KR102129727B1 - Manufacturing process of no-solvent type water-dispersive polyurethane resin for dip coating of suedes - Google Patents

Abstract

The present invention relates to a manufacturing process of no-solvent type water-dispersive polyurethane resin for dip coating of suedes. The process includes a first step in which polycarbonate polyol, polyether polyol, a chain extender, and a dispersant are melted and stirred, mixed and heated with diisocyanate, and mixed and heated with bismuth carboxylate catalyst to perform a reaction; a second step of preparing prepolymer; a third step of preparing a prepolymer dispersion; and a fourth step of reacting polyether amine and low molecular weight amine with the prepolymer dispersion. Accordingly, excellent mechanical strength and durability are implemented while having low viscosity.

Description

Manufacturing method of solvent-free water-dispersible polyurethane resin for suede impregnation coating {MANUFACTURING PROCESS OF NO-SOLVENT TYPE WATER-DISPERSIVE POLYURETHANE RESIN FOR DIP COATING OF SUEDES}

The present invention relates to a method of manufacturing a solvent-free water-dispersible polyurethane resin for suede impregnating coating, and more specifically, fabrics such as suede by adjusting the flowability and viscosity of a polyurethane resin having a solid content of 45% or more to an optimized range. A method of manufacturing a solvent-free water-dispersible polyurethane resin for suede impregnating coating that can provide excellent durability and soft touch even when applied to industrial and automotive materials because it can form a stable coating layer with excellent penetration characteristics when impregnated with will be.

Usually'suede' is a fabric made by imitating lamb's, goat's, and calf's leather with tannic acid or formic acid aldehyde, and gently treating the back to a velvety surface, or by imitating it. It is better known as'taxation' than the name, and, like leather, is weak against moisture and water. However, it is much more water resistant than normal leather and can be restored unless it is completely wet and messed up. The popular belief that suede is vulnerable to water is because it is not well known how to manage suede.

The suede material is widely used for clothing, gloves, belts, handbags, and shoe skins, and is also applied to industrial and automotive materials, and a product coated with a urethane resin on suede to improve the elasticity, filling and feel of the suede fabric. However, as most of the existing suede coatings use solvent-type urethane resins, environmental pollution and harmfulness to the human body due to volatile organic compounds (VOCs) generated in the product or during the manufacturing process have become a problem.

Accordingly, when a water-dispersed polyurethane resin (PUD) that does not use a solvent is used for the coating of suede, it can be manufactured as an environmentally friendly product, but when a general PUD is used for impregnating coating of suede, it has a stiff feel and low flex resistance. , Yellowing and other problems are occurring.

In addition, in order to impregnate the coating with a suede material, it is necessary to easily penetrate the resin into the suede structure, and for this, it is necessary to dilute the PUD and use it as a resin of low viscosity. In addition, in order to secure a sufficient coating weight, it is necessary to apply PUD having a high solid content.

For reference, the general manufacturing process (prepolymer method) of water-dispersible polyurethane (Poly Urethane Dispersion, PUD) is a high speed after mixing the polyol, dispersing agent (ionizing agent), isocyanate and polymerizing the prepolymer at high temperature to produce a prepolymer. After dispersing the prepolymer by injecting the polymerized prepolymer and neutralizing agent into the stirred water, and adjusting the molecular weight while performing the polymerization reaction of the dispersed prepolymer through the addition of the chain extender, the water-dispersible polyurethane resin having an appropriate molecular weight through chain extension To synthesize.

To date, a variety of products have been developed and used for water-dispersible polyurethane (PUD) resins.However, when a polycarbonate-type solvent-free water-dispersible polyurethane is manufactured by a conventional method, viscosity is high during the manufacturing process, and viscosity adjustment in the final product is required. Due to the creamy flow, the disadvantage of poor processability occurs, and thus there are many difficulties in the production of a solvent-free type resin.

In order to solve the problems of the water-dispersible polyurethane (PUD) resin as described above, Republic of Korea Patent Publication No. 10-0812635 (Hyundai Hichem Co., Ltd.) polycarbonate diol (PCD) and anion-imparting functional diol 100 to 120 ℃ The process of heating the furnace to dissolve the anion-imparting functional diol in polycarbonate diol (PCD), the process of removing moisture, the process of introducing a diisocyanate-based compound, the process of nitrogenizing the inside of the reactor, and the addition of a neutralizing agent Polymerizing the prepolymer through a process; Comprising the step of forcibly dispersing the prepolymer in a disperser containing deionized water (DIW), and polymerizing polycarbonate polyurethane (PUD) through a process of adding an extender; It is said that as a method for producing a water-dispersible polycarbonate polyurethane resin comprising filtering using a filter such as a non-woven fabric or cotton cloth, it is said that it is possible to obtain an eco-friendly water-dispersible PC/PU polyurethane resin having excellent physicochemical properties.

In addition, the registered patent publication No. 10-0969046 (Hyundai Motor Co., Ltd.) is a chain extender and 1,6-hexamethylene diisocyanate, 4,4-dicyclohexmethane diisocyanate, isophorone diisocyanate, and mixtures thereof. A first step of preparing a hard segment at the end of the isocyanate group by reacting a diisocyanate compound, which is an aliphatic compound selected from 1: 2.5 to 3 weight ratio; 100 parts by weight of the hard segment; Ether type or ester type polyol 295 to 310 parts by weight; And reacting 65 to 80 parts by weight of the diisocyanate compound to prepare a prepolymer I of a hydroxy group terminal containing a soft segment; 100 parts by weight of the prepolymer I; 2 to 3 parts by weight of a diol having a carboxyl group which is dimethylol propionic acid, dimethylol butanoic acid, or a mixture thereof; And 3 steps of preparing prepolymer II by reacting 2 to 4 parts by weight of diisocyanate compound; And 4 steps of dispersing the prepolymer II to prepare a water-dispersible polyurethane resin having a hard segment at the center of the chain and a soft segment at the end of the chain. Disclosed is a method for producing a polyurethane resin.

And when looking at the registered patent publication No. 10-1609175 (Intermaru Industry Co., Ltd.), there is no discharge of organic solvent, good processability, coating properties, water-resistant polyurethane impregnated suede knitted fabric excellent in abrasion resistance, heat resistance, light resistance, wash fastness In order to manufacture in an environmentally friendly manner, after elution, a water-soluble polyester-based island-in-the-sea yarn having a single yarn fineness of 0.01 to 0.1 denier and a single yarn fineness of 30 to 50% with a shrinkage of 20 to 30 denier/12 pillars of high shrinkage polyester filaments After knitting the interlock knitted fabric having a knitting weight of 260 to 290 g/yd and a thickness of 0.4 to 0.6 mm with interlaced yarn, it is refined and shrunk in hot water at 60 to 100°C to divide the polyester island-in-the-sea yarn, followed by dyeing, presetting, 100 to 100 parts by weight of water-dispersible polyurethane with 15 to 35% solid content, brushed, 0.1 to 5 parts by weight of acrylic thickener, 0.1 to 10 parts by weight of silicone softener, 400 to 500 parts by weight of water, mixed and mixed for 60 to 120 minutes, 1,000 to 1,000 A method for manufacturing a water-soluble polyurethane-impregnated suede knitted fabric is described, characterized by completing impregnation with a water-soluble polyurethane adjusted to a viscosity of 1,500 cps at a 10-20% pickup rate, followed by heat treatment and buffing.

On the other hand, the applicant of the present invention through the registered patent publication No. 10-1860708 (Bix Co., Ltd.) (a) 3 to 20% by weight of an organic silicone compound, (b) 12 to 40% by weight of diisocyanate, (c) 0.5 to 2 catalyst Weight%, (d) 15 to 51% by weight of polycarbonate diol, (e) 15 to 67% by weight of polyether polyol, (f) 2,2-bis(hydroxymethyl)butyl acid (DMBA) 60 to 90 parts by weight of an ionic prepolymer composed of 2 to 10% by weight; (h) 60 to 89% by weight of a hydrophilic polyol, (i) 10 to 39% by weight of a diisocyanate, (j) 10 to 40 parts by weight of a nonionic prepolymer composed of 0.5 to 2% by weight of a catalyst; (k) 1 to 4 parts by weight of a neutralizing agent; (l) An aqueous dispersion polyurethane resin composition for impregnating coating of suede comprising 2 to 8 parts by weight of an amine chain extender and a method for manufacturing the same have been developed.

However, although the water-soluble or water-dispersible polyurethane (PUD) resin according to the above-described method may achieve an environmentally friendly function to some extent, the product may have a tactile, viscous, product-like feel to be used for impregnating coating of a suede material such as the present invention. It was found that it was somewhat insufficient to simultaneously satisfy properties such as elasticity.

In the present invention, by using a combination of polycarbonate polyol, triol, blocking agent, emulsifier, polyether amine, etc., in order to secure good flowability, low viscosity, and excellent coating film formation ability when producing a solvent-free water-dispersible polyurethane resin, The present invention was completed by securing a technique for forming a coating layer having excellent durability and soft touch while forming a sufficient coating film during suede impregnation coating.

Republic of Korea Registered Patent Publication No. 10-0812635 (Announcement date of March 13, 2008) Republic of Korea Registered Patent Publication No. 10-0969046 (published on July 9, 2010) Republic of Korea Registered Patent Publication No. 10-1609175 (Announcement date April 6, 2016) Republic of Korea Registered Patent Publication No. 10-1860708 (announcement date May 24, 2018)

The object of the present invention is polycarbonate polyols, triols, blocking agents, emulsifiers and polyether amines to ensure good flowability, low viscosity, and excellent coating film formation performance when producing a polycarbonate-type solvent-free water-dispersible polyurethane resin. It is to provide a method for producing a solvent-free water-dispersible polyurethane resin for suede impregnating coating, which can form a coating layer having excellent durability and soft touch while forming a sufficient coating film during suede impregnating coating by using, for example.

The method for producing a solvent-free water-dispersible polyurethane resin for suede impregnating coating according to the present invention is 10 to 15% by weight of a polycarbonate polyol having a weight average molecular weight of 1,000 to 3,000 (a), and a polyether polyol having a weight average molecular weight of 1,000 to 3,000 (b) ) 2 to 5% by weight, 0.5 to 0.8% by weight of chain extender (c) for improving flowability and viscosity, 1.0 to 1.6% by weight of dispersant (d), and melt-stirred at a temperature of 50°C, then diisocyanate (e) a first step of adding 5 to 14% by weight and raising the temperature to 90°C, then adding a bismuth carboxylate catalyst and raising the temperature to 120°C to carry out the reaction; After adding 1 to 2% by weight of triol (f) for adjustment of strength and post-curing properties, further reacted, cooled to 60°C, and then reacted with 0.4 to 0.8% by weight of the blocking agent (g) to prepare the prepolymer. A second step of manufacturing; The polyether polyol (h) with a weight average molecular weight of 2,000 to 3,000 (h) 6.8 to 13.5 wt%, isocyanate (i) 1.1 to 2.2 wt%, and a hydrophilic polyether polyol with a weight average molecular weight of 1,000 to 2,000 (j) 2.3 to 4.6 wt% are 120 After dispersing the emulsifying aid prepared by reacting for 2 hours at ℃ and the neutralizing agent having the same molar ratio as the dispersing agent (d) in 40 to 60% by weight of water at 20 to 30°C, the prepolymer prepared in the second step is mixed. And kneading at high speed to prepare a prepolymer dispersion; 5 to 8% by weight of polyether amine (k) having a weight average molecular weight of 1,000 to 3,000 for adjustment of chain extension and flexibility, and 0.05 to 0.3% by weight of low molecular amine (l) in the prepolymer dispersion prepared in the third step It is characterized by consisting of a fourth step.

According to a preferred embodiment of the present invention, the polyether polyol (b) is polytetramethylene glycol (Polytetramethylene glycol, PTMG), polypropylene glycol (Polypropylene glycol) and at least one derived therefrom, using the chain extension The agent (c) uses any one or more polyols selected from 1,3-butanediol (1.3-BDO), 1,4-butanediol (1,4-BDO), and ethylene glycol (EG). Dispersant (d) is a DMBA (Dimethyolbutanoic acid) or DMPA (Dimethyolproponic acid) is selectively used, the diisocyanate (e) is 4,4'- methylene dicyclohexyl diisocyanate (H ₁₂ MDI), isophorone diisocyanate (Isophorone diisocyanate), tetramethyl xylene diisocyanate (Tetramethyl xylene diisocyanate), hexamethylene diisocyanate (Hexamethylene diisocyanate) selected from any one or more aliphatic isocyanate or isophorone diisocyanate (Isophorone diisocyanate) is used.

In addition, the triol (f) uses trimethylolpropane (TMP), and the blocking agent (g) is epsilon-caprolactam, delta-valerolactam, butyl cellosolve ( Butyl cellosolve), phenol (Phenol), cresol (Cresol), resorcinol (Resorcinol) and MK oxime (MEK Oxim) is selected from any one, and the low molecular amine (l) is hydrazine (Hydrazine), Any one selected from 1,3-bisaminomethylcyclohexane and Ethylendiamine is used.

The solvent-free water-dispersible polyurethane resin for suede impregnating coating obtained by the production method of the present invention has properties of 45 to 60% by weight of solid content and a viscosity of 500 to 2,000 cP/25°C.

The solvent-free water-dispersible polyurethane resin for suede impregnating coating obtained by the production method of the present invention has excellent mechanical strength and durability by applying polycarbonate polyol, but also applies an emulsifying aid and polyether amine, even under high solids content of at least 45% by weight. Since it has a low viscosity of 2,000 cP/25°C or less, and also has the advantage of being able to form excellent coating film properties without a curing agent through the application of a high temperature dissociation blocking agent and triol, the suede material to which it is applied forms a sufficient coating film during coating. However, it has an excellent feel and durability.

Hereinafter, a method of manufacturing a solvent-free water-dispersible polyurethane resin for suede impregnating coating according to the present invention will be described, which can be easily carried out by a person skilled in the art to which the present invention pertains. This is for illustrative purposes only, and is not meant to limit the technical spirit and scope of the present invention.

The method for preparing the solvent-free water-dispersible polyurethane resin for suede impregnating coating according to the present invention is 10 to 15% by weight of a polycarbonate polyol having a weight average molecular weight of 1,000 to 3,000 (a), and a polyether polyol having a weight average molecular weight of 1,000 to 3,000 (b) ) 2 to 5% by weight, 0.5 to 0.8% by weight of chain extender (c) for improving flowability and viscosity, 1.0 to 1.6% by weight of dispersant (d), and melt-stirred at a temperature of 50°C, then diisocyanate (e) a first step of adding 5 to 14% by weight and raising the temperature to 90°C, then adding a bismuth carboxylate catalyst and raising the temperature to 120°C to carry out the reaction; After adding 1 to 2% by weight of triol (f) for adjustment of strength and post-curing properties, further reacted, cooled to 60°C, and then reacted with 0.4 to 0.8% by weight of the blocking agent (g) to prepare the prepolymer. A second step of manufacturing; The polyether polyol (h) with a weight average molecular weight of 2,000 to 3,000 (h) 6.8 to 13.5 wt%, isocyanate (i) 1.1 to 2.2 wt%, and a hydrophilic polyether polyol with a weight average molecular weight of 1,000 to 2,000 (j) 2.3 to 4.6 wt% are 120 After dispersing the emulsifying aid prepared by reacting for 2 hours at ℃ and the neutralizing agent having the same molar ratio as the dispersing agent (d) in 40 to 60% by weight of water at 20 to 30°C, the prepolymer prepared in the second step is mixed. And kneading at high speed to prepare a prepolymer dispersion; 5 to 8% by weight of polyether amine (k) having a weight average molecular weight of 1,000 to 3,000 for adjustment of chain extension and flexibility, and 0.05 to 0.3% by weight of low molecular amine (l) in the prepolymer dispersion prepared in the third step It is done in the order of the fourth stage.

The first step is 10 to 15% by weight of polycarbonate polyol (a) having a weight average molecular weight of 1,000 to 3,000, and 2 to 5% by weight of polyether polyol (b) having a weight average molecular weight of 1,000 to 3,000, for improving flowability and viscosity. After adding chain extender (c) 0.5 to 0.8% by weight, dispersant (d) 1.0 to 1.6% by weight, and stirring and stirring at a temperature of 50°C, diisocyanate (e) 5 to 14% by weight and heating up to 90°C Next, it is a process of adding a bismuth carboxylate catalyst and raising the temperature to 120°C to carry out the reaction.

When the polycarbonate polyol (a) is prepared by applying to a solvent-free water-dispersible polyurethane in a conventional manner, the viscosity of the prepolymer is high due to the unique bonding properties, and thus the viscosity is easily increased during the manufacturing process. Due to this, it is difficult to adjust the viscosity in the final product and exhibits a creamy flow, resulting in poor processability and poor permeability to the fabric, as well as insufficient durability to implement a sufficient coating layer, which is expressed in urethane resin. You will not be able to exert the characteristic elasticity.

In other words, when a high-moisture-dispersed polyurethane resin having a solvent-free ionic functional group is synthesized using a conventional polycarbonate polyol, the higher the molecular weight, the higher the viscosity and the lower the stability during dispersion, resulting in a high molecular weight water-dispersible poly There is a problem that the synthesis of urethane resin is difficult. For this reason, it is known that the properties of processability, coating property, elasticity, and rebound resilience are inferior to that of the solvent-type general polyurethane, and thus it is difficult to use polycarbonate polyols in water-dispersible polyurethane resins, and thus, it has been used for limited applications.

However, in the present invention, when the polycarbonate polyol (a) having a weight average molecular weight of 1,000 to 3,000 and diisocyanate (e) are reacted, a partial increase of the molecular weight of the prepolymer was applied by partially applying a blocking agent (g), thereby increasing the excessive viscosity. It was solved that the difficulty of the solvent-free type resin due to this, and finally, it was contemplated that a PUD resin having improved bending resistance, light resistance, water resistance, and heat resistance could be synthesized.

The polyether polyol (b) having a weight average molecular weight of 1,000 to 3,000 mixed with a small amount with respect to the polycarbonate polyol (a) is polytetramethylene glycol, polypropylene glycol, and one or more kinds derived therefrom. It is possible to use polyether polyol, and most preferably, a product manufactured by applying polytetramethylene glycol (PTMG) having a weight average molecular weight of 1,000 to 3,000 showed the best touch and good reactivity.

In addition, the chain extender (c) is for improving flowability and viscosity, 1,3-butanediol (1.3-BDO), 1,4-butanediol (1,4-BDO), ethylene glycol It is preferable to use any one or more polyols selected from (EG), and in the present invention, it is confirmed to be suitable if it contains about 0.5 to 0.8% by weight based on the total weight of the polyurethane resin. As the dispersant (d), DMBA (Dimethyolbutanoic acid) or DMPA (Dimethyolproponic acid) may be selectively used, but DMBA is more preferably used for a solvent-free PUD.

The diisocyanate (e) in the first step is 4,4'-methylene dicyclohexyl diisocyanate (H ₁₂ MDI), isophorone diisocyanate, tetramethyl xylene diisocyanate, hexa Any one or more aliphatic isocyanates or isophorone diisocyanates selected from Hexamethylene diisocyanate may be used, and when considering the gelation and viscosity change of the polyurethane resin, isophorone diisocyanate is the most preferred. desirable.

Next, the second step is a process of preparing prepolymer by adding 1 to 2% by weight of triol (f), further reacting, cooling to 60°C, and reacting with 0.4 to 0.8% by weight of blocking agent (g). , The triol (f) is for adjustment of strength and post-curing properties, and a low molecular weight triol having three OH functional groups may be used, and in the present invention, trimethylolpropane (TMP) is used. It can be used alone or can be reacted by injecting a polyol such as polycarbonate diol (PCD), which can be reacted by dispersing the blocking agent (g) so that the chain of the triol (f) can form a curing structure ( After a, b) and diisocyanate (e) react first, it is preferable to add 1 to 2% by weight of trimethylolpropane based on the entire polyurethane resin and further react.

Here, the blocking agent (g) is applied to the end of an isocynet and dissociates at a high temperature of 90 to 160°C to produce NCO curing. When used for blocking of a curing agent or a urethane resin for a high solids solvent, Although it is sometimes used for the production of water-dispersion isocynet, it is confirmed that it is not used in conventional solvent-free polyurethane resins.

Examples of the blocking agent (g) are epsilon-caprolactam, delta-valerolacactame, butyl cellosolve, phenol, phenol, cresol, resorcinol, and Any one selected from MK Oxim may be used, and for adjusting the reactivity, it is suitable to react with triol (f), cool to 60° C., and then input.

The blocking agent (g) suppresses an increase in viscosity due to an increase in the molecular weight of the prepolymer in the process of preparing a prepolymer as compared to the case where it is synthesized in the ratio of the existing isocyanate, and thus a prepolymer having a relatively low viscosity and a solvent-free number using the same It may be a requirement to produce a dispersed polyurethane resin. Then, the blocking agent (g) is dissociated at a temperature suitable for each blocking agent (g) at the time of coating to activate the NCO group, and a curing agent is not used through reaction with the NCO group and residual -methyl, amine, and -OH, -NH groups. It is grown to a molecular weight sufficient to form a urethane coating film having excellent durability without being required.

The third step is polyether polyol (h) 6.8 to 13.5% by weight having a weight average molecular weight of 2,000 to 3,000, isocyanate (i) 1.1 to 2.2% by weight, hydrophilic polyether polyol having a weight average molecular weight of 1,000 to 2,000 (j) 2.3 to 4.6 After dispersing the emulsifier and the neutralizing agent having the same molar ratio as the dispersant (d) prepared by reacting the weight% at 120°C for 2 hours, dispersing it in 40 to 60% by weight of water at 20 to 30°C, and then preparing in the second step. A process of preparing a prepolymer dispersion by mixing the prepolymers and kneading them at a high speed, wherein the emulsifying aid is a polyether polyol (h) having a weight average molecular weight of 2,000 to 3,000 in order to form a solid and improve compatibility, flowability, and dispersibility. And isocyanate (i) and hydrophilic polyether polyol (j) are appropriately mixed and reacted at 120° C. with a reaction retarder and catalyst for about 2 hours.

In the present invention, a high-speed dispersion of a neutralizing agent (TEA) and an emulsifying aid corresponding to a molar ratio of a dispersant (d) in water of 40 to 60% by weight compared to a polyurethane resin for the production of a polyurethane resin having a solid content of 45% or more in solid content To prepare a stable emulsion having a low viscosity, the prepolymer prepared in the second step is mixed and a prepolymer dispersion is prepared through high-speed stirring for 10 to 30 minutes in deionized water maintained at 20 to 30°C.

The emulsifier is preferably used in an amount of about 10 to 20% by weight compared to the polyurethane resin, and the hydrophilic polyether polyol (j) is for imparting dispersibility, specifically polyethylene glycol (PEG), polyethylene glycol Any one or more selected from macromers (poly(ethylene glycol) macromer) (PEGM) may be used.

In addition, the neutralizing agent may be used, such as triethylamine (Triethylamine, TEA) in the same molar ratio as the dispersing agent (d), as a reaction retardant in the process of preparing the emulsifier, phosphoric acid (H ₃ PO ₄ ), catalyst As the furnace, bismuth-based catalysts, tertiary amine-based catalysts, and organometallic catalysts such as dibutyltin dilaurate may be used.

The final fourth step is through the process of reacting 5 to 8% by weight of polyether amine (k) having a weight average molecular weight of 1,000 to 3,000, and 0.05 to 0.3% by weight of low molecular amine (l) to the prepolymer dispersion prepared in the third step. Water-dispersible polyurethane resin is prepared, the prepolymer dispersion is a polyether amine (k) and low molecular amine (l) for adjusting the chain extension (chain extension) and flexibility at a temperature of 30 ℃ or less the object of the present invention It is to obtain a solvent-free high solids water dispersion polyurethane resin.

The polyether amine (k) may use diamine having a molecular weight of 1,000 to 3,000 prepared from propylene oxide (PO), ethylene oxide (EO), or a mixture thereof, preferably derived from PPG or PEG You can proceed with the chain extension using the old Jeffamine D-2000 (manufactured by Huntsman). In addition, any one or more selected from hydrazine, 1,3-bisaminomethylcyclohexane [1,3-bis(aminomethyl)cyclohexane], and ethylenediamine may be used as the low-molecular amine (l). Preferably, the resin to which hydrazine was applied was found to have the best flexibility.

As described above, when the water-dispersible polyurethane resin prepared through the present invention is used for impregnating coating, distilled water is mixed and diluted in a weight ratio of about 1: 1 to 8 compared to the polyurethane resin, so that the impregnation liquid solid content is 5 to 33 weight. It is preferable to adjust the PUD impregnation solution to be about %.

[Example 1]

-Prepolymer production

In a 4-neck 1L reactor, 200 g of polycarbonate diol (PCDL2000) and 50 g of polypropylene glycol 1000 (PPG1000), 18.1 g of 2,2-bis(hydroxymethyl)butyl acid (DMBA), 1,3-butanediol (1,3- BD) 9 g is uniformly mixed at a temperature of 50°C. Then, 145.8 g of isopropyl diisocyanate (IPDI) was added and stirred to uniformly mix at 90°C. After the exothermic reaction is over, a bismuth carboxylate catalyst is added and reacted at 120° C. for 2 hours. Subsequently, 20.1 g of trimethylolpropane (TMP) was added and further reacted for 1 hour, then cooled to below 60°C, and 8.7 g of MEK Oxim was added thereto, followed by additional reaction for 1 hour, and 0.6 to 0.9 meqNCO When /g terminates the reaction.

-Preparation of emulsifying aids

128.3 g of polypropylene glycol (PPG3000) and 43 g of polyethylene glycol 1000 (PEG1000) were uniformly mixed in a 4-neck 1 L reactor, and then 21.4 g of 4,4'-diphenylmethane diisocyanate (MDI) was uniformly added at 90°C. Stir to mix. After the exothermic reaction is over, a bismuth carboxylate catalyst is added and reacted at 120° C. for 2 hours.

-Dispersion and chain extension

After adding a quantity of TEA compared to DMBA to 734 g (23° C.) of deionized water prepared in advance, 192.7 g of an emulsifying aid is rapidly dispersed. When the dispersion is completed, the water temperature is maintained at 23 ~ 30 ℃ while dispersing the 451.7g prepolymer in a mixed aqueous solution at a high speed of 150rpm or less within 30 minutes, and then adding 100g of Jeffamine D2000 (manufactured by Huntsman) within 30 minutes. The reaction is carried out until there is no change in NCO%. Thereafter, 1.1 g of hydrazine is diluted in 11 g of deionized water and added in small portions. As a result, a water-dispersible polyurethane resin for impregnating coating with a solid content of 50% by weight and a viscosity of 1,200 cps/25°C was obtained.

-Suede impregnated coating

100 g of water-dispersed polyurethane resin obtained through the above process was diluted in 500 g of distilled water to prepare a blend and impregnated with a PET single/double-sided or CDP single-sided/double-sided suede having a thickness of 3.0 mm or more in this solution for 2 minutes. After pressing, a pressing process using a mangle was performed 2 to 5 times, and then, under the temperature of 80°C, 100°C, 120°C, and 160°C, each was dried for 30 seconds to 2 minutes to prepare a suede material.

[Example 2]

Example 2 was prepared in the same manner as in Example 1, except for reducing the amount of TMP and MEK Oxim to 15g and 6.5g, respectively, and adjusting the amount of IPDI in accordance with the changed amount of OH.

[Example 3]

In Example 3, the amount of TMP and MEK Oxim was increased to 30 g and 13 g, respectively, in order to increase the solid content to 60% by weight, to reduce the amount of water used to 596 g and to improve the viscosity and flowability of the prepolymer during dispersion, and the amount of the emulsifier was 300 g. It was adjusted to prepare a resin. In addition, a water-dispersible polyurethane resin was prepared in the same manner as in Example 1, except that the amount of IPDI was adjusted according to the equivalent of the changed -OH and -amine groups.

[Comparative Example 1]

In Comparative Example 1, the amounts of TMP and MEK Oxim were adjusted to 0, and changed accordingly. A water-dispersible polyurethane resin was prepared in the same manner as in Example 1, except that the amount of IPDI was adjusted according to the equivalent of the -OH and -amine groups.

[Experimental Example 1]

The ratio of the raw materials input to prepare the water-dispersible polyurethane resins of Examples 1 to 3 and Comparative Example 1 is as shown in [Table 1] below, and the results of measuring the physical properties of the water-dispersible polyurethane resins are as follows. Table 2].

Raw material (g) ＼ Category Example 1 Example 2 Example 3 Comparative Example 1 (a) PCDL 200 200 200 200 (b) PPG 50 50 50 50 (c) 1,3-BD 9 9 9 9 (d) DMBA 18.1 18.1 18.1 18.1 (e) IPDI 145.8 131.6 173.0 90.2 (f) TMP 20.1 15 30 0 (g) MEK Oxim 8.7 6.5 13 0 (h,i,j) Emulsifier 192.7 192.7 300 192.7 (k) D-2000 100 100 100 100 (l) MH 1.1 1.1 1.1 1.1 water 745 724 596 661

division Example 1 Example 2 Example 3 Comparative Example 1 Solid content (w%) 50 50 60 50 Viscosity (cP) 1,200 2,000 1,800 80,000 Tensile strength (㎏f/㎠) 400 350 350 200 Elongation (%) 600 700 500 400 Flexural strength (times) 100,000≤ 100,000≤ 100,000≤ 100,000≤

○ Tensile strength and elongation: Measured by ASTM E252 method

○ Flexural strength: measured by DIN53343 method

From the results of [Table 2], the polycarbonate type high solid hydrophilic water-dispersible polyurethane resin prepared according to the present invention has a low viscosity of 2,000 cP/25° C. or less and a tensile strength of 350 even when it is prepared with a solid content of 45% by weight or more. It can be seen that it has excellent coating film strength of more than ㎏f/㎠ and a coating film strength that exhibits elongation of 500% or more, and has excellent durability comparable to existing solvent-type resins when impregnated and coated with suede.

Therefore, the water-dispersible polyurethane resin prepared according to the present invention has high durability and soft touch when coated on suede fabrics used for industrial and automobiles as well as household goods that require surface treatment within the scope of the technical idea of the present invention. It can be used in various uses and forms as an eco-friendly material that can implement.

Claims (7)

Polycarbonate polyol having a weight average molecular weight of 1,000 to 3,000 (a) 10 to 15% by weight, polyether polyol having a weight average molecular weight of 1,000 to 3,000 (b) 2 to 5% by weight, chain extender for improving flowability and viscosity ( c) 0.5 to 0.8% by weight, dispersant (d) 1.0 to 1.6% by weight, and then melt-stirred at a temperature of 50°C, diisocyanate (e) 5 to 14% by weight, heated to 90°C, and bismuthcar A first step of adding a carboxylate catalyst and raising the temperature to 120° C. to conduct the reaction;
After adding 1 to 2% by weight of triol (f) for adjustment of strength and post-curing properties, further reacted, cooled to 60°C, and then reacted with 0.4 to 0.8% by weight of blocking agent (g) to prepare the prepolymer. A second step of manufacturing;
The polyether polyol (h) with a weight average molecular weight of 2,000 to 3,000 (h) 6.8 to 13.5 wt%, isocyanate (i) 1.1 to 2.2 wt%, and a hydrophilic polyether polyol with a weight average molecular weight of 1,000 to 2,000 (j) 2.3 to 4.6 wt% are 120 After dispersing the emulsifying aid prepared by reacting for 2 hours at ℃ and the neutralizing agent having the same molar ratio as the dispersant (d) in 40 to 60% by weight of water at 20 to 30°C, the prepolymer prepared in the second step is mixed And kneading at high speed to prepare a prepolymer dispersion;
5 to 8% by weight of polyether amine (k) having a weight average molecular weight of 1,000 to 3,000 for adjustment of chain extension and flexibility, and 0.05 to 0.3% by weight of low molecular amine (l) in the prepolymer dispersion prepared in the third step The fourth step;
Method for producing a solvent-free water-dispersible polyurethane resin for suede impregnating coating, characterized in that consisting of. According to claim 1,
The polyether polyol (b) is a polytetramethylene glycol (Polytetramethylene glycol, PTMG), polypropylene glycol (Polypropylene glycol) and a solvent-free water-dispersible poly for suede impregnating coating, characterized in that using one or more derived from them Manufacturing method of urethane resin. According to claim 1,
The chain extender (c) uses any one or more polyols selected from 1,3-butanediol (1.3-BDO), 1,4-butanediol (1,4-BDO), and ethylene glycol (EG). And, the dispersant (d) is a method for producing a solvent-free water-dispersible polyurethane resin for suede impregnating coating, characterized in that selectively using Dimethyolbutanoic acid (DMBA) or Dimethyolproponic acid (DMPA). According to claim 1,
The diisocyanate (e) is 4,4'-methylene dicyclohexyl diisocyanate (H ₁₂ MDI), isophorone diisocyanate, tetramethyl xylene diisocyanate, hexamethylene diisocyanate (Hexamethylene) diisocyanate) method for producing a solvent-free water-dispersible polyurethane resin for suede impregnating coating, characterized by using any one or more aliphatic isocyanates or isophorone diisocyanate. According to claim 1,
The triol (f) is trimethylolpropane (Trimethylolpropane, TMP) characterized in that using a suede impregnated coating method for producing a water-dispersible polyurethane resin. According to claim 1,
The blocking agent (g) is epsilon-caprolactam, delta-valerolacactame, butyl cellosolve, phenol, phreol, cresol, resorcinol and Any one selected from MK Oxim is used, and the low-molecular amine (l) is hydrazine, 1,3-bisaminomethylcyclohexane (1,3-bis(aminomethyl)cyclohexane), Method for producing a solvent-free water-dispersible polyurethane resin for suede impregnating coating, characterized in that any one selected from Ethylendiamine is used. A solvent-free water-dispersible polyurethane resin for suede impregnating coating obtained in a range of 45 to 60% by weight solids and a viscosity of 500 to 2,000 cP/25°C by the method of any one of claims 1 to 6.