KR101804939B1 - Starch sugar-based waterborne polyurethane resin and manufacturing method thereof - Google Patents

Abstract

The present invention is to provide an aqueous dispersion polyurethane resin which has a carbamate bond formed by a reaction between polyisocyanate and polyol, and in which polyurethane prepolymers having an isocyanate group at the end have a structure in which the whole chain is extended through the medium of sugar mixtures. According to an embodiment of the present invention, the aqueous dispersion polyurethane resin is environment-friendly by using starch derived sugar mixtures as a chain extender during a manufacturing process. Also, the aqueous dispersion polyurethane resin has excellent applicability, film formation and film adhesion. The aqueous dispersion polyurethane resin can be used as a main component applying adhesion to a packaging adhesive or the like.

Description

[0001] The present invention relates to a starch sugar-based waterborne polyurethane resin and a manufacturing method thereof,

The present invention relates to a water-dispersible polyurethane resin and a method for producing the same, and more particularly, to a starch-dispersed water-dispersible polyurethane resin having excellent water dispersibility and adhesion to a coating film, and a method for producing the same.

Polyurethane is a polymer material that is widely used in the fields of automobiles, paints, furniture, and textiles. Conventional polyurethanes have been easily prepared by solution polymerization in organic solvents due to the hydrophobicity of the raw materials. In the 1970s, along with the oil surge, the importance of energy conservation increased rapidly, and with the continuous development of the industrial sector, the problem of environmental pollution became seriously perceived by the general public, and the regulation of volatile organic matter emitted from the chemical industry sector began.

In order to avoid such regulations, the replacement with waterborne polyurethane has been tried. The water-dispersible polyurethane can be defined as a colloidal system in which the polyurethane particles are dispersed in a continuous aqueous medium. Water-dispersible polyurethanes have received attention in the field of environmentally friendly plastics materials for the following reasons. First, water-dispersible polyurethanes have the advantage of inhibiting the use of volatile organic solvents that can cause pollution in the global ecosystem, such as air pollution, ozone depletion, and acid rain. Second, the water-dispersible polyurethane does not require any additional solvent, which is advantageous in terms of cost as compared with the case of using an organic solvent. Third, it has an advantage that superior performance can be achieved in a specific application field by using a conventional organic solvent. Fourth, the water-dispersible polyurethane can be produced with high solids content and high molecular weight. Despite these various advantages, the water-dispersible polyurethane has a low drying rate due to the introduction of a hydrophilic group in the chain, a low hydrolysis capacity, an initial adhesive strength and mechanical properties lower than that of a polyurethane using a conventional organic solvent, And the like. However, various attempts have been made to maximize the advantages and to reinforce the disadvantages. Methods of improving mechanical and thermal properties by hybridization of water-dispersible polyurethane and inorganic materials, and improving scratch resistance, abrasion resistance and hardness through ultraviolet (UV) curing have already been widely used.

The water-dispersible polyurethane is a non-toxic, non-inflammable, environmentally compatible material with a partial hydrophobicity caused by the existing hydrophilic properties and soft segments, and therefore improves the properties through blending with starch Research has been going on. Due to the reaction between excess isocyanate groups (-N = C = O) present in the polyurethane and the hardlock group (-OH) present in the starch, a flexible polyurethane material consisting of soy protein and corn starch foam can also be produced. On the other hand, in order to form a film by applying a blend of polyurethane and starch and drying the film or to prepare a film from a blend of polyurethane and starch, a starch hydrolysis process is required. In this process, carbon dioxide gas is released due to reaction of isocyanate group and water Therefore, there is a problem that the foam is in the form of a foam, and the bonding force between the polyurethane and the starch is weakened.

Regarding the technology for producing a water-dispersible polyurethane, Korean Patent Registration No. 10-1633680 discloses an energetic polyol having two or more hydroxyl groups and containing at least one of an alkyl azide and a nitro group in the structure, a polyisocyanate and an ion Reacting the compound imparted with the terminal isocyanate prepolymer to prepare a terminal isocyanate prepolymer; Dissolving the terminal isocyanate prepolymer in water to prepare an aqueous solution; And adding a chain extender to the aqueous solution to chain-extend the terminal isocyanate prepolymer, thereby producing a water-dispersible energetic polyurethane. Also, Korean Patent No. 10-1609806 discloses a process for producing an isocyanate-terminated polyurethane prepolymer by mixing and reacting a polyol having a hydroxy group, a diol having a carboxyl group and an aliphatic diisocyanate; Neutralizing the isocyanate-terminated polyurethane prepolymer with a tertiary amine to prepare a self-emulsifiable prepolymer; Water-dispersing the self-emulsifiable prepolymer by water; And a step of preparing a water-dispersible polyurethane resin by subjecting a water-dispersed self-emulsifiable prepolymer to water-dispersible polyurethane using 2-methylcyclohexane-1,3,5-triamine as a branching agent. Method is disclosed. Korean Patent Registration No. 10-0829541 discloses a process for producing a polyurethane foam comprising a) ester-based polyol having a weight average molecular weight of 500 to 4,000 and adipic acid and lower alcohols chain-extended with diisocyanate in an equivalent ratio of 1: 1 to 1 : 1.3; b) adding 0.001 to 0.01% by weight of a tin catalyst to the reactant and reacting; c) chain extending the reactant to lower alcohols; d) reacting an ether-based ionic polyol containing a sulfonic acid salt having a weight average molecular weight of 200 to 600 with a sulfonate ion group added to the main chain of the ether polyol; e) adding water to the reactant in an amount of 2.5 times the weight of the reactant; and f) extending the chain by chain extension using an amine having a functional group of 2 to 4 in the reactant to improve the durability of the water dispersible polyurethane. In the prior art, a chain extender is used to extend the chain of the isocyanate-terminated polyurethane prepolymers such as ethylenediamine, hexamethylenediamine, isophoronediamine, ethylene glycol, diethylene glycol, 1,4-butanediol, glycerin, melamine, Diethylenetriamine, triethylenetereamine, N-methyl-diethanolamine, N-butyl-diethanolamine, N-oleyldiethanolamine, N-cyclohexyl-diethanolamine, N, Lower alcohols or polyfunctional amines such as N, N-dimethylethylenediamine and N, N-dimethyl-propylenediamine, 2-methylcyclohexane-1,3,5-triamine and the like are used.

The object of the present invention is to provide a water-dispersible polyurethane resin which is excellent in film-forming ability or coatability of a coating film and which is produced by a non-stone-based eco-friendly material, and a method for producing the same.

The inventors of the present invention have found that when a water dispersible polyurethane is produced by extending a chain of polyurethane prepolymers having an isocyanate group at the terminal thereof, when a specific starch is used as a chain extender, production of a water-dispersible polyurethane resin having excellent water- And the present invention has been completed.

In order to achieve the above object, an example of the present invention relates to a polyurethane resin composition comprising a carbamate bond formed by a reaction between a polyisocyanate and a polyol, and a polyurethane prepolymer having an isocyanate group at a terminal, Wherein the saccharide mixture comprises 2-15% by weight of saccharides having a hexose-based degree of polymerization of 4 and 55-90% by weight of saccharides having a hexose-based degree of polymerization of 4 or higher based on the total weight of the saccharide mixture, And a water-dispersible polyurethane resin.

Another object of the present invention is to provide a polyurethane prepolymer solution having an isocyanate group at its terminal by reacting a polyisocyanate with a polyol in an organic solvent; Neutralizing the polyurethane prepolymer solution with an amine compound to prepare a neutralized polyurethane prepolymer solution; And adding the neutralized polyurethane prepolymer solution to an aqueous solution of a saccharide mixture to induce a chain extension reaction to produce a polyurethane resin, wherein the saccharide mixture is hexose-based And 2 to 15% by weight of a saccharide having a degree of polymerization of 4 and 55 to 90% by weight of saccharides having a hexose-based degree of polymerization of 4 or more. The present invention also provides a method for producing a water-dispersible polyurethane resin.

The water-dispersible polyurethane resin according to one example of the present invention is eco-friendly because it uses a starch-derived sugar mixture as a chain extender during the production process. Further, the water dispersible polyurethane resin according to one example of the present invention is excellent in coatability, film-forming ability, and coating strength. Accordingly, the water-dispersible polyurethane resin according to one embodiment of the present invention can be used as a main component for imparting an adhesive force to a packaging adhesive or the like.

1 is a milky white water-dispersible polyurethane resin prepared by using Syncsta L20 product as a chain extender in Production Example 1 of the present invention.
2 is a gel polyurethane resin prepared using Syncsta L21 product as a chain extender in Comparative Production Example 1 of the present invention.
3 is a gel polyurethane resin prepared using Syncsta L21 product as a chain extender in Comparative Production Example 2 of the present invention.

Hereinafter, the present invention will be described in detail.

One aspect of the present invention relates to a water-dispersible polyurethane resin that is eco-friendly, but also has excellent coatability, film-forming ability, or adhesion of a coating film. The water-dispersible polyurethane resin according to an embodiment of the present invention is characterized in that carbamate bonds formed by the reaction between a polyisocyanate and a polyol and polyurethane prepolymers having an isocyanate group at a terminal are bonded to each other through a saccharide mixture . The carbamate bond is the same as urethane bond. Hereinafter, the water-dispersible polyurethane resin according to one example of the present invention will be described separately for each constituent component.

Polyisocyanate

In the present invention, the polyisocyanate is not limited to a specific type as long as it has two or more isocyanate groups. Examples of the polyisocyanate include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates and aromatic polyisocyanates which are commonly used in the production of polyurethane have. Examples of aliphatic polyisocyanates usable in the present invention include aliphatic polyisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate , 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, Aliphatic diisocyanates such as 12-dodecamethylene diisocyanate; For example, lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, Aliphatic triisocyanates such as triisocyanate hexane and 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane. Examples of the alicyclic polyisocyanates usable in the present invention include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5 , 5-trimethylcyclohexylisocyanate (isophorone diisocyanate), 4,4'-methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate , 1,3- or 1,4-bis (isocyanatemethyl) cyclohexane (common name: hydrogenated xylene diisocyanate) or a mixture thereof, and norbornane diisocyanate; For example, 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethylisocyanate cyclohexane, 2- (3-isocyanate propyl) -2,5-di (isocyanatomethyl) -bicyclo [2.2. (Isocyanatomethyl) -bicyclo (2.2.1) heptane, 3- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) (2.2.1) heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3- isocyanatopropyl) -bicyclo (3-isocyanatopropyl) -bicyclo (2.2.1) heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- Alicyclic triisocyanates such as cyclo (2.2.1) -heptane and 6- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3- isocyanatopropyl) -bicyclo There. Examples of the aromatic aliphatic polyisocyanate usable in the present invention include 1,3- or 1,4-xylene diisocyanate or a mixture thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1, Aromatic aliphatic diisocyanates such as 3- or 1,4-bis (1-isocyanate-1-methylethyl) benzene (common name: tetramethyl xylene diisocyanate) or mixtures thereof, And aromatic aliphatic triisocyanates such as isocyanate methylbenzene. Examples of the aromatic polyisocyanate usable in the present invention include m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 2,4 ' - or 4,4'-diphenylmethane diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof, 4,4'-toluidine diisocyanate, 4,4'-diphenylether di Aromatic diisocyanates such as isocyanate; For example, aromatic triisocyanates such as triphenylmethane-4,4 ', 4 "-triisocyanate, 1,3,5-triisocyanate benzene and 2,4,6-triisocyanatetoluene; Aromatic tetraisocyanates such as 4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate, etc. These polyisocyanates may be used alone or in combination of two or more. The isocyanate is preferably selected from 4,4'-methylenebis (cyclohexyl isocyanate), hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate and the like

Polyol

In the present invention, the polyol is a generic name of a polyhydroxy compound which can be obtained by replacing a large number of hydrogens present on a hydrocarbon with a hydroxyl group. Specifically, a polyol is a product obtained by subjecting one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran) to an addition polymerization of a compound having two or more active hydrogen atoms. Specific examples of the compound having two or more active hydrogens usable in the present invention include ethylene glycol, propylene glycol, butane diol, diethylene glycol, glycerol, hexanetriol, trimethylol propane, pentaerythritol and the like . Further, polyether polyols (for example, polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyoxypropylene diol, polyoxypropylene triol and polyoxybutylene glycol), polyolefin polyols (for example, poly Polyhydric alcohols such as butadiene polyol and polyisoprene polyol), polytetramethylene oxide glycol (PTMG), adipate polyol, lactone polyol, polyester polyol (for example, castor oil) and polyhydric phenols such as resorcinol and bisphenol . In the present invention, the polyol is preferably a polyester polyol. The polyester polyol can be obtained by depolymerizing a polyester with a polyol having two or more hydroxyl groups in one molecule. Examples of the polyesters usable for forming the polyester polyol include polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene terephthalate and the like. Examples of the polyol include ethylene glycol , 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, diethyleneglycol, triethyleneglycol, polyethylene glycol, dipropyleneglycol, 1,3-butanediol, neopentyl But are not limited to, glycols, spiroglycols, dioxane glycols, adamantanediol, 3-methyl-1,5-pentanediol, methyloctanediol, 1,6-hexanediol, 1,4- Propanediol, hexamethylene glycol, octylene glycol, 9-nonanediol, 2,4-diethyl-1,5-pentanediol, and the like. In the present invention, the polyester polyol may be an adipic acid / isophthalic acid copolymer, an adipic acid / diethylene glycol copolymer, an adipic acid / 1,4-butanediol copolymers, adipic acid / ethylene glycol copolymers, adipic acid / isophthalic acid / neo Neopentyl glycol terpolymer, adipic acid / ehtylene glycol / 1,4-butanediol terpolymer, adipic acid, / Isophthalic acid / diethylene glycol ternary copolymer, adipic acid / 1,4-butanediol / neopentyl glycol tertiary Copolymer or adipic acid / ethylene glycol / 1,4-butanediol / neopentyl glycol Employees Polymer, it is preferable to use one or more selected from the group consisting of adipic acid / isophthalic acid copolymer, adipic acid (adipic acid), adipic acid it is more preferable that the copolymer is composed of a combination of an acid / diethylene glycol copolymer and an adipic acid / 1,4-butanediol copolymer. Further, in the present invention, the number average molecular weight of the polyester polyol is preferably 1,000 to 5,000, more preferably 1,500 to 3,000. The ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the polyol constituting the water dispersible polyurethane resin according to one example of the present invention is preferably from 1: 0.2 to 1: 0.9, more preferably from 1: 0.4 to 1: 0.6. The total number of equivalents of the polyisocyanate corresponds to the number of isocyanate groups (NCO) present in the polyisocyanate, and the total number of equivalents of the polyol corresponds to the number of hydroxyl groups (OH) present in the polyol. The water dispersible polyurethane resin according to the present invention is characterized in that the total equivalent number of the polyisocyanate is larger than the total equivalent number of the polyol so that the polyurethane prepolymers have an isocyanate group at the terminal and the terminal isocyanate groups of the polyurethane prepolymers react with the saccharide mixture . On the other hand, if the polyisocyanate and the polyol constituting the water dispersible polyurethane resin according to an example of the present invention have the same equivalent value per mole, the ratio of the total number of moles of the polyisocyanate to the total number of moles of the polyol is equal to the ratio of the number of equivalents Range.

Saccharide mixture

In the water dispersible polyurethane resin according to an example of the present invention, the saccharide mixture reacts with an isocyanate group existing at the end of the polyurethane prepolymers to extend the chains of the polyurethane prepolymers. In the present invention, the saccharide mixture comprises 2-15% by weight of a saccharide having a hexose-based degree of polymerization of 4 and 55-90% by weight of a saccharide having a hexose-based degree of polymerization of 4 or more based on the total weight of the saccharide mixture . In addition, in the present invention, the saccharide mixture preferably comprises 4 to 10% by weight of sugars having a glucose-based degree of polymerization of 4 based on the total weight of the saccharide mixture and 65 to 85% by weight of saccharides having a glucose- %. Further, in the present invention, the saccharide mixture preferably comprises 20 to 35% by weight of saccharides having a glucose-based degree of polymerization of 3 or less, 4 to 10% by weight of saccharides having a glucose-based degree of polymerization of 4, And 70 to 80% by weight of saccharides having a degree of polymerization of 4 or more. In addition, in the present invention, the saccharide mixture is most preferably a saccharide having 1 to 6% by weight of glucose, 7 to 15% by weight of sugars having a glucose-based degree of polymerization of 2, glucose having a degree of polymerization of 3 based on glucose, 8 to 17% by weight of glucose, 4 to 10% by weight of saccharides having a degree of polymerization of 4 based on glucose, 6 to 14% by weight of saccharides having a degree of polymerization of 5 based on glucose and glucose having a degree of polymerization of 6 Based polymer having a degree of polymerization of 7 to 4 to 10% by weight, a glucose-based polymer having a degree of polymerization of 8 to 0.5 to 5% by weight, a glucose-based degree of polymerization of 9 0.5 to 5% by weight of saccharides having a degree of polymerization of 10 or more based on glucose as a balance. The average molecular weight of the saccharide mixture in the present invention is preferably 650 to 1,500, more preferably 700 to 1,000, and most preferably 700 to 900. In the present invention, when the average molecular weight of the saccharide mixture is less than 650, the polyurethane resin formed by the chain extension reaction of the polyurethane prepolymers and the saccharide mixture may become gelled. When the average molecular weight of the saccharide mixture is more than 1,500, the chain extension of the polyurethane prepolymers and saccharide mixture The reaction hardly occurs. The ratio of the total equivalent number of the polyisocyanate constituting the water dispersible polyurethane resin to the total equivalent number of the saccharide mixture is preferably 1: 0.2 to 1: 0.9, more preferably 1: 0.4 to 1: : 0.65 is more preferable. The total equivalent number of the polyisocyanate corresponds to the number of isocyanate groups (NCO) present in the polyisocyanate and the total equivalent number of the saccharide mixture corresponds to the number of reactive hydroxyl groups (OH) present in the saccharide mixture. The saccharide mixture used in the present invention has an average equivalent value of 2 eq / mol. If the polyisocyanate and the saccharide mixture constituting the water dispersible polyurethane resin according to an example of the present invention have the same equivalent value per mole, the ratio of the total number of moles of the polyisocyanate to the total number of moles of the mixture of saccharides is equal to the ratio of the number of equivalents Range.

Another aspect of the present invention relates to a process for producing a water-dispersible polyurethane resin which is eco-friendly, but has excellent coatability, film-forming ability or adhesion to a coating film. A method for producing a water-dispersible polyurethane resin according to another embodiment of the present invention includes the steps of producing a polyurethane prepolymer solution having an isocyanate group at its terminal, preparing a neutralized polyurethane prepolymer solution, and producing a polyurethane resin do. The method for producing a water-dispersible polyurethane resin according to another embodiment of the present invention is preferably a step of producing a polyurethane prepolymer solution having an isocyanate group at the terminal, a step of preparing a neutralized polyurethane prepolymer solution, And a step of removing the organic solvent. Hereinafter, a method for producing a water-dispersible polyurethane resin according to another example of the present invention will be described step by step.

Polyurethane having an isocyanate group at the terminal Prepolymer  The step of preparing the solution

In the method for producing a water-dispersible polyurethane resin according to another example of the present invention, the step of preparing a polyurethane prepolymer solution having an isocyanate group at a terminal thereof comprises reacting a polyisocyanate and a polyol in an organic solvent. Since the polyisocyanate and the polyol are the same as those described above, a description thereof will be omitted. The polyisocyanate is preferably selected from 4,4'-methylenebis (cyclohexyl isocyanate), hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, and the like. In addition, the polyol is preferably a polyester polyol, and specifically includes adipic acid / isophthalic acid copolymer, adipic acid / diethylene glycol copolymer, Adipic acid / 1,4-butanediol copolymer, adipic acid / ethylene glycol copolymer, adipic acid / Isopthalic acid / neopentyl glycol terpolymer, adipic acid / ehtylene glycol / 1,4-butanediol terpolymer Adipic acid / isophthalic acid / diethylene glycol terpolymer, adipic acid / 1,4-butanediol / 1,4-butanediol / Neopentyl glycol ternary copolymer or adipic acid / ethylene glycol / 1,4-butanediol ) / Neopentyl glycol acrylate copolymers, and considering the water dispersibility of the polyurethane resin or the adhesive strength of the coating film, adipic acid / isophthalic acid (referred to as " isopthalic acid copolymer, a combination of adipic acid / diethylene glycol copolymer and adipic acid / 1,4-butanediol copolymer . The ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the polyol is preferably 1: 0.2 to 1: 0.9, more preferably 1: 0.4 to 1: 0.6. On the other hand, the type of the organic solvent is not limited as long as it can dissolve the polyisocyanate and the polyol and can be easily removed due to the strong volatility. Examples thereof include methyl ethyl ketone (MEK), N-methyl- Dimethylformamide, dimethylsulfoxide, and the like. It is also preferable that the reaction of the polyisocyanate with the polyol in the step of preparing the polyurethane prepolymer solution having isocyanate groups at the terminals occurs in the presence of the dispersant. Wherein the dispersing agent is selected from the group consisting of 2,2-dimethylol acetic acid, 2,2-dimethylol propionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, A group composed of N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, 1,3-phenylenediamine-4,6-dicarboxylic acid, diaminobutane sulfonic acid and 2,3-dihydroxypropylphenyl phosphate ≪ / RTI >

Neutralized polyurethane Prepolymer  The step of preparing the solution

In the method for producing a water-dispersible polyurethane resin according to another example of the present invention, the step of preparing a neutralized polyurethane prepolymer solution comprises neutralizing a polyurethane prepolymer solution having an isocyanate group with an amine compound. At this time, it is preferable that the amine compound is a tertiary amine in consideration of the neutralization efficiency. For example, one or more amine compounds may be selected from trimethylamine, triethylamine, N-methylmorpholine, dimethylaminoethanol and ammonia water.

Step of producing polyurethane resin

In the method for producing a water-dispersible polyurethane resin according to another embodiment of the present invention, the step of producing a polyurethane resin comprises adding a neutralized polyurethane prepolymer solution to a mixture of saccharide mixtures and inducing a chain extension reaction. The chain extension reaction is a bonding reaction between an isocyanate group present at the end of the polyurethane prepolymer and a hydroxyl group present in the saccharide mixture. Since the saccharide mixture is the same as the above-mentioned contents, a description thereof will be omitted. The saccharide mixture preferably comprises 2-15% by weight of saccharides having a hexose-based degree of polymerization of 4 and 55-90% by weight of saccharides having a hexose-based degree of polymerization of 4 or more based on the total weight of the saccharide mixture More preferably 4 to 10% by weight of saccharides having a glucose-based degree of polymerization of 4 based on the total weight of the saccharide mixture and 65 to 85% by weight of saccharides having a glucose-based degree of polymerization of 4 or more . In the method for producing a water dispersible polyurethane resin according to another example of the present invention, the ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the saccharide mixture is preferably 1: 0.2 to 1: 0.9, more preferably 1: 1: 0.65.

Step of removing organic solvent

In the method for producing a water-dispersible polyurethane resin according to another embodiment of the present invention, the step of removing the organic solvent is constituted by removing the organic solvent contained in the polyurethane resin formed by the chain extension of the polyurethane prepolymers, do. When the organic solvent contained in the polyurethane resin is removed, the polyurethane resin is uniformly dispersed in water.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the following examples are intended to clearly illustrate the technical features of the present invention and do not limit the scope of protection of the present invention.

1. Analysis of components of starch-containing saccharide mixture products

Syncsta L20 product (solid content of a saccharide mixture: 35% by weight; supplier: Target Co., Ltd.), Syncsta L21 product (solid content of a saccharide mixture: 35% (HPLC content: 35% by weight; supplier: Target Co., Ltd.) was measured using high performance liquid chromatography (HPLC 1200 series, Agilent). The separation column used herein was Aminex HPX 42A (manufacturer: Bio-Rad, USA). The compositional analysis results of the Syncsta L20 product are shown in Table 1, and the compositional analysis results of the Syncsta L21 product are shown in the following Table 2, and the component analysis results of the Syncsta L23 product are shown in the following Table 3.

Syncsta L20 product sugar division Sugar content (wt% based on peak area) Fructose 0.0 Glucose 3.4 DP2 10.9 DP3 12.6 DP4 6.8 DP5 9.7 DP6 17.5 DP7 6.7 DP8 1.7 DP9 1.5 DP10 + 29.2

Syncsta L21 product sugar division Sugar content (wt% based on peak area) Fructose 53.6 Glucose 43.5 DP2 2.4 DP3 0.5 DP4 0.0 DP5 0.0 DP6 0.0 DP7 0.0 DP8 0.0 DP9 0.0 DP10 + 0.0

Sugar separation of Syncsta L23 products Sugar content (wt% based on peak area) Fructose 0.0 Glucose 4.1 DP2 55.6 DP3 18.4 DP4 0.8 DP5 1.4 DP6 2.1 DP7 2.3 DP8 1.9 DP9 0.8 DP10 + 12.6

DP2 in the above Tables 1 to 3 is a dissacchride having a degree of polymerization of 2 based on hexose (especially glucose) and DP3 is a trisaccharide having a degree of polymerization of 3 based on hexose (in particular, glucose) ), DP4 is a tetrasaccharide based on hexose (especially glucose), DP5 is pentasaccharide with a degree of polymerization of 5 based on hexose (especially glucose), DP6 DP7 is a heptasaccharide with a degree of polymerization of 7 based on hexose (especially glucose), DP8 is a hexasaccharide with a degree of polymerization of 6 based on hexose (especially glucose) DP9 is a nonasaccharide having a degree of polymerization of 9 based on hexose (especially glucose), DP10 + is a hexose (especially glucose) -based polymer having a degree of polymerization of 8, ) Based polysaccharide having a degree of polymerization of 10 or more, The.

As shown in Table 1, in the case of the saccharide mixture constituting the Syncsta L20 product, the content of the DP4 saccharides was about 6.8% by weight, the content of the saccharides having a degree of polymerization of hexose (especially glucose) of 4 or more was about 73.1% . On the other hand, as shown in Table 2, the saccharide mixture constituting Syncsta L21 product contained 0.04% by weight of DP4 saccharides and the content of saccharides having a degree of polymerization of 4 or more based on hexose (especially glucose) was 0.0% . In addition, as shown in Table 3, the saccharide mixture constituting the Syncsta L23 product had a very low content of DP4 saccharides of 0.8% by weight, and the content of saccharides having a degree of polymerization of 4 or more based on hexose (especially glucose) was 21.9 Was much lower than the saccharide mixture comprising the Syncsta L20 product in weight percent.

2. Preparation of water-dispersible polyurethane resin

Production Example 1

About 0.065 mole of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation of a mixture of adipic acid and isophthalic acid, about 0.065 mole of a diethylene glycol and adipic acid acid, a mixture of about 0.045 mol of a polyester polyol having a number average molecular weight of about 1,800, 1,4-butanediol and adipic acid, obtained by a dehydration condensation reaction, About 0.03 mol of a polyester polyol having a number average molecular weight of about 2,000, about 0.17 mol of 2,2-dimethylol propionic acid, and about 0.17 mol of 4,4'-methylene bis (cyclo About 0.27 mole of [4,4'-Methylenebis (cyclohexyl isocyanate)] was added to the reactor, and methyl ethyl ketone (MEK) as an organic solvent was added thereto to dilute the solid content to about 75 wt% Deg.] C for about 6 hrs. To yield a polyurethane prepolymer solution had a solids content of about 75% by weight. Then, about 0.17 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 캜 for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 342.86 g of Syncsta L20 product (corresponding to 120 g in terms of the solids content of the saccharide mixture contained in Syncsta L20 product, the average molecular weight of the saccharide mixture contained in Syncsta L20 product is about 800, About 0.15 mole in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. Thereafter, the organic solvent was removed from the polyurethane resin at 45 캜 by using a vacuum pump, and a water-dispersible polyurethane resin having a solid content of about 35% by weight was obtained. Fig. 1 shows a water-dispersible polyurethane resin prepared by the method of Production Example 1. Fig.

Production Example 2

About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,500 obtained by dehydration condensation of a mixture of neopentyl glycol, adipic acid and isophthalic acid, 1,4-butane About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation of a mixture of 1,4-butanediol and adipic acid, 2,2-dimethylol propionic acid (2 , About 0.17 mol of 2-dimethylol propionic acid, and about 0.265 mol of 4,4'-methylenebis (cyclohexyl isocyanate)] were added to the reactor, and an organic solvent such as methyl ethyl ketone (MEK) was added to dilute the solution to a solids content of about 75% by weight, and the reaction was allowed to proceed at about 85 캜 for about 7 hours to obtain a polyurethane prepolymer solution having a solids content of about 75% by weight. Then, about 0.17 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 캜 for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 342.86 g of Syncsta L20 product (corresponding to 120 g in terms of the solids content of the saccharide mixture contained in Syncsta L20 product, the average molecular weight of the saccharide mixture contained in Syncsta L20 product is about 800, About 0.15 mole in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. Thereafter, the organic solvent was removed from the polyurethane resin at 45 캜 by using a vacuum pump, and a water-dispersible polyurethane resin having a solid content of about 35% by weight was obtained.

Production Example 3

About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation reaction of a mixture of adipic acid, isophthalic acid and diethylene glycol, 1,4-butane About 0.065 mole of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation reaction of a mixture of 1,4-butanediol, adipic acid and ethylene glycol, 2,2 About 0.25 mol of 4,4'-methylenebis (cyclohexyl isocyanate) is added to the reactor, and about 0.17 mol of 2,2-dimethylol propionic acid and 4,4'-methylenebis (cyclohexyl isocyanate) (MEK) as an organic solvent was added to dilute the solution to a solids content of about 75 wt%, followed by reaction at about 85 캜 for about 7 hr to prepare a polyurethane prepolymer solution having a solids content of about 75 wt% . Then, about 0.17 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 캜 for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 342.86 g of Syncsta L20 product (equivalent to 120 g in terms of the solids content of the saccharide mixture contained in Syncsta L20 product, and the average molecular weight of the saccharide mixture contained in Syncsta L20 product is about 800, About 0.15 mole in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. Thereafter, the organic solvent was removed from the polyurethane resin at 45 캜 by using a vacuum pump, and a water-dispersible polyurethane resin having a solid content of about 35% by weight was obtained.

Production Example 4

About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by a dehydration condensation reaction of a mixture of adipic acid, isophthalic acid and diethylene glycol, adipic acid 0.065 mole of a polyester polyol having a number average molecular weight of about 2,000, a 2,2-dimethylol propionic acid (2,2-dimethylol propionic acid) compound obtained by a dehydration condensation reaction of a mixture of an acid and an ethylene glycol About 0.265 mole of 4,4'-methylenebis (cyclohexyl isocyanate) was added to the reactor, and methyl ethyl ketone (MEK), which is an organic solvent, was added thereto to obtain a solid content The mixture was diluted to about 75% by weight, and then reacted at about 85 ° C for about 7 hours to obtain a polyurethane prepolymer solution having a solid content of about 75% by weight. Then, about 0.17 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 캜 for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 342.86 g of Syncsta L20 product (corresponding to 120 g in terms of the solids content of the saccharide mixture contained in Syncsta L20 product, the average molecular weight of the saccharide mixture contained in Syncsta L20 product is about 800, About 0.15 mole in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. Thereafter, the organic solvent was removed from the polyurethane resin at 45 캜 by using a vacuum pump, and a water-dispersible polyurethane resin having a solid content of about 35% by weight was obtained.

Production Example 5

About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation reaction of a mixture of adipic acid, isophthalic acid and diethylene glycol, 1,4-butane About 0.065 mole of a polyester polyol having a number average molecular weight of about 2,000, obtained by a dehydration condensation reaction of a mixture of 1,4-butanediol, adipic acid and neopentyl glycol, About 0.27 moles of 4,4'-methylenebis (cyclohexyl isocyanate) and about 0.17 moles of 2,2-dimethylol propionic acid were added to the reactor, Methyl ethyl ketone (MEK), an organic solvent, was added to dilute the solution to a solids content of about 75 wt%, followed by reaction at about 85 캜 for about 7 hr to prepare a polyurethane prepolymer solution having a solids content of about 75 wt% ≪ / RTI > Then, about 0.17 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 캜 for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 342.86 g of Syncsta L20 product (corresponding to 120 g in terms of the solids content of the saccharide mixture contained in Syncsta L20 product, the average molecular weight of the saccharide mixture contained in Syncsta L20 product is about 800, About 0.15 mole in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. Thereafter, the organic solvent was removed from the polyurethane resin at 45 캜 by using a vacuum pump, and a water-dispersible polyurethane resin having a solid content of about 35% by weight was obtained.

Production Example 6

About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by a dehydration condensation reaction of a mixture of adipic acid and diethylene glycol, 1,4-butanediol (1,4- about 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation reaction of a mixture of butanediol, adipic acid, neopentyl glycol and ethylene glycol, About 0.27 moles of 4,4'-methylenebis (cyclohexyl isocyanate) and about 0.17 moles of 2,2-dimethylol propionic acid were added to the reactor, Methyl ethyl ketone (MEK), an organic solvent, was added to dilute the solution to a solids content of about 75 wt%, followed by reaction at about 85 캜 for about 7 hr to prepare a polyurethane prepolymer solution having a solids content of about 75 wt% ≪ / RTI > Then, about 0.17 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 캜 for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 342.86 g of Syncsta L20 product (corresponding to 120 g in terms of the solids content of the saccharide mixture contained in Syncsta L20 product, the average molecular weight of the saccharide mixture contained in Syncsta L20 product is about 800, About 0.15 mole in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. Thereafter, the organic solvent was removed from the polyurethane resin at 45 캜 by using a vacuum pump, and a water-dispersible polyurethane resin having a solid content of about 35% by weight was obtained.

Comparative Production Example 1

About 0.065 mole of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation of a mixture of adipic acid and isophthalic acid, about 0.065 mole of a diethylene glycol and adipic acid acid, a mixture of about 0.045 mol of a polyester polyol having a number average molecular weight of about 1,800, 1,4-butanediol and adipic acid, obtained by a dehydration condensation reaction, About 0.03 mol of a polyester polyol having a number average molecular weight of about 2,000, about 0.17 mol of 2,2-dimethylol propionic acid, and about 0.17 mol of 4,4'-methylene bis (cyclo About 0.27 mole of [4,4'-Methylenebis (cyclohexyl isocyanate)] was added to the reactor, and methyl ethyl ketone (MEK) as an organic solvent was added thereto to dilute the solid content to about 75 wt% Deg.] C for about 6 hrs. To yield a polyurethane prepolymer solution had a solids content of about 75% by weight. Then, 0.34 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 DEG C for about 1 hour to neutralize the polyurethane prepolymer solution. Next, in a stirrer capable of high-speed stirring, 360 g of Syncsta L21 product (equivalent to about 126 g in terms of the solids content of the saccharide mixture contained in the Syncsta L21 product, and the average molecular weight of the saccharide mixture contained in Syncsta L21 product is about 181, About 0.7 mol in terms of the molar amount of the mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. The prepared polyurethane resin was gelled and could not be further tested. Fig. 2 shows the gelled polyurethane resin prepared by the method of Comparative Production Example 2. Fig.

Comparative Preparation Example 2

About 0.065 mole of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation of a mixture of adipic acid and isophthalic acid, about 0.065 mole of a diethylene glycol and adipic acid acid, a mixture of about 0.045 mol of a polyester polyol having a number average molecular weight of about 1,800, 1,4-butanediol and adipic acid, obtained by a dehydration condensation reaction, About 0.03 mol of a polyester polyol having a number average molecular weight of about 2,000, about 0.17 mol of 2,2-dimethylol propionic acid, and about 0.17 mol of 4,4'-methylene bis (cyclo About 0.27 mole of [4,4'-Methylenebis (cyclohexyl isocyanate)] was added to the reactor, and methyl ethyl ketone (MEK) as an organic solvent was added thereto to dilute the solid content to about 75 wt% Deg.] C for about 6 hrs. To yield a polyurethane prepolymer solution had a solids content of about 75% by weight. Then, 0.34 mol of trimethylamine was added to the polyurethane prepolymer solution, and the mixture was stirred at about 60 DEG C for about 1 hour to neutralize the polyurethane prepolymer solution. Next, a stirrer capable of high-speed agitation was charged with 514.29 g of Syncsta L23 (equivalent to about 180 g in terms of the solids content of the saccharide mixture contained in the Syncsta L23 product, and the average molecular weight of the saccharide mixture contained in the Syncsta L23 product was about 600 About 0.3 mole in terms of the molar amount of the saccharide mixture) and water were added and stirred at a high speed to prepare a saccharide mixture aqueous solution. At this time, the added amount of water was adjusted so that the final solid content was 35% by weight when the saccharide mixture aqueous solution and the neutralized polyurethane prepolymer solution were mixed and the organic solvent was evaporated. Then, the neutralized polyurethane prepolymer solution was gradually added while stirring the saccharide mixture aqueous solution in the stirrer at a high speed, and dispersed for about 1 hr to induce chain extension reaction to prepare a polyurethane resin. The prepared polyurethane resin was gelled and could not be further tested. Fig. 3 shows the gelled polyurethane resin prepared by the method of Comparative Preparation Example 3. Fig.

Comparative Preparation Example 3

About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,500 obtained by dehydration condensation of a mixture of neopentyl glycol, adipic acid and isophthalic acid, 1,4-butane About 0.065 mol of a polyester polyol having a number average molecular weight of about 2,000, obtained by dehydration condensation of a mixture of 1,4-butanediol and adipic acid, 2,2-dimethylol propionic acid (2 , About 0.17 mole of 2-dimethylol propionic acid, about 0.265 mole of 4,4'-methylenebis (cyclohexyl isocyanate), and 342.86 g of Syncsta L20 product Converted to the solid content of the saccharide mixture, and the average molecular weight of the saccharide mixture contained in the Syncsta L20 product is about 800, which corresponds to about 0.15 mol in terms of the molar amount of the saccharide mixture) is added to the reactor, and an organic solvent Methyl ethyl ketone ( MEK) was added thereto to dilute the polyurethane resin to a solid content of about 75 wt%, followed by reaction at about 85 캜 for about 7 hr to prepare a polyurethane resin. The prepared polyurethane resin was gelled and could not be further tested.

3. Adhesion measurement of water-dispersible polyurethane resin

To 100 parts by weight of the water-dispersible polyurethane resin prepared in Preparation Examples 1 to 6, about 3 parts by weight of a curing agent of 1,6-hexamethylene diisocyanate (HDI) type was added and mixed, . Thereafter, the adhesive was applied to the surface of the PET film by a bar-coater, and another PET film was laminated on the coated surface by a dry lamination method to prepare a test piece for adhesive force measurement.

In order to evaluate the initial adhesion, the prepared specimens were allowed to stand at room temperature for about 20 minutes. The specimens were cut to a size of about 15 mm × 15 mm, and then the specimens were peeled off at a speed of about 100 mm / min using a universal tensile tester The adhesive strength was evaluated and the average value was measured.

To evaluate the state adhesive strength, the prepared specimens were aged at about 45 ° C for about 24 hr and about 72 hr, respectively, and the specimens were cut to a size of about 15 mm × 15 mm. Five specimens were then weighed using a universal tensile tester And peeled at a rate of 100 mm / min to evaluate the adhesive strength, and then the average value was measured.

Table 4 shows the results of adhesion measurement of the water-dispersible polyurethane resin prepared in Production Examples 1 to 6.

Water-dispersible polyurethane resin Initial adhesion State adhesive force Production Example 1 213 512 Production Example 2 180 320 Production Example 3 175 311 Production Example 4 174 325 Production Example 5 164 333 Production Example 6 170 321

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. Therefore, the scope of protection of the present invention should not be limited to the specific embodiments disclosed as the best mode, but should be construed as including all embodiments belonging to the claims attached hereto.

Claims (15)

A carbamate bond formed by the reaction between a polyisocyanate and a polyol and polyurethane prepolymers having an isocyanate group at the end thereof have a structure in which the entire chain is extended via a saccharide mixture,
Wherein the saccharide mixture comprises 1 to 6 wt% of glucose based on the total weight of the saccharide mixture, 7 to 15 wt% of saccharides having a glucose-based degree of polymerization of 2, saccharides 8 having a glucose-based degree of polymerization of 3, (Glucose) -based polymer having a degree of polymerization of 4: 4 to 10: 1, a glucose-based polymer having a degree of polymerization of 5: 6 to 14% Based polymer having a degree of polymerization of 7 to 4 to 10% by weight, a glucose-based polymer having a degree of polymerization of 8 to 0.5 to 5% by weight, a glucose (glucose) -based polymer having a degree of polymerization of 9 A saccharide having a glucose degree of 10 or more based on a sugar content of 0.5 to 5 wt% and a residual amount.
delete The water dispersible polyurethane resin according to claim 1, wherein the polyisocyanate is 4,4'-methylenebis (cyclohexyl isocyanate).
The water dispersible polyurethane resin according to claim 1, wherein the polyol is a polyester polyol.
The method of claim 4, wherein the polyester polyol is selected from the group consisting of adipic acid / isophthalic acid copolymer, adipic acid / diethylene glycol copolymer, adipic acid adipic acid / 1,4-butanediol copolymers, adipic acid / ethylene glycol copolymers, adipic acid / isophthalic acid copolymers, acid / neopentyl glycol terpolymer, adipic acid / ehtylene glycol / 1,4-butanediol terpolymer, adipic acid / adipic acid / isophthalic acid / diethylene glycol ternary copolymer, adipic acid / 1,4-butanediol / neopentyl glycol neopentyl glycol) terpolymer or adipic acid / ethylene glycol / 1,4-butanediol / neopentyl glycols l) a polyurethane resin selected from the group consisting of a polyurethane resin and a polyurethane resin.
The water dispersible polyurethane resin according to claim 1, wherein the ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the polyol is 1: 0.2 to 1: 0.9.
The water dispersible polyurethane resin according to claim 1, wherein the ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the mixture of saccharides is 1: 0.2 to 1: 0.9.
Reacting a polyisocyanate and a polyol in an organic solvent to prepare a polyurethane prepolymer solution having an isocyanate group at a terminal; And
Adding a polyurethane prepolymer solution to a saccharide mixture aqueous solution and inducing a chain extension reaction to prepare a polyurethane resin,
Wherein the saccharide mixture comprises 1 to 6 wt% of glucose based on the total weight of the saccharide mixture, 7 to 15 wt% of saccharides having a glucose-based degree of polymerization of 2, saccharides 8 having a glucose-based degree of polymerization of 3, (Glucose) -based polymer having a degree of polymerization of 4: 4 to 10: 1, a glucose-based polymer having a degree of polymerization of 5: 6 to 14% Based polymer having a degree of polymerization of 7 to 4 to 10% by weight, a glucose-based polymer having a degree of polymerization of 8 to 0.5 to 5% by weight, a glucose (glucose) -based polymer having a degree of polymerization of 9 A saccharide having a glucose degree of 10 or more based on a sugar content of 0.5 to 5 wt% and a residual amount.
9. The method for producing a water dispersible polyurethane resin according to claim 8, further comprising the step of removing the organic solvent contained in the polyurethane resin.
delete The method for producing a water dispersible polyurethane resin according to claim 8, wherein the polyisocyanate is 4,4'-methylenebis (cyclohexyl isocyanate).
The method for producing a water dispersible polyurethane resin according to claim 8, wherein the polyol is a polyester polyol.
The method according to claim 12, wherein the polyester polyol is selected from the group consisting of adipic acid / isophthalic acid copolymer, adipic acid / diethylene glycol copolymer, adipic acid adipic acid / 1,4-butanediol copolymers, adipic acid / ethylene glycol copolymers, adipic acid / isophthalic acid copolymers, acid / neopentyl glycol terpolymer, adipic acid / ehtylene glycol / 1,4-butanediol terpolymer, adipic acid / adipic acid / isophthalic acid / diethylene glycol ternary copolymer, adipic acid / 1,4-butanediol / neopentyl glycol neopentyl glycol ternary copolymer or adipic acid / ethylene glycol / 1,4-butanediol / neopentyl glyc wherein the polyurethane resin is at least one selected from the group consisting of propylene copolymers, propylene copolymers, and propylene copolymers.
The process for producing a water dispersible polyurethane resin according to claim 8, wherein the ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the polyol is 1: 0.2 to 1: 0.9.
The process for producing a water dispersible polyurethane resin according to claim 8, wherein the ratio of the total equivalent number of the polyisocyanate to the total equivalent number of the mixture of saccharides is 1: 0.2 to 1: 0.9.

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