is general; the printing coating remains less than 60% on the plastic film, and the adhesion is poor.
Water resistance: w is to be1Pouring water-based polyurethane ink binder on a polytetrafluoroethylene plate, drying at 120 ℃ for 2h, soaking in distilled water for 24h, taking out and wiping off water attached to the surface of the polytetrafluoroethylene plate, weighing W2Water resistance is characterized by the water absorption,% water absorption (W)2-W1)/W1The lower the water absorption, the better the water resistance, the lower the X100%.
Tensile property: pouring a certain amount of aqueous polyurethane ink binder on a polytetrafluoroethylene plate, naturally drying for 3 days at room temperature to obtain a polyurethane film with the thickness of about 1mm, placing the film in a vacuum drying oven at 50 ℃ to dry until the quality does not change any more, and then testing the tensile strength of the polyurethane film; placing the film in an environment with 70 ℃/95% humidity for three weeks, taking out and wiping off water attached to the surface of the film, and measuring the hydrolysis tensile strength, wherein the higher the hydrolysis tensile strength is, the better the hydrolysis performance is; the aqueous polyurethane ink binder is placed for six months and then made into a polyurethane film, and the tensile strength of the polyurethane film is tested, wherein the higher the tensile strength is, the better the storage stability is.
TABLE 1
In conclusion, in the embodiment of the invention, the polyether polyol grafted with the sulfonate group and the nonionic chain extender are used as structures for providing hydrophilicity of polyurethane, a solvent-free one-step production process is adopted, the preparation process is simple and convenient, the production efficiency is high, the process is non-toxic and pollution-free, and the obtained ink binder has strong adhesive force, good water resistance, high mechanical property and good storage stability, and can obviously improve the comprehensive performance of printing ink.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (2)
1. The aqueous polyurethane ink binder is characterized by being prepared from the following components in parts by weight:
the diisocyanate is a mixture of isophorone diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (HMDI), and the weight ratio of isophorone diisocyanate to dicyclohexylmethane diisocyanate is 1: 0.2-5;
the polymer polyol is selected from adipic acid type polyester polyol with the number average molecular weight of 1000-3000, and the adipic acid type polyester polyol is selected from one or more of poly (hexanediol adipate) (PHA), poly (neopentyl glycol adipate) (PNA) and poly (hexanediol adipate-neopentyl glycol) copolyester (PHNA);
the phthalic anhydride polyester polyol is polyester polyol based on phthalic anhydride-1, 6 hexanediol;
the structural general formula of the sulfonate polyether polyol is as follows:
The nonionic chain extender is polyethylene glycol monomethyl ether with single functionality based on ethylene oxide polymerization;
the chain extender is at least one selected from 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, 2, 4-trimethyl-1, 3-pentanediol, neopentyl glycol or 1, 6-hexanediol;
the preparation method of the aqueous polyurethane ink binder adopts a solvent-free one-step method and comprises the following steps: in an inert atmosphere, mixing the polymer polyol, polytetramethylene ether glycol, phthalic anhydride polyester polyol, sulfonate polyether polyol, a nonionic chain extender, a micromolecule chain extender and a catalyst, adding diisocyanate, and reacting at 80-100 ℃ for 3-4h to obtain a prepolymerization reaction system; reducing the temperature of the prepolymerization reaction system to below 50 ℃, and adding water for emulsification to obtain the aqueous polyurethane ink binder; the catalyst is selected from environment-friendly organic bismuth catalysts.
2. The aqueous polyurethane ink vehicle of claim 1, wherein the isophorone diisocyanate and dicyclohexylmethane diisocyanate are 1: 0.5-2.
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